Chemical Safety in the Workplace ~~ CHEMICAL HAZARD Chemical hazard SaMCL ENTER + A chemical accident is the unintentional release of one oF headings - flammability, reactivity and health.Sample of HAZARD LABEL FLAMMABILITY Burns readily. | REACTIVITY (STABILITY). H Seubhs aan really detonate risk. with heat or ignition. SPECIAL Avoid water. Solids, Liquids, Particles ist OS Dust (formed by grinding/breaking); large Particles Z Smoke (formed by burning); large particles Jeoet = Fumes (formed by heating); small particles < Droplets (agitating a liquid) & Gases wee Gas, and Vapour (gaseous phase of a chemical substance that is liquid or solid at normal LP temperature and pressure) = = Routes of Exposure Inhalation- breathing in contaminated air (dust, fumes, mist, and smoke) Absorption — Involves skin contact. Chemical can pass through the skin into the blood stream Ingestion — Digestive system (eating). Swallowed accidentally if food, cigarettes or hands are contaminated b Injection — A sharp object (e.g. needle) punctures the skin and injects chemical into blood streamToxic Effect of Chemicals Effects may be local or systemic * ie oe : Local injuries involve area of the body in contact with the chemical and are typically caused by reactive or corrosive chemicals (e.g. strong acids) i ade Systemic injuries involve tissues/organs unrelated to or removed from the contact site when toxins have been transported through the bloodstream ** Certain chemicals may affect a target organ E.g. The substance lead primarily affects the central nervous system (CNS), kidney, and red blood cells Toxic Effect of Chemicals - Acute toxicity results from a single, short exposure Effects usually appear quickly and are often reversible - Chronic toxicity results from repeated exposure over a long period of time. Effects are usually delayed and gradual, and may be irreversible Threshold Limit Values (TLV) TLVs (for chemicals) refer to airborne concentrations of substances, and represents conditions under which it is believed that nearly all workers may be repeatedly exposed without adverse effects TLVs are developed as guidelines to assist in the control of health hazards RELEVANT DEFINITIONS Ambient Concentration Categories Threshold Limit Values The Threshold Limit Value [usually abbreviated, TLV] refers to an ambient airbome concentration of some substance of interest, and represents a condition under which it is believed that nearly all workers may be repeatedly exposed, day after day, without adverse effect. This concentration limit can be, and is, commonly expressed in one of three forms: as an 8-hour Time Weighted Average (TLV-TWA); as a Short Term Exposure Limit (TLV- STEL); and as a Ceiling Value (TLV-C). The overall ambient concentration concept designated by the term or phrase, “Threshold Limit Value. was introduced and promulgated by the American Gonference of Government Industrial Hygienists [the ACGIH]. Currently established TLVs are always under review, and individual listings are modified whenever relevant new information dictates that this be done.re Limits, Maximum Permissible Exposure Limits, Recoaad Exposw) a tration Values in the Workplace ! 7. CiaSiva PELs REL, MAK are commonly expressed in ne ofthe omms! san 8-hour Time Weighted Average (PEL-TWA); as @ Short Term Expost STEL); and as a Ceiling Value (PEL-C). # tt: The Time Weighted Average [usually abbreviated as a “suffix,” “TWA; thus: oo TWA, PEL-TWA, REL-TWA, and/or MAK-TWA] is the employee's ue airborne exposure in any 8-hour work shift of any 40-hour work week to whicl nearly all workers may be repeatedly exposed, day after day, without suffering any adverse effects. It is a value that should never be exceeded. The Short Term Exposure Limit [usually abbreviated as a “suffix,” -STEL; thus: TLV-STEL,PEL-STEL, REL-STEL, and/or MAK-STEL] is the concentration to which workers can be continuously exposed for short periods of time without suffering from: 1. Imitation; 2. Chronic or irreversible tissue damage; or 3. Narcosis of sufficient degree to increase the likelihood of accidental injury, impair self-rescue, or materially reduce work efficiency — provided