Synthesis and optical characterization of bipod carbazole ...

This study includes the synthesis and characterization of novel biscarbazole derivatives which were obtained by connection of two carbazole molecules through their nitrogen positions and substitution of phenyl, α-naphthyl and β-naphthyl on their 3- and 6- positions using the Suzuki-Miyaura Cross Coupling Reaction. The formation of synthesized molecules was determined by infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR), mass spectrometry (MS) and microanalysis methods. Their optical properties were studied using UV-Vis spectroscopy and temperature/excitation power density dependent photoluminescence (PL).

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Although carbazoles have been synthesized with substitutions in all positions (on benzene rings and nitrogen) [ 36 ], substitutions on 3- and 6- positions are very common [ 30 , 32 , 33 , 34 , 35 ]. Various methods with several steps have been used for substitution on the aromatic rings [ 36 , 39 ]. The most common and successfully used method is the Suzuki-Miyaura Cross Coupling Reaction [ 42 , 43 , 44 , 45 , 46 , 47 , 48 ]. The selection of groups expected to substitute on the desired positions is very important due to their crucial effect on the optical properties of the final product.

To identify the potential use of newly synthesized molecules in various applications, their photophysical and electrochemical properties need to be investigated. As an example, Slodek et al. reported a strong dependence of optical properties on the number of carbazole units and length of alkyl chain on said carbazole units in the molecule, as well as the position of substitution of carbazole for a donor-acceptor (D-A) system based on 2,4-dicarbazolyl-substituted quinolines. The low-temperature PL spectra were characterized by the spin-allowed fluorescence (400 nm) and spin-forbidden phosphorescence (490&#;527 nm) bands [ 34 ]. The synthesis and optical characterization of a salicylaldimine difluoroboron complex with tert-butyl group was carried out by Zhang and co-workers. The maximal emission peak of the synthesized compound in THF at 514 nm was ascribed to intramolecular charge transfer (ICT) emission. The peak positions of fluorescence emissions were blue and red-shifted to 506 and 522 nm for crystal structure and ground powder respectively [ 32 ]. Complex yellow (centered at ~574 nm) and red (centered at ~704 nm) colors were observed, with the relative intensities dependent on functional groups in PL spectra, for novel carbazole derivatives synthesized using a condensation reaction between carbazole amines and aromatic aldehydes [ 35 ].

Biscarbazoles as luminescent materials which include two aromatic heterocyclic organic compounds have been designed and synthesized for exploring some applications. These include organic light-emitting diodes (OLEDs) [ 1 , 2 , 3 ], organic photovoltaic and electronic devices [ 4 , 5 , 6 , 7 , 8 , 9 , 10 ], studying biochemical activities [ 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 ] and fundamental points of view [ 19 , 20 ]. Such molecules are especially suited to implementation in OLED technologies because of the electron donation of nitrogen on the carbazole ring. The efficient charge transfer from host carbazoles to connected molecules is provided by a strong π-electron conjugation. Carbazoles have been used as host matrices in highly efficient blue, green, or red electro-phosphorescent devices [ 6 , 7 , 8 , 16 , 21 ]. They also have good thermal properties and structural stability, allowing them to be used as a hole transport layer in OLED technology [ 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 ]. Carbazole/thioxanthene-S, S&#;-dioxide (EBCz-ThX) bipolar molecules synthesized by electron accepting and electron donating groups with a solvent-free green chemistry method were presented as blue phosphorescent light emitting devices [ 31 ]. A green light with a peak maximum at 550 nm under an applied external voltage was reported from a diode based on 2,4-dicarbazolylquinoline [ 32 ]. Multi-carbazole derivatives with twisted and zigzag-shape structures were synthesized and used as sensitizers for dye-sensitized solar cells [ 33 ].

C-4 was obtained from bis[2-(2-(3,6-dibromo-9H-carbazole-9-yl)ethoxy)etyl]ether (C-a2) (0.06 mmol, 0.048 g), 2-naphthylboronic acid (0.24 mmol, 0.041 g) and Pd 2 (dba) 3 (0. mmol, 0. g) were placed in a 100 ml flask, then quickly K 2 CO 3 (aq., 2M, 9 ml), toluene (18 ml) following the General Procedure-II. The light-brown, slightly oily solid was recrystallized from ethanol (0.048 g, 81.6%). FT-IR (γ cm -1 ): and (aromatic C-H stretch), and (symmetric and asymmetric aliphatic C-H stretch), , and (aromatic C=C stretch, naphthalene), (carbazole C=C stretch), (aliphatic C-H bend, asymmetric), (cbz ring stretch), (C-H aliphatic, in-plane, symmetric), (C-O-C asymmetric bend), (aliphatic C-H bend, out-of-plane), (C-O-C symmetric stretch), 811 and 737 (aromatic symmetric C-H bend on β-substituted naphthalene, out-of-plane), 748 and 699 (aromatic symmetric C-H bend on carbazole benzene, out-of-plane,). 1 H NMR (CDCl 3 , δ, ppm): 3.287 (4H, s), 3.725 (2H, t), 4.379 (2H, t), 7.218 (1H, d), 7.927 (1H, s), 7.900 (1H, d), 8.122-8.059 (1H, d), 7.258 (1H, s), 7.514 (2H, m), 7.279 (2H, s), 7.952 (1H, d), 7.361 (1H, d). 13 C NMR (CDCl 3 , δ, ppm): 70.548, 70.650, 125.332, 125.759, 61.434, 133.757, 125.718, 126.099, 143.210, 126.381, 126.030, 138.398, 127.684, 133.510, 128.537, 132.675, 128.233. Anal. Calc. for C 72 H 56 N 2 O 3 (MW=996.43): C, 86.72; H, 5.66; N, 2.81. Found: C, 86.65; H, 5.63; N, 2.85 %. LC-MS (m/z): 996.43 (M + , CH 3 CN, Error % = 0.003).

C-3 was obtained from bis[2-(2-(3,6-dibromo-9H-carbazole-9-yl)ethoxy)etyl]ether (C-a2) (0.04 mmol, 0.032 g), naphthalene-1-boronic acid (0.16 mmol, 0.028 g) and Pd 2 (dba) 3 (0. mmol, 0.001 g) were placed in a 100 ml flask, then quickly K 2 CO 3 (aq., 2M, 6 ml), toluene (12 ml) following the General Procedure-II. The light-brown, slightly oily solid was recrystallized from ethanol (0.024 g, 61.3%). FT-IR (γ cm -1 ): and (aromatic C-H stretch), and (aliphatic C-H stretch, asymmetric and symmetric), , and (aromatic C=C stretch, naphthalene), (carbazole C=C stretch), (aliphatic C-H bend, asymmetric), (carbazole ring stretch), (aliphatic C-H bend, symmetric), (C-O-C asymmetric bend), (aliphatic C-H bend, out-of-plane), (C-N bend), (C-O-C symmetric bend), 801 and 780 (aromatic symmetric C-H bending on α-substituted naphthalene, out-of-plane), 757 and 698 (aromatic symmetric carbazole bend, out-of-plane). 1 H NMR (CDCl 3 , δ, ppm): 3.388 (4H, s), 3.498 (2H, t), 3.635 (2H, t), 7.262 (1H, d), 7.590 (1H, d), 7.608 (1H, d), 7.539 (1H, d), 7.281 (1H, s), 8.060 (1H, m), 7.222-7.135 (2H, m), 7.467 (1H, m), 7.498 (1H, m), 7.377 (1H, d), 7.940 (1H, d). 13 C NMR (CDCl 3 , δ, ppm): 74.010-72.125, 61.406, 133.150, 125.332, 125.759, 141.253, 126.505, 125.926, 138.408, 132.807, 128.106, 127.854, 133.485, 128.185, 127.786. Anal. Calc. for C 72 H 56 N 2 O 3 (MW=996.43): C, 86.72; H, 5.66; N, 2.81. Found: C, 86.68; H, 5.60; N, 2.90. %. LC-MS (m/z): 996.43 (M + , CH 3 CN, Error % = 0.003).

C-2 was obtained from bis[2-(2-(3,6-dibromo-9H-carbazole-9-yl)ethoxy)etyl]ether (C-a2) (0.2 mmol, 0.16 g), PhB(OH) 2 (0.8 mmol, 0.098 g) and Pd 2 (dba) 3 (0.06 mmol, 0.055 g) and K 2 CO 3 (aq., 2M, 3 ml), toluene (6 ml) following the General Procedure-II. The yellow-green, slightly oily solid was recrystallized from ethanol (0.127 g, 80.3%). FT-IR (γ cm -1 ): (aromatic C-H stretch), and (aliphatic C-H, symmetric and asymmetric stretch), (aromatic C=C stretch), (aliphatic C-H bend, asymmetric), (carbazole ring stretch), (aliphatic C-H bend, symmetric), (C-O-C asymmetric bend), (aliphatic C-H bend, out-of-plane), (C-N bend), (C-O-C symmetric bend), 740 and 701 (aromatic C-H bend, out-of-plane, symmetric). 1 H NMR (CDCl 3 , δ, ppm): 3.472 (4H, s), 3.810 (2H, t), 4.291 (2H, t), 7.619 (1H, d), 8.074 (1H, d), 8..106 (1H, d), 8.040 (1H, d), 7.601 (1H, s), 7.401 (1H, s), 7.417 (1H, d), 7.333 (1H, m). 13 C NMR (CDCl 3 , δ, ppm): 70.535, 69.301, 70.901, 60.644, 131.885, 110.831, 123.434 143.323, 123.945, 123.023, 139.521, 128.395, 128.974, 127.237. Anal. Calc. for C 56 H 48 N 2 O 3 (MW=796.37): C, 84.39; H, 6.07; N, 3.51. Found: C, 84.36; H, 6.01; N, 3.55%. LC-MS (m/z): 796.40 (M + , CH 3 CN, Error % = 0.004).

C-1 was obtained from 1,2-bis(2-(3,6-dibromo-9H-carbazole-9-yl) ethoxy)ethane (C-a1) (0.2 mmol, 0.15 g), PhB(OH) 2 (0.8 mmol, 0.098 g) and Pd 2 (dba) 3 (0.06 mmol, 0.055 g) and K 2 CO 3 (aq., 2M, 3 ml), toluene (6 ml) following the General Procedure-II. The yellow, slightly oily solid product was achieved by recrystallization from ethanol (0.020 g, 13.5%). FT-IR (γ cm -1 ): and (aromatic C-H stretch), and (C-H, symmetric and asymmetric stretch), (Aromatic C=C stretch), (C-H, aliphatic, in-plane, asymmetric bend), (carbazole ring stretch), (aliphatic C-H bend, in-plane, symmetric), (C-O-C asymmetric bend), (aliphatic C-H, out-of-plane bending), (C-N bend), (C-O-C symmetric bend), 748 and 702 (aromatic C-H, out-of-plane, symmetric bending). 1 H NMR (CDCl 3 , δ, ppm): 3.475 (2H, s), 3.832 (2H, t), 4.429 (2H, t), 7.526 (1H, d), 8.107 (1H, m), 7.612 (1H, m), 7.612 (1H, d), 7.406 (1H, s), 7,412 (1H, d), 7.390 (1H, s). 13 C NMR (CDCl 3 , δ, ppm): 69.323, 70.527, 58.602, 130.514, 123.191-110.632, 143.323, 139.551, 128.380, 128.959, 129.081. Anal. Calc. for C 54 H 44 N 2 O 2 (MW=752.34): C, 86.14; H, 5.89; N, 3.72. Found: C, 86.00; H, 5.81; N, 3.77%. LC-MS (m/z): 753.30 (M + , CH 3 CN, Error % = 0.128).

Brominated carbazoles ( C-a1 or C-a2 ) (3.33 equivalent), PhB(OH) 2 (13.33 equivalent) and Pd 2 (dba) 3 (1.0 equivalent) were placed in 100 ml flask. K 2 CO 3 (aq., 2M), toluene and two drops of Aliquot 336 were quickly added. The mixture degassed with nitrogen was stirred at 80°C for 48 hours in a nitrogen atmosphere. The reaction was complete and allowed to cool to room temperature. It was then filtered in dichloromethane (3 x 30 ml) and washed with water (200 ml). Organic phase was obtained after separating the layers and drying over Na 2 SO 4 . The solution was evaporated and recrystallized from ethanol.

3,6-dibromocarbazole ( B ) (2.0 equivalent), 1,2-bis(2-chloroethoxy)ethane (1.0 equivalent), TBAI and 50% NaOH solution (10 ml) were added in 100 ml flask and refluxed while it was stirring at 78 ° C for 48 hours [ 49 ]. After the reaction was complete, the mixture was cooled down to room temperature. The mixture was then filtered with dichloromethane (3x30 ml) and washed in water (200 ml). Organic phase was obtained after separating the layers and drying over Na 2 SO 4 . The solution was evaporated and the oily solid product was obtained by recrystallizing from a mixture of chloroform/n-hexane (1:1) (see Figure 1 ).

Carbazole ( A ) (5 mmol, 0.835 g) was firstly dissolved in 100 ml of dichloromethane. SiO 2 (20 g) was then added and stirred. A solution which contained NBS (10 mmol, 1.78 g) dissolved in 150 ml of dichloromethane was added dropwise to the carbazole mixture, and was continuously stirred at room temperature for 24 hours in a dark environment [ 45 ]. The entire mixture was then filtered and the residue was washed with dichloromethane (3 x 30 ml). The combined organic fractions were rinsed with water (200 ml) and, after the phases were separated, the organic layer was collected. The solvent was evaporated after which a light green powder was obtained (1.176 g, yield: 72%). FT-IR (γ cm-1): (N-H stretch), (aromatic C-H stretch), (aromatic C=C stretch), (carbazole ring stretch), (C-N bend), 802 (C-Br bend), 739 and 686 (aromatic C-H out-of-plane bend)

All starting materials were purchased from Merck, Sigma-Aldrich and Fluka Co., and were used after further analytical purifications using silica gel column chromatography. FT-IR spectra were taken using Perkin Elmer BX2 FTIR Spectrometer. Both 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) spectra were obtained in CDCl 3 using an Agilent Tech. 400 NMR Spectrometer. LC-MS spectra were recorded on an Agilent Technologies- Infinity (LC) Quadropole (MS) Mass Spectrometer using acetonitrile as the solvent. Microanalyses were performed with a Thermo Scientific Flash elemental analyzer. The absorption spectra were recorded using a Perkin-Elmer Lambda 25 UV-Vis Spectrometer. The temperature and excitation power density dependent photoluminescence measurements were performed in the temperature range of 20&#;300 K and excitation power densities between 2.6-330 mW/cm 2 . A frequency tripled Nd:YLFQ-switched pulse laser at 349 nm was used for the excitation. The luminescence was collected by suitable lenses and then dispersed with a 500 mm spectrometer using line/mm grating and detected by Intensified Charge Coupled Device (ICCD) camera.

Results

In this work 1,2-bis(2-(3,6-diphenyl-9H-carbazole-9-yl) ethoxy)ethane (C-1), bis[2-(2-(3,6- diphenyl-9H-carbazole-9-yl) ethoxy)etyl]ether (C-2), bis[2-(2-(3,6-di(naphthalene-1-yl)-9H-carbazol-9-yl)ethoxy)etyl]ether (C-3) and bis[2-(2-(3,6-di(naphthalene-2-yl)-9H-carbazol-9-yl) ethoxy)ethyl]ether (C-4) were synthesized. The syntheses of these compounds were started by brominating the 3-and 6- position of the carbazole ring. During this process, SiO2 was used as an efficient-reusable catalyst [42]. Then, two molar equivalents of bromo carbazole were led to react with dichloroether derivatives via SN2 reaction. The oily solid product was obtained by recrystallizing the mixture of chloroform/n-hexane (1:1). Finally, the bromines were replaced by phenyl boronic acid, α-naphthyl boronic acid and β-naphthyl boronic acid moieties via the Suzuki-Miyaura Cross Coupling Reaction. The oily solid products were re-crystallized from ethanol. The yields of C-1, C-2, C-3 and C-4 bipod carbazole derivatives were obtained as 13.5, 80.3, 61.3 and 81.6%, respectively.

In FT-IR spectra, the N-H stretch peak of secondary amines which is only seen in carbazole and 3,6-dibromocarbazole, disappeared due to the reaction between 3,6-dibromocarbazole and 1,2-bis(2-chloroethoxy)ethane. Therefore, the N-H stretch peak was not observed in FT-IR spectra of C-a1, a2, 1, 2, 3, and 4. The C-Br stretch peak was observed in 3,6-dibromocarbazole, C-a1 and C-a2 but not in C-1, 2, 3, and 4. These results indicate that no Br atoms attached on carbazole were left. Br atoms were replaced by substitution of boron acid molecules via the Suzuki-Miyaura Cross Coupling reaction. Symmetric and asymmetric peaks of aliphatic C-H and C-O-C were observed in C-a1, a2, 1, 2, 3 and 4, but not in carbazole or 3,6-dibromocarbazole. This indicates the presence of ether and aliphatic groups. As a result, the syntheses of intermediate and final products were confirmed with FT-IR data.

The 1H-NMR and 13C-NMR spectra data also support successful synthesis of C-1, C-2, C-3 and C-4 (supplementary materials). For example, in 1H-NMR spectra of C-3 molecule, ether peaks labeled as 1, 2, and 3 were observed at δ 3.472-4.291 ppm and aromatic peaks at δ 7.619-8.106 ppm (supplementary materials). In 13C-NMR spectra of the same molecule, ether peaks were observed at δ 60.644-70.901 ppm, and aromatic peaks at δ 110..323 ppm (supplementary materials).

The molecular ion peaks of C-1, C-2, C-3, and C-4 were obtained from LC-MS spectra taken in dichloromethane. The spectra contain peaks of molecular ions and other possible ions (supplementary materials). The results of microanalysis also support successful synthesis of compounds.

In UV-vis spectra, the absorption bands were observed in the range of 225-380 nm for all samples. This range is suitable for our PL measurement using 349 nm laser.

The PL spectra are shown in Figure 2 together with reference sample containing only carbazole for comparison. The reference sample has several relatively narrow peaks over the spectral range between 370 and 500 nm with the most intense peak situated at 420 nm.

Figure 2

In the work done by Zhang et al. [32], three absorption peaks located at 294, 354 and 379 nm were observed for salicylaldimine difluoroboron complex with tert-butyl group. They were attributed to carbazole, π-π* and intramolecular charge transfer (ICT) transitions respectively. The emission peak of the synthesized compound in THF mixure present at 514 nm was ascribed to ICT emission. The peak positions of fluorescence emissions were blue and red-shifted to 506 and 522 nm for crystal structure and ground powder respectively. The optical properties of two 2,4-difluorenylquinoline derivatives with different lengths of alkyl chain at the fluorene unit (one with methyl and other with octyl chain) of donor-acceptor (D-A) type were reported by Slodek et al [50]. They observed bright emission in the blue spectral region at 406 nm, whereas the replacement of fluorine with carbazole unit resulted in a bathochromic shift of peak wavelength with emission bands at 425 and 530 nm.

Due to stronger π-conjugation and efficient intramolecular charge transfer from carbazole to aromatic compounds, the PL spectra of C-1, C-2, C-3 and C-4 depict completely different character compared to carbazole. As first seen, all spectra were dominated with a broad peak at about ~513, 523, 553, 565 nm for samples C-1, C-2, C-3 and C-4, respectively. However, these peaks were decomposed into two peaks using Gauss fitting as shown in the inset.

Figures 3 and 4 show temperature dependent PL peak positions (the one at high energy side of spectrum) and normalized integrated intensities deduced from the Gauss fitting to the experimental data. From figures, the peak wavelengths and integrated intensities are approximately temperature independent for C-1 and C-2. This is consistent with the spatial configuration of structures C-1 and C-2, where the most stable formation is expected at the anti-position of the carbazole and benzene rings. Within the temperature range studied in PL measurement, no changes are expected for both structures. On the other hand, for the samples (C-3 and C-4), in which the α-naphthyl and β-naphthyl are attached to carbazole, the peak wavelengths and integrated intensities increase as the temperature increases. At low temperatures, the rotation around the sigma bond is weak and prefers to be at the most stable anti-position. As the temperature increases the rotation of the sigma bond is expected to increase. A resonance occurs when the electrons of p orbital of carbazole that do not participate in hybridization and p orbital of naphthyl group come to the same parallel plane. This provides a complete resonance on the molecule that causes redshift in the peak wavelength positions and increases in integrated intensities of PL spectra, as observed. The change of integrated intensity within a temperature range of 20-300 K for C-3 is approximately three times, while for C-4 it is about 2.3 times. This is probably due to the difference in stereo-electronic effect of compounds attached to the alpha and beta positions.

Figure 3

Figure 4

Figure 5 shows the excitation power density dependent normalized integrated intensities for all samples. As seen from the figure integrated intensity increases with excitation power density as expected. At high excitation density, a small degree of saturation is realized.

Figure 5

Guide to Chemical Safety for Laboratory Workers

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The Cornell University Chemical Hygiene Plan is developed and coordinated by Environmental Health and Safety. Environmental Health and Safety and the individual laboratories that are regulated by the Standard will share the burden of compliance with the Standard. Many laboratories at the University have developed safety manuals and procedures that already address chemical safety in laboratories. The Lab Standard should not require changes that are a burden to laboratories.

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A hazardous chemical is defined by OSHA as a substance for which there is statistically significant evidence, based on at least one scientific study, showing that acute or chronic harm may result from exposure to that chemical. This broad definition clearly applies to most of the chemicals typically used in laboratories.

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The Chemical Hygiene Plan

Standard Operating Procedures

There are over three thousand research laboratories at Cornell University and most of these involve the use of hazardous chemicals. Many departments have developed comprehensive safety and health manuals. These manuals address specific safety rules, regulations, and standard operating procedures for laboratory workers in the department or college. Most of the laboratories have referred to widely known and accepted laboratory safety practices referenced in Prudent Practices in the Laboratory, published by the National Research Council, or Safety in Academic Chemical Laboratories, published by the American Chemical Society.

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Control Measures

The exposure to hazardous chemicals in the laboratory shall be controlled through the use of good general laboratory practices, standard operating procedures specific to an individual laboratory or department, engineering controls, and personal protective equipment.

General laboratory practices: Environmental Health and Safety provides laboratories with information about general laboratory work practices and rules that are recognized as effective control measures to minimize exposure to hazardous chemicals in the laboratory. The information is referenced from Prudent Practices in the Laboratory and Safety in Academic Chemistry Laboratories. These general procedures include guidelines on use of chemicals, accidents and spills, personal protection, use of fume hoods, and other good laboratory practice information.

Specific laboratory practices: Individual departments or laboratories must develop additional written safety procedures whenever necessary to protect laboratory workers from specific chemical hazards that are unique to their particular area of research. Particular attention should be given to control measures for operations that involve the use of select carcinogens or acutely toxic chemicals. Environmental Health and Safety can assist researchers in developing safety procedures for specific hazards.

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Engineering controls: There are a variety of engineering controls that can be used in the laboratory to control exposures to hazardous chemicals. Some of the engineering controls that will be used in laboratories at Cornell may include dilution ventilation, local exhaust ventilation (fume hoods), and proper storage facilities.

Personal protective equipment: Personal protective equipment will be available to laboratory workers for use to reduce exposures to hazardous chemicals in the laboratory. Common personal protective equipment such as goggles, gloves, face shields, and aprons are recommended for use with hazardous chemicals. Other personal protective equipment such as respirators will be available and recommended for use if necessary. (See Section 10.) Environmental Health and Safety will assist in the proper selection, use, and care of personal protective equipment. Personal protective equipment will be readily available and most equipment is provided at no cost to the employee.

Other: Other control methods that will be used to determine and reduce employee exposures to hazardous chemicals in the laboratory may include exposure monitoring, testing eyewash and emergency shower facilities, developing emergency procedures, proper container selection, and substitution of less toxic chemicals whenever possible.

Fume Hoods

The fume hood inspection program at Cornell consists of an initial comprehensive inspection followed by annual standardized inspections for all campus fume hoods. This initial inspection will provide extensive baseline information including but not limited to hood usage, type of hood, room and building information, as well as average face velocity measurements. Follow-up inspection for proper use and face velocity measurements will be done routinely each year or when requests for inspections are made. After each inspection, hoods will be labeled with inspection stickers regarding face velocity measurements and safety operating tips. All inspection information will be recorded on a standard form and will be kept on file at Environmental Health and Safety.

The fume hood inspections consist of three parts:

1. Recording of information identifying building, room, hood usage, type of hood, person in charge, etc.

2. Measurement of hood average face velocity.

3. Determination of acceptability of hood and discussion of results with hood operator and/or person in charge.

Whenever possible, a dry ice capture test will be performed on the hood being evaluated. The results of this procedure will be posted near the face of the hood.

Hoods will be classified as acceptable or unacceptable based on the face velocity measurement. An average face velocity of 80 fpm or greater (hood sash fully open) is acceptable. The hood will be considered unacceptable if it cannot achieve an 80 fpm average with the sash at two feet (2.0') opening or greater. If a hood is found to be unacceptable, a warning sign indicating that the hood has been

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inspected and found not to provide optimum protection will then be attached to the center of the sash window or another suitable but conspicuous location. Instructions are included explaining proper procedures to have the hood repaired or maintenance service performed. EH&S will coordinate fume hood repairs with the Facilities and Campus Services shops to ensure a timely and accurate repair process. Upon completion of these services, Environmental Health and Safety must be contacted to reinspect the hood.

The proper functioning and maintenance of other protective equipment used in the lab is the responsibility of a variety of service groups. Maintenance Management, Facilities Engineering, Environmental Health and Safety, and other groups provide and service equipment such as fire extinguishers, eyewash/shower facilities, spill response equipment, and mechanical ventilation. Periodic inspections and maintenance by these groups ensure proper functioning and adequate performance of the equipment.

Information and Training

Cornell will provide employees with information and training to ensure that they are apprised of the hazards of chemicals present in their work area. This training and information will come from a variety of sources.

Environmental Health and Safety has been providing training programs for laboratory workers for several years. These programs include information on chemical safety, Right-to-Know, Hazard Communication, the Lab Standard, radiation safety, spill response, eye protection, and how to obtain additional safety information.

The program "Chemical Safety for Laboratory Workers" is currently being presented each month to newly hired laboratory personnel. These programs are publicized by and a letter sent to every new Cornell employee. Anyone who has not yet attended is encouraged to attend. This "Chemical Safety for Laboratory Workers" training program is also currently being given for new graduate students and undergraduate students working with chemicals in laboratories.

Notebooks of Material Safety Data Sheets (MSDSs) for chemicals commonly used in laboratories are located in each department, and new MSDSs for new chemical purchases are sent on to the departments as they are received at EH&S. Employees are encouraged to consult these MSDS notebooks, or to call or write to EH&S for additional MSDSs. Chemical information request forms are included in these notebooks, in the training program handouts, and on our Web site for the convenience of employees. The EH&S Web site also gives information to employees for obtaining MSDSs from various internal and external Web sites.

Environmental Health and Safety will provide information to laboratories, including the Chemical Hygiene Plan, Material Safety Data Sheets (MSDSs), OSHA Permissible Exposure Limits, and specific topical information from employee requests. Environmental Health and Safety personnel are available on a daily basis to answer questions and provide information to employees about chemical safety in laboratories.

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Other sources of information and training may come from informal group or individual discussions with a supervisor, posted notices, and handout booklets. Properly labeled containers will give immediate warning information to workers about specific chemical hazards. Many departments have safety committees and safety manuals that provide information on laboratory safety. Employees are encouraged to contact their department safety representative and EH&S for information about safety in laboratories.

Prior Approval for High Hazard Work

Environmental Health and Safety can assist in identifying circumstances when there should be prior approval before implementation of a particular laboratory operation. Due to the large variety of research being conducted in laboratories at the University, it is impossible to apply one prior approval process that can include all laboratories. Instead, high hazard types of activities should be identified by the principal investigator or person responsible for the work, and any type of approval process should be addressed in the laboratory's or Department's standard operating procedures.

Environmental Health and Safety will assist in providing information to researchers about work with select carcinogens, highly toxic gases, and other high hazard chemicals. General guidelines and recommendations for the safe handling, use and control of high hazard materials can be provided through MSDSs, and reference sources such as Prudent Practices in the Laboratory, and Safety in Academic Chemistry Laboratories. In certain instances, prior approval from a research related committee may be required before beginning an operation or activity.

Currently, there are some circumstances where prior approval is required before work can begin. These include:

• Research using live vertebrate animals - Institutional Animal Care and Use Committee (3-).

• Biohazards - College of Veterinary Medicine Biohazards Committee (Veterinary College, 3-), Environmental Health (non-Veterinary College biohazards, 5-).

• Recombinant DNA use - Recombinant DNA Committee (5-).

• Use of Radioactive Materials - Environmental Health and Safety (5-).

Medical Consultation and Medical Examinations

Medical consultation and medical examinations will be made available to laboratory workers who work with hazardous chemicals, as required. All work related medical examinations and consultations will be performed by or under the direct supervision of a licensed physician and will be provided at no cost to the employee through the Gannett Health Center.

The opportunity to receive medical attention will be provided to employees who work with hazardous chemicals under the following circumstances:

3.3

• Whenever an employee develops signs or symptoms associated with a hazardous chemical to which the employee may have been exposed in the laboratory.

• Where exposure monitoring reveals an exposure level routinely above the action level (or in the absence of an action level, the Permissible Exposure Limit) for an OSHA regulated substance for which there are exposure monitoring and medical surveillance requirements.

• In the event of a spill, leak, explosion or other occurrence resulting in the likelihood of a hazardous exposure, the affected employee will be provided an opportunity for a medical consultation. The consultation shall be for the purpose of determining the need for a medical examination.

All records of medical consultation, examinations, tests or written opinions shall be maintained at Gannett Health Center in accordance with 29 CFR .20. The Gannett Health Center is located at 10 Central Avenue and the number is 255-. Exposure monitoring records of contaminate levels in laboratories will be maintained in Environmental Health and Safety at 125 Humphreys Service Building. The number at EH&S is 255-.

Personnel Responsible for the Chemical Hygiene Plan

Environmental Health and Safety will provide technical information and program support to assist in compliance with the OSHA Laboratory Standard. Environmental Health and Safety will maintain the Chemical Hygiene Plan (CHP) and the institutional Chemical Hygiene Officer responsibilities will reside within EH&S. However, it will be the responsibility of the individual supervisor (usually the principal investigator), department or college to be in compliance with the components of the plan.

Provisions for Additional Employee Protection for Work with Particularly Hazardous Substances

The Chemical Hygiene Plan includes provisions for additional employee protection for work with particularly hazardous substances. Research involving the use of particularly hazardous substances, such as select carcinogens, reproductive toxins, or acutely toxic chemicals may require prior review to ensure that adequate controls are in place which will protect the worker. Environmental Health and Safety will assist with the review and make recommendations for additional employee protection.

Additional employee protection may require the use of additional provisions such as:

• Establishment of a designated area

• Use of containment devices such as fume hoods or glove boxes

• Procedures for safe removal of contaminated waste

• Decontamination procedures

• Personal and area air monitoring

• Leak detection systems

3.4

The provision for additional controls may require the expertise and recommendations of various groups including EH&S, Facilities Engineering, technical committees, and outside consulting companies. These groups have all been previously involved with review and implementation of controls for high hazard research. All additional provisions for work with particularly hazardous materials must be incorporated into the standard operation procedures for those materials.

3.5

GENERAL PRINCIPLES FOR WORK WITH LABORATORY CHEMICALS

The following are general principles that can be applied to almost all uses of hazardous chemicals in laboratories:

1. It is prudent to minimize all chemical exposures: Because few laboratory chemicals are without hazards, general precautions for handling all laboratory chemicals shall be adopted, rather than specific guidelines for particular chemicals. Skin contact with chemicals should be avoided as a cardinal rule.

2. Avoid underestimation of risk: Even for substances of no known significant hazard, exposure shall be minimized; for work with substances which present special hazards, special precautions shall be taken. One should assume that any mixture may be more toxic than its most toxic component and that all substances of unknown toxicity are potentially toxic.

3. Provide adequate ventilation: The best way to prevent exposure to airborne substances is to prevent their escape into the working atmosphere by the use of hoods and other ventilation devices.

4. Institute a chemical hygiene program: Follow the Cornell Chemical Hygiene Plan. This must be a regular, continuing effort, not merely a standby or short-term activity. The Chemical Hygiene Plan recommendations shall be followed in academic teaching laboratories as well as by full-time laboratory workers.

5. Observe exposure limits: The Permissible Exposure Limits (PELs) of OSHA and the current Threshold Limit Values (TLVs) of the American Conference of Governmental Industrial Hygienists shall not be exceeded. The Permissible Exposure Limits and Threshold Limit Values can be obtained by contacting the Department of Environmental Health and Safety at 255-.

4.0

GENERAL RULES FOR WORK WITH LABORATORY CHEMICALS

The following are general safety and health rules that must be followed for essentially all
laboratory work with hazardous chemicals. It is required that laboratories review and comply with these
basic safety rules. Laboratories may need to modify these rules to provide additional controls to protect
employees from chemical and physical hazards associated with the particular operation being conducted.

