Industrial Hygiene ERT 312 Lecture 7 – Identification, Evaluation and Control Identification Able to identify the hazard from single exposure or potential combined effects from multiple exposures Require deep study on the chemical process, operating conditions and operating procedures Source of information; 2 Process design descriptions Operating instructions Safety reviews Equipment specs Etc. 3 4 Material Safety Data Sheets (MSDS) Chemical Safety Data Sheets (CSDS) MSDS lists the physical properties of a substance that may be required to determine the potential hazards of the substance Manufacturer/supplier is responsible to provide the MSDS to their customers * Example of MSDS 5 Evaluation To determine the extent and degree of employee exposure to toxicants and physical hazards in the workplace Once exposure data obtained, comparison is being made to acceptable occupational health standards eg: TLVs, PELs and IDLH concentrations (page 56) Then, the decision on proper control measure can be made accordingly in order to reduce the risk 6 Threshold Limit Value (TLV) of a chemical substance is a level to which it is believed a worker can be exposed day after day for a working lifetime without adverse health effects The Permissible Exposure Limit (PEL or OSHA PEL) is a legal limit for exposure of an employee to a substance or physical agent. For substances it is usually expressed in parts per million (ppm), or sometimes in milligrams per cubic metre (mg/m3) IDLH is an initials for Immediately Dangerous to Life and Health, and is defined by the NIOSH as exposure to airborne contaminants that is "likely to cause death or immediate or delayed permanent adverse health effects or prevent escape from such an environment” 7 Table 2.7 – established by ACGIH 8 TLVs units – ppm, mg/m3, For dust – mg/m3 or mppcf For vapors, concentration in ppm; Cppm = = 22.4 T 1 3 ( )( )(mg / m ) M 273 P T 3 0.08205( )(mg / m ) PM Equation 1 Equation 2 T (temperature, Kelvin), P (absolute pressure, atm) M (molecular weight, g/g-mol) 9 Problem 2.7 (Crowl & Louvar, 2002) How much acetone liquid (ml) required to produce a vapor concentration of 200 ppm in a room of dimension 3 x 4 x 10 m? Given T is 25°C, P is 1 atm, molecular weight is 58.1 and specific gravity is 0.7899. 10 11 Evaluation Exposure of Organic Toxicants The simplest way to determine worker exposures is through continuous monitoring of the air concentrations. For computation of continuous concentration data C(t) the TWA concentration, 1 TWA C (t )dt 80 tw C(t) tw 12 Equation 3 the concentration of the toxicant in the air, ppm @ mg/m3 the worker shift time in hours Sometimes, continuous monitoring is not feasible. Therefore, intermittent samples representing worker exposure at fixed points of time are obtained. C1T1 C2T2 ... CnTn TWA 8 Single Component Exposure, workers are overexposed if the sum of conc. > permitted TWA 13 Equation 4 Example 3.3 (Crowl & Louvar, 2002) Determine the 8-hr TWA worker exposure if the worker is exposed to toluene vapors as follows; Solution: Duration (h) Concentration (ppm) 2 110 2 330 4 90 C1T1 C2T2 ... CnTn TWA 8 Answer: 155 ppm 14 Equation 5 For a case of more than 1 toxicant is present in the workplace; the combined exposures from multiple toxicants with different TLV-TWAs is determined by; Ci i 1 (TLV TWA) i n n Ci (TLV-TWA)i 15 If the sum of the equation > 1, workers are overexposed Equation 6 the total number of toxicants the conc. of toxicant i with respect to the other toxicants the TLV-TWA for toxicant sp. i The mixture also TLV-TWA can be computed using equation below; n (TLV TWA) mix C i 1 i Ci i 1 (TLV TWA ) i n If the total mixture conc. > (TLVTWA)mix , workers are overexposed 16 Equation 7 Example 3.2 (Crowl & Louvar, 2002) Air contains 5 ppm of diethylamine (TLV-TWA = 10 ppm), 20 ppm cyclohexanol (TLV-TWA = 50 ppm) and 10 ppm of propylene oxide (TLV-TWA = 20 ppm). What is the mixture TLV-TWA and has this level been exceeded? 17 Evaluation of exposure to dusts Dusts particle size range of 0.2-0.5 µm Particles > 0.5 µm unable to penetrate the lungs Particle < 0.2 µm settle out too slowly, most exhaled with the air Units: mg/m3 @ mg/mppcf n TLVmix 18 C i 1 i Ci i 1 TLV i n Equation 8 Example 3-5 (Crowl & Louvar, 2002) Determine the TLV for a uniform mixture of dusts containing the following particles; Type of dust Concentration (wt.