also that the corresponding TWA has not been exceeded. STELs are usually 15-minute (except for those materials for which an alternative time limit has been specified) Time Weighted Average exposures which should never be exceeded during any of the specified time intervals during the work day, even if the corresponding TWA has not been exceeded. In the event any time limit other than 15 minutes is specified for some material or compound, the previous definition still holds, except as modified by the different time limit. The Ceiling Value concentration [usually abbreviated as a “suffix,” ~C; thus: TLV- C, PELC, REL-C, and/or MAK-C] is a concentration that should never be exceeded, even instantaneously, at any time during the work day. In the event that instantaneous monitoring is not feasible, then the Ceiling Value can be assessed as a 15-minute Time Weighted Average exposure which should not be exceeded at any time during the work day, EXCEPT when the subject vapor can cause immediate irritation with exceedingly short exposures. The Breathing Zone of an individual is a roughly hemispherical volume immediately forward of that person's shoulders and face, centered ly on the Adam's Apple, and having a radius of 6 to 9 inches (15 to 23 cm). ZThe i 5 SORE Lethal Dose (usually abbreviated, LDS0) isthe toxicant dose a which me agli ion of the same species will die within a specified period of time, aise perimental conditions. This dosage number is usually expressed as mien of toxicant per kilogram of body weight [mg/kg]. ‘¢ Upper and Lower Explosive Limits (abbreviated UEL and LEL) refer to the upper and lower vapor concentration boundaries, for some specific compound or material of interest, within which the vapor-air mixture will propagate a flame [i.e., explode] if ignited. The Explosive Range for any chemical or compound is the range of concentrations that exist between its Upper and Lower Explosive Limits. For example, the LEL and UEL for n-hexane are, respectively, 1.2 & 7.7%; thus this chemical’s Explosive Range is 1.2 to 7.7% in air. When considering the Explosive Range for any specific chemical, it is important to note that for any concentration of that chemical that falls outside of this range, the vapor-air mixture possessing that concentration will not propagate a flame when a source of ignition is introduced. For chemical concentrations lower than the LEL, there is an insufficient amount of the combustible chemical to permit flame propagation, and for concentrations greater than the UEL, there is insufficient ambient oxygen to permit flame propagation. The Flash Point of any compound is that temperature to which it must be heated before its vapors can be ignited by a free flame in the presence of air. It is a measure of the flammability of any material, and as such it is a reasonably good criterion for this characteristic. The lower the Flash Point, the more flammable a material is. This value is affected by the relative volatility and the chemical composition of the material in question. Thus, ranked in the order of decreasing flammability, we would find the following to hold true (for a particular Flash Point designated as Ee Fpure hydrocarbons < Foxygenated hydrocarbons < F partially halogenated hydrocarbons, €¢C. As typical examples, Fgasoline = 45°C, Fisopropano! = 12°C, & Fiubricating oil = 232°C, @XC. Certain materials (ie., carbon tetrachloride, CCl) do not have a Flash Point, since there is no temperature at which their vapors can be ignitedChem tcal Storage — Hazard Class * \t a minimum, chemicals Should be segregated as: a — Corrosives Oxidizers = s ted Poisons or Toxic Chemicals Reactive (water or time sensitivey 9 ih bate. A ie ge, Time Weighted Average Concentration that existed during the Time ea crvals given by the sum of the individual Tis used in this calculation, ie, the Pei 1 Ti § masts th Time Interval from the overall’ time period, which for a TWA Gn ‘ontrast to a STEL) would total up to a full 8 hours, ie, E7_, Ti = 8 hours. ‘i = the ith Concentration Value of the single of imerest — ic, th bient gas or particulate concentration — that existed the specific ith ‘Time| EX. A worker was exposed, over his work shift, 10 various levels of n-pentane, and for varying periods of time, as shown in the tabulated exposure history below. The appropriate ACGIH (American Conference of Government Industrial Hygienists) Standards that apply to n-pentane are: the TLV-TWA = 600 ppm(vol), and the TLV-STEL= 750 ppm(vol). What was this employee's 8-hour TWA exposure to n-pentane? 