Accidents and spills:

Eye Contact: Promptly flush eyes with water for at least 15 minutes. Use both hands to hold the eyelids open so that the entire surface of the eye may be rinsed. Seek immediate medical attention.

Inhalation or Ingestion: Seek medical attention.
Skin Contact: Promptly flush the affected area with water and remove any contaminated clothing. If
symptoms persist after washing for 15 minutes or longer, seek medical attention.

If medical attention is necessary, call 911 or contact the Gannett Health Center at 255-.

For large spills call 911. For spill clean-up assistance for incidental spills and disposal of chemical waste,
contact Environmental Health and Safety at 255-.
In the event of a fire call 911. If you extinguish a small fire with a portable fire extinguisher it must be

reported to Environmental Health and Safety at 255-.

Avoidance of "routine" exposure:

Develop and encourage safe habits. Avoid unnecessary exposure to chemicals by any route (inhalation,
absorption through skin, or ingestion).
Do not smell or taste chemicals.

Inspect gloves and test glove boxes before use.
Do not allow the release of toxic substances in cold rooms and warm rooms, since these generally have
contained, recirculated atmospheres.

Children in Labs:

Children are not permitted in Cornell University laboratories and other areas where hazardous materials and equipment are used. Access to these areas is restricted to authorized Cornell faculty, staff, students, and other individuals conducting business on campus.

5.0

Supervisors of laboratories and areas where hazardous materials and equipment is used or stored are responsible for ensuring that children are not allowed in these areas.

Choice of chemicals:

Use only those chemicals for which controls are available to minimize exposure to employees and
students.
Substitute less hazardous chemicals for high hazard chemicals whenever possible.

Use the smallest possible quantities of chemicals feasible for a protocol.
Whenever possible, do not generate mixed hazardous wastes, for example, radioactivity with a flammable
solvent.

Search existing inventories and use chemicals in stock before purchasing new chemicals.

Eating, smoking, etc.:

To prevent exposure to hazardous chemicals through ingestion, eating, drinking, gum chewing, or application of cosmetics in areas where laboratory chemicals are present is prohibited.

Smoking is prohibited in all lab areas at Cornell.

Personal hygiene is very important. Wash your hands thoroughly after using any chemicals or other laboratory protocols and especially before eating or drinking.

Prohibit storage, handling or consumption of food or beverages in storage areas, refrigerators, glassware or utensils that are also used for laboratory operations. Refrigerators for the storage of food must be labeled, "For Food Storage Only. No Chemicals or Samples."

Equipment and glassware:

Handle and store laboratory glassware with care to avoid damage.
Inspect all glassware for damage prior to each use. Do not use damaged glassware.
Use extra care with Dewar flasks and other evacuated glass apparatus. Shield or wrap them to contain

chemicals and fragments should an implosion occur.

All high vacuum glassware should be taped when possible to minimize shrapnel in the event of an
implosion.
Use equipment only for its designed purpose.

5.1

Horseplay:

Practical jokes or other behavior that might confuse, startle, or distract another worker is prohibited.

Mouth suction:

Do not use mouth suction for pipeting or starting a siphon! Even if you don't get any liquid in your mouth, you are sucking the fumes.

Personal apparel:

Confine long hair, loose clothing, and jewelry.
Wear shoes at all times in the laboratory. Avoid wearing sandals, perforated or open toed shoes.
Wear a lab coat when working with chemicals. Shorts should not be worn in a lab when using corrosives

or other chemicals that present a skin contact hazard.

Personal protection:

Appropriate eye protection must be worn by all persons, including visitors, where chemicals are stored or handled.

Wear appropriate gloves when the potential for contact with toxic materials exists. Inspect the gloves before each use, wash them before removal, and replace them periodically. Discard disposable gloves immediately following overt contamination with highly toxic materials. EH&S can provide information on the resistance to chemicals of common glove materials, as well as assistance in the selection of the proper glove type. (See Section 11.)

Use appropriate respiratory equipment only when air contaminant exposure levels are not sufficiently controlled by engineering, work practice, or administrative controls. (See Section 10.)

Remove laboratory coats immediately on significant contamination. Contaminated lab coats must be designated as such before being removed to a commercial laundry to protect workers in such establishments.

Planning:

Seek information and advice about hazards, plan appropriate protective procedures, and plan positioning of equipment before beginning any new operation.

Protocols using highly hazardous materials, equipment or methods must have prior approval from your supervisor or safety committee.

5.2

Unattended operations:

Leave lights on and place an appropriate warning sign on the door (listing the nature of the experiment in progress, your name, and a contact number). Provide for the containment of toxic substances in the event of failure of a utility service (such as cooling water) to an unattended operation.

Whenever possible, use automatic shutoff devices on long term or unattended operations, such as a loss of cooling water shutoff, over-temperature shutoff, etc.

Use of the fume hood:

Use the fume hood for operations that might result in the release of toxic chemical vapors, fumes or dust. Benchtop use of chemicals that present an inhalation hazard is prohibited.

Confirm adequate hood performance before use; check the telltale. Conduct a dry ice capture test when using new materials for the first time or whenever substantial changes have been made to an experimental setup in a hood.

Keep the hood sash lowered to the height recommended by EH&S. Keep materials stored in hoods to a minimum and do not allow them to block vents or airflow.

When conducting long-term experiments with acutely toxic materials do not use a hood with an automatic night or timed setback.

Vigilance:

Be alert to unsafe conditions and see that they are corrected when detected.

Waste disposal:

Comply with all waste disposal procedures provided by EH&S. (See Section 7.)

Working alone:

Avoid working alone when using hazardous chemicals or processes.

Use a buddy system or a notification protocol with Cornell Police or others in a facility if you must work alone.

5.3

Original Text

. Occupational exposure to hazardous chemicals in laboratories.

Becomes effective May 1, .

(a)

Scope and application.

(1)

This section shall apply to all employers engaged in the laboratory use of hazardous chemicals as defined below.

(2)

Where this section applies, it shall supersede, for laboratories, the requirements of all other OSHA health standards in 29 CFR part , subpart Z, except as follows:

(i)

For any OSHA health standard, only the requirement to limit employee exposure to the specific permissible exposure limit shall apply for laboratories, unless that particular standard states otherwise or unless the conditions of paragraph (a)(2)(iii) of this section apply.

(ii)

Prohibition of eye and skin contact where specified by any OSHA health standard shall be observed.

(iii) Where the action level (or in the absence of an action level, the permissible exposure limit) routinely exceeded from an OSHA regulated substance with exposure monitoring and medical surveillance requirements, paragraphs (d) and (g)(1)(ii) of this section shall apply.

(3)

This section shall not apply to:

(i)

Uses of hazardous chemicals which do not meet the definition of laboratory use, and in such cases, the employer shall comply with the relevant standard in 29 CFR part , subpart Z, even if such use occurs in a laboratory.

(ii)

Laboratory use of hazardous chemicals which provide no potential for employee exposure. Examples of such conditions might include:

(A)

Procedures using chemically-impregnated test media such as Dip-and-Read tests where a reagent strip is dipped into the specimen to be tested and the results are interpreted by comparing the color reaction to a color chart supplied by the manufacturer of the test strip; and

(B)

Commercially prepared kits such as those used in performing pregnancy tests in which all of the reagents needed to conduct the test are contained in the kit.

(b)

Definitions

"Action level" means a concentration designated in 29 CFR part for a specific substance, calculated as an eight-hour time-weighted average, which initiates certain required activities such as exposure monitoring and medical surveillance.

6.0

"Assistant Secretary" means the Assistant Secretary of Labor for Occupational Safety and Health,

U.S. Department of Labor, or designee.

"Carcinogen" (see "select carcinogen").

"Chemical Hygiene Officer" means an employee who is designated by the employer, and who is qualified by training or experience, to provide technical guidance in the development and implementation of the provisions of the Chemical Hygiene Plan. This definition is not intended to place limitations on the position description or job classification that the designated individual shall hold within the employer's organizational structure.

"Chemical Hygiene Plan" means a written program developed and implemented by the employer which sets forth procedures, equipment, personal protective equipment and work practices that (i) are capable of protecting employees from the health hazards presented by hazardous chemicals used in that particular workplace and (ii) meets the requirements of paragraph (e) of this section.

"Combustible liquid" means any liquid having a flash point at or above 100 ?F (37.8 ?C), but below 200 ?F (93.3 ?C), except any mixture having components with flash points of 200 ?F

(93.3 ?C), or higher, the total volume of which make up 99 percent or more of the total volume of the mixture.

"Compressed gas" means: (i) A gas or mixture of gases having, in a container, an absolute pressure exceeding 40 psi at 70 ?F (21.1 ?C); or (ii) A gas or mixture of gases having, in a container, an absolute pressure exceeding 104 psi at 130 ?F (54.4 ?C) regardless of the pressure at 70 ?F

(21.1 ?C); or (iii) A liquid having a vapor pressure exceeding 40 psi at 100 ?F (37.8 ?C) as determined by ASTM D-323-72.

"Designated area" means an area which may be use for work with "select carcinogens," reproductive toxins or substances which have a high degree of acute toxicity. A designated area may be the entire laboratory, an area of a laboratory or a device such as a laboratory hood.

"Emergency" means any occurrence such as, but not limited to, equipment failure, rupture of containers or failure of control equipment which results in an uncontrolled release of a hazardous chemical into the workplace.

"Employee" means an individual employed in a laboratory workplace who may be exposed to hazardous chemicals in the course of his or her assignments.

"Explosive" means a chemical that causes a sudden, almost instantaneous release of pressure, gas, and heat when subjected to sudden shock, pressure, or high temperature.

"Flammable" means a chemical that falls into one of the following categories:

(i) "Aerosol, flammable" means an aerosol that, when tested by the method described in 16 CFR .45, yields a flame projection exceeding 18 inches at full valve opening, or a flashback (a flame extending back to the valve) at any degree of valve opening:

6.1

(ii) "Gas, flammable" means:

(A)

A gas that, at ambient temperature and pressure, forms a flammable mixture with air at a concentration of 13 percent by volume or less; or

(B)

A gas that, at ambient temperature and pressure, forms a range of flammable mixtures with air wider than 12 percent by volume, regardless of the lower limit.

(iii) "Liquid, flammable" means any liquid having a flash point below 100 ?F (37.8 ?C), except any mixture having components with flash points of 100 ?F (37.8 ?C) or higher, the total of which make up 99 percent or more of the total volume of the mixture.

(iv) "Solid, flammable" means a solid, other than a blasting agent or explosive as defined in .109(a), that is liable to cause fire through friction, absorption of moisture, spontaneous chemical change, or retained heat from manufacturing or processing, or which can be ignited readily and when ignited burns so vigorously and persistently as to create a serious hazard.

A chemical shall be considered to be a flammable solid if, when tested by the method described in 16 CFR .44, it ignites and burns with a self-sustained flame at a rate greater than one-tenth of an inch per second along its major axis.

"Flashpoint" means the minimum temperature at which a liquid gives off a vapor in sufficient concentration to ignite when tested as follows:

(I)

Tailgate Closed Tester (See American National Standard Method of Test for Flash Point by Tag Closed Tester, Z11.24- (ATM D 56-79))- for liquids with a viscosity of less than 45 Saybolt Universal Seconds (SUS) at 100 ?F (37.8 ?C), that do not contain suspended solids and do not have a tendency to form a surface film under test; or

(ii)

Pensky-Martens Closed Tester (see American National Standard Method of Test for Flash Point by Pensky-Martens Closed Tester, Z11.7- (ASTM D93-79)- for liquids with a viscosity equal to or greater than 45 SUS at 100 ?F(37.8 ?C), or that contain suspended solids, or that have a tendency to form a surface film under test; or

(iii) Setaflash Closed Tester (see American National Standard Method of Test for Flash Point by Setaflash Closed Tester (ASTM D-78)).

Organic peroxides, which undergo auto accelerating thermal decomposition, are excluded from any of the flashpoint determination methods specified above.

"Hazardous chemical" means a chemical for which there is statistically significant evidence based on at least one study conducted in accordance with established scientific principles that acute or chronic health effects may occur in exposed employees. The term "health hazard" includes chemicals which are carcinogens, toxic or highly toxic agents, reproductive toxins, irritants, corrosives, sensitizers, hepatotoxins, nephrotoxins, neurotoxins, agents which act on the hematopoietic systems, and agents which damage the lungs, skin, eyes, or mucous membranes.

6.2

Appendices A and B of the Hazard Communication Standard (29 CFR .) provide further guidance in defining the scope of health hazards and determining whether or not a chemical is to be considered hazardous for purposes of this standard.

"Laboratory" means a facility where the "laboratory use of hazardous chemicals" occurs. It is a workplace where relatively small quantities of hazardous chemicals are used on a nonproduction basis.

"Laboratory scale" means work with substances in which the containers used for reactions, transfers, and other handling of substances are designed to be easily and safely manipulated by one person. "Laboratory scale" excludes those workplaces whose function is to produce commercial quantities of materials.

"Laboratory-type hood" means a device located in a laboratory, enclosed on five sides with a moveable sash or fixed partial enclosure on the remaining side; constructed and maintained to draw air from the laboratory and to prevent or minimize the escape of air contaminants into the laboratory; and allows chemical manipulations to be conducted in the enclosure without insertion of any portion of the employee's body other than hands and arms.

Walk-in hoods with adjustable sashes meet the above definition provided that the sashes are adjusted during use so that the airflow and the exhaust of air contaminants are not compromised and employees do not work inside the enclosure during the release of airborne hazardous chemicals.

"Laboratory use of hazardous chemicals" means handling or use of such chemicals in which all of the following conditions are met:

(i)

Chemical manipulations are carried out on a "laboratory scale;"

(ii)

Multiple chemical procedures or chemicals are used;

(iii) The procedures involved are not part of a production process, nor in anyway simulate a production process; and

(iv) "Protective laboratory practices and equipment" are available and in common use to minimize the potential for employee exposure to hazardous chemicals.

"Medical consultation" means a consultation which takes place between an employee and a licensed physician for the purpose of determining what medical examinations or procedures, if any, are appropriate in cases where a significant exposure to a hazardous chemical may have taken place.

"Organic peroxide" means an organic compound that contains the bivalent -O-O- structure and which may be considered to be a structural derivative of hydrogen peroxide where one or both of the hydrogen atoms has been replaced by an organic radical.

"Oxidizer" means a chemical other than a blasting agent or explosive as defined in .109(a), that initiates or promotes combustion in other materials, thereby causing fire either of itself or through the release of oxygen or other gases.

6.3

"Physical hazard" means a chemical for which there is scientifically valid evidence that it is a combustible liquid, a compressed gas, explosive, flammable, an organic peroxide, an oxidizer, pyrophoric, unstable (reactive) or water-reactive.

"Protective laboratory practices and equipment" means those laboratory procedures, practice and equipment accepted by laboratory health and safety experts as effective, or that the employer can show to be effective, in minimizing the potential for employee exposure to hazardous chemicals.

"Reproductive toxins" means chemicals which affect the reproductive capabilities including chromosomal damage (mutations) and effects on fetuses (teratogenesis).

"Select carcinogen" means any substance which meets one of the following criteria:

(i)

It is regulated by OSHA as a carcinogen; or

(ii)

It is listed under the category, "known to be carcinogens," in the Annual Report on Carcinogens published by the National Toxicology Program (NTP) (latest edition); or

(iii) It is listed under Group 1 ("carcinogenic to humans") by the International Agency for Research on Cancer Monographs (IARC) (latest editions); or

(iv) It is listed in either Group 2A or 2B by IARC or under the category, "reasonably anticipated to be carcinogens" by NTP, and causes statistically significant tumor incidence in experimental animals in accordance with any of the following criteria:

(A)

After inhalation exposure of 6-7 hours per day, 5 days per week, for a significant portion of a lifetime to dosages of less than 10 mg/m3;

(B)

After repeated skin application of less than 300 (mg/kg of body weight) per week; or

(C)

After oral dosages of less than 50 mg/kg of body weight per day.

"Unstable (reactive)" means a chemical which is the pure state, or as produced or transported, will vigorously polymerize, decompose, condense, or will become self-reactive under conditions of shocks, pressure or temperature.

"Water-reactive" means a chemical that reacts with water to release a gas that is either flammable or presents a health hazard.

(c) Permissible exposure limits. For laboratory uses of OSHA regulated substances, the employer shall assure that laboratory employees' exposures to such substances do not exceed the permissible exposure limits specified in 29 CFR part , subpart Z.

(d) Employee exposure determination

(1)

Initial monitoring. The employer shall measure the employee's exposure to any substance regulated by a standard which requires monitoring if there is reason to believe that exposure levels for that substance routinely exceed the action level (or in the absence of an action level, the PEL).

(2)

Periodic monitoring. If the initial monitoring prescribed by paragraph (d)(1) of this section discloses employee exposure over the action level (or in the absence of an action level, the PEL), the employer shall immediately comply with the exposure monitoring provisions of the relevant standard.

(3)

Termination of monitoring. Monitoring may be terminated in accordance with the relevant standard.

(4)

Employee notification of monitoring results. The employer shall, within 15 working days after the receipt of any monitoring results, notify the employee of these results in writing, either individually or by posting results in an appropriate location that is accessible to employees.

6.4

(e) Chemical hygiene plan--General. (Appendix A of this section is non-mandatory but provides guidance to assist employers in the development of the Chemical Hygiene Plan.)

(1)

Where hazardous chemicals as defined by this standard are used in the workplace, the employer shall develop and carry out the provisions of a written Chemical Hygiene Plan which is:

(i)

Capable of protecting employees from health hazards associated with hazardous chemicals in that laboratory and

(ii)

Capable of keeping exposures below the limits specified in paragraph (c) of this section.

(2)

The Chemical Hygiene Plan shall be readily available to employees, employee representatives and, upon request, to the Assistant Secretary.

(3)

The Chemical Hygiene Plan shall include each of the following elements and shall indicate specific measures that the employer will take to ensure laboratory employee protection:

(i)

Standard operating procedures relevant to safety and health considerations to be followed when laboratory work involves the use of hazardous chemicals;

(ii)

Criteria that the employer will use to determine and implement control measures to reduce employee exposure to hazardous chemicals including engineering controls, the use of personal protective equipment and hygiene practices; particular attention shall be given to the selection of control measures for chemicals that are known to be extremely hazardous;

(iii) A requirement that fume hood and other protective equipment are functioning properly and specific measures that shall be taken to ensure proper and adequate performance of such equipment;

(iv)

Provision for employee information and training as prescribed in paragraph (f) of this section;

(v)

The circumstances under which a particular laboratory operation, procedure or activity shall require prior approval from the employer or the employer's designee before implementation;

(vi)

Provisions for medical consultation and medical examinations in accordance with paragraph (g) of this section;

(vii) Designation of personnel responsible for implementation of the Chemical Hygiene Plan including the assignment of a Chemical Hygiene Officer and, if appropriate, establishment of a Chemical Hygiene Committee; and (viii) Provisions for additional employee protection for work with particularly hazardous substances. These include "select carcinogens," reproductive toxins and substances which have a high degree of acute toxicity. Specific consideration shall be given to the following provisions which shall be included where appropriate:

(A)

Establishment of a designated area;

(B)

Use of containment devices such as fume hoods or glove boxes;

(C)

Procedures for safe removal of contaminated waste; and

(D)

Decontamination procedures.

(4)

The employer shall review and evaluate the effectiveness of the Chemical Hygiene Plan at least annually and update it as necessary.

6.5

(f)

Employee information and training.

(1)

The employer shall provide employees with information and training to ensure that they are apprised of the hazards of chemicals present in their work area.

(2)

Such information shall be provided at the time of an employee's initial assignment to a work area where hazardous chemicals are present and prior to assignments involving new exposure situations. The frequency of refresher information and training shall be determined by the employer.

(3)

Information. Employees shall be informed of:

(i)

The contents of this standard and its appendices which shall be made available to employees;

(ii)

The location and availability of the employer's Chemical Hygiene Plan;

(iii) The permissible exposure limits for OSHA regulated substances or recommended exposure limits for other hazardous chemicals where there is no applicable OSHA standard;

(iv)

Signs and symptoms associated with exposures to hazardous chemicals used in the laboratory; and

(v)

The location and availability of known reference material on the hazards, safe handling, storage and disposal of hazardous chemicals found in the laboratory including, but not limited to, Material Safety Data Sheets received from the chemical suppler.

(4)

Training.

(i)

Employee training shall include:

(A)

Methods and observations that may be used to detect the presence or release of a hazardous chemical (such as monitoring conducted by the employer, continuous monitoring devices, visual appearance or odor of hazardous chemicals when being released, etc.);

(B)

The physical and health hazards of chemicals in the work area; and

(C)

The measures employees can take to protect themselves from these hazards, including specific procedures the employer has implemented to protect employees from exposure to hazardous chemicals, such as appropriate work practices, emergency procedures, and personal protective equipment to be used.

(ii)

The employee shall be trained on the applicable details of the employer's written Chemical Hygiene Plan.

(g)

Medical consultation and medical examinations.

(1)

The employer shall provide all employees who work with hazardous chemicals an opportunity to receive medical attention, including any follow-up examinations which the examining physician determines to be necessary, under the following circumstances:

(i)

Whenever an employee develops signs or symptoms associated with a hazardous chemical to which the employee may have been exposed in the laboratory, the employee shall be provided an opportunity to receive an appropriate medical examination.

(ii)

Where exposure monitoring reveals an exposure level routinely above the action level (or in the absence of an action level, the PEL) for an OSHA regulated substance for which there are exposure monitoring and medical surveillance requirements, medical surveillance shall be established for the affected employee as prescribed by the particular standard.

(iii) Whenever an event takes place in the work area such as a spill, leak, explosion or other occurrence resulting in the likelihood of a hazardous exposure, the affected employee shall be provided an opportunity for a medical consultation. Such consultation shall be for the purpose of determining the need for a medical examination.

(2)

All medical examinations and consultations shall be performed by or under the direct supervision of a licensed physician and shall be provided without cost to the employee, without loss of pay and at a reasonable time and place.

(3)

Information provided to the physician. The employer shall provide the following information to the physician:

(i)

The identity of the hazardous chemical(s) to which the employee may have been exposed;

(ii)

A description of the conditions under which the exposure occurred including quantitative exposure data, if available; and

(iii) A description of the signs and symptoms of exposure that the employee is experiencing, if any.

(4)

Physician's written opinion.

(i)

For examination or consultation required under this standard, the employer shall obtain a written opinion from the examining physician which shall include the following:

(A)

Any recommendation for further medical follow-up;

(B)

The results of the medical examination and any associated tests;

(C)

Any medical condition which may be revealed in the course of the examination which may place the employee at increased risk as a result of exposure to a hazardous chemical found in the workplace; and

(D)

A statement that the employee has been informed by the physician of the results of the consultation or medical examination and any medical condition that may require further examination or treatment.

(ii)

The written opinion shall not reveal specific findings of diagnoses unrelated to occupational exposure.

(h)

Hazard identification.

(1)

With respect to labels and material safety data sheets:

(i)

Employers shall ensure that labels on incoming containers of hazardous chemicals are not removed or defaced.

(ii)

Employers shall maintain any material safety data sheets that are received with incoming shipments of hazardous chemicals, and ensure that they are readily accessible to laboratory employees.

(2)

The following provisions shall apply to chemical substances developed in the laboratory:

(i)

If the composition of the chemical substance which is produced exclusively for the laboratory's use is known, the employer shall determine if it is hazardous chemical as defined in paragraph (b) of this section. If the chemical is determined to be hazardous, the employer shall provide appropriate training as required under paragraph (f) of this section.

(ii)

If the chemical produced is a byproduct whose composition is not known, the employer shall assume that the substance is hazardous and shall implement paragraph (e) of this section.

(iii) If the chemical substance is produced for another user outside of the laboratory, the employer shall comply with the Hazard Communication Standard(29 CFR .) including the requirements for preparation of material safety data sheets and labeling.

(i)

Use of respirator.

6.6

6.7

Where the use of respirators is necessary to maintain exposure below permissible exposure limits, the employer shall provide, at no cost to the employee, the proper respiratory equipment. Respirators shall be selected and used in accordance with the requirements of 29 CFR .134.

(j)

Recordkeeping.

(1)

The employer shall establish and maintain for each employee an accurate record of any measurements taken to monitor employee exposures and any medical consultation and examinations including tests or written opinions required by this standard.

(2)

The employer shall assure that such records are kept, transferred, and made available in accordance with 29 CFR .20.

(k)

Dates.

(1)

Effective date: This section shall become effective May 1,.

(2)

Start-up dates.

(i)

Employers shall have developed and implemented a written Chemical Hygiene Plan no later than January 31, .

(ii)

Paragraph (a)(2) of this section shall not take effect until the employer has developed and implemented a written Chemical Hygiene Plan.

(iii) If the chemical substance is produced for another user outside of the laboratory, the employer shall comply with the Hazard Communication Standard(29 CFR .) including the requirements for preparation of material safety data sheets and labeling.

6.8

(l) Appendices. The information contained in the appendices is not intended, by itself, to create any additional obligations not otherwise imposed or to detract from any existing obligation.

6.9

Appendix A to 29 CFR .

National Research Council Recommendations Concerning Chemical Hygiene in Laboratories (Non-Mandatory)

A. General Principals for Work with Laboratory Chemicals

1. Minimize all Chemical Exposures

2. Avoid Underestimation of Risk

3. Provide Adequate Ventilation

4. Institute a Chemical Hygiene Program

5. Observe the PELs and TLVs

B. Responsibilities

1. Chief Executive Officer

2. Supervisor of Administrative Unit

3. Chemical Hygiene Officer

4. Laboratory Supervisor

5. Project Director

6. Laboratory Worker

C. The Laboratory Facility

1. Design

2. Maintenance

3. Usage

4. Ventilation

D. Components of the Chemical Hygiene Plan

1. Basic Rules and Procedures

2. Chemical Procurement, Distribution, and Storage

3. Environmental Monitoring

4. Housekeeping, Maintenance and Inspections

5. Medical Program

6. Personal Protective Apparel and Equipment

7. Record

8. Signs and Labels

9. Spills and Accidents

10. Training and Information

11. Waste Disposal

E. General Procedures for Working With Chemicals

1. General Rules for all Laboratory Work with Chemicals

2. Allergens and Embryotoxins

3. Chemicals of Moderate Chronic or High Acute Toxicity

4. Chemicals of High Chronic Toxicity

5. Animal Work with Chemicals of High Chronic Toxicity

6.10

F. Safety Recommendations

G. Material Safety Data Sheets

Foreword

As guidance for each employer's development of an appropriate laboratory Chemical Hygiene Plan, the following non-mandatory recommendations are provided. They were extracted from "Prudent Practices for Handling Hazardous Chemicals in Laboratories" (referred to below as "Prudent Practices"), which was published in by the National Research Council and is available from the National Academy Press, Constitution Ave., NW., Washington DC .

"Prudent Practices" is cited because of its wide distribution and acceptance and because of its preparation by members of the laboratory community through the sponsorship of the National Research Council. However, none of the recommendations given here will modify any requirements of the laboratory standard. This Appendix merely presents pertinent recommendations from "Prudent Practices", organized into a form convenient for quick reference during operation of a laboratory facility and during development and application of a Chemical Hygiene Plan. Users of this appendix should consult "Prudent Practices" for a more extended presentation and justification for each recommendation.

"Prudent Practices" deals with both safety and chemical hazards while the laboratory standard is concerned primarily with chemical hazards. Therefore, only those recommendations directed primarily toward control of toxic exposures are cited in this appendix, with the term "chemical hygiene" being substituted for the word "safety". However, since conditions producing or threatening physical injury often pose toxic risks as well, page references concerning major categories of safety hazards in the laboratory are given in section F.

The recommendations from "Prudent Practices" have been paraphrased, combined, or otherwise reorganized, and headings have been added. However, their sense has not been changed.

Corresponding Sections of the Standard and this Appendix

The following table is given for the convenience of those who are developing a Chemical Hygiene Plan which will satisfy the requirements of paragraph (e) of the standard. It indicates those sections of this appendix which are most pertinent to each of the sections of paragraph (e) and related paragraphs.

Paragraph and topic in laboratory standard Relevant appendix section

(e)(3)(i) Standard operating procedure for handling toxic chemicals. ...........................................C, D, E
(e)(3)(ii) Criteria to be used for implementation of measures to reduce exposures. .................................D
(e)(3)(iii) Fume hood performance .................................................................................................... C4b
(e)(3)(iv) Employee information and training (incl. emergency procedures). ................................ D10, D9
(e)(3)(v) Requirements for prior approval of laboratory activities .............................................. E2b, E4b
(e)(3)(vi) Medical consultation and medical examinations............................................................ D5, E4f

6.11

(e)(3)(vii) Chemical hygiene responsibilities............................................................................................ B
(e)(3)(viii) Special precautions for work with particularly hazardous substances. ......................E2, E3, E4

In this appendix, those recommendations directed primarily at administrators and supervisors are given in sections A-D. Those recommendations of primary concern to employees who are actually handling laboratory chemicals are given in section E. (Reference to page numbers in "Prudent Practices" are given in parentheses.)

A. General Principles for Work with Laboratory Chemicals

In addition to the more detailed recommendations listed below in sections B-E, "Prudent Practices" expresses certain general principles, including the following:

1. It is prudent to minimize all chemical exposures.

2. Because few laboratory chemicals are without hazards, general precautions for handling all laboratory chemicals should be adopted, rather than specific guidelines for particular chemicals (2,10). Skin contact with chemicals should be avoided as a cardinal rule (198).
1. Avoid underestimation of risk.

2. Even for substances of no known significant hazard, exposure should be minimized; for work with substances which present special hazards, special precautions should be taken (10,37,38). One should assume that any mixture will be more toxic than its most toxic component (30,103) and that all substances of unknown toxicity are toxic (3,34).
1. Provide adequate ventilation.

2. The best way to prevent exposure to airborne substances is to prevent their escape into the working atmosphere by use of hoods and other ventilation devices (32,198).
1. Institute a chemical hygiene program.

2. A mandatory chemical hygiene program designed to minimize exposures is needed; it should be a regular, continuing effort, not merely a standby or short-term activity (6,11). Its recommendations should be followed in academic teaching laboratories as well as by full-time laboratory workers (13).
1. Observe the PELs, TLVs.

The Permissible Exposure Limits of OSHA and the Threshold Limit Values of the American Conference of Governmental Industrial Hygienists should not be exceeded (13).

6.12

B. Chemical Hygiene Responsibilities

Responsibility for chemical hygiene rests at all levels (6,11,21) including the:

1. Chief executive officer, who has ultimate responsibility for chemical hygiene within the institution and must, with other administrators, provide continuing support for institutional chemical hygiene (7,11).

2. Supervisor of the department or other administrative unit, who is responsible for chemical hygiene in that unit (7).
   1. Chemical hygiene officer(s), whose appointment is essential (7) and who must:
      1. Work with administrators and other employees to develop and implement appropriate chemical hygiene policies and practices (7);

      2. Monitor procurement, use, and disposal of chemicals used in the lab (8);

      3. See that appropriate audits are maintained (8);

      4. Help project directors develop precautions and adequate facilities (10);

      5. Know the current legal requirements concerning regulated substances (50); and

      6. Seek ways to improve the chemical hygiene program (8,11).

   1. Laboratory supervisor, who has overall responsibility for chemical hygiene in the laboratory
      1. including responsibility to:

      2. Ensure that workers know and follow the chemical hygiene rules, that protective equipment is available and in working order, and that appropriate training has been provided (21,22);

      3. Provide regular, formal chemical hygiene and housekeeping inspections including routine inspections of emergency equipment (21,171);

      4. Know the current legal requirements concerning regulated substances (50,231);

      5. Determine the required levels of protective apparel and equipment (156,160,162); and

      6. Ensure that facilities and training for use of any material being ordered are adequate (215).

3. Project director or director of other specific operations, who has primary responsibility for chemical hygiene procedures for that operation (7).
   1. Laboratory worker, who is responsible for:
      1. Planning and conducting each operation in accordance with the institutional chemical hygiene procedures (7,21,22,230); and

      2. Developing good personal chemical hygiene habits (22).

6.13

C. The Laboratory Facility

1. Design. The laboratory facility should have:

(a)

An appropriate general ventilation system (see C(4) below) with air intakes and exhausts located so as to avoid intake of contaminated air (194);

(b)

Adequate, well-ventilated stockrooms/storerooms (218,219);

(c)

Laboratory hoods and sinks (12,162);

(d)

Other safety equipment including eyewash fountains and drench showers (162,169); and

(e)

Arrangements for waste disposal (12,240).

1. Maintenance. Chemical-hygiene-related equipment (hoods, incinerator, etc.) should undergo continuing appraisal and be modified if inadequate (11,12).

2. Usage. The work conducted (10) and its scale (12) must be appropriate to the physical facilities available and, especially, to the quality of ventilation (13).
   1. Ventilation
      1. General laboratory ventilation. This system should: Provide a source of air for breathing and for input to local ventilation devices (199); it should not be relied on for protection from toxic substances released into the laboratory (198); ensure that laboratory air is continually replaced, preventing an increase of air concentrations of toxic substances during the working day (194); direct air flow into the laboratory from non-laboratory areas and out to the exterior of the building (194).

