A simple, fast, sensitive, and economical field method was developed and evaluated for the determination of hexavalent chromium (CrVI) in environmental and workplace air samples. By means of ultrasonic extraction in combination with a strong anion-exchange solid-phase extraction (SAE-SPE) technique, the filtration, isolation, and determination of CrVI in the presence of trivalent chromium (CrIII) and potential interferents was achieved. The method entails (1) ultrasonication in basic ammonium buffer solution to extract CrVI from environmental matrixes; (2) SAE-SPE to separate CrVI from CrIII and interferences; (3) elution/acidification of the eluate; (4) complexation of chromium with 1,5-diphenylcarbazide; and (5) spectrophotometric determination of the colored chromium-diphenylcarbazone complex. Several critical parameters were optimized in order to effect the extraction of both soluble (K2CrO4) and insoluble (PbCrO4) forms of CrVI without inducing CrIII oxidation or CrVI reduction. The method allowed for the dissolution and purification of CrVI from environmental and workplace air sample matrixes for up to 24 samples simultaneously in less than 90 min (including ultrasonication). The results demonstrated that the method was simple, fast, quantitative, and sufficiently sensitive for the determination of occupational exposures of CrVI. The method is applicable for on-site monitoring of CrVI in environmental and industrial hygiene samples.
A polysulfone microporous membrane module was investigated for control of 1-butanol-contaminated gas streams. A diurnal loading condition, using two different butanol concentrations, was used to simulate startup and stop conditions associated with shift work. The membrane module was also used to remove 1-butanol from air under continuous loading conditions in a bioreactor. The reactors were seeded with a mixed bacterial consortium capable of butanol biodegradation. Biokinetic parameters for butanol utilization were determined for the culture to be a maximum specific utilization rate (k) equal to 4.3 d -1 and a half saturation constant (K s ) equal to 8.9 mg L -1. A biofilter running only with diurnal loading conditions giving a "40-hr workweek" had an average 1-butanol removal rate of 29% (111 ppm, 74 gm -3 hr -1 ) from a 350-ppm influent at the end of an 8-hr operational day. End-of-day removal varied between 4 and 67% during the operational period. With continuous steady-state operation followed by placement on a diurnal loading schedule and influent butanol concentrations increased to 700 ppm, butanol removal averaged 38% (269 ppm, 145 gm -3 hr -1 ). Under continuous loading, steady-state conditions, 1-butanol removal from the airstream was greater than 99% (200 ppm, 73 gm -3 hr -1 ). These results suggest that the bioreactor can be operated on a diurnal schedule or 40-hr week operational schedule without any decline in performance.
1,6-Hexamethylene diisocyanate (HDI) exposures were measured during polyurethane enamel spray painting at four Air Force bases. Breathing zone samples were collected for HDI monomer and polyisocyanates (oligomers) using three sampling methods: NIOSH Method 5521, the Iso-Chek sampler, and the total aerosol mass method (TAMM). Exposures to HDI monomer are low when compared to current occupational exposure limits; the highest 8-hr time-weighted average (TWA) exposure found was 3.5 micrograms/m3, below the American Conference of Governmental Industrial Hygienists (ACGIH) threshold limit value (TLV) of 34 micrograms/m3. HDI oligomer levels were higher; mean task exposures indicated by either the Iso-Chek sampler or TAMM are above the Oregon ceiling limit of 1 mg/m3. Eight-hour TWA exposures, however, were much lower, with only one exceeding the Oregon standard of 0.5 mg/m3. Poor worker practices commonly observed during this study included: standing in downwind positions so paint overspray passed through breathing zones; spraying toward other painters; and using excessive paint spray gun air cap pressures. Workers should stand in upwind orientation relative to the aircraft being painted, causing overspray to move away from the painter's breathing zone; adjust their position to prevent spraying other painters or limit paint application to one worker at a time; and use air cap pressure gauges prior to spraying to limit spray gun air cap pressures and reduce paint overspray generation rates. These improved techniques will result in reduced worker exposures to isocyanates.
A comparison study of isocyanate sampling methods for 1,6-hexamethylene diisocyanate (HDI) monomer and HDI-based polyisocyanates was conducted in spray painting environments. This study compared the performance of the Iso-chek sampler against existing and proposed National Institute of Occupational Safety and Health (NIOSH) and Occupational Safety and Health Administration (OSHA) monitoring methods for HDI-based isocyanates. Six methods for monitoring HDI monomer and polyisocyanate levels were compared. Fifty-eight sampling sets were collected during spray painting of aircraft and aircraft parts at four U.S. Air Force bases. Impinger and cassette samplers were mounted side-by-side on a mannequin located in paint overspray areas. For HDI monomer sampling results, there were no significant differences between NIOSH 5521, NIOSH 5522, OSHA 42, MAP (the proposed NIOSH method), and the Iso-Chek. For HDI-based polyisocyanates, NIOSH 5522, NIOSH 5521, Iso-Chek, and the Total Aerosol Mass Method (TAMM) were significantly different from one another. There was no significant difference between MAP and the NIOSH 5522 polyisocyanate sampling results. This study suggests the Iso-Chek and MAP sampling methods compare favorably with established methods for monitoring in HDI spray painting environments and the Total Aerosol Mass Method provides a reasonable upper boundary for estimating HDI polyisocyanate concentrations. The results also reemphasize aerosol sampling physics and sampler geometries must be carefully considered and appropriate samplers used when measuring exposures in spray paint environments where particulates are of the inhalable size.
A dense-phase latex rubber tube and a polyporous propylene hollow-fiber membrane module (HFMM) were investigated for control of benzene-contaminated gas streams. The abiotic mass flux observed through the latex tube was 3.9 13 mg/(min.m(2)) for 150 ppm of benzene at various gas and liquid flow rates, while a 100-fold lower mass flux was observed in the HFMM. After seeding with an aromatic-degrading culture enriched from activated sludge, the observed removal was 80% of 150 ppm, corresponding to a mass flux of 45 mg/(min.m(2)). The observed mass flux through the HFMM during biofiltration also rose, to 0.4 mg/(min.m(2)). Because the HFMM had a 50-fold higher surface area than the latex tube, the observed benzene removal was 99.8%. Compared to conventional biofilters, the two reactors had modest elimination capacities, 2.5 18 g/(m(3).h) in the latex tube membrane bioreactor and 4.8 58 g/(m(3).h) in the HFMM. Although the HFMM had a higher elimination capacity, the gas-phase pressure drop was much greater.
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