2.0 hours 451 ppm (vol) 3.0 hours 728 ppm (vol.) LShours 619 ppm vol.) 1.5 hours 501 ppm (vol.)To solve this problem, we must apply above Equ.1 Twa aes TG + TaCp ++ TaCn Peidt Ty +T2 +e 4+Ty Twa = 2482) + (3)(728) + (1.5)(619) + (1.5)(601) 195.75, 24305415 a + The Time Weighted Average ~ 596 During the concluding 15 minutes of the final 1.5-hour segment of his workday, what would this worker's exposure to n-pentane have to have been so that his overall 8-hour TWA would have been in violation of the established ACGIH Threshold Limit Value? G00 = Lea TGs _ (2)(451) + (3)(728) + (1.5)(619) + (1.25)(501) + 0.256 aE An a 243415415 600= 580.09+= © > 600-580.09 > 19.91 C > (19.91)(32) > 637 The final 15-minute concentration level of n-pentane> 637 ppm(vol). Globally Harmonized System of Classification and Labeling of ChemicalsEX: An Office Machine Repair Technician was exposed to a relatively high concentration level of ozone from a malfunctioning copier he had been called upon to repair. He observed the operation of the machine for. ad minutes in order 40 diagnose its problems. He then fixed the copier by replacing a defective part Finally, he observed the operation of the then properly functioning machine for an additional 30 minutes to ensure that it was, in fact, working properly. His ozone exposures for the day on which he fixed this machine were as follows: Task Description Exposure Time Ozone Exposures Diagnostic Effort 30 min 289 ppb (vol.) Repair Effort 60 min 42 ppb (vol.) Repair Observing Time 30 min 93 ppb (vol.) Balance of the Work Day 6 hours 8 ppb (vol.) S16 7 > (5280) wilt + G.0X42) + (0503) + (e.0Ks) O35 +107 05+ 60 The PEL-TWA for ozone is 0.1 ppm (vol), and the PEL-STEL for this material is 4.3ppm (vol). What was this worker's 8-hour TWA to ozone? Did this worker experience a PEL-STEL violation? 1,000 ppb (vol.) = 1 ppm {vol.), PEL-TWA ozone = 100 ppb (vol.), & PEL-STEL ozone = 300 ppb (vol.). The same Office Machine Repair Technician had an ozone cone. of222 ppb(vol. If this technician spent 2.5 of the final 6 hours of that workday in his repair end if all his other repairs on that day mentioned indoor 8-ppb ozone background level, what would his new 8-hour TWA TO OZONE HAVE BEEN? (0.5)(289) + (1)(42) + (0.5)(93) + (3.5)(8) + (25)(222) bea 0541405435425 + The TWA = 102 ppb (vol.) > 0.1 ppm (vol.). + Clearly, this Technician had experienced an 8-hour TWA ozone exposure that exceeded the established OSHA PEL-TWA of 0.1 ppm (vol.)— 102 ppb (vol,) >0.1 ppm (vol).Tor any of the csablished parameters [66 . or the MAK], resulting from the combined effects of toxic, or hazardous components, whether s@* i air system that is being evaluated. To repeat ene me, air matrix, whether there is only a single vo ponent in it, or many such components. [Recommended Exposure Limit — Time Weighted Average % REL =11 mn TWA TWA, TWAs , ... 4 TWAn SOLE 71 ‘REL, REL, we REL2 iy iy RELn Effective Percent E: Level from the perspective of the] jure being| pe Weighted Average Concentration of the ith component in th mixture being evaluated. the listed Recommended Exposure Limit (or, in this case, the RIEL-TWA)} Js equal to oF less than 100%, then it can be inferred that the] Effective REX. for the mixture has not been excecded: if this % REL is greatcr| than 100%. then the inference is that the Effective REL for the mixture has been} x. John Smith, an Industrial Hygienist, working for the ABC Company| determined the following Time Weighted Average employee exposures to the| lowing list of four solvent vapors, for those workers who operated the| ompany's paint spray booth: What was the % T LV exposure of these workers? TWA TLV-IWA ‘12 ppm(vol) 50 ppm(vol) 17 ppm(vol) 100 ppm(vol) 55 ppm(ool) 200 ppm(vol) 91 ppm(vol) -- 400 ppm(vol) TWA, TWAz 