      2. Hoods. A laboratory hood with 2.5 linear feet of hood space per person should be provided for every 2 workers if they spend most of their time working with chemicals (199); each hood should have a continuous monitoring device to allow convenient confirmation of adequate hood performance before use (200,209). If this is not possible, work with substances of unknown toxicity should be avoided (13) or other types of local ventilation devices should be provided (199). See pp. 201-206 for a discussion of hood design, construction, and evaluation.

      3. Other local ventilation devices. Ventilated storage cabinets, canopy hoods, snorkels, etc. should be provided as needed (199). Each canopy hood and snorkel should have a separate exhaust duct(207).

      4. Special ventilation areas. Exhaust air from glove boxes and isolation rooms should be passed though scrubbers or other treatment before release into the regular exhaust system (208). Cold rooms and warm rooms should have provisions for rapid escape and for escape in the event of electrical failure (209).

      5. Modifications. Any alteration of the ventilation system should be made only if thorough testing indicates that worker protection from airborne toxic substances will continue to be adequate(12,193,204).

      6. Performance. Rate: 4-12 room air changes/hour is normally adequate general ventilation if local exhaust systems such as hoods are used as the primary method of control (94).

      7. Quality. General air flow should not be turbulent and should be relatively uniform throughout the laboratory, with no high velocity or static areas (194,195); airflow into and within the hood should not be excessively turbulent (200); hood face velocity should be adequate (typically 60-100 lfpm) (200,204).

      8. Evaluation. Quality and quantity of ventilation should be evaluated on installation (202), regularly monitored (at least every 3 months) (6,12,14,195), and reevaluated whenever a change in local ventilation devices is made (12,195,207). See pp.195-198 for methods of evaluation and for calculation of estimated airborne contaminant concentrations.

6.14

D. Components of the Chemical Hygiene Plan

1. Basic Rules and Procedures (Recommendations for these are given in section E, below).
   1. Chemical Procurement, Distribution, and Storage
      1. Procurement. Before a substance is received, information on proper handling, storage, and disposal should be known to those who will be involved (215,26). No container should be accepted without an adequate identifying label (216). Preferably, all substances should be received in a central location (216).

      2. Stockrooms/storerooms. Toxic substances should be segregated in a well-identified area with local exhaust ventilation (221). Chemicals which are highly toxic (227) or other chemicals whose containers have been opened should be in unbreakable secondary containers (219). Stored chemicals should be examined periodically (at least annually) for replacement, deterioration, and container integrity (218-19). Stockrooms/storerooms should not be used as preparation or repackaging areas, should be open during normal working hours, and should be controlled by one person (219).

      3. Distribution. When chemicals are hand carried, the container should be placed in an outside container or bucket. Freight-only elevators should be used if possible (223).

      4. Laboratory storage. Amounts permitted should be as small as practical. Storage of bench tops and in hoods is inadvisable. Exposure to heat or direct sunlight should be avoided. Periodic inventories should be conducted, with unneeded items being discarded or returned to the storeroom/stockroom (225-6, 229).

   1. Environmental Monitoring.

   2. Regular instrumental monitoring of airborne concentrations is not usually justified or practical in laboratories but may be appropriate when testing or redesigning hoods or other ventilation devices (12) or when a highly toxic substance is stored or used regularly (e.g., 3 times/week) (13).
   1. Housekeeping, Maintenance, and Inspections
      1. Cleaning. Floors should be cleaned regularly (24).

      2. Inspections. Formal housekeeping and chemical hygiene inspections should be held at least quarterly (6,21) for units which have frequent personnel changes and semiannually for others; informal inspections should be continual (21).

      3. Maintenance. Eye wash fountains should be inspected at intervals of not less than 3 months (6). Respirators for routine use should be inspected periodically by the laboratory supervisor (169). Safety showers should be tested routinely (169). Other safety equipment should be inspected regularly (e.g., every 3-6 months) (6,24, 171). Procedures to prevent restarting of out-of-service equipment should be established (25).

      4. Passageways. Stairways and hallways should not be used as storage areas (24). Access to exits, emergency equipment, and utility controls should never be blocked (24).

   1. Medical Program
      1. Compliance with regulations. Regular medical surveillance should be established to the extent required by regulations (12).

      2. Routine surveillance. Anyone whose work involve regular and frequent handling of toxicologically significant quantities of a chemical should consult a qualified physician to determine on an individual basis whether a regular schedule of medical surveillance is desirable (11,50).

      3. First aid. Personnel trained in first aid should be available during working hours and an emergency room with medical personnel should be nearby (173). Se pp. 176-178 for description of some emergency first aid procedures.

   1. Protective Apparel and Equipment These should include for each laboratory:
      1. Protective apparel compatible with the required degree of protection for substances being handled (158-161);

      2. An easily accessible drench-type safety shower (162,169);

      3. An eyewash fountain (162);

      4. A fire extinguisher (162-164);

      5. Respiratory protection (164-169), fire alarm and for emergency use (162) should be available nearby; and

      6. Other items designated by the laboratory supervisor (156,160).

   1. Records
      1. Accident records should be written and retained (174).

      2. Chemical Hygiene Plan records should document that the facilities and precautions were compatible with current knowledge and regulations (7).

      3. Inventory and usage records for high-risk substances should be kept as specified in sections E(3)(e) below.

      4. Medical records should be retained by the institution in accordance with the requirements of state and federal regulations (12).

   1. Signs and Labels Prominent signs and labels of the following types should be posted:
      1. Emergency numbers of emergency personnel/facilities, supervisor, and laboratory workers (28);

      2. Identity label, showing contents of containers (including waste receptacles) and associated hazards (27,48);

      3. Location signs for safety showers, eyewash stations, other safety and first aid equipment, exits (27) and areas where food and beverage consumption and storage are permitted (24); and (d) Warnings at areas or equipment where special or unusual hazards exist (27).

   1. Spills and Accidents
      1. A written emergency plan should be established and communicated to all personnel; it should include procedures for ventilation failure (200), evacuation, medical care, reporting, and drill (172).

      2. There should be an alarm system to alert people in all parts of the facility including isolation areas such as cold rooms (172).

      3. A spill control policy should be developed and should include consideration of prevention, containment, cleanup, and reporting (175).

      4. All accidents or near accidents should be carefully analyzed with the results distributed to all who might benefit (8,28).

   1. Information and Training Program
      1. Aim: To assure that all individuals at risk are adequately informed about the work in the laboratory, its risks, and what to do if an accident occurs (5,15).

      2. Emergency and Personal Protection Training: Every laboratory worker should know the location and proper use of available protective apparel and equipment (154,169). Some of the full-time personnel of the laboratory should be trained in the proper use of emergency equipment and procedures (6). Such training as well as first aid instruction should be available to (154) and encouraged for (176) everyone who might need it.

      3. Receiving and stockroom/storeroom personnel should know about hazards, handling equipment, protective apparel, and relevant regulations (217).

      4. Frequency of Training: The training and education program should be a regular, continuing activity--not simply an annual presentation (15).

      5. Literature/Consultation: Literature and consulting advice concerning chemical hygiene should be readily available to laboratory personnel, who should be encouraged to use these information resources (14).

   1. Waste Disposal Program.
      1. Aim: To assure that minimal harm to people, other organisms, and the environment will result from the disposal of waste laboratory chemicals (5).

      2. Content (14,232,233,240): The waste disposal program should specify how waste is to be collected, segregated, stored, and transported and include consideration of what materials can be incinerated. Transport from the institution must be in accordance with DOT regulations (244).

      3. Discarding Chemical Stocks: Unlabeled containers of chemicals and solutions should undergo prompt disposal; if partially used, they should not opened (24,27). Before a worker's employment in the laboratory ends, chemicals for which that person was responsible should be discarded or returned to storage (226).

      4. Frequency of Disposal: Waste should be removed from laboratories to a central waste storage area at least once per week and from the central waste storage area at regular intervals (14).

      5. Method of Disposal: Incineration in an environmentally acceptable manner is the most practical disposal method for combustible laboratory waste (14,238,241). Indiscriminate disposal by pouring waste chemicals down the drain (14,231,242) or adding them to mixed refuse for landfill burial is unacceptable (14). Hoods should not be used as a means of disposal for volatile chemicals (40,200). Disposal by recycling (233,243) or chemical decontamination (40,230) should be used when possible.

6.15

6.16

6.17

E. Basic Rules and Procedures for Working with Chemicals: The Chemical Hygiene Plan should require that laboratory workers know and follow its rules and procedures. In addition to the procedures of the subprograms mentioned above, these should include the rules listed below.

1. General Rules

The following should be used for essentially all laboratory work with chemicals:

(a) Accidents and spills:

Eye Contact: Promptly flush eyes with water for a prolonged period (15 minute) and seek medical attention (33,172).

Ingestion: Encourage the victim to drink large amounts of water (178).

Skin Contact: Promptly flush the affected area with water(33,172,178) and remove any contaminated clothing (172,178). If symptoms persist after washing, seek medical attention (33).

Clean-up. Promptly clean up spills, using appropriate protective apparel and equipment and proper disposal (24,33). See pp. 233-237 for specific clean-up recommendations.

6.18

(b) Avoidance of "routine" exposure: Develop and encourage safe habits (23); avoid unnecessary exposure to chemicals by any route (23); Do not smell or taste chemical (32). Vent apparatus which may discharge toxic chemicals (vacuum pumps, distillation columns, etc.) into local exhaust devices

(199). Inspect gloves (157) and test glove boxes (208) before use. Do not allow release of toxic substances in cold rooms and warm rooms, since these

have contained recirculated atmospheres (209).

(c)

Choice of chemicals: Use only those chemicals for which the quality of the available ventilation system is appropriate (13).

(d)

Eating, smoking, etc.: Avoid eating, drinking, smoking, gum chewing, or application of cosmetics in areas where laboratory chemicals are present (22,24,32,40); wash hands before conducting these activities (23,24). Avoid storage, handling or consumption of food or beverages in storage areas, refrigerators, glassware or utensils which are also used for laboratory operations (23,24,226).

(e)

Equipment and glassware: Handle and store laboratory glassware with care to avoid damage; do no use damaged glassware (25). Use extra care with Dewar flasks and other evacuated glass apparatus; shield or wrap them to contain chemicals and fragments should implosion occur (25). Use equipment only for its designed purpose (23,26).

(f)

Exiting: Wash areas of exposed skin well before leaving the laboratory (23).

(g)

Horseplay: Avoid practical jokes or the behavior which might confuse, startle or distract another worker (23).

(h)

Mouth suction: Do not use mouth suction for pipeting or starting a siphon (23,32).

(i)

Personal apparel: Confine long hair and loose clothing (23, 158). Wear shoes at all times in the laboratory but do not wear sandals, perforated shoes, or sneakers (158).

(j)

Personal housekeeping: Keep the work area clean and uncluttered, with chemicals and equipment being properly labeled and stored; clean up the work area on completion of an operation or at the end of each day (24).

(k)

Personal protection: Assure that appropriate eye protection (154-156) is worn by all persons, including visitors, where chemicals are stored or handled (22,23,33,154).

Wear appropriate gloves when the potential for contact with toxic materials exists (157); inspect the gloves before each use, wash them before removal, and replace them periodically (157). (A table of resistance to chemicals of common glove materials is given on p.159).

Use appropriate (164-168) respiratory equipment when air contaminant concentrations are not sufficiently restricted by engineering controls (164-165), inspecting the respirator before use (169). Use any other protective and emergency apparel and

6.19

equipment as appropriate (22,157-162). Avoid use of contact lenses in the laboratory unless necessary; if they are used, inform supervisor so special precautions can be taken (155).

Remove laboratory coats immediately on significant contamination (161).

(l)

Planning: Seek information and advice about hazards (7), plan appropriate protective procedures, and plan positioning of equipment before beginning any new operation (22,23).

(m)

Unattended operations: Leave lights on, place an appropriate sign on the door, and provide for containment of toxic substances in the event of failure of a utility service (such as cooling water) to an unattended operation (27,128).

(n)

Use of hood: Use the hood for operations which might result in release of toxic chemical vapors or dust (198-199). As a rule of thumb, use a hood or other local ventilation device when working with any appreciably volatile substance with a TLV of less than 50 ppm (13). Confirm adequate hood performance before use; keep hood closed at all times except when adjustments within the hood are being made (200). Keep materials stored in hoods to a minimum and do not allow them to block vents or air flow (200). Leave the hood "on" when it is not in active use if toxic substances are stored in it or if it is uncertain whether adequate general laboratory ventilation will be maintained when it is "off" (200).

(o)

Vigilance: Be alert to unsafe conditions and see that they are corrected when detected (22).

(p)

Waste disposal: Assure that the plan for each laboratory operation includes plans and training for waste disposal (230).

Deposit chemical waste in appropriately labeled receptacles and follow all other waste disposal procedures of the Chemical Hygiene Plan (22,24).

Do not discharge to the sewer concentrated acids or bases (231); highly toxic, malodorous, or lachrymatory substances (231); or any substances which might interfere with the biological activity of wastewater treatment plants, create fire or explosion hazards, cause structural damage or obstruct flow (242).

(q) Working alone: Avoid working alone in a building; do not work alone in a laboratory if the procedures being conducted are hazardous (28).

2. Working with Allergens and Embryotoxins

(a)

Allergens (examples: diazomethane, isocyanates, bichromates): Wear suitable gloves to prevent hand contact with allergens or substances of unknown allergenic activity (35).

(b)

Embryotoxins (34-35) (examples: organomercurials, lead compounds, formamide): If you are a woman of childbearing age, handle these substances only in a hood whose satisfactory performance has been confirmed using appropriate protective apparel (especially gloves) to prevent skin contact.

6.20

Review each use of these materials with the research supervisor and review continuing uses annually or whenever a procedural change is made. Store these substances, properly labeled, in an adequately ventilated area and in an unbreakable secondary container. Notify supervisors of all incidents of exposure or spills and consult a qualified physician when appropriate.

3. Work with Chemicals of Moderate Chronic or High Acute Toxicity (Examples: diisopropylflurophosphate (41), hydrofluoric acid (43) , hydrogen cyanide (45)).

Supplemental rules to be followed in addition to those mentioned above (Procedure B of "Prudent Practices", pp. 39-41):

(a)

Aim: To minimize exposure to these toxic substances by any route using all reasonable precautions (39).

(b)

Applicability: These precautions are appropriate for substances with moderate chronic or high acute toxicity used in significant quantities (39).

(c)

Location: Use and store these substances only in areas of restricted access with special warning signs (40,229). Always use a hood (previously evaluated to confirm adequate performance with a face velocity of at least 60 linear feet per minute) (40) or other containment device for procedures which may result in the generation of aerosols or vapors containing the substance (39); trap released vapors to prevent their discharge with the hood exhaust (40).

(d)

Personal protection: Always avoid skin contact by use of gloves and long sleeves (and other protective apparel as appropriate) (39). Always wash hands and arms immediately after working with these materials (40).

(e)

Records: Maintain records of the amounts of these materials on hand, amounts used, and the names of the workers involved (40,229).

(f)

Prevention of spills and accidents: Be prepared for accidents and spills (41).

Assure that at least 2 people are present at all times if a compound in use is highly toxic or of unknown toxicity (39).

Store breakable containers of these substances in chemically resistant trays; also work and mount apparatus above such trays or cover work and storage surface with removable, absorbent, plastic backed paper (40). If a major spill occurs outside the hood, evacuate the area; assure that cleanup personnel wear suitable protective apparel and equipment (41).

(g) Waste: Thoroughly decontaminate or incinerate contaminated clothing or shoes (41). If possible, chemically decontaminate by chemical conversion (40). Store contaminated waste in closed, suitably labeled, impervious containers (for liquids, in glass or plastic bottles half-filled with vermiculite) (40).

6.21

4. Work with Chemicals of High Chronic Toxicity

(Examples: dimethyl mercury and nickel carbonyl (48), Benzo-a-pyrene (51), Nnitrosodiethylamine (54), other human carcinogens or substances with high carcinogenic potency in animals (38).)

Further supplemental rules to be followed, in addition to all these mentioned above, for work with substances of known high chronic toxicity (in quantities above a few milligrams to a few grams, depending on the substance) (47). (Procedure A of" Prudent Practices" pp. 47-50).

(a)

Access: Conduct all transfers and work with these substances in a "controlled area": a restricted access hood, glove box, or portion of a lab, designated for use of highly toxic substances, for which all people with access are aware of the substances being used and necessary precautions (48).

(b)

Approvals: Prepare a plan for use and disposal of these materials and obtain the approval of the laboratory supervisor (48).

(c)

Non-contamination/Decontamination: Protect vacuum pumps against contamination by scrubbers or HEPA filters and vent them into the hood (49). Decontaminate vacuum pumps or other contaminated equipment, including glassware, in the hood before removing them from the controlled area (49,50). Decontaminate the controlled area before normal work is resumed there (50).

(d)

Exiting: On leaving a controlled area, remove any protective apparel (placing it in an appropriate, labeled container) and thoroughly wash hands, forearms, face, and neck (49).

(e)

Housekeeping: Use a wet mop or a vacuum cleaner equipped with a HEPA filter instead of dry sweeping if the toxic substance was a dry powder (50).

(f)

Medical surveillance: If using toxicologically significant quantities of such a substance a regular basis (e.g., 3 times per week), consult a qualified physician concerning desirability of regular medical surveillance (50).

(g)

Records: Keep accurate records of the amounts of these substances stored (229) and used, the dates of use, and names of users (48).

(h)

Signs and labels: Assure that the controlled area is conspicuously marked with warning and restricted access signs (49) and that all containers of these substances are appropriately labeled with identity and warning labels (48).

(i)

Spills: Assure that contingency plans, equipment, and materials to minimize exposures of people and property in case of accident are available (233-4).

(j)

Storage: Store containers of these chemicals only in a ventilated, limited access (48,227,229) area in appropriately labeled, unbreakable, chemically resistant, secondary containers (48,229).

(k)

Glove boxes: For a negative pressure glove box, ventilation rate must be at least 2 volume changes/hour and pressure at least 0.5 inches of water (48). For a positive pressure glove box, thoroughly check for leaks before each use (49). In either case, trap

6.22

the exit gases or filter them through a HEPA filter and then release them into the hood

(49).

(l) Waste: Use chemical decontamination whenever possible; ensure that containers of contaminated waste (including washings from contaminated flasks) are transferred from the controlled area in a secondary container under the supervision of authorized personnel (49,50,233).

5. Animal Work with Chemicals of High Chronic Toxicity

(a)

Access: For large scale studies, special facilities with restricted access are preferable (56).

(b)

Administration of the toxic substance: When possible, administer the substance by injection or gavage instead of in he diet. If administration is in the diet, use caging system under negative pressure or under laminar airflow directed toward HEPA filters (56).

(c)

Aerosol suppression: Devise procedures which minimize formation and dispersal of contaminated aerosols, including those from food, urine, and feces (e.g., use HEPA filtered vacuum equipment for cleaning, moisten contaminated bedding before removal from the cage, mix diets in closed containers in a hood) (55,56).

(d)

Personal protection: When working in the animal room, wear plastic or rubber gloves, fully buttoned laboratory coat or jumpsuit and, if needed because of incomplete suppression of aerosols, other apparel and equipment (shoe and head coverings, respirator) (56).

(e)

Waste disposal: Dispose of contaminated animal tissues and excreta by incineration, if the available incinerator can convert the contaminant to non-toxic products (238); otherwise, package the waste appropriately for burial in an EPA-approved site (239).

F. Safety Recommendations

The above recommendations from "Prudent Practices" do not include those which are directed primarily toward prevention of physical injury rather than toxic exposure. However, failure of precautions against injury will often have the secondary effect of causing toxic exposures. Therefore, we list below page references for recommendations concerning some of the major categories of safety hazards which also have implications for chemical hygiene:

1. Corrosive agents: (35-36).

2. Electrically powered laboratory apparatus: (179-92).

3. Fires, explosions: (26,57-74,162-164,174-175,219-220,226-227).

4. Low temperature procedures: (26,88).

5. Pressurized and vacuum operations (including use of compressed gas cylinders): (27,).

6.23

G. Material Safety Data Sheets

Material safety data sheets are presented in "Prudent Practices" for the chemicals listed below.

(Asterisks denote that comprehensive material safety data sheets are provided).

*Acetyl peroxide (105)
*Acrolein (106)
*Acrylonitrile (107)
Ammonia (anhydrous) (91)
*Aniline (109)
*Benzene (110)
*Benzo(a)pyrne (112)
*Bis(chloromethyl) ether (113)
Boron trichloride (91)
Boron trifluoride (92)
Bromine (114)
*Tert-butyl hydroperoxide (148)
*Carbon disulfide (116)
Carbon monoxide (92)
*Carbon tetrachloride (118)
*Chlorine (119)
Chlorine trifluoride (94)
Chloroform (121)
Chloromethane (93)
Diethyl ether (122)
Diisopropyl flurophosphate (41)
Dimethylformamide (123)
Dimethyl sulfate (125)
Dioxane (126)
Ethylene dibromide (128)
*Fluorine (95)
*Formaldehyde (130)
*Hydrazine and salts (132)
Hydrofluoric acid (43)
Hydrogen bromide (98)
Hydrogen chloride (98)
Hydrogen cyanide (133)
Hydrogen sulfide (135)
Mercury and compounds (52)
Methanol (137)
*Morpholine (138)
Nickel carbonyl (99)
*Nitrobenzene (139)
Nitrogen dioxide (100)

6.24

N-nitrosodiethylamine (54) Peracetic acid (141) Phenol (142) Phosgene (143) Pyridine (144) Sodium azide (145) *Sodium cyanide (147) Sulfur dioxide (101) *Trichloroethylene (149) Vinyl chloride (150)

6.25

Appendix B to 29 CFR .

References (Non-Mandatory)

The following references are provided to assist the employer in the development of a Chemical Hygiene Plan. The materials listed below are offered as non-mandatory guidance. References listed here do not imply specific endorsement of a book, opinion, technique, policy or a specific solution for a safety or health problem. Other references not listed here may better meet the needs of a specific laboratory.

(a)

Materials for the development of the Chemical Hygiene Plan:

American Chemical Society, Safety in Academic Chemistry Laboratories, 4th edition, .

Fawcett, H.H. and W.S. Wood, Safety and Accident Prevention in Chemical Operations, 2nd edition, Wiley-Interscience, New York, .

Flury, Patricia A., Environmental Health and Safety in the Hospital Laboratory, Charles C. Thomas Publisher, Springfield IL, .

Green, Michael E. and Turk, Amos, Safety in Working with Chemicals, Macmillan Publishing Co., NY, .

Kaufman, James A., Laboratory Safety Guidelines, Dow Chemical Co., Box , Midland, MI , .

National Institutes of Health, NIH Guidelines for the Laboratory Use of Chemical Carcinogens, NIH Pub. No. 81-, GPO, Washington, DC , .

National Research Council, Prudent Practices for Disposal of Chemicals from Laboratories, National Academy Press, Washington, DC,.

National Research Council, Prudent Practices for Handling Hazardous Chemicals in Laboratories, National Academy Press, Washington, DC, .

Renfrew, Malcolm, Ed., Safety in the Chemical Laboratory, Vol.IV, J.Chem.Ed., American Chemical Society, Easton, PA, .

Steere, Norman V., Ed., Safety in the Chemical Laboratory, J.Chem.Ed., American Chemical Society, Easton, PA. , Vol.I,, Vol.II,, Vol.III,.

Steere, Norman V., Handbook of Laboratory Safety, The Chemical Rubber Company Cleveland, OH, .

Young, Jay A., Ed., Improving Safety in the Chemical Laboratory, John Wiley & Sons, Inc. New York, .

(b)

Hazardous Substances Information:

American Conference of Governmental Industrial Hygienists, Threshold Limit Values for Chemical Substances and Physical Agents in the Workroom Environment with Intended Changes, P. O. Box Cincinnati, OH (latest edition).

Annual Report on Carcinogens, National Toxicology Program, U.S. Department of Health and Human Services, Public Health Service, U.S. Government Printing Office, Washington, DC, (latest edition).

Best Company, Best Safety Directory, Vols. I and II, Oldwick, N.J., .

Bretherick, L., Handbook of Reactive Chemical Hazards, 2nd edition, Butterworths, London, .

Bretherick, L., Hazards in the Chemical Laboratory, 3rd edition, Royal Society of Chemistry, London, .

Code of Federal Regulations, 29 CFR part subpart Z. U.S.Govt. Printing Office,
Washington, DC (latest edition).

IARC Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Man, World Health Organization Publications Center, 49 Sheridan Avenue, Albany, New York (latest editions).

NIOSH/OSHA Pocket Guide to Chemical Hazards. NIOSH Pub. No. 85- 114, U.S. Government Printing Office, Washington, DC, (or latest edition).

Occupational Health Guidelines, NIOSH/OSHA NIOSH Publication No.81-23 U.S. Government Printing Office, Washington, DC, .

Patty, F.A., Industrial Hygiene and Toxicology, John Wiley & Sons,Inc., New York, NY (Five Volumes).

Registry of Toxic Effects of Chemical Substances, U. S. Department of Health and Human Services, Public Health Service, Centers for Disease Control, National Institute for Occupational Safety and Health. Revised Annually, for sale from Superintendent of Documents, U.S. Govt. Printing Office, Washington, DC .

The Merck Index: An Encyclopedia of Chemicals and Drugs, Merck and Company Inc. Rahway, N.J., (or latest edition).

Sax, N.I. Dangerous Properties of Industrial Materials, 5th edition, Van Nostrand Reinhold, NY., .

Sittig, Marshall, Handbook of Toxic and Hazardous Chemicals, Noyes Publications, Park Ridge, NJ, .

(c)

Information on Ventilation:

American Conference of Government Industrial Hygienists, Industrial Ventilation, 16th edition, Lansing, MI, .

American National Standards Institute, Inc., Fundamentals Governing the Design and Operation of Local Exhaust Systems, ANSI Z9.2- American National Standards Institute, N.Y. .

Imad, A.P. and Watson, C.L. Ventilation Index: An Easy Way to Decide about Hazardous Liquids, Professional Safety, pp.15-18, April .

National Fire Protection Association, Fire Protection for Laboratories Using Chemicals NFPA-45, .

6.26

6.27

Safety Standard for Laboratories in Health Related Institutions, NFPA 56c, .

Fire Protection Guide on Hazardous Materials, 7th edition, . National Fire Protection Association, Batterymarch Park, Quincy, MA .

5. Scientific Apparatus Makers Association (SAMA), Standard for Laboratory Fume Hoods, SAMA LF7-. 16th Street, NW., Washington, DC .

(d) Information on Availability of Referenced Material:

1. American National Standards Institute (ANSI), Broadway, New York, NY .

2. American Society for Testing and Materials (ASTM), Race Street, Philadelphia, PA .

(Approved by the Office of Management and Budget under control number -)

6.28

CHEMICAL WASTE DISPOSAL PROCEDURES

Table of Contents

Page Subject

7.1 Introduction

7.2 Reduction of Waste

7.3 Consolidation of Solvents

7.3 Materials Which Are Not Legally Disposable

7.3 Explosive and Highly Reactive Chemicals

7.4 Heavy Metals

7.4 Non-Chemical Paraphernalia 7.5-6 Disposal of Nonhazardous Laboratory Waste Chemicals as Trash 7.7-8 Procedures for the Preparation of Hazardous Waste Chemicals for Disposal by

Environmental Health and Safety 7.9-16 Disposal of Laboratory Wastes to Sanitary Sewer

7.17 APPENDIX A - Neutralization procedures

7.18 APPENDIX B - Waste Oil Collection and Disposal

7.18 References

Environmental Health and Safety

May,

7.0

CHEMICAL WASTE DISPOSAL PROCEDURES

Introduction

Procedures for the handling of chemical waste are undergoing significant and continuous changes commensurate with society's heightened awareness and concern for the environment. These changes are resulting in ever increasing regulations and a corresponding escalation of incurred costs for disposal. In general, current regulations and laws hold the University responsible for any adverse effects from these chemicals forever, regardless of the manner in which they were disposed of or where they are. In Cornell disposed of approximately 44 tons of chemical waste.

The New York State Department of Environmental Conservation (DEC) has jurisdiction over the disposal program, as a result of New York's legislative action to assume authorization to implement the Resource Conservation and Recovery Act (RCRA) in conjunction with federal regulatory programs initiated by the Environmental Protection Agency (EPA). The Department of Transportation (DOT) regulations govern the labeling, packaging and transportation of chemical waste. Environmental Health and Safety is the federally registered university department charged with the management of such waste. Federal and state regulations provide criminal penalties for the abandonment, misrepresentation, or improper disposal of hazardous waste.

In the event of a chemical spill or emergency the Environmental Health and Safety Hazardous Materials Team (HazMat Team) should be contacted by calling the Campus Police at 911.

This document deals solely with the disposal of waste that is not radioactive. For assistance or information on disposal of radioactive material, including both licensed material (material authorized under a Cornell Radioactive Permit) and non-regulated radioactive material such as uranium and thorium salts, contact Environmental Health and Safety at 255-. Please note the following: 1) A detailed description of chemical composition must be provided for all liquid radioactive waste; and 2) procedures that produce mixed waste including both radioactive and hazardous chemical material must be approved in advance by the Cornell Radiation Safety Committee.

These procedures and suggestions are presented for the following purposes:

1.) To ensure that the University is in compliance with all federal, state and local laws applicable to the management and disposal of hazardous materials.

2.) To reduce the impact of hazardous materials on the environment by implementing a waste minimization program.

3.) To reduce the University's costs and liability associated with the management and disposal of hazardous waste.

7.1

4.) To provide staff at Cornell University with a comprehensive reference source for proper

preparation (packing, labeling, etc.) of hazardous materials designated for on- or off-site

disposal.

The book, Prudent Practices in the Laboratory, Handling and Disposal of Chemicals, National Academy Press, , has attained a status as the standard authority on questions related to the technical aspects of the treatment and disposal of chemical waste. Laboratories should have a copy available for the use of researchers. Prudent Practices can be ordered through the Cornell Campus Book Store.

How to approach questions of treatment and disposal often requires judgment which is best exercised by scientists in the laboratory, but adherence to the regulations is a must.

Experiments that will produce a large volume of hazardous waste or any quantity of particularly difficult hazardous waste should be discussed with Environmental Health and Safety and planned for well in advance. A member of the EH&S HazMat team can be reached at 255-, 8:00 AM to 4:00 PM Monday thru Friday.

The companies which pick up chemical waste come to Cornell about four times a year. They stay for about five days and monitor the packaging of waste (at an average cost of $35,000 per visit). They examine each labeled bottle and, in some cases, make an analytical test to decide whether or not they are willing to accept the material. By taking the waste, the company is sharing the responsibility for the materials, so it is understandable that they have a conservative outlook. If material is not accepted for shipment, the problem is left with the University. Rejected material will be returned to the generating laboratory for further identification.

REDUCTION OF WASTE

The level of hazardous waste can be reduced by limiting the purchase of chemicals to the quantities that will be used. The RCRA regulations stress this approach and DEC has mandated that the University implement a program to reduce the volume of hazardous waste generated. Disposal facilities charge $50 or more (depending on the type of chemical) to dispose of a gallon of waste solvent, so the cost of disposal often exceeds the original purchase price.

Faculty and staff still continually ask Environmental Health and Safety to dispose of new, factory-sealed jars of chemicals. Lab workers, faculty and staff are urged to make available to others the excess chemicals in their laboratories. The Department of Chemistry and Chemical Biology maintains a chemical recycling program for the campus. Contact John Terry at 255- or check their Web site at: http://www.chem.cornell.edu/jht1/

Experiments in teaching and research labs should be done on as small a scale as is feasible.

7.2

CONSOLIDATION OF SOLVENTS

Current regulations prohibit the disposal of hazardous waste chemicals in landfills, so all such materials are shipped for incineration or treatment.

Laboratory workers are urged to consolidate solvents as much as possible. A large percentage of chemical waste is shipped in 55-gallon drums known as labpacks. These drums contain bottles of solvent or chemicals (about 15 one-gallon bottles) along with absorbent material. Some material, if in sufficient quantity, is shipped as bulk liquid in the 55-gallon drums. If permitted by regulations, the latter procedure is far less costly.

The charge for disposal of labpacks is based on the number of drums of waste, whether the drum is completely filled with solvents or contains (as in most cases) partially filled bottles packed according to DOT regulations. Thus, the cost of the disposal of a partially filled bottle is the same as the cost of one which is full. Given this situation, partially filled bottles become very expensive for the amount of material being shipped. In part, this explains the high disposal cost per gallon of material. In order to reduce this empty but costly space, compatible solvents may be combined in a single container. When solvents are thus combined, the approximate volume percent of each solvent should be noted on the disposal tag. However, halogenated solvents should not be combined for disposal with solvents which do not contain halogens, because of differences in handling and ultimate disposal techniques. Solutions of halogenated and non-halogenated solvents will be considered as halogenated solvents and disposed of accordingly.