%) TLV (mppcf) Nonasbestiform 70 20 Quartz 30 2.7 Solution: Answer: 6.8 mppcf 19 Evaluation of exposure to Noise Noise levels are measured in decibels (dB) A dB is a relative logarithmic scale used to compare the intensities of two sounds. If one sound is at intensity I and another sound is at intensity Io, then the difference in intensity levels in dB is given; Noise intensity (dB) = - 10 log10(I/Io) 20 21 Example 3.6 (Crowl & Louvar, 2002) Determine whether the following noise level permissible with no additional control features: 22 Noise Level (dBa) Duration (hr) Max. allowed (hr) 85 3.6 No limit 95 3.0 4 110 0.5 0.5 is Solution: Ci i 1 (TLV TWA) i n (TLV – TWA)mix, noise = Ci 3.6 3 0.5 1.75 i 1 (TLV TWA) no limit 4 0.5 i n The sum > 1.0, workers are immediately required to wear ear protection. For long term plan, noise reduction control should be applied. 23 Evaluation of exposure to Toxic Vapors Enclosure volume, V Ventilation rate, Qv (volume/time) C ppm QmR gT kQ v PM Equation 9 24 Volatile concentration, C (mass/volume) Volatile rate out, kQvC (mass/time) 106 Evolution rate of volatile, Qm (mass/time) Assumptions The calculated concentration is an average concentration in the enclosure. Localized conditions could result in significantly higher concentrations; workers directly above an open container might be exposed to higher concentrations A steady-state condition is assumed; that is, the accumulation term in the mass balance is 0 The non-ideal mixing factor, k varies from 0.1 – 0.5 for most practical situations. For perfect mixing, k = 1 25 Example 3.7 (Crowl & Louvar, 2002) An open toluene container in an enclosure is weighed as a function of time, and it is determined that the average evaporation rate is 0.1 g/min. the ventilation rate is 100 ft3/min. the temperature is 80oF and the pressure is 1 atm. Estimate the concentration of toluene vapor in the enclosure, and compare your answer to the TLV for toluene of 50 ppm. 26 Solution Use equation 9 to solve the problem From data given; Qm 0.1 g/min Rg 0.7302 ft3.atm/lb-mol.oR T 80oF = 540oR Qv 100 ft3/min M 92 lbm/lb-mol P 1 atm k ? C ppm QmR gT kQ v PM 106 Answer: kCppm = 9.43 ppm K varies from 0.1 – 0.5, therefore Cppm may vary from 18.9 – 94.3 ppm. Actual vapor sampling is recommended to ensure that TLV is not exceeded 27 Estimating the vaporization rate of a liquid Qm Qm Open Vessel Chemical Spill Volatile Substances 28 General expression for vaporization rate, Qm (mass/time): MKA( P p) Qm RgTL sat M K Rg TL 29 Equation 10 Molecular weight of volatile substance mass transfer coefficient (length/time) for an area A ideal gas constant absolute temperature of the liquid For most cases, Psat >> p; MKAP Qm RgTL sat Equation 11 The equation is used to estimate the evaporation rate of volatile from an open vessel or a spill of liquid 30 To estimate the concentration of volatile in enclosure resulting from evaporation of a liquid; Equa. 11 used in Equa .9 Most events, T = TL K 31 sat C ppm KATP 6 10 kQv PTL Equation 12 sat C ppm KAP 6 10 kQv P gas mass transfer coefficient Equation 13 Estimation of K, gas mass transfer coefficient; K aD a D 32 constant gas-phase diffusion coeeficient 2/3 Equation 14 To determine the ratio of the mass transfer coefficient between species K and a reference species Ko; K D K o Do 2/3 Equation 15 The gas-phase diffusion coefficients are estimated from the molecular weight, M of the species; D Mo Do M 33 Equation 16 Combined equation 15 & 16, simplified; Mo K Ko M Kwater 34 0.83 cm/s 1/ 3 Equation 17 Example 3.8 (Crowl & Louvar, 2002) A large open tank with a 5-ft diameter contains toluene. Estimate the evaporation rate from this tank assuming a temperature of 77oF and a pressure of 1 atm. If the ventilation rate is 3000 ft3/min, estimate the concentration of toluene in this workplace enclosure. 35 Evaluation of exposure during vessel filling operations For this case, volatile emissions are generated from 2 sources: Evaporation of a liquid, (Qm)1 Displacement of the vapor in the vapor space by the liquid filling the vessel, (Qm)2 Therefore, the net generation of volatile; (Qm) = (Qm)1 + (Qm)2 36 Equation 18 Total Source = Evaporation + Displaced Air Volatile in Vapor Evaporation Liquid Vessel 37 MKAP (Qm )1 RgTL (Qm ) 2 rf Vc v rf v 38 sat Equation 19 Equation 20 constant filling rate of the vessel (time-1) density of the volatile vapor Hence, the net source term; Equation 20 sat MP Qm (Qm )1 (Qm ) 2 (rf Vc KA) RgTL Equation 21 sat C ppm 39 P 6 (rf Vc KA) 10 kQv P Problem 3.24 (Crowl & Louvar, 2002) 55-gallon drums are being filled with 2-butoxyethanol. The drums are being splash-filled at the rate of 30 drums per hour. The bung opening through which the drums are being filled has an area of 8 cm2. estimate the ambient vapor concentration if the ventilation rate is 3000 ft3/min. the vapor pressure for 2-butoxyethanol is 0.6 mm Hg under these conditions. 2-butoxyethanol chemical formula: HOCH2C2HOC4H9 40 Solution: 41 Appendix A 42 Appendix B Conversion of Fahrenheit (°F) to Rankine (°R) 1st step Convert Fahrenheit to Celcius 2nd step Convert Celcius to Kelvin K 3rd step Convert Kelvin to Rankine TF 32 TC 1 .8 T TC 273.15 TR 1.8TK 43