4 TWAn: ee REL, i ‘RELz es as REL! an TWA Twa, % TLV =10010 73 Fry == b3 mn TWAn azigt a7 ig) ISSh yon TLV =1001D 7-1 Fv, 100(22 + 2 + soo + goo! = 92-25 Note: Ifthe © REL is cgual to oF less than 1006, then it can be inferred that the Effective REL for the mixture has not been execeded; if this % REL is greater then the inference is that the Effective REL for the mixture has beenKraft pulp mill employees involved in bleaching Kraft paper are Potentially exposed to both chlorine and chlorine dioxide. For these two chemicals, the published PEL-TWAs and PEL-STELs are as follows: Bleaching Gas PEL-TWA PEL-STEL Chlorine 500 ppb(vol) 1,000 ppb(vol) Chlorine Dioxide 100 ppb(vol) 300 ppb(vol) On a heavy bleaching day, one employee's dosimeters indicated that his 8-hour TWA exposures to these two materials had been 0.42 Ppm(vol) for chlorine, and 0.08 Ppm(vol) for chlorine dioxide. What was this employee's overall % PEL exposure to these hazardous vapors? Was his employer in violation of any OSHA Standards? We have the Employee's average 8- ppb(vol), and his 8-hour TWA chi Let us start with the ‘hour TWA chlorine exposure = 420 lorine dioxide counterpart = 80 ppb(vol). %PEL-TWA determination, using Equation % TLV =100[5 7 , 44 = oot 4 Waa, | TWA, 1 Thy, TLV, | TLV2 Tu, ! % PEL-TWA =100[3 7, ~~!) = 100/222 4 8) -164 500 100 | This is clearly a bad situation; it represents the case where the employee has | experienced approximately a 164% combined exposure ae to these two vapors. Now let us develop the “invalid” %PEL-STEL, that we may possibly be able to use as a measure of how good or bad things might be from the perspective of the Short Term Exposure Limit, again using Equation #2; thus: % TLV =20010 7.1 Frye] = LOOPEAL + WAS 4... 4 TWAny TLV, ‘TLV, TLV, TWA — 195429 4. 80, % PEL-STEL =100[D 7-1 Tw, ! = 10010 mg Saat =68.7 +. This Worker's %PEL (based on the 8-hour PEL-TWA Standard) = 164%,ey uae employer, the company operating the Kraft pulp mill, is in an itaoplieg erely so, as a matter of fact — of the established PEL-TWA Standard, nen ‘0 an environment that contains, simultaneously, both of these two very lous, toxic, and irritating chemicals. It is also interesting to note that neither of these two chemicals’ individual PEL-TWAs has been exceeded — at least as the exposures have been defined in this problem — when each is considered by itself. Effective Exposure Limit that exists for any equilibrium vapor phase that is in contact with any well-defined liquid mixture containing two or more different volatile components. It can be applied to any of the established parameters [ie., the TLV, the PEL, the REL, or the MAK]; the value of the individual Exposure Limit Standard for each of the components in the liquid mixture must be known. Equation #3 assumes that the overall composition of the vapor phase existing, above a volatile liquid mixture will be identical to the mass composition of the liquid mixture, and although this would rarely — if ever — be true, the Equation is considered to be a useful tool for determining “Order-of-Magnitude- “Approximations” for the concentrations of the components in the vapor phase. This Equation was proposed for use by the ACGIH; therefore, it is used most commonly for the determination of this organization's Exposure Limit Standard — namely, the TLY; it can, however, be applied to any of the commonly used Exposure Limit Standards. Where: ‘TLVeffective = the Effective Exposure Limit — in this case a Threshold Limit Value. This parameter can be evaluated for any of the established Exposure Limits — i.c.. for a PEL. REL. or RAK. ete. Remember, however, that this relationship applies only to the vapor phase existing above a mixiure of volatile liquids. The user must understand that the result of this calculation represents an Order-of Magnitude-Approximation” only. Also the calculated TLVeffective in this case will always be expressed in mass concentration units, mg /m?. NEVER the more common volumetric unit, ppm(vol) fi — the Weight Fraction of the ith component in the mixture of volatile liquid components being na aft eoupeme of nes considered. i¢.the [Sor ofthe liga mire 