MATERIALS WHICH ARE NOT LEGALLY DISPOSABLE

As a prerequisite to shipping chemical waste, the identity of the material must be established. In the case of materials for which no information is available, Environmental Health and Safety will absorb the cost to have one or two samples characterized by a competent laboratory. The cost incurred to identify larger numbers of samples is the responsibility of the generating department.

A recurring problem is "orphan" waste. Orphan waste material is waste (with no information) left behind by students, staff and faculty who have left Cornell University. Some suggestions for dealing with this problem can be found in Prudent Practices. The best method of dealing with such "orphan" waste is to prevent its occurrence by having as much chemical waste removed as possible before a generator leaves. (Some departments have spent thousands of dollars on dealing with "orphan" wastes.)

Trade names or initials are not sufficient identification. Environmental Health and Safety has Material Safety Data Sheets on most trade name products. These sheets have sufficient information to allow identification, and, thereby, disposal of such products.

7.3

EXPLOSIVE AND HIGHLY REACTIVE CHEMICALS

Few laboratory chemicals are explosive but, at times, potentially explosive materials can be generated in synthetic work or merely by storage. Picric acid (2,4,6, trinitrophenol), a potentially explosive compound, is sometimes used in laboratories. It is usually purchased containing 10-15 percent water, in which state it is relatively safe. However, if allowed to dry, it should be treated as a dangerous explosive and Environmental Health and Safety should be notified. Prudent Practices has a list of shock-sensitive compounds which includes, among others, acryl and alkyl nitrites, alkyl perchlorates, azides, diazo compounds, dry diazonium salts, peroxides, hydroperoxides, and poly nitro alkyl/aromatic compounds. Many common laboratory chemicals can form explosive peroxides on exposure to air over time. A list of such chemicals can be found in Prudent Practices. The compounds on this list should be dated when opened and disposed of in specified periods of time. For example, diisopropyl ether is particularly susceptible to peroxide formation and, if its use is required, it should be completely used or disposed of within three months of opening. If older stocks of isopropyl ether are discovered, Environmental Health and Safety should be notified before handling.

Ether, dioxane and tetrahydrofuran are susceptible to peroxide formation. Once opened, stocks of these chemicals should be used within six months. After six months they must be tested for peroxide formation. Test strips for determining the amount of peroxides in solvents are available from the Chemistry Department stockroom. If the amount of peroxide is over 80 parts per million, the material should be discarded. (Note: No one knows if 80 ppm is reasonable; it's the number used in the University of Wisconsin manual.) If a peroxide bearing solvent is not discarded after six months the peroxide must be destroyed using the appropriate procedures. Recently, chemical manufacturers have been printing expiration dates on stocks of peroxide-forming chemicals, and the materials should be disposed of after this period has expired. Prudent Practices deals with the treatment and disposal of potentially explosive materials. Some water-reactive and pyrophoric compounds may also be decomposed using simple procedures. Such procedures are available in Prudent Practices and other references. These procedures must be carried out in the laboratory in which the material is generated and in the container in which the waste was originally accumulated. For assistance call Environmental Health and Safety at 255-.

Another class of materials which cannot be disposed of without pre-treatment is those which evolve gases. Any waste material which requires vent-caps cannot be accepted by Environmental Health and Safety.

HEAVY METALS

The EPA has banned heavy metals from land disposal. Alternate methods of treatment and disposal are under investigation but, none of these have received final approval from EPA.

At the moment limited disposal methods are available for mercury and other heavy metal compounds, and these materials currently picked up by Environmental Health and Safety. Metallic are mercury will be recycled by EH&S. The mercury should be separated from the glassware apparatus, such as thermometers and manometer by the researcher, using proper precautions. All heavy metal compounds should be kept separate from other materials to facilitate disposal.

7.4

NON-CHEMICAL PARAPHERNALIA

Plastic ware, disposable gloves, glassware, paper towels, tools, pumps, and the like, which are contaminated with chemical waste, cannot be disposed of by Environmental Health and Safety. Such items must be decontaminated and reused, or disposed of as ordinary trash. The appropriate method of decontamination is the responsibility of the laboratory. The resulting rinsate solution will be accepted for disposal as chemical waste. For disposing of empty bottles, EPA regulations require that containers be rinsed three times with a 30-second drain time between rinses before being discarded or reused.

Hypodermic syringes and needles are considered regulated medical waste, and must be disposed of according to state and federal regulations. See the College of Veterinary Medicine document, "Disposal of Medical Waste," for instructions on the disposal of "sharps." All syringes, needles and other "sharps" should be placed in an approved rigid, leak-proof, and puncture-resistant container. The Veterinary College also takes dry materials (paper products, bench paper, gloves, etc.) contaminated with trace amounts of mutagens, reduced osmium tetroxide and other materials. For additional information, including obtaining a copy of "Disposal of Medical Waste," call the Office of the Director of Biosafety, NYSCVM, 253-, or the Incinerator Operator at 253-.

DISPOSAL OF NONHAZARDOUS LABORATORY WASTE CHEMICALS AS TRASH

The following table, adapted from Prudent Practices, lists solid chemicals which are not considered hazardous and are therefore suitable for disposal with regular trash. However, neither custodians nor trash collectors can readily distinguish between hazardous and nonhazardous wastes. Therefore, the packaging of such waste for disposal must be secure, and its transfer to the dumpster carried out by laboratory personnel.

A. Organic Chemicals

Enzymes

Sugars and sugar alcohols

Starch

Naturally occurring amino acids and salts

Citric acid and its Na, K, Mg, Ca, NH4 salts

Lactic acid and its Na, K, Mg, Ca, NH 4 salts

B. Inorganic Chemicals

Silica
Sulfates: Na, K, Mg, Ca, Sr, NH4
Phosphates: Na, K, Mg, Ca, Sr, NH4
Carbonates: Na, K, Mg, Ca, Sr, NH4
Oxides: B, Mg, Ca, Sr, Al, Si, Ti, Mn, Fe, Co, Cu
Chlorides: Ca, Na, K, Mg, NH4
Borates: Na, K, Mg, Ca

7.5

C. Laboratory Materials Not Contaminated with Hazardous Chemicals

Chromatographic adsorbent
Glassware
Filter papers
Filter aids
Rubber and plastic protective clothing

Other examples of nonhazardous biochemicals include polysaccharides, nucleic acids and naturally occurring precursors, and dry biological media.

INSTRUCTIONS FOR PACKAGING:

1. Package securely for the dumpster by using at least two layers of packaging so that material cannot spill during collection.

2. Leave label on innermost container.

3. Label outer container "Non-hazardous" waste.

4. Place containers in the dumpster yourself, since custodians do not handle even nonhazardous laboratory chemicals.

7.6

PROCEDURES FOR THE PREPARATION OF HAZARDOUS WASTE CHEMICALS
FOR DISPOSAL BY ENVIRONMENTAL HEALTH & SAFETY

1. Call EH&S at 255- to request new numbered two-part stick-on 5"x4" disposal stickers.

2. Complete the two-part stick-on label with all of the spaces filled in (i.e., bldg. and room number, name of requester, number, chemical type, chemical name and weight or volume of all ingredients in each container). No trade names please. (Some ingredients may take more room than can be written on the numbered label. If this is the case, please tape (1) one additional copy of the ingredients on a small piece of paper to the container and send a second copy to EH&S along with the tear off portion of the label.) Due to the large number of laboratories serviced, we no longer accept calls for routine chemical pick-ups unless it is an emergency situation. After receiving copies of the labels at EH&S, we will respond on a first come first served basis. Please make sure that the date on the label is the date that you send the labels to EH&S via campus mail.

Additional information on completing the label is as follows:

Building & Room: Indicates the area where the hazardous waste is generated, and directs EH&S personnel to the pickup.

Name and Number: Identifies the individual faculty or staff member generating the hazardous waste and assuming responsibility for its description. This information is important if questions about the material subsequently arise and must be answered.

Date: Both federal and state legislation stipulate 90 days as the length of time EH&S may possess the hazardous waste, subsequent to removing it from the individual laboratories and prior to final shipment to an approved disposal facility. Therefore, individual faculty and staff members should fill in the date on which EH&S was notified to pick up the chemicals.

Type: Identifies the general characteristics of the hazardous waste chemicals and indicates which classes of waste should not be mixed or packaged together to facilitate disposal procedures.

Chemical Name: Precisely identify the exact composition of the hazardous waste in each container. Both federal and state legislation prohibit the use of code numbers, trade names and initials in the transportation and disposal of hazardous waste. Hazardous waste consisting of multiple elements or compounds requires the identification of each constituent, and the percentage by volume it occupies in the container if known. Note: The weight (in grams) or volume (in milliliters) of all ingredients in each container must be listed in this section, along with the chemical name and percent composition.

Waste oils containing PCBs must indicate the parts per million (ppm) of PCBs. If this is unknown, the material can be tested by calling 255- and obtaining a computerized sample number and sampling bottle to analyze the oil.

7.7

Unknown chemicals and chemical waste can be identified by a competent testing laboratory. However, it is the responsibility of the generator of the waste to field test the material before it is sent in to be analyzed so that the testing lab has as much information on the unknown material as possible. For example, if you know the pH or water and solvent solubility of the material, or if the history of use of the material is known, this is valuable information for the testing lab. Please supply this information with the sample. Call 255- to obtain a computerized sample number and sampling bottle to analyze the unknown chemical or waste.

1. Use only screw top chemical glassware or plasticware for disposal. Soda pop, glass or plastic milk bottles, Clorox bleach bottles, or rubber/glass stoppered containers will not be allowed for waste disposal. Any waste bottle/ container that emits a noxious smell or is cracked or damaged in any way must be placed in an overpack container or transferred to a new bottle/container.

2. Place all containers in a Department of Transportation (DOT) approved box which has markings located on one side of the box ( i.e., UN/4G/X,Y or Z/S/DATE OF MANUFACTURE/USA, etc.). The DOT boxes have a styrofoam insert for four 4-liter bottles. If the waste containers/bottles are smaller than the 4 liter space, please place as many smaller containers/ bottles in the space as you can. Cardboard pieces must be placed between the smaller bottles to prevent breakage during transportation to the chemical waste facility. These boxes are not supplied by EH&S; however, if you have difficulty locating boxes, we will assist in locating them and will communicate to you where you can pick them up.

7.8

Sample of the numbered two-part stick-on 5"x4" disposal sticker.

DISPOSAL OF LABORATORY WASTES TO SANITARY SEWER

Guide for Drain Disposal of Laboratory Chemicals

1.0 INTRODUCTION

This guide was prepared by Cornell's Environmental Health and Safety (EH&S) with assistance from a faculty committee consisting of experts in the areas of toxicology, chemistry, and environmental engineering.

Staff at the Ithaca Area Waste Water Treatment Plant, the destination of Cornell's wastewater, were consulted in developing these guidelines to assure that local government regulations are followed.

2.0 RESPONSIBILITIES

Within individual laboratories, authorization for specific operations, delineation of appropriate safety procedures and instruction about these procedures is a responsibility of the principal investigator.

It is the responsibility of each Cornell laboratory worker to be sure that chemical waste generated from their activities is disposed of properly. Some materials can be safely let into the sanitary sewer and others can cause damage to health, the environment or the functioning of the wastewater plant.

Inappropriate chemicals put down the drain may be incorporated into sludge formed in waste water treatment, contaminating it enough to be classified as a hazardous waste where otherwise it might have been recycled. After treated waste water leaves the plant, it flows to Cayuga Lake, a major recreational and drinking water resource for this area. The stewardship of this important natural resource is our collective responsibility.

Laboratory workers should consult this guide before undertaking drain disposal of any lab chemicals.

3.0 GENERAL GUIDELINES

What

Send down the drain only those materials found on the safe list. Compounds not listed are not suitable for drain disposal.

Where

Drain disposal must only be used when the drain flows to a sanitary sewer system* which eventually goes to the waste water treatment plant. Storm drain systems flow directly into surface water (Fall or Cascadilla Creeks, for example) and should NEVER be used for chemical disposal. Floor drains may

7.9

flow to storm sewers and should never be used for disposal. Laboratory sinks should be used for disposal of chemicals on the safe list as discussed below.

How Much

Quantities of chemical waste for drain disposal should be limited generally to a few hundred grams or milliliters or less per day. Larger amounts should have prior approval from EH&S. Only materials listed as safe for drain disposal in this document are approved for drain disposal in quantities up to 100 grams or 100 milliliter per discharge. Disposal should be followed by flushing with at least 100fold excess of water at the sink. (That means for 100 ml of chemical run the water for about two minutes at maximum flow.)

Note: Sulfuric, hydrochloric, acetic and phosphoric acids may be discharged in larger quantities since they must be neutralized to a pH of between 5.5 and 9.0 before they can be drain disposed to the sanitary sewer.

*Sanitary sewer is the system of sinks, toilets, drains and associated pipes that send waste water to a treatment plant where it is biologically and chemically treated before discharge into the environment.

Safety

Understand the hazards and toxicity of the materials you work with by consulting material safety data sheets (available in every department in large red notebooks, on the Internet, or through EH&S). Work slowly to avoid splashes and wear the proper protective equipment (lab coat, goggles, face shield, gloves) during drain disposal.

Chemicals that are not appropriate for drain disposal are collected by Environmental Health and Safety. See pages 7.7-9 of this section.

4.0 NOT SAFE FOR DRAIN DISPOSAL

THE FOLLOWING MATERIALS ARE PROHIBITED FROM DRAIN DISPOSAL BY THE CITY OF ITHACA:

• Ashes, cinders, sand, mud, straw, shavings, metal, glass, rags, feathers, tar, plastics, wood, manure, hair and fleshings, entrails, paint residues, solid or viscous substances capable of causing obstruction to the flow of sewers.

• Some chemicals that are not appropriate for drain disposal include: Halogenated hydrocarbons Nitro compounds Mercaptans Flammables (immiscible in water) Explosives such as azides and peroxides Water soluble polymers that could form gels in the sewer system Water reactive materials Malodorous chemicals

7.10

Toxic chemicals such as carcinogens, mutagens, teratogens

• Substances that boil below 50? C.

• Mixtures that have a component not found on the safe list.

• Any material not found on the safe list.

Check with Environmental Health and Safety at 255- if you are not certain about drain disposal for a particular material. We may also be able to provide you with instructions for laboratory detoxification for some materials.

5.0 SAFE FOR DRAIN DISPOSAL

Inorganics

Dilute solutions of inorganic salts where both caution and anion are listed below are suitable for drain disposal. Materials listed are considered to be relatively low in toxicity. Compounds of any of these ions that are strongly acidic or basic should be neutralized before drain disposal.

Cations Anions

Al+3 BO3-3

Ca+2 B4O7-2

Fe+2, +3 Br-
H+ CO3-2

K+ Cl-

Li+ HSO-3

Mg+2 OCN-

Na+ OH

NH4+ I-
-

Sn+2 NO3

Sr2+ PO4-3
Ti+3,+4 SO4-2

Zr+2 SCN

• Mineral acids and bases should be neutralized to pH 5.5 to 9 range before disposal, following procedures in Appendix A.

• Copper and Zinc have specific discharge limits required by the Sewage Treatment Plant. Contact Environmental Health and Safety at 255- prior to discharging any copper or zinc.

7.11

Organics

Materials listed below in quantities up to about 100g or 100 ml at a time are suitable for disposal down the drain while flushing with excess water. These materials are soluble to at least 3 percent, present low toxicity hazards and are readily biodegradable.

Alcohols

Alkanols with 4 or fewer carbon atoms:

methanol ethanol propanol and isomers butanol and isomers

Alkanediols with 7 or fewer carbon atoms

ethylene glycol propylene glycol butylene glycol butanediol + isomers pentylene glycol pentanediol + isomers hexylene glycol hexanediol + isomers heptamethylene glycol heptanediol + isomers

Alkoxyalkanols with 6 or fewer carbon atoms:

methoxyethanol ethoxyethanol butoxyethanol 2-methoxyethoxyethanol n-C4H9OCH2CH2OCH2CH2OH (2(2-butoxyethoxy)ethanol)

Aldehydes

Aliphatic aldehydes with 4 or fewer carbon atoms:

formaldehyde (10% or less aqueous solution)
propanal (propionaldehyde)
butanal (butyraldehyde)
isobutyraldehyde

7.12

Amides

RCONH2 and RCONHR with 4 or fewer carbon atoms and RCONR2 with 10 or fewer carbon atoms:

formamide N-methyl formamide N,N-diethyl formamide N,N-dimethyl formamide N-ethyl formamide acetamide N-methyl acetamide N,N-dimethyl acetamide N-ethyl acetamide propionamide N-methyl propionamide N, N-dimethyl propionamide butyramide isobutyramide

*

Amines

Aliphatic amines with 6 or fewer carbon atoms:

methylamine ethylamine trimethylamine N-ethyl methylamine N-methyl propylamine dimethyl propylamine isopropylamine 1-ethyl propylamine butylamine methyl butylamine N-ethyl butylamine isobutylamine amylamine hexylamine

Aliphatic diamines with 6 or fewer carbon atoms:

1,2- or 1,3- propanediamine (1,2- or 1,3- diaminopropane)

*Amines with a disagreeable odor, such as dimethylamine and 1,4-butanediamine should be neutralized, and the resulting salt solutions flushed down the drain, diluted with at least 100 volumes of water. Disposal limit is 100ml of material.

7.13

Carboxylic Acids

*

Alkanoic acids with 5 or fewer carbon atom:

formic acid acetic acid propionic acid butyric acid isobutyric acid valeric acid isovaleric acid

Alkanedioic acids with 5 or fewer carbon atoms:

oxalic acid (1,2-ethanedioic acid) malonic acid (1,3-propanedioic acid) succinic acid (1,4-butanedioic acid) glutaric acid (1,5-pentanedioic acid)

Hydroxyalkanoic acids with 5 or fewer carbon atoms:

lactic acid (2- hydroxypropanoic acid) 3-hydroxybutyric acid 2-hydroxy isobutyric acid

Aminoalkanoic acids with 6 or fewer carbon atoms and the ammonium, sodium and potassium salts of these acids.

Amino acids and the ammonium, sodium and potassium salts of these acids.

*Organic acids with a disagreeable odor, such as butyric acids and valeric acids should be neutralized and the resulting salt solutions flushed down the drain, diluted with at least 100 volumes of water. Disposal limit is 100 ml. of material.

Esters

Esters with 4 or fewer carbon atoms:

methyl formate ethyl formate isopropyl formate propyl formate methyl acetate ethyl acetate methyl propionate Isopropyl acetate

7.14

Ketones

Ketones with 4 or fewer carbon atoms:

acetone
methyl ethyl ketone (butanone)
methyl isopropyl ketone (3-methyl butanone)

Sulfonic Acids and the Ammonium, Sodium, and Potassium Salts of these Acids:

methane sulfonic acid, sodium or potassium salt ethane sulfonic acid, sodium or potassium salt 1-propane sulfonic acid, sodium or potassium salt 1-butane sulfonic acid, sodium or potassium salt 1-pentane sulfonic acid, sodium or potassium salt 1-hexane sulfonic acid, sodium or potassium salt 1-heptane sulfonic acid, sodium or potassium salt 1-octane sulfonic acid, sodium or potassium salt 1-decane sulfonic acid, sodium or potassium salt 1-dodecane sulfonic acid, sodium or potassium salt 1-tetradecane sulfonic acid, sodium or potassium salt 1-hexadecane sulfonic acid, sodium or potassium salt

7.15

6.0 RADIOACTIVE MATERIALS

Radioactive materials may not be drain disposed with the following exceptions:

• Wash and rinse water used for cleaning contaminated glassware that has been double rinsed may be drain disposed. The first two rinses of the glassware must be collected in liquid radioactive waste containers.

• With specific written permission from the Radiation Safety Officer, in accordance with procedures stipulated by Federal, State, and Local regulations, Cornell's license to use radiation, and the University Radiation Safety Committee, certain radioactive materials may be approved for drain disposal. Call (Environmental Health and Safety) for specific information.

7.16

APPENDIX A NEUTRALIZATION PROCEDURES General

If you are looking for more details, kindly visit Molecular Structure of 1,2-Bis(2-Chloroethoxy) Ethane.

• Do neutralizations in a fume hood behind a safety shield, as fumes and heat may be generated. Wear lab coat or apron, gloves and goggles.

• Keep containers cool during process.

• Work slowly.

• After neutralization is complete, flush to sewer with 20 parts water.

Acid Neutralization

1. While stirring, add acids to large amounts of an ice water solution of base such as sodium carbonate, calcium hydroxide, or sodium hydroxide for concentrated acids.

2. When a pH of at least 5.5 is achieved, dispose of the solution into the sewer, followed by 20 parts water.

Base Neutralization

1. Add the base to a large vessel containing water. Slowly add a 1M solution of HCI.

2. When a pH of 9 or less is achieved, dispose of solution into sewer system followed by 20 parts water.

7.17

APPENDIX B

WASTE OIL COLLECTION AND DISPOSAL

1.0 WASTE OIL COLLECTION (INCLUDING VACUUM PUMP OILS)

Oil should be collected locally and stored temporarily in approved and properly marked containers (30 or 55 gallons drums) provided by Environmental Health and Safety. The Containers must be stored inside the building. The containers must be clearly marked "Waste Oil Only: No Solvents."

2.0 DISPOSAL OF WASTE OILS

When the oil drums are full please contact the Cornell Purchasing Department at 255- to obtain information on the disposal of oils. A contract with a recycling company has been made through Purchasing. You must supply a purchase order number or an account number to facilitate the pick up of oils in your department or facility.

References:

National Research Council, Prudent Practices in the Laboratory, Handling and Disposal of Chemicals,
National Academy Press, .
American Chemical Society, Safety in Academic Chemistry Laboratories, .
Safety Manuals from the Universities of Wisconsin and Cincinnati.

Ithaca Area Sewer Ordinance

7.18

Cornell Chemical Hygiene Plan

USER'S GUIDE TO FUME HOODS

Procedures for Increasing the Effectiveness of Laboratory Hoods

Revised December,

A laboratory fume hood system is designed to protect the operator from undesirable substances being used, so its most important function is containment. While users have little control over a system that is already in place, they can greatly increase or decrease its effectiveness by the way the hood is used. The purpose of this document is to make those who use hoods aware of some of the factors that contribute to the effectiveness of a hood system.

Hood Basics

There are a wide variety of fume hoods on campus and some of these suggestions may not be applicable to all systems. The basic structure of a fume hood is not unlike a conventional fireplace and chimney combination. They usually have dampers that permit ventilation of the laboratory when the hood is not in use. In some cases, hoods with vertical sashes are designed to automatically exhaust about the same amount of air from the room even when the sash is closed. In other cases, the hoods have dampers that change the ratio of room air that goes through the hood compared to that which bypasses the system.

8.0

As shown in Figure 1, most hoods have an arrangement of movable panels, called baffles, with openings or slots at their edges. Air exhausted from the hood is drawn out through the slots. The slots are always at the top and the bottom, with some systems having a middle adjustable slot or slots on the vertical edges of the baffles. The ratio of air that is drawn into the top and bottom slots can be varied by repositioning the baffles. Hood manufacturers claim that the upper exhaust slot should be opened when working with lighter than air vapors and the lower exhaust slot should be used to collect heavier than air vapors. Experts dispute this claim as a useful concept, noting that, except in unusual circumstances, the amount of material mixing with the air has minimal effect on the density of the mixture. You should check the setting of the upper slot. This should be between one-half and three-quarters of an inch. If this setting is not fully open, efficiency can drop by a large factor due to turbulence in the upper portion of the hood. The bottom slot is usually open one to four inches depending upon the design of the hood.

Good Work Practices and Changes You Can Make

Keep the Sash Down

For hoods that have a movable front sash, keeping the opening as small as reasonably possible usually increases the flow rate through the aperture and enhances effectiveness. The sash also operates as a safety shield. It is strongly recommended that the hood sash be closed to within one or two inches when not in use. In many cases, such a practice not only saves energy, but can increase efficiency of other hoods on the same system.

Have an Airfoil Installed

A source of undesirable turbulence results when air entering the hood impacts on the front edge of the floor of the hood. This effect can be minimized by the installation of an airfoil along the front edge of the hood. Experiments conducted in the Chemistry Department showed a significant decrease in turbulence when such devices were installed. These devices are relatively inexpensive (around $100) and can be purchased for existing hoods through fume hood suppliers. Contact the Purchasing Department for vendors selling these devices. These devices are simple enough to be fabricated on campus; if you are interested, call the Sheet Metal Shop at 255-.

Use an Airflow Indicator

It is possible that without the knowledge of the user, the fan motor may not be operating, with the result that the individual does not have the protection expected from the system. Inexpensive (around $100) flow monitors that serve as indicators are available from scientific supply houses. These are listed under airflow monitors, manometers and vaneometers. A simple telltale consisting of an eight-inch narrow length of light material will also serve this purpose.

Keep Laboratory Doors and Windows Closed

In closed buildings, ventilation and fume hood systems are usually designed on the assumption that doors to the laboratory and windows will be in the closed position. If the doors and windows are left open, unplanned airflow patterns may degrade the efficiency of a hood.

8.1

Limit Traffic

Pedestrian traffic in front of the hood induces turbulence and can overcome the capture of vapors and pull them back out of the hood and into the operator's breathing zone. A painted line or length of tape placed on the floor of the room two feet away from the hood will discourage traffic this close to the hood.

Reduce Clutter

Achieving even, laminar airflow across the deck or bench surface of the hood increases the effectiveness of a hood system. The presence of objects in the hood tends to increase turbulence, so the more cluttered the working surface, the lower the efficiency and the less protection you have. For this reason, the number of objects in a hood should be kept to a workable minimum. In particular, keep the number of chemicals stored in a hood as low as possible. Not only does such storage decrease hood efficiency, but it also increases the possibility and seriousness of accidental fires. Solvents should be placed in vented cabinets rather than wasting useful and expensive hood space. When circumstances dictate such storage of chemicals, they should not be placed near the exhaust slots or in the front six inches. Shelving constructed of noncombustible materials may be placed in a hood as long as the bottom shelf is several inches off the deck of the hood and as long as it is placed in a way that does not interfere with the flow of air through the hood.

Work Far into the Hood

You can substantially increase your protection by putting experimental materials as far back into the hood as practical. By moving a fume source from the plane of the hood face back six inches into the hood's interior, the capture rate for volatile materials can be greatly improved. Operations should not be carried out within six inches from the plane of the sash and as a useful reminder, paint a line or place a strip of tape at this six-inch limit. However, in attempting to work as far back in the hood as possible, you should realize that the concentration of escaping vapors falls off very rapidly from the plane of the sash outward. Therefore, one's face should not be within the plane of the sash.

Other Considerations

Explosions

The glass sash offers protection from accidents and, when possible, it is safest to keep the sash between your face and the experiment. But the glass face is not designed to protect against explosions. When an explosive hazard is present, rounded safety shields should be placed between the operator and the experiment and as close as possible to the plane of the hood sash. Full-face protection should also be used in such circumstances. Evaporations and digestions involving perchloric acid must not be carried out in hoods that were not designed for that purpose. Perchloric acid can condense in the ductwork and result in an explosion hazard.

8.2

Exhaust

Care should be taken with the use of paper products, aluminum foil and other lightweight materials within the hood. For example, a single piece of Kleenex, if sucked into the exhaust ducts, can potentially cause a profound deterioration in the velocity of air flowing into the hood.

Drains

Run water in hood drains at least once a week if the drains are not normally used. This is to prevent the drain traps from drying out and possibly perturbing airflow in the system.

Power Outages

In case of a loss of power, the hood sash should be lowered to within an inch or so of the closed position so the chimney effect will keep some air flowing into the hood. Electric powered devices in the hoods should be disconnected to minimize accidents when the power is restored.

Adjustments to the Hood System

Get Assistance for Mechanical Changes

Venting of laboratory apparatus (e.g., vacuum pumps and storage cabinets) into the face or side of a hood can disrupt the design flow and lower efficiency. When such venting is deemed necessary, the connection should be further along the exhaust ducts of the hood system rather than into the face of the hood. To avoid the possibility of disrupting the efficient operation of the system, such installations should not be undertaken without consultation with Facilities Engineering, EH&S and the appropriate technical shops.

Likewise, installation of a new fume hood cannot be undertaken without the possibility of seriously disrupting the existing ventilation system and at times making other hoods in the building much less efficient. You should never consider doing this work yourself.

Environmental Health and Safety's Role

Environmental Health and Safety performs annual testing of fume hoods on campus. If the existing inspection sticker on your fume hood indicates a year or more has passed since we last inspected that hood, please call us. If your fume hood doesn't have an inspection sticker or if you have questions concerning the hood's operation, contact Environmental Health and Safety at 255- for air flow measurements or questions.

Please remember that all fume hood purchase requests need prior review and approval through our office. We can also provide information regarding the selection, purchase and inspection requirements for laminar flow clean benches, biosafety cabinets and portable fume hoods.

8.3

Mechanical Problems

If your fume hood suddenly seems to stop working and you suspect mechanical problems, ask your building coordinator to call Customer Service. If maintenance workers are going to be working on your hood system, you should remove all chemicals from the hood.

Points to Remember

Many advisory notices of this sort are read but forgotten over time. To emphasize the more important operating factors, remember the following:

1. Make sure the hood is working (telltale indicates airflow).

2. Keep the sash as low as practical--sash is a safety shield.

3. Keep lab equipment elevated at least one inch off work surface.

4. Keep the hood free from clutter--don't block baffle openings.

5. Work at least six inches into hood.

6. Minimize rapid movements in front of hood.

Training programs on the safe use of fume hoods are available from Environmental Health and Safety.

Additional Information

For additional information on fume hoods and laboratory ventilation systems please see the following:

ANSI/AIHA Standard Z9.5-, Laboratory Ventilation. A paper copy of this document is available at the EH&S office at 125 Humphreys Service Building. Cornell University Design and Construction Standards, " Laboratories." available by request from EH&S or at: http://cds.pdc.cornell.edu/DesignStandards/Mechanical/Laboratories.htm

ANSI/ASHRAE Standard 110-, Method of Testing Performance of Laboratory Fume Hoods. A paper copy of this document is available at the EH&S office at 125 Humphreys Service Building. "Fume Hood Evaluation Procedures," as used by EH&S for testing fume hoods at Cornell. "The Dry Ice Capture Test as Performed on Fume Hoods at Cornell," as used by EH&S for determining the ability of a hood to capture vapors and fumes. "Cornell EH&S Fume Hood Shell Selection Guide," developed to help lab staff and designers select the appropriate fume hood.

8.4

BASIC TOXICOLOGY

Introduction

As a laboratory worker, you use a variety of chemicals as part of your daily work routine. Many of these substances are potentially hazardous to your health and that of your co-workers. The actual hazards that a chemical may present depend not only on the properties of the chemical, but also on the manner in which it is used, and the resulting exposure to the worker. With the proper handling, even highly toxic or dangerous chemicals can be used safely. On the other hand, chemicals that are not highly toxic can be extremely hazardous if handled improperly.

Whether or not a chemical exposure will result in injury depends on many factors. In addition to the dose, the outcome of exposure is determined by the way in which a chemical enters the body, the properties of the chemical itself, and the susceptibility of the individual receiving the dose. Understanding these factors will help you know what precautions to take to reduce your exposures.

Routes of Entry

Skin:

Symptoms of skin exposure to chemicals include dry, whitened skin, redness and swelling, rashes or blisters, and itching. Protect your hands against abrasions and lacerations that may increase chemical entry. Wear the correct gloves and other protective clothing to prevent or minimize skin contact with hazardous chemicals. Any time contact occurs, you should rinse promptly and thoroughly, for at least ten minutes, with lots of water. Remember that the longer the chemical is in contact with the skin, the more damage it may do. Rinse first, and then seek medical advice when necessary.

Eyes:

You should always be careful to protect your eyes since most chemicals are hazardous to this delicate tissue. Chemical splash goggles provide better protection than safety glasses. If you get a chemical in your eye, immediately flush the eye with large amounts of clean water for at least fifteen minutes.

Respiratory Tract:

Factors that affect the absorption of gases and vapor by your body include the chemical's vapor pressure, its concentration in the inhaled air, and its chemical properties. Symptoms of exposure to gases include headache, eye, nose and throat irritation, and increased mucus production. Narcotic effects may also result from the inhalation of certain chemicals (hydrocarbon solvents, for example), and they include symptoms such as headache, dizziness, confusion, and collapse.

Should you experience these symptoms, immediately reduce your exposure by working under a hood, closing containers, opening windows, or leaving the area. If your symptoms persist, get medical attention. You may wish to consider the use of a respirator, however, good work practices and the use of a properly working fume hood generally obviate the need for respiratory protection in a lab context.

Gastrointestinal Tract

You can greatly limit this route of entry by never storing or using foods or beverages in the laboratory. Always wash your hands thoroughly after using chemicals.

9.0

Some Terms Used To Describe Toxic Effects

The actual dose that a person receives depends on the concentration of the chemical as well as the frequency and duration of exposure.

SOME KNOWN HUMAN FACTORS INFLUENCING

ACUTE TOXICITY TERATOGENS SUSCEPTIBILITY Single short exposure Alcohol ingestion Obesity Effects usually appear quickly Organic mercury compounds Nutritional Habits Effects often reversible Lead compounds Physical condition

Ionizing radiation Medical condition

Some drugs Drinking and smoking Sensitization Pregnancy

SOME SUBSTANCES KNOWN
TO CAUSE MALE

CHRONIC TOXICITY REPRODUCTIVE EFFECTS
Repeated exposure 1,2-Dibromo-3-chloropropane
Effects usually delayed Some pesticides
Usually irreversible Ionizing radiation

Some drugs

Evaluating Toxicity Data

It is conventional to summarize the acute toxicity of a compound by stating the dose at which 50% of the animals are affected. In tests for lethality, this dose is called an LD50. Remember that chronic exposure may have effects that are very different and not at all related to effects from acute exposure.

Estimating Human Lethal Doses

Class Animal LD50 Probable Lethal Dose for Example 70 kg Person (150 lbs.)

Super Toxic Less than 5 mg/kg A taste (7 drops or less) Botulinum toxin

Extremely Toxic 5 - 50 mg/kg < 1 teaspoonful Arsenic trioxide, Strychnine

Very Toxic 50 - 500 mg/kg < 1 ounce Phenol, Caffeine

Moderately Toxic 0.5 - 5 g/kg < 1 pint Aspirin, Sodium chloride

Slightly Toxic 5 - 15 g/kg < 1 quart Ethyl alcohol, acetone

The safe use of toxic chemicals is a dilemma faced not only by laboratory and chemical workers but by everyone. Estimating the hazard posed by the use of a chemical is controversial and complex. It involves much more than determining its toxicity. The severity of a chemical hazard depends not only on the toxicity but on its chemical and physical properties and the manner and quantity in which it is used. By learning about the potential hazards of the substances you use, and by practicing appropriate procedures for those substances, you can work safely in an informed and intelligent manner.

9.1

Respiratory Protection

Respirators are generally not recommended for laboratory workers. Engineering controls, meaning the use of dilution ventilation and fume hoods and other devices which capture vapors, fumes and gases and remove them from the breathing zone of the user, are preferred over the use of respirators in most laboratory environments. There are certain exceptions to this general rule such as the changing out of cylinders of toxic gases and emergency response to chemical spills. The use of respirators is heavily regulated by OSHA. A laboratory worker at Cornell may not purchase a respirator and bring it to their lab for their personal use. The use of all types of respiratory protection at Cornell is governed by the Cornell EH&S Respiratory Protection Program.

There are some situations, as alluded to above, where respiratory protection is appropriate for laboratory workers:

• The use of dust masks for weighing powdery or dusty hazardous materials. (Note: The use of dust masks may or may not be regulated by OSHA depending upon the circumstances of use. If you think that you need to use a dust mask when weighing out materials that have an inhalation hazard you must contact EH&S for prior approval for the use of a dust mask.)

• The large volume use of certain hazardous chemicals, such as formaldehyde, in a room where dilution ventilation or capture devices will not be able to offer adequate protection.

• Changing out cylinders of hazardous gases. (Additional training is required.)

• Cleaning up chemical spills. (Additional training is required.)
  • To reduce exposure to some chemicals to which certain individuals may become sensitive. (This would be a rare and unusual situation.)

  • There are some situations in which the use of a respirator would be prohibited:
• When the air in a laboratory is severely contaminated and immediately dangerous to life and health (IDLH).

• When the air in a room does not have enough oxygen to support life (<19.5%).

• When dangerous vapors are present that have inadequate warning properties (such as odor), should the respirator fail.

• When the air contaminants can also penetrate or damage skin and eyes unless other suitable protection is also worn.

Information About Respirators

To get more information concerning the use of respirators at Cornell call EH&S at 255-. If you are approved for the use of a respirator after meeting the requirements of the OSHA Standards and the Cornell EH&S Respiratory Protection Program, in most cases, you may purchase a respirator from the Cornell Distribution Center on Palm Rd. If your use of a respirator is required to perform your job duties, your department will pay for the respirator. You will also receive training on the use and maintenance of your respirator.

10.0

Hand Protection and Glove Selection

Including Glove Selection for Some Specific Chemicals
Tom Shelley, Cornell EH&S
Revised September,

Introduction

Glove selection is difficult for many lab staff. Different references seem to give conflicting information and the many available styles and types of glove materials add another layer of confusion. The process of glove selection can also be very time consuming. Consequently, many chemical users select a glove that may not be appropriate for the chemicals in use.

Due to the publicity surrounding the death of a prominent Dartmouth researcher, Federal OSHA has placed a strong emphasis on hand protection in the workplace, especially in academic and R&D labs. In OSHA made substantial changes to the PPE Standard, 29 CFR .138 - Hand Protection. The revised requirements are as follows:

Hazard assessment and equipment selection
Employee training
Record keeping requirements
Guidelines for selecting PPE, and
Hazard assessment certification

Cornell EH&S Occupational Health and Safety Section has developed a revised written Personal Protective Equipment Program reflecting the changes in the OSHA standard.

Supervisors are responsible for the selection, availability and use of gloves and other personal protective equipment in the workplace. Cornell EH&S can assist supervisors with the requirements of the revised OSHA standard. Please contact us at 255- for additional information.

The various glove manufacturers use different formulations for their polymers. A glove from one firm may not have the same chemical resistance as a glove that appears to be an identical glove made by another firm. Therefore, it is prudent to check the glove selection charts provided by the glove manufacturer for the gloves you use to determine their suitability for use with any particular chemical.

However, glove selection based on the manufacturers' glove selection charts is often impossible, as only a limited range of chemicals have been tested for use with a specific manufacturer's glove. Many research grade chemicals are used in such small quantities that the various glove manufacturers will probably never test them. If a chemical is not listed on a glove selection chart it is advisable to have a specialist in personal protective equipment (PPE) make the glove selection for you. In this case the PPE specialist would attempt to match the known characteristics of the chemical to be used with the known characteristics of the polymers commonly used to make gloves to select a glove that would be appropriate. This glove selection document includes a compilation of gloves recommended by EH&S for specific chemicals.

11.0

In some cases it may be required to hire a testing laboratory specializing in PPE to physically test a variety of gloves with the chemical to be used to scientifically select an appropriate glove. We have contacted a local testing firm that is capable of testing gloves for chemical resistance for a modest fee. If you have an especially hazardous chemical for which glove selection is difficult, we can make arrangements to have various gloves tested with the chemical in question.

The glove selection for the materials listed below is offered for anyone using these chemicals at Cornell. If a particular manufacturer's glove charts vary from the glove selections below, follow the manufacturer's glove charts for the model of glove recommended or contact EH&S at 255- for a second opinion on glove selection for the chemical in use. The Cornell Distribution Center carries an assortment of 4 mil and 8 mil disposable nitrile gloves. They also carry or can order for you a wide variety of other types of gloves.

Latex gloves, especially thin, disposable exam gloves, are widely used in labs, shops and many other work environments. Our concern is two-fold: latex gloves offer little protection from commonly used chemicals and many people, up to 20% of the population by some estimates, have developed the allergen to latex products.

The use of latex gloves is only appropriate for:

most biological materials
nonhazardous chemicals
very dilute, aqueous solutions of hazardous chemicals*
clean work area requirements
medical or veterinary applications

*Less than 1% for most hazardous chemicals or less than 0.1% if a known or suspect human carcinogen is in use in aqueous solution.

Latex gloves offer no protection against many common lab and shop chemicals. They will severely degrade, often in a matter of seconds or minutes, when used with some materials.

Staff required to wear latex gloves should receive training on the potential health effects related to latex. Hypoallergenic, non-powdered gloves should be used when possible. If a good substitute glove material is available, use gloves made of a material other than latex. A general-purpose substitute for latex products is lightweight nitrile gloves.

Many of the recommendations below are for "incidental contact." This means that, as with many chemical procedures, no or very little actual contact with a chemical in use is anticipated. The gloves specified are basically there to prevent chemical contact with the skin when something goes wrong--a spill or splash to the hand, over spray from a dispensing device, etc. As soon as practical after the chemical makes contact with the gloved hand the gloves are removed and replaced. Often a glove specified for incidental contact is not suitable for extended contact, when the gloved hands may come into substantial contact with or actually may become covered with or immersed in the chemical in use.

11.1

Generally speaking, a more substantial glove is required for extended contact than for incidental contact, although there are exceptions.

The practice of double gloving is recommended for many materials listed below. Two pairs of gloves are worn, one over the other. This affords a double layer of protection. If the outer glove starts to degrade or tears open, the inner glove continues to offer protection until the gloves are removed and replaced. The best practice is to check the outer glove frequently, watching for signs of degradation (change of color, change of texture, etc.). With the first sign of degradation remove the outer glove and reglove.

There are different approaches to double gloving. The most common practice is to wear a thin disposable glove (4 mil nitrile) under a heavier glove (8 mil nitrile). The outer glove is the primary protective barrier while the under glove retains dexterity and acts a vapor barrier in the event of mechanical failure or the permeation of the chemical in use through the outer glove. Alternately, you can wear the heavier (and usually more expensive and durable) nitrile glove as the under glove and wear thinner disposable nitrile gloves over those, changing the thinner outer gloves frequently. It is sometimes desirable to double glove with two sets of gloves made from different materials. Here, in the event of the failure of one material, the second, different material will act as a protective barrier until the gloves can be removed. The technique of using gloves of different materials is often advisable when a mixture of hazardous materials is in use. One type of material gives protection against one component or class of chemicals in the mixture and the second glove material gives protection against other components of the mixture. The requirements for double gloving and the materials of the gloves selected are specific to the chemical(s) in use.

For those materials that are rated "supertoxic", which are easily absorbed through the skin, the glove material generally recommended is Norfoil (Silver Shield by North Hand Protection, 4H by Safety4, or New Barrier? brand by Ansell Edmont). Norfoil is a thin, five-layer laminate with each layer made of a different polymer. They are chemically resistant to a wide range of materials that readily attack other glove materials. (Note that one of the common lab chemicals for which they are not recommended is chloroform.) Norfoil gloves look odd, like they were stamped out of a common garbage bag. They tend to be somewhat bulky but dexterity is regained by using a heavier weight (8 mil) disposable nitrile glove over the Norfoil glove. These gloves and others are also available at the Cornell Distribution Center and from lab safety supply houses.

Definitions for terms used in glove selection charts, the materials of which gloves are made and those used to describe different characteristics of gloves are listed towards the end of this document.

References used in preparation of this document are listed at the end.

If there is a chemical for which you have a question concerning glove selection that is not on the following list, please use the Glove Selection Request Form to be found at the end of this document.

11.2

Glove Selection for Some Specific Chemicals in Use at Cornell University

For quick glove selection see the table on pages 11.16-18.

Acetic acid (glacial or concentrated solutions): nitrile gloves (incidental contact); neoprene or butyl
rubber gloves are recommended if contact with acetic acid above 10% is probable for an extended period
of time.

Acetic anhydride: double glove with heavier weight (8 mil) nitrile gloves (incidental contact).
Acetic anhydride is very corrosive to human tissues (skin, eyes, mucus membranes) and a poison by
inhalation. For handling larger quantities of pure material only heavier weight (.28-.33 mm) butyl rubber
or neoprene gloves are recommended.

Acetone: heavier weight (8 mil) natural rubber (incidental contact); for extended contact with acetone
the only recommended glove type is butyl rubber.

If you are cleaning parts with acetone, or have any other use of acetone where there is more than
incidental contact, you must use butyl rubber gloves. Natural rubber gloves have about a 10 minute
breakthrough time and are for incidental contact only. Nitrile gloves have a less than four minute
breakthrough time and are not recommended for any use of acetone.

Acetonitrile: nitrile gloves or double glove with nitrile gloves (incidental contact)

For transfer of acetonitrile or for large scale use, only heavier weight butyl rubber or poplyvinyl acetate
gloves are recommended. Acetonitrile permeates though disposable latex exam gloves in a matter of
seconds and latex gloves should never be used to handle this material.

Acrylamide: nitrile gloves or double glove with nitrile gloves (incidental contact); butyl rubber gloves
are recommended for extended contact (such as repackaging pure acrylamide into smaller containers)

Acrylamide is readily absorbed through unbroken skin. Acrylamide is a carcinogen, mutagen, teratogen
and a potent neurotoxin with no known antidote, so adequate hand protection is essential when using this
chemical. Note that once acrylamide solutions are polymerized the resulting gels are no longer hazardous
and, assuming that they are not contaminated with other hazardous materials, they may be disposed of in
the ordinary trash.

Note: See Heavy Metal Salts for proper disposal of gloves and other dry waste contaminated with
acrylamide.

bis- Acrylamide: nitrile gloves

Bis-Acrylamide (N,N'-dihydroxy-ethylene-bis-acrylamide) does not share the more extreme toxic
characteristics of acrylamide. However, its toxicological properties have not been fully investigated and
it should be treated as a hazardous material.

11.3

Ammonium hydroxide: nitrile gloves; for extended contact heavier weight neoprene or butyl rubber gloves are superior to nitrile gloves

Benzotriazole, 1,2,3-: nitrile gloves

Carbon disulfide: double glove with heavier weight (8 mil) nitrile gloves (incidental contact) or use 15 mil or heavier nitrile gloves; remove outer glove at once if exposed to carbon disulfide

Most nitrile gloves have a breakthrough time of only 8 to 20 minutes and thus offer little protection when exposed to carbon disulfide. For operations involving the use of larger amounts of carbon disulfide, when transferring carbon disulfide from one container to another or for other potentially extended contact, the only gloves recommended are viton and polyvinyl acetate (PVA).

Carbon tetrachloride: double glove with heavier weight (8 mil) nitrile gloves (incidental contact) or use 15 mil or heavier nitrile gloves; remove outer glove at once if exposed to carbon tetrachloride

Most nitrile gloves have a breakthrough time of only a few minutes and thus offer little protection when exposed to carbon tetrachloride. For operations involving the use of larger amounts of carbon tetrachloride, when transferring carbon tetrachloride from one container to another or for other potentially extended contact, the only gloves recommended are viton. Viton gloves are expensive, but they are the standard glove to use with carbon tetrachloride.

Carbon tetrachloride is a poison, carcinogen, mutagen and teratogen. It is readily absorbed through unbroken skin. Alcohol and acetone are known to enhance the toxicity of carbon tetrachloride. The dose required to cause poisoning in humans varies significantly, with the ingestion of as little as 2 ml. having caused death. Carbon tetrachloride is also a substantial ozone depleting chemical and its use has been banned commercially. If you can find a substitute for carbon tetrachloride, it is strongly recommended that you use an alternative material.

Catechol: nitrile gloves

Chloroform: double glove with heavier weight (8 mil) nitrile gloves (incidental contact) or use 15 mil or heavier nitrile gloves; remove outer glove at once if exposed to chloroform

Thin (3-4 mil) Nitrile gloves have a 4 minute breakthrough time and thus offer little protection when exposed to chloroform. For operations involving the use of larger amounts of chloroform, such as transferring chloroform from one container to another or for large-scale extractions, etc., the only gloves recommended are viton or polyvinyl acetate (PVA). Viton gloves are expensive, but they are the standard glove to use with chloroform.

Cobalt Chloride: See Heavy Metal Salts.

Copper (Cupric) Sulfate: nitrile gloves

11.4

3,3'-Diaminobenzidine (DAB): nitrile gloves (incidental contact); double glove with nitrile gloves when handling the pure material or concentrated stock solutions

Note: See Heavy Metal Salts for proper disposal of gloves and other dry waste contaminated with DBA.

Diazomethane in Ether (a derivatizing reagent): double glove with heavier weight (8 mil) nitrile gloves (incidental contact) or use 15 mil or heavier nitrile gloves; remove outer glove at once if exposed to diazomethane in ether.

For possible extended contact, such as when transferring diazomethane in ether or when making reagent solutions containing this material, the only recommended glove would be a Norfoil glove, due to the extreme hazards associated with this material. Diazomethane is an extreme poison, a cancer suspect agent, extremely flammable, easily detonated and has an autoignition temperature of 100? C. (an ordinary light bulb would cause a sufficient quantity of the vapor in air to autodetonate). This is easily one of the most dangerous materials in use in labs at Cornell. If there is any way you can substitute another material for diazomethane in ether it is strongly recommended that you do so.

Dichloromethane: See Methylene Chloride.

Diethyl pyrocarbonate: nitrile gloves (incidental contact); double glove with nitrile gloves when handling the pure material or concentrated stock solutions

Dimethyl sulfoxide (DMSO): heavier weight natural rubber gloves (15-18 mil; not 4 mil latex exam gloves) (incidental contact); butyl rubber gloves are recommended for extended contact; if you are allergic to natural latex products you may double glove with heavier weight (8 mil) disposable nitrile gloves (incidental contact) or use 15 mil or heavier nitrile gloves; remove outer glove at once if exposed to DMSO.

Nitrile gloves are not recommended for use with DMSO if extended contact with the hands is expected. Some brands of nitrile gloves have degradation times of five minutes when used with DMSO. DMSO freely penetrates the skin and may carry dissolved chemicals with it into the body, so hand protection is especially important if you are working with any hazardous materials dissolved in DMSO.

1,4-Dioxane (dioxane): double glove with heavier weight (8 mil) nitrile gloves (incidental contact) or use 15 mil or heavier nitrile gloves; remove outer glove at once if exposed to dioxane

Most nitrile gloves have a breakthrough time of only a few minutes and thus offer little protection when exposed to dioxane. For operations involving the use of larger amounts of dioxane, when transferring dioxane from one container to another or for other potentially extended contact, the only gloves recommended are butyl rubber gloves. Dioxane is one of the few commonly used lab chemicals that readily degrades viton gloves.

Dioxane is only moderately toxic, but it is a listed carcinogen, mutagen and teratogen. It is readily absorbed through unbroken skin so hand protection is especially important when working with this material.

11.5

Dithiothreitol (Cleland's Reagent): nitrile gloves

Ethanol: nitrile gloves

Ethidium bromide (EtBr): nitrile gloves (incidental contact); double glove with nitrile gloves when handling the pure material or concentrated stock solutions

Note: See Heavy Metal Salts for proper disposal of gloves and other dry waste contaminated with EtBr

Ethyl Ether (diethyl ether, ether): double glove with heavier weight (8 mil) nitrile gloves (incidental contact) or use 15 mil or heavier nitrile gloves; remove outer glove at once if exposed to ether

Ether is one of those chemicals that attacks almost all known commonly used glove materials. It permeates through viton, butyl rubber, neoprene, nitrile and natural rubber in a matter of minutes. The only recommended glove material for extended contact is polyvinyl acetate (PVA), such as the PVA? brand made by Ansell Edmont.

Formaldehyde: nitrile gloves

Formamide: nitrile gloves (incidental contact); butyl rubber gloves are the only gloves recommended for direct contact with the pure material.

Formamide is often used in the pure form. If you use pure formamide in a procedure where there is probable contact with the skin, it is strongly recommended that you wear butyl rubber gloves.

Formic acid: double glove with heavier weight (8 mil) nitrile gloves (incidental contact)

Formic acid is very corrosive to human tissues (skin, eyes, mucus membranes). For handling larger quantities of pure material only heavier weight (.28-.33 mm) butyl rubber or neoprene gloves are recommended.

Gallic acid: nitrile gloves

Heavy Metal Salts (especially those that are easily soluble in water): nitrile gloves or double glove in some cases*

For most inorganic (ionic) salts of heavy metals the human skin is usually an effective barrier against absorption of the heavy metal ions. If there are cracks in the skin, areas of inflammation, insect bites, cuts or other breaches of the integrity of the skin, heavy metal ions may be passed directly through the skin. The salts of many heavy metals are toxic or highly toxic and rated as poisons: arsenic, bismuth, cadmium, chromium, cobalt, lead, mercury, nickel, osmium, silver and uranium. Some of these materials are also listed as corrosives (chromium trioxide), inhalation hazards (osmium tetroxide), known or suspect carcinogens and mutagens (lead and lead salts, mercury and its salts, etc.) or radioactive (uranium). Disposable nitrile gloves are generally acceptable for the use of the pure salts and stock (concentrated) or dilute solutions for the common salts of the above metals (acetates, chlorides, sulfates,

11.6

nitrates, anhydrides, oxides, hydroxides, etc.) where only incidental contact will be made with these materials or their solutions.

Several heavy metal salts are more easily absorbed by the skin than others. Osmium tetroxide is readily absorbed by the skin and is very toxic. Lead acetate is absorbed 1-1/2 times more easily than other lead salts. Mercuric chloride can be absorbed fairly easily, especially if there are cracks, cuts or other breaks in the skin. It is also very toxic. It is recommended to *double glove* with nitrile gloves when using these materials, especially when handing the pure compounds or their strong solutions.

It is important that used gloves, and other dry materials, contaminated with heavy metals are not disposed of in the ordinary trash. Place all heavy metal contaminated gloves in a separate waste stream (container). The College of Veterinary Medicine maintains a Medical Waste Program. Gloves (and other dry waste items) contaminated with trace amounts of heavy metals may be sent to the Vet College for disposal. EH&S can furnish the guidelines provided by the Vet College or you may contact Dr. Larry Thompson at 253- or Denver Metzler at 253- for information on this program. It is important that the materials being disposed of are clearly identified on the Medical Waste Tracking Tag you will be required to complete as part of the disposal process, such as "Trace contaminated with lead acetate." (Note that this method of disposal is also acceptable for trace contaminated gloves and other dry waste generated from the use of carcinogens, mutagens and other materials that can not be disposed of in the ordinary trash.) Uncontaminated or decontaminated gloves may be disposed of as ordinary trash.

Heptane: double glove with heavier weight (8 mil) nitrile gloves (incidental contact) or use 15 mil or heavier nitrile gloves

For extended contact, as when using heptane for large scale extractions, refilling secondary containers or as a cleaning fluid, a heavier weight nitrile (35 mils or thicker), viton or PVA gloves are recommended. Note that the permeation time for heptane through 4 mil nitrile gloves is about 8 minutes and through latex exam gloves is even less time; subsequently, these gloves are not recommended for use with heptane.

Hexamethylenediamine (1,6-diaminohexane): heavier weight (8 mil) nitrile gloves (incidental contact); use a heavier weight neoprene glove when handling the pure material or concentrated stock solutions (extended contact)

Hexane: double glove with heavier weight (8 mil) nitrile gloves (incidental contact) or use 15 mil or heavier nitrile gloves

For extended contact, as when using hexane for large scale extractions, refilling secondary containers or as a cleaning fluid, a heavier weight nitrile (35 mils or thicker), viton or PVA gloves are recommended. Note that the permeation time for hexane through 4 mil nitrile gloves is about 12 minutes and through latex exam gloves is only about 5-6 minutes; subsequently, these gloves are not recommended for use with hexane.

Hydrochloric Acid (concentrated and strong solutions): nitrile gloves (incidental contact)

11.7

A heavier weight neoprene or butyl rubber glove would be superior for long-term use with more
concentrated solutions, such as cleaning glassware that has been soaking in an HCl bath or other larger-
scale use of HCl.

Hydrofluoric acid (HF): double glove with heavier weight (8 mil) nitrile gloves (incidental contact) or
use 15 mil or heavier nitrile gloves

Note that additional protective equipment must always be worn when using larger quantities of HF.
Nitrile or rubber sleeves, rubber aprons, face shields and splash goggles (not safety glasses) should also
be worn. All users of HF must maintain an HF first aid kit in their lab. HF users are advised to contact
EH&S for an "HF Users Information Packet."

Isopropanol: nitrile gloves

Lead Acetate: See Heavy Metal Salts.

Laser dyes: nitrile gloves
Mecuric Chloride: See Heavy Metal Salts.

Mercury: nitrile gloves

Methanol (methyl alcohol): nitrile gloves

Methanol should never be allowed to make contact with the skin, as it is fairly easily absorbed by the
skin. Methanol is a poison.

Methylene Chloride: double glove with heavier weight (8 mil) nitrile gloves (incidental contact)

Methylene chloride will permeate through thin (3-4 mil) nitrile gloves in four minutes or less. If you are
double gloved, as recommended, and you splash or spill methylene chloride on your gloves, stop what
you are doing and change the outer glove immediately. If you allow methylene chloride to remain on the
outer nitrile glove for more than two to four minutes you must discard both sets of gloves and re-double
glove. Methylene chloride permeates disposable latex exam gloves in a matter of seconds and latex
gloves should never be used to handle this material.

For use of methylene chloride where contact with the glove is anticipated, such as stripping paint or
gluing plastics, only polyvinyl acetate (PVA) or viton gloves are recommended. These gloves come in
.28-.33 mm thickness. PVA offers the best protection.

Methyl sulfonic acid, ethyl ester (EMS) (ethyl methanesulfonate): nitrile gloves (incidental contact);
double glove with nitrile gloves when handling the pure material or concentrated stock solutions

Note: See Heavy Metal Salts for proper disposal of gloves and other dry waste contaminated with EMS.
Monoethanolamine: nitrile gloves

11.8

Nickel chloride: See Heavy Metal Salts.

N-Methylethanolamine: : double glove with heavier weight (8 mil) nitrile gloves (incidental contact);

remove outer glove at once if exposed to N-methylethanolamine

Viton, neoprene or butyl rubber gloves are recommended for extensive use of N-methyl-ethanolamine such as working with the pure material or making solutions.

Organophosphorous compounds: double glove with heavier weight (8 mil) nitrile gloves (incidental contact) or use 15 mil or heavier nitrile gloves

Osmium Tetroxide: See Heavy Metal Salts.

Paraformaldehyde: nitrile gloves

Petroleum ether: nitrile gloves (incidental contact); or heavy weight nitrile or viton for extended contact.

Phenol: double glove with heavier weight (8 mil) nitrile gloves (incidental contact); neoprene or butyl rubber gloves are recommended for extensive use of phenol such as working with the pure material or making solutions.

Nitrile gloves have a 30-minute breakthrough time with phenol. If working with double gloved nitrile gloves, change the outer glove frequently if exposed to this material.

Phenol-chloroform mixtures: double glove with heavier weight (8 mil) nitrile gloves (incidental contact) or use 15 mil or heavier nitrile gloves; remove outer glove at once if exposed to mixture.

Viton gloves are recommended for work with phenol-chloroform mixtures when probable exposure to the mixtures exists, such as when making up the mixtures. See the entries for phenol and chloroform.

Phenylmethylsulfonyl fluoride (PMSF): nitrile gloves (incidental contact); double glove with nitrile gloves when handling the pure material or concentrated stock solutions.

Phenylmethylsulfonyl fluoride is corrosive (causes burns) on contact with the skin, eyes and mucus membranes. It is also a highly toxic cholinesterase inhibitor and central nervous system poison. Avoid all contact.

Note: See Heavy Metal Salts for proper disposal of gloves and other dry waste contaminated with PMSF.

Polychlorinated biphenyls (PCBs): For weighing out of pure or concentrated materials, wear an 8 mil or heavier nitrile glove over a neoprene glove. For dilute solutions in corn oil (1 p.p.m. or less) neoprene gloves (20 mil) are recommended.

Note: See Heavy Metal Salts for proper disposal of gloves and other dry waste contaminated with PCBs. Polyoxyethylenesorbitan monolaurate (Tween 20): nitrile gloves

11.9

Psoralen: nitrile gloves (incidental contact); double glove with nitrile gloves when handling the pure material or concentrated stock solutions

Psoralen is corrosive (causes burns) on contact with the skin, eyes and mucus membranes. It is anticipated to be a carcinogen, it is a mutagen and a strong photosensitizer. Avoid all contact.

Note: See Heavy Metal Salts for proper disposal of gloves and other dry waste contaminated with psoralen.

Pump oil: butyl rubber gloves

If you are changing pump oil or servicing pumps where contact with the oil may occur, the only recommended glove type is butyl rubber.

Silane based silanization or drivatization compounds: double glove with heavier weight (8 mil) nitrile gloves (incidental contact) or use 15 mil or heavier nitrile gloves; remove outer glove at once if signs of degradation occur.

Silver nitrate: See Heavy Metal Salts.

Sodium dodecyl sulfate (SDS): nitrile gloves

Sodium azide: nitrile gloves or double glove with nitrile gloves (incidental contact)

Sulfuric acid: heavier weight (8 mil) nitrile gloves (incidental contact); heavier weight (20 mil or greater)
neoprene or butyl rubbber gloves (extended contact)

Tetrahydrofuran (THF): double glove with heavier weight (8 mil) nitrile gloves (incidental contact) or
use 15 mil or heavier nitrile gloves; remove outer glove at once if THF contacts glove

For extended contact, such as when using THF for larger scale reactions, refilling secondary containers or
as a cleaning fluid, only Norfoil gloves are recommended. Polyvinyl acetate (PVA) gives some limited
protection (up to 1-1/2 hours for some gloves) but are inferior to the Norfoil gloves. Note that the
permeation time for THF through 4 mil nitrile gloves and latex exam gloves is almost instantaneous;
subsequently, these gloves are not recommended for use with THF.

3,3',5,5'-Tetramethylbenzidine (TMB): nitrile gloves (incidental contact); double glove with nitrile
gloves when handling the pure material or concentrated stock solutions

Note: See Heavy Metal Salts for proper disposal of gloves and other dry waste contaminated with TMB.

N, N, N', N'-Tetramethylethylenediamine (TEMED): nitrile gloves (incidental contact); double glove
with nitrile gloves when handling the pure material or concentrated stock solutions.

TEMED is corrosive (causes burns) on contact with the skin, eyes and mucus membranes.
Toluene: double glove with heavier weight (8 mil) nitrile gloves (incidental contact) or use 15 mil or
heavier nitrile gloves; remove outer glove at once if exposed to toluen.

11.10

For extended contact, such as when using toluene for larger scale reactions, refilling secondary containers or as a cleaning fluid, only viton or polyvinyl acetate (PVA) gloves are recommended. Note that the permeation time for toluene through 4 mil nitrile gloves is less than 4 minutes and through latex exam gloves is less than that; subsequently, these gloves are not recommended for use with toluene.

Trichloromethyl chloroformate (diphosgene): This chemical, usually supplied in sealed glass ampules, is very air/moisture reactive, a corrosive and it is considered to be highly toxic by all routes of exposure. It must be used in a vented glove box or environmental chamber under dry nitrogen or argon. Glove boxes are usually fitted with substantial butyl rubber gloves, however, one manufacturer recommends that "heavy" gloves be worn over the glove box gloves. I would recommend using 8 mil or heavier nitrile gloves over the butyl rubber glove box gloves. Please contact EH&S if you have any questions concerning the special procedures required for the use of this chemical.

Triton-X100: nitrile gloves

Xylene: nitrile gloves (incidental contact)

For use of xylene where contact with the glove is anticipated, such as pouring of new or used xylene into containers or other operations, polyvinyl acetate (PVA) or viton gloves are recommended.

Definitions

Breakthrough is the time elapsed between the initial contact with a chemical and its detection inside a glove. Breakthrough time is directly proportional to glove material thickness for most materials.

Butyl rubber is a synthetic rubber (butylene and isoprene copolymer) that provides the highest permeation resistance to gases and water vapor of any protective material used to make gloves. Butyl rubber is an excellent choice for protection against esters and ketones, especially for extended contact with acetone.

Degradation is a change in one or more of the physical properties of a glove due to chemical contact. Some of these changes, such as discoloring, swelling, shrinkage or stiffness, may be visually detected but others are invisible. Degradation almost always results in a loss of performance of a glove and is an indicator of how long a glove will last. Degradation is usually detected by a change in weight of a glove and degradation ratings are often based on % change in weight over time.

Double gloving (see introduction, above) is the use of two layers of gloves to provide improved hand protection when using certain hazardous chemicals. This affords a double layer of protection. If the outer glove starts to degrade or tears open, the inner glove continues to offer protection until the gloves are removed and replaced. Gauge or thickness of gloves is generally measured in mils. Higher gauge (thicker) gloves generally offer more protection. Generally speaking, doubling the thickness halves the permeation rate.

11.11

Finish refers to the surface texture of a glove material. Most laboratory gloves have a smooth finish.
Textured surfaces are added to glove materials to provide a better grip on objects being handled.

Flock lining is a natural or synthetic shredded fiber that covers the inside of a glove to provide comfort
by absorbing perspiration and providing ease in putting on and removing the glove.

Hypalon is a synthetic polymer that offers superior resistance to oxidizing agents and ozone. It is
frequently used for glove box gloves.

Lower detection limit (LDL) is the minimum level detected with analytical test equipment, measured in
parts per million (ppm) detected at breakthrough time.

Mil is the standard unit for measuring the gauge or thickness of glove materials. A mil is one-thousandth
of an inch or 0.001". A millimeter is 39.37 mils; a mil is . mm.

Natural rubber (or latex), produced from the sap of certain species of tropical trees, is used to make
gloves that are suitable for the handling of biological materials, human blood and other body fluids,
electronics assembly, food service and other applications where the work needs to be kept clean. Latex
gloves are generally not suitable for use with most laboratory chemicals (see introduction, above). Latex
products are also a health concern because of their protein component, to which many people are allergic.
Natural rubber is often blended with other polymers to achieve various characteristics of those materials.