1+ ‘TLVi — the Threshold Limit Value [TLV] — this could be any established Exposure Limit — of the ith component, must always be expressed in mass-based units of concentration. mg/m*, NEVER the more common volume-based unit, ppm(vol).. "3 The following three Equations, ds 4, 5, and 6, are used to convert sets of Mass-Based Concentration units to their Volume-Based Concentration equivalents [e-g., converting from concentrations expressed in units such as mg/m? to those in one of the common vollumetric= | based sets of units, such as ppm(vol)}. The first Equation, #4, would be used to affect this conversion under conditions of Normal Temperature and Pressure [NTP]; the second, #5, would be used for conversions at Standard Temperature and Pressure [STP] conditions, while the third, #6, applies to any mass-to-volume-based concentration conversion, regardless of the conditions of ambient temperature and pressure. Equation 4 2445 Coot = Taw, |mass) @NTP the Volume-Based Concentration of the component of inferest, namely. the Ith component. i ppmvol) the Mass-Rased Concentration of the same component. namely the ith component. in mg fom & MW, = the Molecular Weight of the same ith component Eution 2a Cut = Fig UGaee] @STP Equation #6: Cm Fe ni snvconieet ose ‘T = the ambient Absolute Temperature. in wome witahle unit of able tempetire. scat pebanis 1P~ dhe amabnent Baronets Pres R = the Univers Ges Couwmn sone satel [barometric provre and entperane conlitons for Cuanple” any of the flowing vale of ts Vutversal Cas Constant could Be sed = o.on2 iteretmorpneres) 62 z6fltterXmum He) 1,63 1 LUBE Feet) Cntisbarey ORHCmotey oar Ono! . memoryv > i vapor degreasing Solvent is made up of the following four chemicals, according to the following proportions by weight: Component Weight % Molecular Number Component ___in Solvent ___TLV-TWA Weight 1.__Freon 1i_25% __1,000 ppm(vol) _137.38 2. Freon 113 55% 1,000 ppm(vol} 187.38 = Methyl Chloroform 15% 350 ppm(vol) _133.41 4. Methylene Chloride 5% 50 ppm(vol) _84.93 Assuming that the composition of the degreasing vapor is equal to that of the liquid mixture [a very unlikely condition}, what would be the “Order-of- Magnitude-Approximation” for the Effective TLV Exposure Limit fin both mg/m3 & ppm(vol)] for the vapor space in this vapor degreaser? You may assume that this machine is operated at STP. What would the: corresponding “Order-of-Magnitude- Approximations” for the vapor space concentrations of each of these four components be [again, in both mg/m3 & ppm(vol)] on the assumption that these four concentrations, in combination, actually resulted in this vapor space being operated at the calculated overall Effective TLV Exposure Limit? oe a Mic] @ STP Conditions 1. For Freon tt: 137.38, 137.380 Conte = Qype TLV-TWA pees = 6.175 mpi” 2. For Freon 113: 187.38 187,380 Comodo 7245 0) = “ag = BE TLV-TWAp me 1:3 = 8.361 mg/m? TLV-TWA secmyine commae = 190 mein” 1?aa Rant Tae EE eo t eee Bin, 1, or Freon U1: 2. For Freoa 113: ee + Be gure Re 1 Come Co, 3. For Methy! Chloroform: Cone epcenten 4. For Memylene Chloride: Coe en ] (ae. 85) TW mW, ~. The effective overall TLV for this mixture of solvent vapors = 2,262 mg/m3. may = 04261.910.25) = 56547 Cymans ~ 565 00/0 evn = @,261.99055) = 124408 Carns ~ 1244 angie = (2,261.9)(0.15)= 339.28 Crepcasnaeen ~ 339 mph = (2,261.9)0.08) = 113.10 Conepimecaseee ~ 113 magi? Wace =| TO ES oe sans * Kuo * Zod 18 1 a 1 Waee © Teniet Ae i Cut, # FGlcae,] @ sTP Consens [ean a8) 1, Foe Feo tt nat snare Corse © BAGG) « SEE = oe Coma = 02 preted 2. For Prova 11: = BA = TER Cotemnen = pygg BON = Apa = ETE Comauis = 1496p) 3, For Methyt Chloroform: BA 1.03.27 Colgan * Tyg OMT = aay = 5697 Coampmanon ~ ST 9HKYON) 4. or Methylene Chloride: » BA 2SMsT Co aeperere * Eagi(tt00) = SESE Campos commas ~ SO ppIEVOHD = MHconcentrations. Freon 11 Concentration Freon 113 Concentration Methyl Chloroform Concentration Methylene Chloride Concentration Finally, summarizing these results, which are the data set that was asked for in the problem statement, we have the following tabulation of the ambient solvent = 565 mg/m3 =92 ppm(vol) = 57 ppm(vol) 113 mg/m3 =30 ppm(vol)