Neoprene is a synthetic rubber that is especially resistant to oils and petroleum products. It is also good
for corrosives, alcohols, and many solvents. Neoprene is probably the best substitute material for the
replacement of latex gloves for janitorial services, shop workers,
mechanics and other trades.

Nitrile, also referred to as NBR or acrylonitrile-butadiene, offers superior chemical resistance as well as
puncture and abrasion resistance. 4 and 8 mil nitrile gloves are most often specified for general lab use
for handling a wide variety of chemicals.

Norfoil (see introduction, above) is a lightweight, flexible laminate of several layers of polymers which
offers superior resistance to permeation by a wide range of hazardous materials which often quickly
degrade other glove materials. They are often used as an underglove with a tighter fitting glove of
another material as an overglove to restore dexterity. Brand names of Norfoil gloves are Silver Shield by
North Hand Protection, 4H by Safety4, and New Barrier? brand by Ansell Edmont.

Overglove is a glove worn over another glove (underglove) when double gloving to provide multiple
layers of resistance to hazardous chemicals. The overglove protects the underglove from chemical
degradation and permeation. It is changed out when it begins to be chemically attacked to protect the
underglove.
Penetration is the nonchemical transport of a chemical through a glove, usually by pinholes or
microscopic tears or cracks resulting from degradation.

11.12

Permeation is the process by which a chemical passes through a glove's protective film. Permeation occurs at the molecular level and often leaves the appearance of the glove unchanged. The rate of permeation of a chemical through a glove is one of the determining factors in the effectiveness of a glove for use with a particular chemical. Generally speaking, the permeation rate is inversely proportional to thickness (gauge), although the length of time of exposure and temperature can be important factors for some glove materials. Permeation is an indicator of how long gloves are safe to wear.

Permeation rate at steady state is the maximum rate at which a chemical passes through a glove material, usually expressed in milligrams per square meter per second (mg./m.2/sec.).

Permeation breakthrough is the time in minutes it takes for a chemical to permeate through a glove. Generally speaking, doubling the thickness of a glove quadruples breakthrough time.

Polyvinyl alcohol, or PVA, gloves give superior service for handling solvents, such as chloroform, that attack most other glove materials. PVA is water soluble and may not be used with any water-based materials.

Powdered gloves have an interior coating of cornstarch or other absorbent material. Powdered gloves are usually easier to take on and off and are often more comfortable for the wearer, but the powder may contribute to allergic responses in some individuals.

Supported means that the polymer of the glove is a coating over a fabric liner. This two- component glove style offers more durable hand protection. Very few gloves for laboratory use are supported.

Underglove is a glove worn under another glove (overglove) when double gloving to provide multiple layers of resistance to hazardous chemicals.

Unsupported means that a glove is made only of a pure polymer or mix of polymers. Unsupported gloves tend to offer greater dexterity and tactile sensitivity but less protection from physical damage.

Vinyl or polyvinyl chloride (PVC) gloves are economical substitutes for latex gloves for food service or assembly work but they are not resistant to many common laboratory chemicals and are not recommended for general laboratory work.

Viton is a very chemically resistant fluoroelastomer synthetic rubber. It protects against PCBs, benzene, aniline and most chlorinated and aromatic solvents. For some chemicals, such as chloroform, it is the only resistant material commonly available. Viton gloves are expensive, but they have a very long lifespan.

11.13

References Used

Ansell Edmont, Chemical Resistance Guide, . For gloves made by this firm.
Best, Guide to Chemical-Resistant Best Gloves, . For gloves made by this firm.
Cole-Parmer, '97-'98 Catalog, pp.-. This is a very generic, but useful, materials compatibility

chart.
Fisher Safety, Sept., , Safety Products Reference Manual, p. 223, 225 and 227. These charts are

specific to gloves sold by Fisher. There is also a good overview of glove selection on pp. 220-222 of this
catalog.
Lab Safety Supply, Aug., General Catalog, pp.99. This chart is specific to gloves sold by Lab

Safety Supply.

Material Safety Data Sheets, from both manufacturers' and MDL-OHS data base at EH&S.
Merk Index, 10th Edition, .
National Toxicology Program (NTP) chemical information sheets (available at EH&S). These

information sheets are very well written and give information on specific gloves selected by NTP.
NIOSH, Registry of Toxic Effects of Chemical Substances, -2.
Pioneer Industrial Products, Chemical Resistance Guide, no date. For gloves made by this firm.
Safety 4 A/S, 4H Chemical Protection Guide, Sept. . A chart for 4H brand gloves.
VWR Scientific Products, '97-'98 Catalog, p. 788-9. This chart is applicable only to Best gloves sold by

VWR.

Electronic Resources

For those of you with Windows-based computers, Best has an electronic version of their glove selection chart available on their Web site at: http://www.bestglove.com You can download the software and install it on your PC. It does not have a Mac version.

11.14

---------------------------- Cut Here ------------------------

Glove Selection Request Form

Name of chemical(s) _____________________________________________
Please give the full name. Abbreviations may be difficult to find in the literature.
How is this chemical(s) being used? __________________________________
How much is being used during a procedure? ____________________________
Do you anticipate that the chemical may/will be in contact with the gloves? _______
Explain if possible. ______________________________________________
Your name ____________________________________________________
Building _________________ Room No. ___________ Dept. ____________
address ___________________________ No. _____________

---------------------------- Cut Here -------------------------
Copy and paste this form into an addressed to . Please give your a subject,
such as "Glove Selection Request."

11.15

Cornell University Chemical Hygiene Plan
Glove Selection Guide

Chemical Incidental Contact Extended Contact Acetic Acid nitrile neoprene, butyl rubber Acetic Anhydride nitrile (8 mil), double glove butyl rubber, neoprene Acetone natural rubber (latex) (8 mil) butyl rubber Acetonitrile nitrile butyl rubber, polyvinyl acetate (PVA) Acrylamide nitrile butyl rubber bis-Acrylamide nitrile Ammonium Hydroxide nitrile neoprene, butyl rubber Arsenic Salts nitrile Benzotriazole, 1,2,3nitrile Bismuth Salts nitrile Cadmium Salts nitrile Carbon Disulfide nitrile (8 mil), double glove viton, polyvinyl acetate (PVA) Carbon Tetrachloride nitrile (8 mil), double glove viton Catechol nitrile Chloroform nitrile (8 mil), double glove viton, polyvinyl acetate (PVA) Chromium Salts nitrile Cobalt Chloride nitrile Cobalt Salts nitrile Copper (Cupric) Sulfate nitrile 3,3'-Diaminobenzidine (DAB) nitrile nitrile, double glove Diazomethane in Ether nitrile (8 mil), double glove Norfoil Dichloromethane nitrile (8 mil), double glove polyvinyl acetate (PVA) or viton Diethyl Pyrocarbonate nitrile nitrile, double glove Dimethyl Sulfoxide (DMSO) 1natural rubber (latex)(15-18 mil) butyl rubber 1,4-Dioxane nitrile (8 mil), double glove butyl rubber Dithiothreitol nitrile Ethanol nitrile Ethidium Bromide (EtBr) nitrile nitrile, double glove Ethyl Ether nitrile (8 mil), double glove polyvinyl acetate (PVA) Formaldehyde nitrile Formamide nitrile butyl rubber Formic Acid nitrile (8 mil), double glove butyl rubber, neoprene (30 mils) Gallic Acid nitrile Heptane nitrile (8 mil), double glove nitrile (35 mil or thicker), viton, PVA Hexamethylenediamine (1,6-Diaminohexane) nitrile (8mil) neoprene Hexane nitrile (8 mil), double glove nitrile (35 mil or thicker), viton, PVA

11.16

Hydrochloric Acid nitrile neoprene, butyl rubber Hydrofluoric Acid (HF) nitrile (8 mil), double glove Isopropanol nitrile Laser Dyes nitrile Lead Acetate nitrile, double glove Lead Salts nitrile Mercuric Chloride nitrile, double glove Mercury nitrile Mercury Salts nitrile Methanol nitrile Methylene Chloride nitrile (8 mil), double glove polyvinyl acetate, viton Methyl Sulfonic Acid, Ethyl Ester (EMS) (Ethyl Methanesulfonate) nitrile nitrile, double glove Monoethanolamine nitrile Nickel Chloride nitrile Nickel Salts nitrile N-Methylethanolamine nitrile (8 mil), double glove viton, neoprene, butyl rubber Organophosphorous compounds nitrile (8 mil), double glove Osmium Salts nitrile Osmium Tetroxide nitrile, double glove Paraformaldehyde nitrile Phenol nitrile (8 mil), double glove neoprene, butyl rubber Phenol-Chloroform mixtures nitrile (8 mil), double glove viton Phenylmethylsulfonyl Fluoride (PMSF) nitrile nitrile, double glove Polychlorinated Biphenyls (PCB's) nitrile (8 mil) glove over a neoprene glove neoprene (20 mil) Polyoxyethylenesorbitan Monolaurate (Tween 20) nitrile Psoralen nitrile nitrile, double glove Pump Oil butyl rubber Silane based silanization or derivatization compounds nitrile (8 mil), double glove Silver Nitrate nitrile Silver Salts nitrile Sodium Dodecyl Sulfate (SDS) nitrile Sodium Azide nitrile Sulfuric Acid nitrile (8 mil) neoprene, butyl rubber (20 mil or greater) Tetrahydrofuran (THF) nitrile (8 mil), double glove Norfoil 3,3',5,5'-Tetramethyl-Benzidine (TMB) nitrile nitrile, double glove

11.17

N,N,N',N'-Tetramethylethylenediamine (TEMED) nitrile nitrile, double glove Toluene nitrile (8 mil), double glove viton, polyvinyl acetate (PVA) Trichloromethyl Chloroformate (diphosgene) nitrile (8 mil) over butyl rubber glove box gloves Material must be used in a glove box. Triton-X 100 nitrile (8 mil), double glove Uranium Salts nitrile Xylene nitrile polyvinyl acetate (PVA), viton

1 If you are allergic to natural rubber products, you may double glove with 8 mil nitrile gloves.

Created 10/22/99 Tom Shelley

The SOP Form

The OSHA Lab Standard mandates that those responsible for laboratory operations develop Standard Operating Procedures (SOPs) "relevant to safety and health considerations to be followed when laboratory work involves the use of hazardous chemicals." (29 CFR .(e)(3) (i)) This is especially the case if your lab operations include the routine use of " 'select carcinogens,' reproductive toxins and substances which have a high degree of acute toxicity." (29 CFR .(e)(3) (viii))

A revised version of the SOP Form has been created for your use. Please use the new version provided when completing new SOPs. The "How to Prepare an SOP" describes in detail how to complete the SOP Form. If you have questions concerning the creation of an SOP please contact the Cornell University Chemical Hygiene Officer at 255-.

Table of Contents

Page Subject 12.1-3 Blank SOP Form 12.4-8 How to Prepare an SOP Form 12.9 Chemical User Authorization Form 12.10-20 Cornell University Select Carcinogens 12.21-25 Chemicals Known to Cause Reproductive Toxicity 12.26-29 Cornell Acutely Toxic Chemicals 12.29 Poison Inhalation List 12.30-33 Peroxide Forming Compounds

11.18

12.34

The Safe Use of Perchloric Acid

Revised 11/13/98 by Tom Shelley

12.19

STANDARD OPERATING PROCEDURE
for
CARCINOGENS AND HIGHLY TOXIC MATERIALS

Location(s): ___________________________________________________

Chemical(s): __________________________________________________

Specific Hazards: _______________________________________________

1. Purchasing: All purchases of this material must have written approval from the Principal Investigator or _______________________ before ordering. The user is responsible to ensure that a current Material Safety Data Sheet (MSDS) is obtained unless a current one is already available within the laboratory. Quantities of this material will be limited to ________________, or the smallest amount necessary to complete the experiment.

2. Storage: Materials will be stored according to compatibility and label recommendations in a designated area: ________________________________________. Storage areas will be regularly inspected by _________________________________ to ensure safety. Periodic inventory reductions will be scheduled.
   1. Authorized personnel: Use of this material requires prior written approval from the PI or __________________________, Title: ____________________. Use will be limited to the following personnel (check all that apply):

   2. Principal Investigator ____ Graduate students____
      Technical staff ____ Post doctoral employees____ Undergraduates ____
      Other (describe) _________________________
      
3. Training requirements: The user must demonstrate competency and familiarity regarding the safe handling and use of this material prior to purchase. Training should include the following:

4. Use location: Materials shall be used only in the following designated areas in room ______.
   Check all that apply:
   demarcated area in lab (describe)________________________________________
   fume hood _____ glove box _____ other (describe) _______________________
   
   1. Personal protective equipment: All personnel are required to wear the following personal protective equipment whenever handling this material (check all that apply):

   2. Safety goggles _____ Chemical safety goggles _____ Face shield _____
      Gloves (type/use):
      Incidental Contact: _____________________________________________
      Extended Contact: ______________________________________________
      Lab coat _____ Rubber apron _____ Tyvek clothing _____
      Respirator (type) ______________ Other (describe) ___________________
      
   1. Waste disposal: The authorized person using this material is responsible for the safe collection, preparation and proper disposal of waste unless otherwise stated below. Waste shall be disposed of as soon as possible and in accordance with all laboratory and University procedures.

   2. Specific instructions:
5. Decontamination: Specific instructions:

6. Exposures: Emergency procedures to be followed (from MSDS):

Review of current MSDS Special training provided by the department/supervisor Review of the OSHA Lab Standard Review of the departmental safety manual Review of the Chemical Hygiene Plan Safety meetings and seminars Laboratory safety training (EH&S)

12.20

Skin/eye contact--symptoms: First aid:

Ingestion-- symptoms: First aid:

Inhalation--symptoms: First aid:

1. Spills: Spill cleanup materials to be used, location of materials, PPE to be used, disposal of cleanup materials, etc. Please be as complete as possible:

2. numbers:
   Cornell Campus Police: 911 (accidents, spills)
   Environmental Health and Safety: 5-
   Gannett Health Center: 5-
   

3. Other: Special precautions, incompatible/reactive materials, usable shelf life, etc. Please be as specific as possible:

12.21

Prepared by: ________________________________

Date: _____________

Reviewed/Revised: _________________

A copy of the completed SOP must be filed with the Cornell Chemical Hygiene Officer at EH&S, 125 Humphreys Service Building.

Revised 11/13/98 by Tom Shelley

12.22

How to Prepare an SOP

Using the Cornell University "Standard Operating Procedure for Carcinogens and Highly Toxic Materials" Form

Prepared by Tom Shelley

11/17/97

Part A: Some Frequently Asked Questions

When is an SOP required? The OSHA Lab Standard mandates that those responsible for laboratory operations develop Standard Operating Procedures (SOPs) "relevant to safety and health considerations to be followed when laboratory work involves the use of hazardous chemicals." (29 CFR .(e)(3) (i)) This is especially the case if your lab operations include the routine use of " 'select carcinogens,' reproductive toxins [or] substances which have a high degree of acute toxicity." (29 CFR .(e)(3) (viii))

How do I know if a chemical I am using is a select carcinogen or acutely toxic? If any of the following questions are answered with "yes."

Is the chemical on the list "Cornell University Select Carcinogens?"

Is the chemical on the list "Cornell University Acutely Toxic Chemicals?"

Does the chemical have an NFPA/HMIS health hazard rating1 of 4?

Is the chemical rated HIGHLY TOXIC? (LD50 of 50 mg./kg. or less.)2

Is the chemical rated SUPER TOXIC? (LD50 of 5 mg./kg. or less.)2

Is the chemical a poison inhalation hazard?

Note: Not all carcinogens and acutely toxic chemicals are listed in the above references. If you can't locate a chemical in these lists and you have reason to believe that it is a carcinogen or acutely toxic, you must refer to the MSDS for the chemical (or other sources of chemical safety information) to determine the hazardous characteristics of the chemical.

[See the document "How to Obtain an MSDS" if you do not have one available for the chemical.]

In addition, SOPs may need to be prepared for very flammable chemicals (NFPA/HMIS flammability rating1 of 4) and very reactive chemicals (NFPA/HMIS reactivity rating1 of 3 or 4) such as strong corrosives, oxidizers and reducing agents, depending upon the extent and duration of use.

12.23

Do I need to prepare an SOP for all of the carcinogens and acutely toxic chemicals I use in my lab? An SOP may not be required if a chemical meets the following criteria:

1) It is nota known human carcinogen, 2) It is not a poison inhalation hazard, 3) It does not require an antidote for ordinary lab usage (certain cyanide compounds, for example, require an antidote to be on hand in the lab for first aid treatment in the event of the exposure of an employee to the chemical), 4) It is used very infrequently (not as a component of an on-going or frequently performed experiment or process), and 5) It is used in very small quantities, meaning less than one-half of the LD50 for an "average" person calculated as:

LD50 in mg./kg. x 74 / (in grams) 2

Do I need to prepare a separate SOP for each chemical in use in my lab? An SOP may be prepared for an experiment or process using more than one carcinogen or acutely toxic chemical. Or, an SOP may be prepared for a class of chemicals having similar hazardous characteristics. Examples of the above conditions are:

a) Chlorine, phosgene and carbon monoxide are combined in varying proportions in an evacuated reaction vessel and the by-products are studied using various analytical procedures. The starting materials are all poison inhalation hazards and an SOP may be written for the process in which they are used.

b) Copper and zinc cyanides are used in a plating bath with the evolution of small amounts of hydrogen cyanide. The starting materials and one by-product are highly toxic and an SOP may be written for the process in which they are used.

c) Benzene, carbon tetrachloride, chloroform and methylene chloride are frequently used as components of solvent systems in an organic chemistry lab. They are all select carcinogens. An SOP may be written for the class of solvents used in the lab that are known or suspect carcinogens.

d) Dichlorobenzidine, benzo[a]pyrene and N-nitrosomethyethyl-amine are used as mutagens in a microbiology laboratory. An SOP may be written for the class of carcinogens used as mutagens in this microbiology laboratory.

e) Inorganic arsenic, chromium, lead and nickel compounds are used to prepare standards used in an environmental analytical laboratory. The compounds, all select carcinogens, may have an SOP prepared for the class of compounds which are carcinogenic metal compounds.

Can Dr. Smith's lab use the SOP for formaldehyde that our lab wrote? If the process for the use of formaldehyde is the same in both labs, then the same SOP may be used with appropriate changes under location, storage, authorized personnel and other information that is specific to each lab. We strongly encourage departments and colleges to develop "generic" SOPs for

12.24

commonly used chemicals and processes which can then be customized for each individual lab in the department or College.

Part B: How to Complete the SOP Form

A Step-By-Step Guide

Location(s) means the building and room number(s) where a chemical or process is used.

Chemical(s) means the full name of the chemical(s) used in a process. The chemical(s) name may be abbreviated in subsequent sections of the SOP form. Also include the CAS number of each compound, if known, and an approximate quantity of the material that would need to be kept on hand, if known.

Specific Hazards means the known hazard statements concerning the chemical(s) listed above. This information is usually available from the MSDS and consists of short statements or phrases identifying specific hazards, such as "very toxic," "highly flammable," "carcinogen," "peroxide former," "irritant," etc.

Purchasing identifies the person giving written approval to purchase the chemical(s) and the limit on the amount of the chemical(s) that may be purchased at any one time. This person is usually the principal investigator or a designated responsible person, such as a lab supervisor, technician, post doc or a senior graduate student.

Storage identifies the area(s) designated for the storage of the chemical(s). This must be as specific as possible, such as, "the flammable materials storage cabinet to the north of the fume hood in room 312" or "the cabinet on the south wall of room 312."

[Please see the documents "Brief Guide to the Proper Storage of Chemicals" and "Safe Storage of Chemicals" for information on the storage of chemicals.]

Authorized personnel identifies the person who gives approval for the use of the chemical(s), usually the principal investigator or lab supervisor. Check the appropriate entries on the list of possible users provided. If "Other" is checked, please explain.

Training requirements may vary greatly depending upon the chemical(s) in use. The user must demonstrate knowledge of a) the hazards of the chemical(s) and b) procedures for the safe handling of the chemical(s). The list of written programs and other training materials provided is not inclusive. Additional written materials may be added at the discretion of the person responsible for training.

Note: There is a requirement that written records verifying the training given to all chemical users must be maintained by each department. A "Chemical(s) User Authorization Form," which can be used to verify the training for users of hazardous chemicals, is provided for your convenience. A copy of the completed Authorization Form must be kept in or near the lab where the chemical(s) is used.

12.25

Use location designates the room and specific areas where the chemical(s) is used in the room. If "Other" is checked, please explain. Be as specific as possible.

Personal protective equipment requirements may vary greatly depending upon the chemical(s) in use. Please check all items that apply. If additional safety equipment or conditions are required, please record these items in Section 12 below. Please note the following:

1) There is a requirement to use chemical splash goggles when corrosive liquids or other materials with a potential to splash the eyes or face are in use. 2) Glove selection is particularly critical for carcinogens and acutely toxic materials. Many glove selection charts are available and the MSDSs for many chemicals make recommendations for the type of hand protection required. EH&S can facilitate the selection of hand protection. Call 255- for assistance in glove selection if necessary. Incidental contact means the type and use of the glove to be worn when no contact with the chemical(s) is anticipated under normal conditions of use. Extended contact means the type and use of the glove to be worn when contact with the chemical(s) is anticipated, such as the immersion of the hands in a chemical when it is used as a cleaning agent, etc. 3) Respirators are rarely needed in a lab setting. Generally speaking, all use of chemicals which pose an inhalation hazard must be conducted in a functional fume hood in a lab setting. All use of respirators at Cornell must be approved by EH&S. Call 255- for assistance with respiratory protection if this is required for the chemical(s) in use. [Please see the document "Cornell University Respiratory Protection Program."] 4) Shorts, sandals, open toed shoes and other apparel which allow the legs and feet to be exposed are prohibited when corrosives and other chemicals which pose a skin exposure hazard are in use. 5) Note that long hair, jewelry and other items may present a hazard when hazardous chemicals and energized systems are in use and appropriate precautions should be taken as required.

Waste disposal must follow the procedures outlined in Section 7 of the Cornell Chemical Hygiene Plan. Please be as specific as possible in describing the waste disposal procedures for the chemical(s) in use.

Decontamination procedures must be developed when possible. For example, if an acid or base can be neutralized with sodium bicarbonate describe how this is done. If special conditions exist, such as the chemical(s) is only easily soluble in acetone, please make a note of these conditions. If a method is available that can be used to detoxify the chemical(s) or the byproducts of an experiment or process using the chemical(s) as the last step in an experiment or process used in your lab, please attach a copy of a detailed procedure for this process. It may not be possible to develop decontamination or detoxification methods for all chemicals.

12.26

Exposures lists symptoms, first aid and other emergency procedures to be followed in the event that a person is exposed to the chemical(s) in use. The required information may be obtained from an MSDS for the chemical(s).

[See the document "How to Obtain an MSDS" if you do not have one available for the chemical.]

Spills describes procedures to be used in the event of a spill or other uncontrolled release of the chemical(s). There is a requirement that lab staff using the chemical(s) be trained on the procedures used to clean up a spill. It is also important that users of the chemical(s) are trained to recognize when they are able to clean up the spill without the help of others (an incidental spill) and when the assistance of others is required (an emergency response). EH&S can facilitate the development of procedures for spill cleanup. The principle investigator, supervisor or responsible person is required to meet the above training requirements.

numbers are those to be used in the event of an emergency. Call 911 for all spills that are not incidental spills, accidents damaging property (explosions, fires) and substantial personal injuries. All lab injuries must be reported to the supervisor of the lab and a "Cornell University Accident Report" must be completed.

Other specifies any special precaution that must be taken for the handling, use and storage of the chemical(s). Please be as specific as possible.

A copy of the completed SOP must be filed with EH&S electronically or by campus mail to 125 Humphreys Service Building.

Please use extra pages as required.

1 NFPA is the National Fire Protection Association which has developed a system of rating the hazards of chemicals on a scale of 0-4 for health, flammability and reactivity. HMIS is a similar but proprietary system used by some chemical companies. The rating scales range from 0 for "no hazard" to 4 for "extremely hazardous" for each of the hazardous characteristics listed above. Many chemical company catalogs contain an explanation of the NFPA/HMIS rating system.

2The LD50, or Lethal Dose 50, is the amount of a chemical which will cause 50% of a population of test animals to die when the chemical is administered via a particular route of exposure for a specified length of time.

Revised 11/16/98 Tom Shelley

12.27

12.28

Chemical User Authorization Form

I hereby certify that I have read the Standard Operating Procedure, the MSDS and associated materials concerning the use of

in this lab.
I also certify that I understand and agree to the following:

? I must follow the written Standard Operating Procedure for the chemical(s) listed above.

• I understand the requirements for the use of personal protective equipment and other safety devices required for the use of the chemical(s) listed above.

• I am aware of the location of and procedures for the use of first aid supplies for exposure to the chemical(s) listed above.

Supervisor's Name (Please Print) Signature Date Signature

1. _______________________ ____________________ _________

2. _______________________ ____________________ _________

3. _______________________ ____________________ _________

4. _______________________ ____________________ _________

5. _______________________ ____________________ _________

6. _______________________ ____________________ _________

7. _______________________ ____________________ _________

8. _______________________ ____________________ _________

12.29

12.30

Cornell University Select Carcinogens

Chemical CAS Number A-alpha-C (2-Amino-9H-pyrido[2,3-b]indole) -68-5 Acetaldehyde 75-07-0 Acetamide 60-35-5 Acetochlor -82-1 2-Acetylaminofluorene 53-96-3 Acifluorfen -59-9 Acrylamide 79-06-1 Acrylonitrile 107-13-1 Actinomycin D 50-7-60 Adriamycin (Doxorubicin hydrochloride) -92-8 AF-2;[2-(2-furyl)-3-(5-nitro-2-furyl)]acrylamide -53-7 Aflatoxins -68-2 Alachlor -60-8 Alcoholic beverages, when associated with alcohol abuse n/a Aldrin 309-00-2 Allyl chloride 107-05-1 Aluminum products n/a 2-Aminoanthraquinone 117-79-3 p-Aminoazobenzene 60-09-3 ortho-Aminoazotoluene 97-56-3 4-Aminobiphenyl (4-aminodiphenyl) 92-67-1 3-Amino-9-ethylcarbazole hydrochloride -97-3 1-Amino-2-methylanthraquinone 82-28-0 2-Amino-5-(5-nitro-2-furyl)-1,3,4-thiadiazole 712-68-5 Amitrole 61-82-5 Analgesic mixtures containing phenacetin n/a Androgenic (anabolic) steroids n/a Aniline 62-53-3 ortho-Anisidine 90-04-0 ortho-Anisidine hydrochloride 134-29-2 Antimony oxide (antimony trioxide) -64-4 Aramite 140-57-8 Arsenic (inorganic arsenic compounds) various Asbestos -21-4 Auramine 492-80-8 Azaserine 115-02-6 Azathioprine 446-86-6

12.31

Azacitidine 320-67-2 Azobenzene 103-33-3 Benz[a]anthracene 56-55-3 Benzene 71-43-2 Benzidine [and its salts] 92-87-5 Benzidine-based dyes various Benzo[b]fluoranthene 205-99-2 Benzo[j]fluoranthene 205-82-3 Benzo[k]fluoranthene 207-08-9 Benzofuran 271-89-6 Benzo[a]pyrene 50-32-8 Benzotrichloride 98-07-7 Benzyl chloride 100-44-7 Benzyl violet 4B -09-3 Beryllium and beryllium compounds various Betel quid with tobacco n/a Bis(2-chloroethyl)ether 111-44-4 N,N-Bis(2-chloroethyl)-2- naphthylamine (Chlornapazine) 494-03-1 Bischloroethyl nitrosourea (BCNU) (Carmustine) 154-93-8 Bis(chloromethyl)ether 542-88-1 Bitumens, extracts of steam-refined and air refined various Bleomycins various Bracken fern n/a Bromodichloromethane 75-27-4 Bromoform 75-25-2 1,3-Butadiene 106-99-0 1,4-Butanediol dimethanesulfonate (Busulfan) 55-98-1 Butylated hydroxyanisole (BHA) -16-5 beta-Butyrolactone -88-0 Cadmium and cadmium compounds various Caffeic acid 331-39-5 Captafol -06-1 Captan 133-06-2 Carbon tetrachloride 56-23-5 Carbon-black extracts n/a Carrageenan, degraded n/a Ceramic fibers (airborne particles of respirable size) n/a Certain combined chemotherapy drugs for lymphomas n/a Chlorambucil 305-03-3 Chloramphenicol 56-75-7 Chlordane 57-74-9 Chlordecone (Kepone) 143-50-0 Chlordimeform -98-3

12.32

Chlorendic acid (approximately 60 percent chlorine by weight) 115-28-6 Chlorinated Parrafins (C12, 60% chlorine) -26-2 alpha-Chlorinated toluenes various p-Chloroaniline 106-47-8 Chlorodibromomethane 124-48-1 Chloroethane (ethyl chloride) 75-00-3 1-(2-Chloroethyl)-3-cyclohexyl-1-nitrosourea (CCNU) (Lomustine) -47-4 1-(2-Chloroethyl)-3-(4-methylcyclohexyl)-1-nitrosourea (Methyl-CCNU) -09-6 Chloroform 67-66-3 Chloromethyl methyl ether (technical grade) 107-30-2 3-Chloro-2-methylpropene 563-47-3 4-Chloro-ortho-phenylenediamine 95-83-0 p-Chloro-o-toluidine 95-69-2 Chlorophenols various Chlorophenoxy herbicides various Chlorothalonil -45-6 Chlorozotocin -90-5 Chromium (hexavalent compounds) various Chrysene 218-01-9 C. I. Acid Red 114 -94-5 C. I. Basic Red 9 monohydrochloride 569-61-9 Ciclosporin (Cyclosporin A; Cyclosporine) -13-3 Cinnamyl anthranilate 87-29-6 Cisplatin -27-1 Citrus Red No. 2 -53-8 Coal gasification n/a Coal-tar pitches n/a Coal-tars n/a Cobalt metal powder -48-4 Cobalt [II] oxide -96-6 Coke Production oven emissions n/a Conjugated estrogens n/a Creosotes n/a para-Cresidine 120-71-8 Cupferron 135-20-6 Cycasin -08-7 Cyclophosphamide (anhydrous) 50-18-0 Cyclophosphamide (hydrated) -19-2 D&C Orange No. 17 -63-1 D&C Red No. 8 -56-0 D&C Red No. 9 -02-1 D&C Red No. 19 81-88-9 Dacarbazine -03-4 Daminozide -84-5

12.33

Dantron (Chrysazin; 1,8-Dihydroxyanthraquinone) 117-10-2 Daunomycin -8-13 DDD (Dichlorodiphenyldichloroethane) 72-5-48 DDE (Dichlorodiphenyldichloroethylene) 72-55-9 DDT (Dichlorodiphenyltrichloroethane) 50-29-3 DDVP (Dichlorvos) 62-73-7 N,N'-Diacetylbenzidine 613-35-4 2,4-Diaminoanisole 615-05-4 2,4-Diaminoanisole sulfate -41-7 4,4'-Diaminodiphenyl ether (4,4'-Oxydianiline) 101-80-4 2,4-Diaminotoluene 95-80-7 Diaminotoluene (mixed) n/a Dibenz[a,h]acridine 226-36-8 Dibenz[a,j]acridine 224-42-0 Dibenz[a,h]anthracene 53-70-3 7H-Dibenzo[c,g]carbazole 194-59-2 Dibenzo[a,e]pyrene 192-65-4 Dibenzo[a,h]pyrene 189-64-0 Dibenzo[a,i]pyrene 189-55-9 Dibenzo[a,l]pyrene 191-30-0 1,2-Dibromo-3-chloropropane (DBCP) 96-12-8 1,2-Dibromoethane 106-93-4 2,3-Dibromo-1-propanol 96-13-9 p-Dichlorobenzene 106-46-7 3,3'-Dichlorobenzidine 91-9-41 3,3'-Dichlorobenzidine 2HCl 612-83-9 1,4-Dichloro-2-butene 764-41-0 3,3'-Dichloro-4,4'-diaminodiphenyl ether -86-8 1,1-Dichloroethane 75-34-3 1,2-Dichloroethane 107-06-2 Dichloromethane (Methylene chloride) 75-09-2 1,2-Dichloropropane 78-87-5 1,3-Dichloropropene (technical grade) 542-75-6 Dieldrin 60-57-1 Dienestrol 84-17-3 Diepoxybutane -53-5 Diesel engine exhaust n/a Di(2-ethylhexyl)phthalate 117-81-7 1,2-Diethylhydrazine -80-1 Diethyl sulfate 64-67-5 Diethylstilbestrol 56-53-1 Diglycidyl resorcinol ether (DGRE) 101-90-6 Dihydrosafrole 94-58-6 Diisopropyl sulfate -10-6 3,3'-Dimethoxybenzidine (ortho-Dianisidine) 119-90-4

12.34

3,3'-Dimethoxybenzidine dihydrochloride (ortho-dianisidine dihydrochloride) -40-0 para-Dimethylaminoazobenzene 60-11-7 4-Dimethylaminoazobenzene 60-11-7 trans-2-[(Dimethylamino)methylimino]-5-[2-(5-nitro-2-furyl)vinyl]-1,3,4-oxadiazole -54-0 7,12-Dimethylbenz(a)anthracene 57-97-6 3,3'-Dimethylbenzidine (ortho-Tolidine) 119-93-7 3,3'-Dimethylbenzidine dihydrochloride 612-82-8 Dimethylcarbamoyl chloride 79-44-7 1,1-Dimethylhydrazine (UDMH) 57-14-7 1,2-Dimethylhydrazine 540-73-8 Dimethyl sulfate 77-78-1 Dimethylvinyl Chloride 513-37-1 1,6-Dinitropyrene -64-8 1,8-Dinitropyrene -65-9 2,4-Dinitrotoluene 121-14-2 2,6-Dinitrotoluene 606-20-2 1,4-Dioxane 123-91-1 Diphenylhydantoin (Phenytoin) 57-41-0 Diphenylhydantoin (Phenytoin), sodium salt 630-93-3 Direct Black 38 (technical grade) -37-7 Direct Blue 6 (technical grade) -46-2 Direct Brown 95 (technical grade) -86-6 Disperse Blue 1 -45-8

Epichlorohydrin 106-89-8 Erionite -42-8 Estradiol 17B 50-28-2 Estrone 53-16-7 Ethinylestradiol 57-63-6 Ethyl acrylate 140-88-5 Ethyl methanesulfonate 62-50-0 Ethyl-4,4'-dichlorobenzilate 510-15-6 Ethylene dibromide 106-93-4 Ethylene dichloride (1,2-Dichloroethane) 107-06-2 N-Ethyl-N-nitrosourea 759-73-9 Ethylene oxide 75-21-8 Ethylene thiourea 96-45-7 Ethyleneimine 151-56-4

Folpet 133-07-3 Formaldehyde (gas or aqueous solution) 50-00-0 2-(2-Formylhydrazino)-4-(5-nitro-2-furyl) thiazole -75-0 Furan 110-00-9 Furazolidone 67-45-8 Furmecyclox -05-0

12.35

Fusarin C Gasoline engine exhaust (condensates/extracts) n/a Glasswool fibers (airborne particles of respirable size) n/a Glu-P-1 (2-Amino-6-methyldipyrido[1,2- a:3', 2'-d]imidazole) -11-4 Glu-P-2 (2-Aminodipyrido[1,2-a:3',2'-d]imidazole) -10-3 Glycidaldehyde 765-34-4 Glycidol 556-52-5 Griseofulvin 126-07-8 Gyromitrin (Acetaldehyde methylformylhydrazone) -02-8 HC Blue 1 -94-3 Heptachlor 76-44-8 Heptachlor epoxide -57-3 Hexachlorobenzene 118-74-1 Hexachlorocyclohexanes (technical grade) various Hexachlorodibenzodioxin -46-8 Hexachloroethane 67-72-1 Hexamethylphosphoramide 680-31-9 Hydrazine 302-01-2 Hydrazine sulfate -93-2 Hydrazobenzene (1,2-Diphenylhydrazine) 122-66-7 Indeno [1,2,3-cd]pyrene 193-39-5 IQ (2-Amino-3-methylimidazo[4,5-f]quinoline) -96-6 Iron dextran complex -66-4 Isosafrole 120-58-1 Kepone (Chlordecone) 143-50-0 Lactofen -63-4 Lasiocarpine 303-34-4 Lead acetate 301-04-2 Lead and lead compounds various Lead phosphate -27-7 Lindane and other hexachlorocyclohexane isomers various Mancozeb -01-7 Maneb -38-2 Me-A-alpha-C (2-Amino-3-methyl-9H-pyrido[2, 3-b]indole) -83-7 Medroxyprogesterone acetate 71-58-9 MeIQ(2-Amino-3,4-dimethylimidazo[4,5-f]quinoline) MeIQx(2-Amino-3,8-dimethylimidazo[4,5-f]quinoxaline) -04-0 Melphalan 148-82-3 Merphalan 531-76-0

12.36

Mestranol 72-33-3 Methoxsalen with ultraviolet A therapy n/a 8-Methoxypsoralen with ultraviolet A therapy 298-81-7 5-Methoxypsoralen with ultraviolet A therapy 484-20-8 2-Methylaziridine (Propyleneimine) 75-55-8 Methylazoxymethanol 590-96-5 Methylazoxymethanol acetate 592-62-1 3-Methylcholanthrene 56-49-5 5-Methylchrysene -24-3 4,4'-Methylene bis(2-chloroaniline) (MOCA) 101-14-4 4,4'-Methylene bis(N,N-dimethyl)benzenamine 101-61-1 4,4'-Methylene bis(2-methylaniline) 838-88-0 4,4'-Methylenedianiline 101-77-9 4,4'-Methylenedianiline dihydrochloride -44-8 Methylhydrazine and its salts -44-8 Methyl chloromethyl ether 107-30-2 Methyl-CCNU -09-6 Methyl iodide 74-88-4 Methyl methanesulfonate 66-27-3 2-Methyl-1-nitroanthraquinone (of uncertain purity) 129-15-7 N-Methyl-N'-nitro-N-nitrosoguanidine (MNNG) 70-25-7 N-Methyl-N-nitrosourea N-Methylolacrylamide 924-42-5 Methylthiouracil 56-04-2 Metiram - Metronidazole 443-48-1 Michler's ketone 90-94-8 Mineral Oils, untreated and mildly treated n/a Mirex -85-5 Mitomycin C 50-07-7 MOPP Monocrotaline 135-22-0 5-(Morpholinomethyl)-3-[(5-nitro-fufurylidene)-amino]-2-oxazolidinone 139-91-3 Mustard gas 505-60-2

Nafenopin -19-5 1-Naphthylamine 134-32-7 2-Naphthylamine 91-59-8 3-Naphthylamine Nickel and certain nickel compounds various Nickel carbonyl - Nickel refinery dust, from the pyrometallurgical process -02-0 Nickel subsulfide -72-2 Niridazole 61-57-4 Nitrilotriacetic acid 139-13-9

12.37

Nitrilotriacetic acid, trisodium salt monohydrate -53-8 5-Nitroacenaphthene 602-87-9 5-Nitro-o-anisidine 99-59-2 o-Nitroanisole 91-23-6 4-Nitrobiphenyl 92-93-3 6-Nitrochrysene -02-8 Nitrofen (technical grade) -755 2-Nitrofluorene 607-57-8 Nitrofurazone 59-87-0 1-[(5-Nitrofurfurylidene)amino]-2-imidazollidinone 555-84-0 1-[(5-Nitrofurfurylidene)-N-[4-(5-Nitro-2-furyl)-2 thiazolyl]acetamide 531-82-8 Nitrogen mustard (Mechlorethamine) 51-75-2 Nitrogen mustard hydrochloride (Mechlorethamine hydrochloride) 55-86-7 Nitrogen mustard N-oxide 126-85-2 Nitrogen mustard N-oxide hydrochloride 302-70-5 2-Nitropropane 79-46-9 4-Nitropyrene -92-4 N-Nitrosodi-n-butylamine 924-16-3 N-Nitrosodiethanolamine -54-7 N-Nitrosodiethylamine 55-18-5 N-Nitrosodimethylamine 62-75-9 p-Nitrosodiphenylamine 156-10-5 N-Nitrosodiphenylamine 86-30-6 N-Nitrosodi-n-propylamine N-Nitroso-N-ethylurea 759-73-9 3-(N-Nitrosomethylamino)propionitrile -49-3 4-(N-Nitrosomethylamino)-1-(3-pyridyl)-1-butanone (NNK) -91-4 N-Nitrosomethylethylamine -95-6 N-Nitroso-N-methylurea 684-93-5 N-Nitroso-N-methylurethane 615--532 N-Nitrosomethylvinylamine -40-0 N-Nitrosomorpholine 59-89-2 N-Nitrosonornicotine -55-8 N-Nitrosopiperidine 100-75-4 N-Nitrosopyrrolidine 930-55-2 N-Nitrososarcosine -22-9 Norethisterone (Norethindrone) 68-22-4

Ochratoxin A 303-47-9 Oestrogen replacement therapy n/a Oestrogen, nonstreoidal Oestrogen, steroidal Oil Orange SS -17-5 Oral contraceptives, combined n/a Oral contraceptives, sequential n/a

12.38

4,4'-Oxydianiline 101-80-4 Oxadiazon -30-9 Oxymetholone 434-07-1 Oxazepam 604-75-1

Panfuran S 794-93-4 Pentachlorophenol 87-86-5 Phenacetin 62-44-2 Phenazopyridine hydrochloride 136-40-3 Phenesterin -10-9 Phenobarbital 50-06-6 Phenoxybenzamine Phenoxybenzamine hydrochloride 63-92-3 Phenyl glycidyl ether 122-60-1 Phenylhydrazine and its salts various o-Phenylphenate, sodium 132-27-4 Phenytoin 57-41-0 PhiP(2-Amino-1-methyl-6-phenylimidazol[4,5-b]pyridine) -23-5 Polybrominated biphenyls various Polychlorinated biphenyls various Polychlorinated biphenyls (containing 60 or more percent chlorine by molecular various weight) Polychlorinated dibenzo-p-dioxins various Polychlorinated dibenzofurans various Polycyclic aromatic hydrocarbons various Polygeenan -98-1 Ponceau MX -53-3 Ponceau 3R -09-8 Potassium bromate -01-2 Procarbazine 671-16-9 Procarbazine hydrochloride 366-70-1 Procymidone -16-8 Progesterone 57-83-0 Progestins various 1,3-Propane sultone -71-4 Progargite -35-8 beta-Propiolactone 57-57-8 Propylene oxide 75-56-9 Propylthiouracil 51-52-5

Radionuclides various Radon -92-2 Reserpine 50-55-5 Residual (heavy) fuel oils n/a

12.39

Saccharin 81-07-2 Saccharin, sodium 128-44-9 Safrole 94-59-7 Selenium sulfide -34-6 Shale-oils -34-9 Silica, crystalline (airborne particles of respirable size) n/a Sodium ortho-phenylphenate Soots, tars, and mineral oils (untreated and mildly treated oils and used engine oils) n/a Sterigmatocystin -13-2 Streptozotocin -66-4 Styrene 100-42-5 Styrene oxide 96-09-3 Sulfallate 95-06-7 Talc containing asbestiform fibers n/a Terrazole -15-9 Testosterone and its esters 58-22-0 2,3,7,8-Tetrachlorodibenzo-para-dioxin (TCDD) -01-6 1,1,2,2-Tetrachloroethane 79-34-5 Tetrachloroethylene (Perchloroethylene) 127-18-4 p-a,a,a-Tetrachlorotoluene -25-1 Tetranitromethane 509-14-8 Thioacetamide 62-55-5 4,4'-Thiodianiline 139-65-1 Thiourea 62-56-6 Thorium dioxide -20-1 Tobacco, oral use of smokeless products n/a Tobacco smoke n/a Toluene diisocyanate -62-5 ortho-Toluidine 95-53-4 ortho-Toluidine hydrochloride 636-21-5 para-Toluidine 106-49-0 Toxaphene (Polychorinated camphenes) -35-2 Treosulfan (Tresoluphan) 299-75-2 Trichlormethine (Trimustine hydrochloride) 817-09-4 2,4,6-Trichlorophenol 88-06-2 1,2,3-Trichloropropane 96-18-4 Triphenyltin hydroxide 76-87-9 Trichloroethylene 79-01-6 Tris(aziridinyl)-para-benzoquinone (Triaziquone) 68-76-8 Tris(1-aziridinyl)phosphine sulfide (Thiotepa) 52-24-4 Tris(2-chloroethyl) phosphate 115-96-8 Tris(2,3-dibromopropyl)phosphate 126-72-7 Trp-P-1 (Tryptophan-P-1) (3-Amino-1,4-dimethyl-5H-pyrido[4,3-b]indole) -06-0 Trp-P-2 (Tryptophan-P-2) (3-Amino-1-methyl-5H-pyrido[4,3-b]indole) -07-1

12.40

Trypan blue (commercial grade) 72-57-1 Unleaded gasoline (wholly vaporized) n/a Uracil mustard 66-75-1 Urethane (Ethyl carbamate) 51-79-6 Vinyl bromide 593-60-2 Vinyl chloride 75-01-4 4-Vinyl-1-cyclohexene diepoxide (Vinyl cyclohexene dioxide) 106-87-6 Vinyl trichloride (1,1,2-Trichloroethane) 79-00-5 2,6-Xylidine (2,6-Dimethylaniline) 87-62-7 Zineb -67-7

12.41

Chemicals Known To Cause Reproductive Toxicity

Developmental Toxicity

Chemical CAS Number

Acetohydroxamic acid 546-88-3 Actinomycin D 50-76-0 All-trans retinoic acid 302-79-4 Alprazolam -97-7 Amikacin sulfate -55-5 Aminoglutethimide 125-84-8 Aminoglycosides various Aminopterin 54-62-6 Angiotensin converting enzyme (ACE) inhibitors various Anisindione 117-37-3 Aspirin (NOTE: It is especially important not to use aspirin during the last three 50-78-2 months of pregnancy, unless specifically directed to do so by a because it may cause problems in the unborn child or complications during delivery.)

Barbiturates various Benomyl -35-2 Benzphetamine hydrochloride -22-3 Benzodiazepines various Bischloroethyl nitrosourea (BCNU) (Carmustine) -93-8 Bromoxynil -84-5 Butabarbital sodium 143-81-7 1,4-Butanediol dimethylsulfonate (Busulfan) 55-98-1

Carbon disulfide 75-15-0 Carbon monoxide 630-08-0 Carboplatin -94-4 Chenodiol 474-25-9 Chlorcyclizine hydrochloride -21-9 Chlorambucil 305-03-3 Chlordecone (Kepone) 143-50-0 Chlordiazepoxide 58-25-3 Chlordiazepoxide hydrochloride 438-41-5 1-(2-Chloroethyl)-3-cyclohexyl-l-nitrosourea (CCNU) (Lomustine) -47-4 Clomiphene citrate 50-41-9 Clorazepate dipotassium -90-7 Cocaine 50-36-2 Colchicine 64-86-8

12.42

Conjugated estrogens n/a Cyanazine -46-2 Cycloheximide 66-81-9 Cyclophosphamide (anhydrous) 50-18-0 Cyclophosphamide (hydrated) -19-2 Cyhexatin -70-5 Cytarabine 147-94-4 Danazol -88-5 Daunorubicin hydrochloride -50-6 Demeclocycline hydrochloride (internal use) 64-73-3 Diazepam 439-14-5 Dicumarol 66-76-2 Diethylstilbestrol (DES) 56-53-1 Dinocap -45-3 Dinoseb 88-85-7 Diphenylhydantoin (Phenytoin) 57-41-0 Doxycycline (internal use) 564-25-0 Doxycycline calcium (internal use) -85-4 Doxycycline hyclate (internal use) -14-5 Doxycycline monohydrate (internal use) -28-1 Ergotamine tartrate 379-79-3 Ethyl alcohol in alcoholic beverages n/a Ethylene glycol monoethyl ether 110-80-5 Ethylene glycol monomethyl ether 109-86-4 Ethylene glycol monoethyl ether acetate 111-15-9 Ethylene glycol monomethyl ether acetate 110-49-6 Ethylene thiourea 96-45-7 Etoposide -42-0 Etretinate -48-0 Fluorouracil 51-21-8 Fluoxymesterone 76-43-7 Flurazepam hydrochloride -18-5 Flutamide -84-7 Halazepam -17-3 Hexachlorobenzene 118-74-1 Ifosfamide -73-2 Iodine-131 -66-0 Isotretinoin -48-2 Lead -92-1

12.43

Lithium carbonate 554-13-2 Lithium citrate 919-16-4 Lorazepam 846-49-1 Lovastatin -75-5 Medroxyprogesterone acetate 71-58-9 Megestrol acetate 595-33-5 Melphalan 148-82-3 Menotropins -68-0 Meprobamate 57-53-4 Mercaptopurine -76-1 Mercury and mercury compounds various Methacycline hydrochloride -95-9 Methimazole 60-56-0 Methotrexate 59-05-2 Methotrexate sodium -56-6 Methyl bromide as a structural fumigant 74-83-9 Methyl mercury (dimethyl mercury) 593-74-8 Methyltestosterone 58-18-4 Midazolam hydrochloride -96-8 Minocycline hydrochloride (internal use) -98-7 Misoprostol -46-2 Mitoxantrone hydrochloride -82-3 Nafarelin acetate -42-0 Neomycin sulfate (internal use) -10-3 Netilmicin sulfate -57-2 Nicotine 54-11-5 Nitrogen mustard (Mechlorethamine) 51-75-2 Nitrogen mustard hydrochloride (Mechlorethamine hydrochloride) 55-86-7 Norethisterone (Norethindrone) 68-22-4 Norethisterone acetate (Norethindrone acetate) 51-98-9 Norethisterone (Norethindrone)/Ethinyl estradiol 68-22-4/57-63-6 Norethisterone (Norethindrone)/Mestranol 68-22-4/72-33-3 Norgestrel -00-2 Oxazepam 604-75-1 Oxytetracycline (internal use) 79-57-2 Oxytetracycline hydrochloride(internal use) -46-0 Paramethadione 115-67-3 Penicillamine 52-67-5 Pentobarbital sodium 63-98-9 Phenprocoumon 435-97-2 Pipobroman 54-91-1

12.44

Plicamycin -89-7 Polybrominated biphenyls 922-66-0 Polychlorinated biphenyls various Procarbazine hydrochloride 366-70-1 Propylthiouracil 51-52-5 Retinol/retinyl esters, when in daily dosages in excess of 10,000 IU, or 3,000 retinol equivalents. (NOTE: Retinol/retinyl esters are required and essential for maintenance of normal reproductive function. The recommended daily level during pregnancy is 8,000 IU.) Ribavirin Secobarbital sodium 309-43-3 Streptomycin sulfate -74-0 Tamoxifen citrate -24-1 Temazepam 846-50-4 Testosterone cypionate 58-20-8 Testosterone enanthate 315-37-7 2,3,7,8-Tetrachlorodibenzo-para-dioxin (TCDD) -01-6 Tetracyclines (internal use) various Tetracycline (internal use) 60-54-8 Tetracycline hydrochloride (internal use) 64-75-5 Thalidomide 50-35-1 Thioguanine 154-42-7 Tobacco smoke (primary) n/a Tobramycin sulfate 108-88-3 Triazolam -01-5 Trilostane -35-3 Trimethadione 127-48-0 Uracil mustard 66-75-1 Urethane 51-79-6 Urofollitropin -91-5 Valproate (Valproic acid) 99-66-1 Vinblastine sulfate 143-67-9 Vincristine sulfate -78-2 Warfarin 81-81-2 Female Reproductive Toxicity Aminopterin 54-62-6

12.45

Anabolic steroids n/a Aspirin(NOTE: It is especially important not to use aspirin during the last three 50-78-2 months of pregnancy, unless specifically directed to do so by a physician because it may cause problems in the unborn child or complications during delivery.) Carbon disulfide 75-15-0 Cocaine 50-36-2 Cyclophosphamide (anhydrous) 50-18-0 Cyclophosphamide (hydrated) -19-2 Ethylene oxide 75-21-8 Lead Tobacco smoke (primary) n/a Uracil mustard 66-75-1 Male Reproductive Toxicity Anabolic steroids n/a Benomyl -35-2 Carbon disulfide 75-15-0 Colchicine 64-86-8 Cyclophosphamide (anhydrous) 50-18-0 1,2-Dibromo-3-chloropropane (DBCP) 96-12-8 m-Dinitrobenzene 99-65-0 o-Dinitrobenzene 528-29-0 p-Dinitrobenzene 100-25-4 Dinoseb 88-85-7 Ethylene glycol monoethyl ether 110-80-5 Ethylene glycol monomethyl ether 109-86-4 Ethylene glycol monoethyl ether acetate 111-15-9 Ethylene glycol monomethyl ether acetate 110-49-6 Hexamethylphosphoramide 680-31-9 Lead -92-1 Nitrofurantoin 67-20-9 Tobacco smoke (primary) n/a Uracil mustard 66-75-1

Last Update: 8/20/97 Tom Shelley

12.46

Cornell Acutely Toxic Chemicals

Based on OSHA Standard 29 CFR .119 App A

CHEMICAL NAME CAS NUMBER

Acetaldehyde 75-07-0 Acrolein (2-Propenal) 107-02-8 Acrylyl Chloride 814-68-6 Allyl Chloride 107-05-1 Allylamine 107-11-9 Alkylaluminums Varies Ammonia, Anhydrous -41-7 Ammonia solutions (greater than 44% ammonia by weight) -41-7 Ammonium Perchlorate -98-9 Ammonium Permanganate -36-2 Arsine (also called Arsenic Hydride) -42-1 Bis(Chloromethyl) Ether 542-88-1 Boron Trichloride -34-5 Boron Trifluoride -07-2 Bromine -95-6 Bromine Chloride -41-7 Bromine Pentafluoride -30-2 Bromine Trifluoride -71-5 3-Bromopropyne (also called Propargyl Bromide) 106-96-7 Butyl Hydroperoxide (Tertiary) 75-91-2 Butyl Perbenzoate (Tertiary) 614-45-9 Carbonyl Chloride (see Phosgene) 75-44-5 Carbonyl Fluoride 353-50-4 Cellulose Nitrate (concentration greater than 12.6% nitrogen) -70-0 Chlorine -50-5 Chlorine Dioxide -04-4 Chlorine Pentafluoride -63-3 Chlorine Trifluoride -91-2 Chlorodiethylaluminum (also called Diethylaluminum Choride) 91-10-6 1-Chloro-2, 4-Dinitrobenzene 97-00-7 Chloromethyl Methyl Ether 107-30-2 Chloropicrin 76-06-2 Chloropicrin and Methyl Bromide mixture None Chloropicrin and Methyl Chloride mixture None Commune Hydroperoxide 80-15-9 Cyanogen 460-19-5

12.47

Cyanogen Chloride 506-77-4 Cyanuric Fluoride 675-14-9 Diacetyl Peroxide (concentration greater than 70%) 110-22-5 Diazomethane 334-88-3 Dibenzoyl Peroxide 94-36-0 Diborane -45-7 Dibutyl Peroxide (Tertiary) 110-05-4 Dichloro Acetylene -29-4 Dichlorosilane -96-0 Diethylzinc 557-20-0 Diisopropyl Peroxydicarbonate 105-64-6 Dilauroyl Peroxide 105-74-8 Dimethyldichlorosilane 75-78-5 Dimethylhydrazine, 1,1-57-14-7 Dimethylamine, Anhydrous 124-40-3 2, 4-Dinitroaniline 97-02-9 Ethyl Methyl Ketone Peroxide (also Methyl Ethyl Ketone -23-4

Peroxide; concentration greater than 60%) Ethyl Nitrite 109-95-5 Ethylamine 75-04-7 Ethylene Fluorohydrin 371-62-0 Ethylene Oxide 75-21-8 Ethyleneimine 151-56-4 Fluorine -41-4 Formaldehyde (Formalin) 50-00-0 Furan 110-00-9 Hexafluoroacetone 684-16-2 Hydrochloric Acid, Anhydrous -01-0 Hydrofluoric Acid, Anhydrous -39-3 Hydrogen Bromide -10-6 Hydrogen Chloride -01-0 Hydrogen Cyanide, Anhydrous 74-90-8 Hydrogen Fluoride -39-3 Hydrogen Peroxide (52% by weight or greater) -84-1 Hydrogen Selenide -07-5 Hydrogen Sulfide -06-4 Hydroxylamine -49-8 Iron, Pentacarbonyl -40-6 Isopropylamine 75-31-0 Ketene 463-51-4 Methacrylaldehyde 78-85-3 Methacryloyl Chloride 920-46-7 Methacryloyloxyethyl Isocyanate -80-7 Methyl Acrylonitrile 126-98-7 Methylamine, Anhydrous 74-89-5

12.48

Methyl Bromide 74-83-9 Methyl Chloride 74-87-3 Methyl Chloroformate 79-22-1 Methyl Ethyl Ketone Peroxide (concentration greater than 60%) -23-4 Methyl Fluoroacetate 453-18-9 Methyl Fluorosulfate 421-20-5 Methyl Hydrazine 60-34-4 Methyl Iodide 74-88-4 Methyl Isocyanate 624-83-9 Methyl Mercaptan 74-93-1 Methyl Vinyl Ketone 79-84-4 Methyltrichlorosilane 75-79-6 Nickel Carbonyl (Nickel Tetracarbonyl) -39-3 Nitric Acid -37-2 (94.5% or greater by weight) Nitric Oxide -44-0 Nitroaniline (para-Nitroaniline) 100-01-6 Nitromethane 75-52-5 Nitrogen Dioxide -44-0 Nitrogen Oxides -44-0 (NO; NO(2); N2O4; N2O3) Nitrogen Tetroxide (also called Nitrogen Peroxide) -72-6 Nitrogen Trifluoride -54-2 Nitrogen Trioxide -73-7 Oleum (65% to 80% by weight; also called Fuming Sulfuric -94-7 Acid) Osmium Tetroxide -12-0 Oxygen Difluoride (Fluorine Monoxide) -41-7 Ozone -15-6 Pentaborane -22-7 Peracetic Acid (concentration greater than 60% Acetic Acid; 79-21-0 also called Peroxyacetic Acid) Perchloric Acid (concentration greater than 60% by weight) -90-3 Perchloromethyl Mercaptan 594-42-3 Perchloryl Fluoride -94-6 Peroxyacetic Acid (concentration greater than 60% Acetic Acid; 79-21-0

also called Peracetic Acid) Phosgene (also called Carbonyl Chloride) 75-44-5 Phosphine (Hydrogen Phosphide) -51-2 Sulfur Dioxide (liquid) -09-5 Sulfur Pentafluoride -22-7 Sulfur Tetrafluoride -60-0 Sulfur Trioxide (also called Sulfuric Anhydride) -11-9 Sulfuric Anhydride (also called Sulfur Trioxide) -11-9 Tellurium Hexafluoride -80-4

12.49

Tetrafluoroethylene 116-14-3 Tetrafluorohydrazine -47-2 Tetramethyl Lead 75-74-1 Thionyl Chloride -09-7 Trichloro (chloromethyl) Silane -25-4 Trichloro (dichlorophenyl) Silane -85-5 Trichlorosilane -78-2 Trifluorochloroethylene 79-38-9 Trimethyoxysilane -90-3

Poison Inhalation List (Revised 5/23/95)

arsenic pentafluoride methyl chloride arsine methyl mercaptan boron trichloride methyl silane boron trifluoride nitric oxide bromine pentafluoride nitrogen dioxide bromine trifluoride nitrogen trifluoride bromotrifluoroethylene nitrogen trioxide carbonyl fluoride oxygen difluoride carbonyl sulfide phosgene chlorine phosphine chlorine pentachloride phosphorous pentafluoride chlorine trifluoride selenium hexafluoride chloropicrin (in mixes) silane cyanogen chloride silicon tetrachloride diborane silicon tetrafluoride dichlorosilane stibine digermane sulfur dioxide dimethylamine sulfur tetrafluoride dinitrogen tetroxide tellurium hexafluoride disilane tetraethyldithiopyrophosphate ethylene oxide tetraethylpyrophosphate fluorine triethylaluminum germane triethylborane hexamethyltetraphosphate triethylgallium hydrogen bromide trimethylaluminum hydrogen chloride trimethylamine hydrogen cyanide trimethylgallium hydrogen fluoride vinyl bromide hydrogen iodide vinyl chloride hydrogen selenide vinyl fluoride hydrogen sulfide

12.50

Peroxide Forming Compounds

Many liquid organic compounds, a few solid and gaseous organic compounds and a few inorganic solids form peroxides upon storage. Most organic peroxides are sensitive to shock, heat or friction to varying degrees. These compounds form by the reaction of the chemical with oxygen allowed in the head space of chemical containers once the container is opened for the first time. Peroxides form at varying rates depending upon the compound. Some peroxides quickly build up to an explosive level and some are only explosive on concentration, such as when a solvent is distilled. Although there is no agreement upon what level of peroxides present a significant hazard, several sources suggest that the "safe" range of peroxide formation is 100 ppm or less. We recommend that all peroxide forming chemicals be tested at the end of the appropriate storage period (see below). If peroxides are detected at a level above 100 ppm, the material must be decontaminated with standard procedures for removing peroxides or discarded as hazardous waste if the material can not be drain disposed. Test strips for the detection of peroxides may be purchased from the Chemistry Department stock room in S. T. Olin Research Wing or from VWR, Fisher Scientific or other lab supply houses. Several chemical methods for the detection of peroxides are also available.

Control and Safe Use of Peroxide Formers

Peroxide formation may be controlled by the following methods:

• Date all incoming containers of peroxide formers when received and again when opened.

• Many chemical companies now routinely print an expiration date on containers of the worst peroxide formers.

• Purchase the smallest possible container size for your needs.

• Store peroxide formers in sealed, air-impermeable containers such as dark amber glass with a tight-fitting cap.

• Iron inhibits the formation of peroxides in some materials, which is why diethyl ether and some other materials are purchased in metal cans. Ground glass stoppered bottles and plastic containers are not advisable, however, plastic squeeze bottles may be used for small quantities of some materials, such as 2-propanol, for immediate use.

• Store peroxide formers in the dark.

• Inhibitors are added to some chemicals and the purchase of peroxide formers with
  added inhibitors is encouraged.
  

• Store peroxide formers, especially those in Table A below, under nitrogen or other inert gas or keep and use them in an inert atmosphere chamber. Note: Some inhibitors actually need small amounts of oxygen to prevent peroxide formation and it is recommended that inhibited chemicals are not stored under an inert atmosphere.

Avoid the distillation of peroxide formers without first testing for the existence of peroxides in the material. Most explosions with the use of peroxide formers occur when a material is distilled to dryness. Leave at least 10-20% bottoms. Stir such distillations with a mechanical stirrer or a bubbling inert gas. Air or an oxygen containing mixture should never be used for bubbling or stirring.

12.51

Safe Storage Periods for Peroxide Formers

Unopened chemicals from manufacturer 18 months (or expiration date)

Opened containers:
Chemicals in Table A. 3 months
Chemicals in Tables B. and D. 12 months
Uninhibited chemicals in Table C. 24 hours
Inhibited chemicals in Table C. 12 months

(Do not store under an inert atmosphere)

A. Chemicals that form explosive levels of peroxides without concentration.

Butadienea Isopropyl ether Sodium amide (sodamide) Chloroprenea Potassium metal Tetrafluoroethylenea Divinylacetylene Potassium amide Vinylidene chloride

B. Chemicals that form explosive levels of peroxides on concentration

Acetal Diethyl ether 2-Pentanol Acetaldehyde Diethylene glycol dimethyl ether (diglyme) 4-Penten-1-ol Benzyl alcohol Dioxanes 1-Phenylethanol 2-Butanol Ethylene glycol dimethyl ether (glyme) 2-Phenylethanol Cumene 4-Heptanol 2-Propanol Cyclohexanol 2-Hexanol Tetrahydrofuran 2-Cyclohexen-1-ol Methylacetylene Tetrahydronaphthalene Cyclohexene 3-Methyl-1-butanol Vinyl ethers Decahydronaphthalene Methylcyclopentane Other secondary alcohols Diacetylene Methyl isobutyl ketone Dicyclopentadiene 4-Methyl-2-pentanol

C. Chemicals that may autopolymerize as a result of peroxide accumulation

Acrylic acidb Methyl methacrylateb Vinyl chloride Acrylonitrileb Styrene Vinylpyridine Butadienec Tetrafluoroethylenec Vinyladiene chloride Chloroprenec Vinyl acetate Chlorotrifluoroethylene Vinylacetylene

12.52

D. Chemicals that may form peroxides but cannot clearly be placed in sections A - C.

Acrolein o-Chlorophenetole Allyl etherd p-Chlorophenetole Allyl ethyl ether Cyclooctened Allyl phenyl ether Cyclopropyl methyl ether p-(n-Amyloxy)benzoyl chloride Diallyl etherd n-Amyl ether p-Di-n-butoxybenzene Benzyl n-butyl etherd 1,2-Dibenzyloxyethaned Benxyl etherd p-Dibenzyloxybenzened Benzyl ethyl etherd 1,2-Dichloroethyl ethyl ether Benzyl methyl ether 2,4-Dichlorophenetole Benzyl 1-napthyl etherd Diethoxymethaned 1,2-Bis(2-chloroethoxy)ethane 2,2-Diethoxypropane Bis(2 ethoxyethyl)ether Diethyl ethoxymethylenemalonate Bis(2-(methoxyethoxy)ethyl) ether Diethyl fumarated Bis(2-chloroethyl)ether Diethyl acetald Bis(2-ethoxyethyl)adipate Diethyketenef Bis(2-ethoxyethyl) phthalate m,o,p-diethoxybenzene Bis(2-methoxyethyl) carbonate 1,2-Diethoxyethane Bis(2-methoxyethyl) ether Dimethoxymethaned Bis(2-methoxyethyl) phthalate 1,1-Dimethoxyethaned Bis(2-methoxymethyl) adipate Dimethylketenef Bis(2-n-butoxyethyl) phthalate 3,3-Dimethoxypropene Bis(2-phenoxyethyl) ether 2,4-Dinitrophenetole Bis(4-chlorobutyl) ether 1,3-Dioxepaned Bis(chloromethyl) ethere Di(1-propynyl)etherf 2-Bromomethyl ethyl ether Di(2-propynyl)ether B-Bromophenetole Di-n-propoxymethaned o-Bromophenetole 1,2-Epoxy-3-isopropoxypropaned p-Bromophenetole 1,2-Epoxy-3-phenoxypropane 3-Bromopropyl phenyl ether p-Ethoxyacethophenone 1,3-Butadiyne 1-(2-Ethoxyethoxy)ethyl acetate Buten-3-yne 2-Ethoxyethyl acetate tert-Butyl ethyl ether (2-Ethoxyethyl)-o-benzoyl benzoate tert-Butyl methyl ether 1-Ethoxynaphthalene n-Butyl phenyl ether o,p-Ethoxyphenyl isocyanate n-Butyl vinyl ether 1-Ethoxy-2-propyne Chloroacetaldehyde diethylacetald 3-Ethoxyopropionitrile 2-Chlorobutadiene 2-Ethylacrylaldehyde oxime 1-(2-Chloroethoxy)-2-phenoxyethane -2-Ethylbutanol Chloroethylene Ethyl B-ethoxypropionate Chloromethyl methyl ethere 2-Ethylhexanal B-Chlorophenetole Ethyl vinyl ether

12.53

Furan m-Nitrophenetole 2,5-Hexadiyn-1-ol 1-Octene 4,5-Hexadien-2-yn-1-ol Oxybis(2-ethyl acetate) n-Hexyl ether Oxybis(2-ethyl benzoate) o,p-Iodophenetole B,B-oxydipropionitrile Isoamyl benzyl etherd 1-Pentene Isoamyl etherd Phenoxyacetyl chloride Isobutyl vinyl ether a-Phenoxypropionyl chloride Isophoroned Phenyl o-propyl ether B-Isopropoxypropionitriled p-Phenylphenetone Isopropyl 2,4,5-trichlorophenoxyacetate n-Propyl ether Limonene n-Propyl isopropyl ether 1,5-p-Methadiene Sodium 8,11,14-eicosatetraenoate Methyl p-(n-amyloxy)benzoate Sodium ethoxyacetylidef 4-Methyl-2-pentanone Tetrahydropyran n-Methylphenetole Triethylene glycol diacetate 2-Methyltetrahydrofuran Triethylene glycol dipropionate 3-Methoxy-1-butyl acetate 1,3,3-Trimethoxypropened 2-Methoxyethanol 1,1,2,3-Tetrachloro 1,3-butadiene 3-Methoxyethyl acetate 4-Vinyl cyclohexene 2-Methoxyethyl vinyl ether Vinylene carbonate Methonxy-1,3,5,7-cyclooctatetraene Vinylidene chlorided B-Methoxypropionitrile

NOTES:

a

When stored as a liquid monomer.

b

Although these chemicals form peroxides, no explosions involving these monomers have been reported.
When stored in liquid form, these chemicals form explosive levels of peroxides without concentration. They may also be stored as a gas in gas cylinders.
When stored as a gas, these chemicals may autopolymerize as a result of peroxide accumulation.

d

These chemicals easily form peroxides and should probably be considered under Part B.

e

OSHA - regulated carcinogen.

f

Extremely reactive and unstable compound.

References:

Prudent Practices in the Laboratory, National Research Council, .
"Review of Safety Guidelines for Peroxidizable Organic Chemicals," Chemical Health and Safety,
September/October .

12.54

The Safe Use of Perchloric Acid

Perchloric acid is a very strong oxidizing agent, often used for the hot digestion of a variety of materials. Perchloric acid as used in the cold, dilute form in certain biochemical protocols is relatively safe. It can cause violent explosions if misused or when concentrated above the normal commercial strength of 72%. Anhydrous perchloric acid should never be prepared as it is unstable at room temperature and will decompose with a violent explosion. The following rules for the hot use of perchloric acid must be followed at all times:

• Hot perchloric acid work may only be conducted in a rated perchloric acid hood or, under special, well-controlled circumstances, with a high efficiency scrubber.

• A perchloric acid hood must be washed down after every use or once per week, which-ever comes first.

• Do not store or use organic materials, such as solvents, in a perchloric acid use hood.

• If a vacuum is needed for perchloric acid work use a water aspirator rather than a mechanical pump. Perchloric acid contact with hydrocarbon based oils or greases in a conventional mechanical vacuum pump may result in an explosion.

• Use the minimum amount of material possible.

• Purchase the smallest quantity available for your needs.

• Store perchloric acid away from all oxidizable materials, using secondary containment.

• All containers of perchloric acid in storage must be inspected frequently. Discolored perchloric acid is dangerous and must be disposed of at once.

• Do not use or store perchloric acid on wooden lab furniture or cracked or porous benchtop materials.

• When possible, use alternative techniques not requiring perchloric acid.

• Do not attempt to clean up spills of concentrated perchloric acid yourself as contact with oxidizable materials can cause an immediate explosion. If you spill perchloric acid call 911 and EH&S will respond to clean up the spill.

References:

Prudent Practices in the Laboratory, National Research Council, . CRC Handbook of Laboratory Safety, 3rd Ed., CRC Press, .

12.55

INCOMPATIBLE CHEMICAL COMBINATIONS

Substances in the left-hand column should be stored and handled so they cannot contact corresponding substances in the right-hand column. The following list contains some of the chemicals commonly found in laboratories, but it should not be considered exhaustive. Information for the specific chemical you are using, can usually be found in the "REACTIVITY" or "INCOMPATIBILITIES" section of the Material Safety Data Sheet. EH&S has a copy of Rapid Guide to Chemical Incompatibilities, by Pohanish and Greene, which lists the incompatibilities of hundreds of chemicals. You may come to our office at 125 Humphreys Service Building and use this valuable reference at any time.

Alkaline and alkaline earth metals, such as sodium, potassium, cesium, lithium, magnesium, calcium Carbon dioxide, carbon tetrachloride and other chlorinated hydrocarbons, any free acid or halogen . Do not use water, foam or dry chemical on fires involving these metals. Acetic anhydride Chromic acid, nitric acid, hydroxyl-containing compounds, ethylene glycol, perchloric acid, peroxides and permanganates. Acetone Concentrated nitric and sulfuric acid mixtures. Acetylene Copper, silver, mercury and halogens. Aluminum alkyls Halogenated hydrocarbons, water. Ammonia (anhydrous) Silver, mercury, chlorine, calcium hypochlorite, iodine, bromine, hydrogen fluoride, chlorine dioxide. Ammonium nitrate Acids, metal powders, flammable liquids, chlorates, nitrites, sulfur, finely divided organics or combustibles. Aniline Nitric acid, hydrogen peroxide. Benzoyl peroxide Chloroform, organic materials. Bromine Ammonia, acetylene, butadiene, butane and other petroleum gases, sodium carbide, turpentine, benzene and finely divided metals. Calcium carbide Water (see also acetylene). Calcium hypochlorite Methyl carbitol, phenol, glycerol, nitromethane, iron oxide, ammonia, activated carbon. Calcium Oxide Water. Carbon, activated Calcium hypochlorite. Chlorates Ammonium salts, acids, metal powders, sulfur, finely divided organics or combustibles. Chlorine Ammonia, acetylene, butadiene, butane and other

13.0

petroleum gases, hydrogen, sodium carbide, turpentine, benzene and finely divided metals. Chlorine dioxide Ammonia, methane, phosphine and hydrogen sulfide. Chlorosulfonic acid Organic materials, water, powdered metals. Chromic acid Acetic acid, naphthalene, camphor, glycerine, turpentine, alcohol and other flammable liquids, paper or cellulose. Copper Acetylene, hydrogen peroxide, ethylene oxide. Cumene hydroperoxide Acids, organic or mineral. Ethylene oxide Acids, bases, copper, magnesium perchlorate. Fluorine Almost all oxidizable substances. Hydrocyanic acid Nitric acid, alkalis. Hydrogen peroxide Copper, chromium, iron, most metals or their salts, any flammable liquid, combustible materials, aniline, nitromethane. Hydrides Water, air, carbon dioxide, chlorinated hydrocarbons. Hydrofluoric acid, anhydrous (hydrogen fluoride) Ammonia (anhydrous or aqueous), organic peroxides. Hydrogen sulfide Fuming nitric acid, oxidizing gases. Hydrocarbons (benzene, butane, propane, gasoline, turpentine, etc.) Fluorine, chlorine, bromine, chromic acid, sodium peroxide, fuming nitric acid. Hydroxylamine Barium oxide, lead dioxide, phosphorus pentachloride and trichloride, zinc, potassium dichromate. Iodine Acetylene, ammonia (anhydrous or aqueous). Maleic anhydride Sodium hydroxide, pyridine and other tertiary amines. Mercury Acetylene, fulminic acid, ammonia, oxalic acid. Nitrates Acids, metal powders, flammable liquids, chlorates, sulfur, finely divided organics or combustibles. Nitric acid (concentrated) Acetic acid, aniline, chromic acid, hydrocyanic, acid, hydrogen sulfide, flammable liquids, flammable gases, nitratable substances, organic peroxides, chlorates.

13.1

Oxygen Oil, grease, hydrogen, flammable liquids, solids, or gases. Oxalic acid Silver, mercury, organic peroxides. Perchlorates Acids. Perchloric acid Acetic anhydride, bismuth and its alloys, alcohol, paper, wood, grease, oil, organic amines or antioxidants. Peroxides, organic Acids (organic or mineral); avoid friction. Phosphorus (white) Air, oxygen. Phosphorus pentoxide Propargyl alcohol. Potassium chlorate Acids (see also chlorates). Potassium perchlorate Acids (see also perchloric acid). Potassium permanganate Glycerine, ethylene glycol, benzaldehyde, any free acid. Silver Acetylene, oxalic acid, tartaric acid, fulminic acid, ammonium compouunds. Sodium See alkaline metals (above). Sodium amide Air, water. Sodium nitrate Ammonium nitrate and other ammonium salts. Sodium oxide Water, any free acid. Sodium peroxide Any oxidizable substance, such as ethanol, methanol, glacial acetic acid, acetic anhydride, benzaldehyde, carbon disulfide, glycerine, ethylene glycol, ethyl acetate, methyl acetate and furfural. Sulfuric acid Chlorates, perchlorates, permanganates, organic peroxides. UDMH (1,1-Dimethylhydrazine) Oxidizing agents such as hydrogen peroxide and fuming nitric acid. Zirconium Prohibit water, carbon tetrachloride, foam and dry chemical on zirconium fires.

Reference Materials on Chemical Safety

All of the following references are available for your use at the Environmental Health and Safety office at 125 Humphreys Service Building.

13.2

ACS Task Force on Laboratory Waste Management, Laboratory Waste Management: A Guidebook, American Chemical Society, . The best available reference on lab waste management. American Chemical Society, Safety in Academic Chemistry Laboratories, Sixth Edition, American Chemical Society , . A concise, highly readable, basic safety manual. Armour, M. A., Hazardous Laboratory Chemicals Disposal Guide, Second Edition, CRC Press, . Very useful reference on the detoxification of hazardous laboratory chemicals. Ash, M. and Ash, I., Gardner's Chemical Synonyms and Trade Names, Gower, . This is a very useful reference for identifying the components of commercial products. Barlow, S. M. and Sullivan, F. M., Reproductive Hazards of Industrial Chemicals, Academic Press,

.
A detailed reproductive hazard analysis is given for a wide variety of chemicals,
many of which are commonly used in laboratories.

Benedetti, B. P., Ed., Flammable and Combustible Liquids Code Handbook, Third Edition, National Fire Protection Association, . Industry standard handbook for the use of flammable liquids. Budavari, S., Ed., The Merk Index, Merk & Co., Inc., "An encyclopedia of chemicals, drugs and biologicals." Clayton, G. D. and Clayton, F. C., Patty's Industrial Hygiene and Toxicology, Fourth Edition, John

Wiley and Sons, Inc.,
An encyclopedic ten volume work covering all aspects of industrial hygiene,
hazardous chemicals and toxicology.

Compressed Gas Association, Handbook of Compressed Gases, Third Edition, Chapman and Hall, . Industry standard handbook for the use of compressed gases. Forsberg, K. and Mansdorf, S. Z., Quick Selection Guide to Chemical Protective Clothing, Third Edition, Van Nostrand Reinhold, .

16.1

A very useful pocket guide for the selection of gloves and chemically resistant clothing. Furr, A. Keith, ed., CRC Handbook of Laboratory Safety, Fourth Edition, CRC Press, Inc., . Comprehensive laboratory safety resource that provides specific procedures for many laboratory operations.

Klaassen, C. D., Amdur, M. O. and Doull, J., Casarett and Doull's Toxicology, Third Edition, Macmillan Publishing Co., . The classic, standard treatise on toxicology.

Lewis, Richard J., Sr., Ed., Hawley's Condensed Chemical Dictionary, 13th Edition, Van Nostrand Reinhold, . Very useful general reference in a dictionary format. Lewis, Richard J., Sr., Ed., Rapid Guide to Hazardous Chemicals in the Workplace, Van Nostrand Reinhold, . A useful paperback quick-reference to the properties of hazardous chemicals. Lunn, G. and Sansone, E. B., Destruction of Hazardous Chemicals in the Laboratory, Second Edition, John Wiley and Sons, Inc., . Very useful reference on the detoxification of hazardous laboratory chemicals.

Meyer, E., Chemistry of Hazardous Materials, Third Edition, Prentice-Hall, . A thorough treatment of the chemistry of various hazardous materials. Good background material.

National Research Council Committee on Prudent Practices for Handling, Storage and Disposal of Chemicals in Laboratories, Prudent Practices in the Laboratory, National Academy Press, Washington, D. C., .

Designed as a reference tool for laboratory personnel. Recommends procedures for the safe handling and disposal of hazardous substances, and for the development of comprehensive safety programs.

NIOSH, Registry of Toxic Effects of Chemical Substances (RTECS), Edition, NTIS Order Number: PB90-INZ.*

16.2

Cross-indexed information on over 133,000 different chemicals. RTECS is a compendium of data extracted from the open scientific literature. The data are arranged in alphabetical order by prime chemical name. Six types of toxicity data are included in the file: (1) primary irritation; (2) mutagenic effects; (3) reproductive effects; (4) tumorgenic effects; (5) acute toxicity; and (6) other multiple dose toxicity. Specific numeric toxicity values such as LD50, LC50, TDLo, and TCLo are noted as well as species studied and route of administration used. For each citation, the bibliographic source is listed thereby enabling the user to access the actual studies cited. A standard reference for toxicologists.

NIOSH/OSHA, Pocket Guide to Chemical Hazards, , DHHS (NIOSH) Publication No. 97-140, GPO Stock No. 017-033--8. *

Quick reference for hundreds of hazardous chemicals for which there are specific Federal regulations. Contains key data on exposure levels, properties, incompatibilities, personal protection, and health hazards. Also available on the Web at: http://www.cdc.gov/niosh/npg/npg.html

Patnaik, P., A Comprehensive Guide to the Hazardous Properties of Chemical Substances, Van Nostrand Reinhold, .

An authoritative guide to the properties, hazards, toxicology and disposal of hundreds of hazardous chemicals. These concise entries would be very useful for those planning a wide variety of experiments.

Pipitone, D. A., Safe Storage of Laboratory Chemicals, John Wiley and Sons, .

A classic text on the storage of chemicals.

Reinhardt, P., A., Leonard, K. L., and Ashbrook, P. C., Pollution Prevention and Waste Minimization in Laboratories, CRC Press, Inc., .

A useful collection of in-depth essays on lab waste minimization.

Richardson, J. H., and Barkley, W. E., Ed., Biosafety in Microbiological and Biomedical Laboratories, Centers for Disease Control and National Institutes of Health, Second Edition, , HHS Publication No. (CDC) 88-.*

Comprehensive, "official" guidelines for the use of biohazardous materials.

Sax, N. I., Cancer Causing Chemicals, Van Nostrand Co., Inc., .

A comprehensive, although slightly dated, list of all classes of carcinogens and
their properties and effects.

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Sax, N. I., Dangerous Properties of Industrial Materials, Sixth Edition, Van Nostrand Reinhold Co.,

.
Contains very brief "hazard analysis" information for over 10,000 industrial laboratory substances.
Emphasis is on flammability, explosivity, and reactivity data. Gives a limited amount of toxicity
information. Lists some references.

Sax, N. I. and Lewis, R. J., Sr., Rapid Guide to Hazardous Chemicals in the Workplace, Van Nostrand Co., Inc., . A compact book with basic information on about 700 common hazardous chemicals.

Shepard, T. H., Catalog of Teratogenic Agents, Fifth Edition, John Hopkins University Press, . A comprehensive, although slightly dated, list of all classes of teratogens and their properties and effects.

Stopford, W. and Bunn, W. B., Ed., Effects of Exposure to Toxic Gases--First Aid and Medical Treatment, Third Edition, Matheson Gas Products, . This is considered the standard reference for the topic. Urben, P. G., Bretherick's Handbook of Reactive Chemical Hazards, Fifth Edition, Butterwoirth-

Heinemann, .
A very comprehensive compilation of the incompatibilities of thousands of hazardous chemicals.
Extremely useful for planning experiments.

Walters, D. B., Safe Handling of Chemical Carcinogens, Mutagens, Teratogens and Highly Toxic Substances, Ann Arbor Science, . Detailed essays on the handling of highly hazardous chemicals.

* For sale by Superintendent of Documents, U.S. Government Printing Office, Washington, D. C. .

16.4

FEDERAL HAZARD COMMUNICATION STANDARD

Basic Purpose

The Federal Hazard Communication Standard was designed to require employers to furnish their employees with information concerning the hazards of chemicals used in the workplace and protective measures employees can take to reduce their exposure to those chemicals.

Requirements of the Standard

Employers are required to provide information to employees about the hazardous chemicals to which they are exposed. For employees routinely exposed to hazardous chemicals, employers are required to take the following steps:

1. Develop an inventory of hazardous chemicals known to be present in the work place, make this list available to employees.

2. Material Safety Data Sheets (MSDSs) are to be obtained from chemical manufacturers and distributors, and maintained in a file that must be accessible to employees. Ask your supervisor for the location of the red Toxic Substances Notebook, which contains the MSDSs, or call Environmental Health and Safety (255-).

3. Employers are required to ensure that the labels on incoming containers list the identity of the contents as well as appropriate hazard warnings. The labels are not to be defaced or removed. When chemicals are transferred from an incoming container to a portable container, the portable container must be labeled with the identity and hazards of that chemical.

4. Employers are required to establish an information and training program for employees. The information and training on hazardous chemicals is to be provided prior to the assignment of an employee to a department, and whenever a new hazard is introduced into the work area.

5. Employers are required to prepare a written hazard communication program. This program must describe how the employer will convey labeling, MSDS, and various other information and training to employees. The written program must also include a list of hazardous chemicals used in the work place, as well as the method employers will use to inform employees of the hazards of non-routine tasks. The written Hazard Communication program for Cornell University, which is available for employees' review, is located at Environmental Health and Safety, 125 Humphreys Service Building (255-), and is also available at Campus Police, G-2 Barton Hall, where it is accessible on a 24-hour basis.

Of Special Interest to Laboratory Workers:

For laboratory operations, the following aspects of the Hazard Communication Program will apply:

1. Labels on incoming containers will not be removed or defaced.

2. Material safety data sheets that are received with the products must be maintained and will be available to laboratory personnel.

3. Employees will be informed of the potential hazards of chemicals through an appropriate information and training program.

16.5

The MSDS

This section provides information for researchers who may need to prepare an MSDS. An MSDS must be prepared for a newly created hazardous chemical or an intermediate product produced in a chemical reaction if:

1) The newly created chemical or intermediate is going to be shipped by the originator off the Cornell Campus or,

2) The newly created chemical or intermediate is going to be kept in the lab on an on-going basis for use by researchers, current or future, in the lab where it was originally made or at other research facilities at Cornell.

Note: If a newly created hazardous chemical is going to be used by a number of persons over time it may be required that a Right-to-Know chemical container label be prepared for the new chemical.

Section 16 is broken down into two parts. The first part (16.1-16.4) is a blank MSDS form (OSHA Form 174) which you may print out and use to create an MSDS for a chemical you have produced. The second part (16.5-16.8) is an annotated Form 174 with instructions on completing the Form. It is important to consider that all sections must be completed when writing an MSDS. If a particular characteristic is unknown, you must state "unknown" or "not available" or "N/A." Under Section V, Health Hazard Data, you may be able to say, "The toxicological effects of this chemical have not (or not fully) been investigated."

If you need help completing an MSDS, please contact EH&S at 255-.

Prepared by Tom Shelley, 11/13/98

16.6

Material Safety Data Sheet U.S. Department of Labor

May be used to comply with Occupational Safety and Health Administration OSHA's Hazard Communication Standard, (Non-Mandatory Form) 29 CFR .. This Standard must be Form Approved consulted for specific requirements. OMB No. -

Section I

Manufacturer's Name Emergency Number Address (Number, Street, City, State, and ZIP Code) Number for Information Date Prepared Signature of Preparer (optional)

Section II - Hazard Ingredients/Identity Information

Hazardous Components (Specific Chemical Identity; Common Name(s)) OSHA PEL ACGIH TLV Other Limits Recommended % (optional

16.7

Section III - Physical/Chemical Characteristics

Boiling Point Specific Gravity (H2O = 1) Vapor Pressure (mm Hg.) Melting Point Vapor Density (AIR = 1) Evaporation Rate (Butyl Acetate = 1) Solubility in Water Appearance and Odor

Section IV - Fire and Explosion Hazard Data

Flash Point (Method Used) Flammable Limits LEL UEL Extinguishing Media Special Fire Fighting Procedures Unusual Fire and Explosion Hazards

Section V - Reactivity Data

Stability Unstable Conditions to Avoid Stable Incompatibility (Materials to Avoid) Hazardous Decomposition or Byproducts Hazardous Polymerization May Occur Conditions to Avoid Will Not Occur

16.8

Section VI - Health Hazard Data

Route(s) of Entry: Inhalation? Skin? Ingestion? Health Hazards (Acute and Chronic) Carcinogenicity: NTP? IARC Monographs? OSHA Regulated? Signs and Symptoms of Exposure Medical Conditions Generally Aggravated by Exposure Emergency and First Aid Procedures

Section VII - Precautions for Safe Handling and Use

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Section VIII - Control Measures

Respiratory Protection (Specify Type) Ventilation Local Exhaust Special Mechanical (General) Other Protective Gloves Eye Protection Other Protective Clothing or Equipment Work/Hygienic Practices

Section IX - Special Precautions

Precautions to be taken in Handling and Storing Other Precautions

Each MSDS must be reviewed for correctness and completeness every three years. Reviewed by ________________________ Reviewed by ________________________ Revision date ________________________ Revision date _______________________

16.10

HOW TO UNDERSTAND MATERIAL SAFETY DATA SHEETS

Chemical manufacturers are required by law to supply "Material Safety Data Sheets" (OSHA Form 174 or its equivalent) upon request by their customers. These sheets have nine sections giving a variety of information about the chemical. Following is a section-by-section reproduction and explanation of a Material Safety Data Sheet (MSDS).

U.S. DEPARTMENT OF LABOR
Occupational Safety and Health Administration

MATERIAL SAFETY DATA SHEET

Required For compliance with OSHA Act of
Public Law 91-596 (CFR )

SECTION I Product Name Size Chemical Name Formula Manufacturer Address For Information on Health Hazards Call For Other Information Call Signature and date

This section gives the name and address of the manufacturer and an emergency number where questions about toxicity and chemical hazards can be directed. Large chemical manufacturers have 24hour hotlines manned by chemical safety professionals who can answer questions regarding spills, leaks, chemical exposure, fire hazard, etc. Other information that may be contained in Section I:

Trade Name: This is the manufacturer's name for the product.

Chemical Name and Synonyms: This refers to the generic or standard names for the chemical.

Chemical Family: This classification allows one to group the substance along with a class of similar substances, such as mineral dusts, acids, caustics, etc. The potential hazards of a substance can sometimes be gauged by experience with other chemicals of that class.

SECTION II - HAZARDOUS INGREDIENTS OF MIXTURES Principal Hazardous component(s) % TVL (Units)

This section describes the percent composition of the substance, listing chemicals present in the mixture. It lists Threshold Limit Values for the different chemicals that are present.

16.11

Threshold Limit values (TLV's) are values for airborne toxic materials that are to be used as guides in the control of health hazards. They represent concentrations to which nearly all workers (workers without special sensitivities) can be exposed to for long periods of time without harmful effect. TLV's are usually expressed as parts per million (ppm), the parts of gas or vapor in each million parts of air. TLV's are also expressed as mg/m3, the milligrams of dust or vapor per cubic meter of air.

SECTION III - PHYSICAL DATA Boiling Point (oF) Specific Gravity (H2O=1) Vapor Pressure (mm Hg) Percent Volatile By Volume (%) Vapor Density (Air=1) Evaporation Rate (Butyl Acetate=1) Solubility in Water Appearance and Odor

Vapor Pressure: Vapor pressure (VP) can be used as a measure of how volatile a substance is. That is, how quickly it evaporates. VP is measured in units of millimeters of mercury (mm Hg). For comparison, the VP of water (at 20o Centigrade) is 17.5 mm Hg. The VP of Vaseline (a nonvolatile substance) would be close to zero mm Hg, while the VP of diethyl ether (a very volatile substance) is 440 mm Hg.

Vapor Density: This figure tells whether the vapor is lighter or heavier than air. The density of air is 1.0. A density greater than 1.0 indicates a heavier vapor, a density less than 1.0 indicates a lighter vapor. Vapors heavier than air (gasoline vapor for instance) can flow along just above the ground and can collect in depressions where they may pose a fire and explosion hazard.

Specific Gravity: This figure tells whether the liquid is lighter or heavier than water. Water has a density of 1.0.

Percent Volatile by Volume: Tells how much of the substance will evaporate away.

SECTION IV - FIRE AND EXPLOSION HAZARD DATA Flash Point (oF) Flammable Limits in Air (% by Vol.) Lower Upper Extinguisher Media Autoignition Temperature (oF) Special Fire Fighting Procedures Explosion Hazards

This section gives information, which is important for preventing and extinguishing fires and explosions. If a fire does occur, this information should be made available to fire fighters.

Flash Point: This is the lowest temperature at which a liquid gives off enough vapor to ignite when a source of ignition is present. At or above this temperature, a fire or explosion hazard may exist if the substance is used in the presence of spark or flame.

Flammable Limits: In order to be flammable, a substance must be mixed with a certain amount of air (as in an automobile carburetor). A mixture that is too "lean" (not enough chemical) or too "rich" (not enough air) will not ignite. The Lower Explosive Limit (LEL) and the Upper Explosive Limit (UEL) define the range of concentration in which combustion can occur.

16.12

This section describes the potential health effects resulting from overexposure to the chemical, and gives emergency and first aid procedures. The symptoms and effects listed are the effects of exposure at hazardous levels: most chemicals are safe in normal use and the vast majority of workers never suffer toxic harm. However, any chemical can be toxic in high concentrations, and the precautions outlined in the MSDS must be followed.

The Health Hazards section often contains information on the toxicity of the substance. The data most often presented are the results of animal experiments. For example, "LD50 (mouse) = 250 mg/kg." The usual measure of toxicity is dose level expressed as weight of chemical per unit body weight of the animal-usually milligrams of chemical per kilogram of body weight (mg/kg). The LD50 or "Lethal Dose Fifty," is the dose of substance that will cause the death of half the experimental animals. The LC50 is the concentration of the substance in air that will cause the death of half the experimental animals.

A rough and somewhat arbitrary classification: when evaluating rodent LD50's, materials with an oral LD50 less than 50 mg/kg are considered highly toxic, and those with an oral LD50 of 50-500 mg/kg are considered moderately toxic.

Health hazard information may also distinguish the effects of acute and chronic exposure. An acute exposure is a single, massive exposure, while chronic exposure is regular exposure to small amounts of a substance over a long period of time.

SECTION VI - REACTIVITY DATA Stability Unstable Conditions to avoid Stable Incompatibility (Materials to Avoid) Hazardous Decomposition Products Hazardous Polymerization Conditions to Avoid May Occur Will Not Occur

Chemical substances may be hazardous not just in them, but may be hazardous when they decompose (break down into other substances) or when they react with other chemicals.

16.13

Stability: Unstable indicates that a chemical can decompose spontaneously under normal temperatures, pressures, and mechanical shocks. Rapid decomposition may be hazardous because it produces heat and may cause fire or explosion. Stable compounds do not decompose under normal conditions.

Incompatibility: Certain chemicals should never be mixed because the mixture creates hazardous conditions. Incompatible chemicals should not be stored together where an accident could cause them to mix.

Hazardous Decomposition Products: Other chemical substances may be created when a chemical burns or decomposes.

Hazardous Polymerization: Some chemicals can undergo a type of chemical reaction (rapid polymerization) which may produce enough heat to cause containers to explode. Conditions to avoid are listed in this section.

SECTION VIII - SPECIAL PROTECTION INFORMATION Respiratory Protection (Specify type) Ventilation Local Exhaust Special Mechanical (general) Other Protective Gloves Eye protection Other Protective clothing or Equipment

These sections describe other precautionary and protection information. Some of the precautions presented are intended for large-scale users and may not be necessary for use of small quantities of chemical. Any questions about precautions or health effects should be referred to Environmental Health and Safety.

16.14

Labeling Requirements for Secondary Chemical Containers

All chemical containers come with a label. The original label of most containers purchased in recent years provides detailed information on the properties and health hazards of the chemical and should never be defaced or removed unless the container is empty and well rinsed. All containers should be dated and inventoried upon arrival and dated again when first opened. As a general rule, if a material is transferred from an original container to other containers, such as making a solution of a chemical or repackaging into smaller bottles for redistribution within a research or teaching lab, all such secondary containers need to be properly labeled with the full name of the materials in the container, the concentration if a solution or mixture, the date and the name or initials of the person making the solution or repackaging the chemical.

The OSHA Lab Standard and the OSHA Hazard Communication Standard have specific requirements for the labeling of chemicals. The Lab Standard states that "Employers shall ensure that labels on incoming containers of hazardous chemicals are not removed or defaced." The Standard, as written, has no specific requirements for chemicals that are repackaged in secondary containers. However, various letters of interpretation from OSHA and enforcement actions have pointed to the use of hazard warnings on secondary containers of laboratory chemicals as a prime means of hazard identification, which is mandated by the Standard. Because this is considered "best practice", Cornell EH&S has instituted a labeling program for secondary containers based upon contemporary, widely used and accepted labeling procedures:

If a chemical is designated as a hazardous material, that is having the characteristics of corrosivity, ignitability, toxicity (generally meaning a highly toxic material with an LD50 of 50 mg./kg. or less), reactivity, etc., and if it is made into a solution or repackaged as a solid or liquid in a concentration greater than 1% (0.1% for a carcinogen) it should have a so called Right-To-Know (RTK) label which duplicates the hazard warnings and target organs, precautions and first aid steps found on the original label.

In a non-lab setting, such as a shop, greenhouse or hospital, the Hazcom Standard dictates that all repackaged chemicals, including commercial products that are a mixture of chemicals, need a RTK label. Without the proper labeling of chemicals a work place is not in compliance with Federal regulations.

Right-To-Know labels are available for many common materials from various labeling companies. However, they are quite expensive. To facilitate the proper and compliant labeling of secondary chemical containers EH&S offers free RTK labels for solutions or repackaged chemicals to the campus community. We now have several hundred labels available on the EH&S Web site. These chemical labels include:

• many commonly used hazardous lab chemicals

• some rarely used specialty chemical labels made for specific labs

• some commercial products used by Buildings Care, shops, the Vet College clinics, and other units at Cornell

17.0

All of the available labels are on the EH&S Web site in html and pdf formats at:

http://www.ehs.cornell.edu/labels/index.html

In addition to the listed chemical labels, our office can make a RTK label for any material for which we can obtain an MSDS. If you need a label made for a material not listed on our Web site, please contact us at 255-.

Revised 10/99 by Tom Shelley.

17.1

CORNELL UNIVERSITY Date___________________ Environmental Health and Safety 125 Humphreys Service Building

"Right-to-Know"
Chemical Information Request Form

Information requests may be submitted by or in writing at any time. This form is provided to assist employees in requesting information concerning the health and safety hazards of hazardous materials found in the workplace. Use this form or, for your convenience, the version found on our Web site. If you have questions, call Environmental Health and Safety at 255-. Send your written requests to Environmental Health and Safety, 125 Humphreys Service Building, Ithaca, NY, .

Name Department

Campus Campus Address

List chemicals for which you would like us to send Material Safety Data Sheets. If a trade product, or if the substance is uncommon, please provide manufacturer's name.

List chemicals for which you would like more detailed information or list specific questions you have. Include pertinent details such as physical form of substance, amount used, and conditions of use.

18.0

If you want to learn more, please visit our website Where to buy 1,2-Bis(2-Chloroethoxy) Ethane.