Estimation of required monitoring time for obtaining validation data in enclosed spaces

Methods for estimating airborne contaminant concentrations at specific locations within enclosed spaces, such as mathematical models and computational fluid dynamics (CFD), often are validated against directly measured concentrations. However, concentration variation with time introduces uncertainty into the measured concentration. Failure to determine monitoring time requirements can lead to errors in quantifying representative concentrations, which are likely to be attributed to errors in the method being validated. In the current study, to obtain the representative concentrations at multiple locations with a direct reading instrument, we used the standard deviation ratio (SDR) method to determine the required minimum monitoring time within a specified precision limit. To demonstrate the use of the SDR approach in constructing precision confidence intervals, tracer gas concentrations at nine sampling locations in an experimental room were measured to obtain population parameters. Three flow rates of 0.9, 3.3 and 5.5 m(3) min(-1) were employed and contaminant concentrations were measured using a photoionization analyser. Monitoring time requirements varied substantially with location within the room and were strongly dependent upon the flow rate of air through the room. The proposed method would be very useful for industrial hygienists and indoor air researchers who sometimes need to obtain several hundred measured concentrations for validation purposes or to perform tests under repeatable conditions in enclosed spaces. This study also showed that the proposed method can be used to devise efficient indoor monitoring strategies.     

Size-selective sampling of particulates using a physiologic sampling pump

Recent laboratory research indicates physiologic sampling of gas and vapor may provide more representative estimates of personal exposures than traditional methods. Modifications to the physiologic sampling pump (PSP) used in that research are described which extend its usefulness to size-selective sampling of particulates. PSPs used in previous research varied motor speed to keep sampling proportional to the subject's inhalation. This caused airflow and particle velocities through the collection device to continually change making those pumps unsuitable for sampling particulates. The modified implementation of the PSP pulls a constant airflow into and through a cyclone, then uses valves to either direct the airflow through, or divert the airflow around, the sampling filter. By using physiologic inputs to regulate the fraction of each second that air flows through the sampling filter, samples may be collected in proportion to inhalation rate. To evaluate the performance of a functional prototype 5 different sizes of monodisperse aerosols of ammonium fluorescein were generated by a vibrating orifice aerosol generator and introduced into a calm air chamber. To simulate different inhalation rates the valves of the PSP were energized using 9 different duty cycles. Efficiency curves are presented and compared to a standard respirable convention by bias mapping. The performance of the modified cyclone used in the PSP sampling head compared favorably with a commercially available cyclone of the same model, operating at a constant airflow (± 10% over almost all the size distributions of concern). The new method makes physiologic sampling of the respirable fraction of particulates feasible.     

Portable XRF analysis of occupational air filter samples from different workplaces using different samplers: final results, summary and conclusions

This paper concludes a five-year program on research into the use of a portable X-ray fluorescence (XRF) analyzer for analyzing lead in air sampling filters from different industrial environments, including mining, manufacturing and recycling. The results from four of these environments have already been reported. The results from two additional metal processes are presented here. At both of these sites, lead was a minor component of the total airborne metals and interferences from other elements were minimal. Nevertheless, only results from the three sites where lead was the most abundant metal were used in the overall calculation of method accuracy. The XRF analyzer was used to interrogate the filters, which were then subjected to acid digestion and analysis by inductively-coupled plasma optical-emission spectroscopy (ICP-OES). The filter samples were collected using different filter-holders or "samplers" where the size (diameter), depth and homogeneity of aerosol deposit varied from sampler to sampler. The aerosol collection efficiencies of the samplers were expected to differ, especially for larger particles. The distribution of particles once having entered the sampler was also expected to differ between samplers. Samplers were paired to allow the between-sampler variability to be addressed, and, in some cases, internal sampler wall deposits were evaluated and compared to the filter catch. It was found, rather surprisingly, that analysis of the filter deposits (by ICP-OES) of all the samplers gave equivalent results. It was also found that deposits on some of the sampler walls, which in some protocols are considered part of the sample, could be significant in comparison to the filter deposit. If it is concluded that wall-deposits should be analyzed, then XRF analysis of the filter can only give a minimum estimate of the concentration. Techniques for the statistical analysis of field data were also developed as part of this program and have been reported elsewhere. The results, based on data from the three workplaces where lead was the major element present in the samples, are summarized here. A limit of detection and a limit of quantitation are provided. Analysis of some samples using a second analyzer with a different X-ray source technology indicated reasonable agreement for some metals (but this was not evaluated for lead). Provided it is only necessary to analyze the filters, most personal samplers will provide acceptable results when used with portable XRF analysis for lead around applicable limit values.     

用大型底栖动物和ODP系统评价珠江的有机污染

采用大型底栖动物需氧有机体百分率ODP(oxygen demander percentage)法对广州珠江前航道、西航道和流溪河的下游段进行河流有机污染评价.结果显示:底栖动物需氧类群密度在三河段间分布确有显著性差异,并根据其ODP可以判断流溪河水质相对较好,水质级别为中国地表水环境质量标准(EQSSW)Ⅳ级,西航道和前航道水质级别都为Ⅴ级.通过测试,这一方法能成功地应用在珠江及流溪河,且该法可以较好地匹配于EQSSW五级评价系统,初步认为ODP系统可以成为一个较好的河流水质生物监测方法.图3表4参13     

Validation of an evacuated canister method for measuring part-per-billion levels of chemical warfare agent simulants

The National Institute for Occupational Safety and Health (NIOSH) research on direct-reading instruments (DRIs) needed an instantaneous sampling method to provide independent confirmation of the concentrations of chemical warfare agent (CWA) simulants. It was determined that evacuated canisters would be the method of choice. There is no method specifically validated for volatile organic compounds (VOCs) in the NIOSH Manual of Analytical Methods. The purpose of this study was to validate an evacuated canister method for sampling seven specific VOCs that can be used as a simulant for CWA agents (cyclohexane) or influence the DRI measurement of CWA agents (acetone, chloroform, methylene chloride, methyl ethyl ketone, hexane, and carbon tetrachloride [CCl4]). The method used 6-L evacuated stainless-steel fused silica-lined canisters to sample the atmosphere containing VOCs. The contents of the canisters were then introduced into an autosampler/preconcentrator using a microscale purge and trap (MPT) method. The MPT method trapped and concentrated the VOCs in the air sample and removed most of the carbon dioxide and water vapor. After preconcentration, the samples were analyzed using a gas chromatograph with a mass selective detector. The method was tested, evaluated, and validated using the NIOSH recommended guidelines. The evaluation consisted of determining the optimum concentration range for the method; the sample stability over 30 days; and the accuracy, precision, and bias of the method. This method meets the NIOSH guidelines for six of the seven compounds (excluding acetone) tested in the range of 2.3-50 parts per billion (ppb), making it suitable for sampling of these VOCs at the ppb level.     

Feasibility of detection and quantification of gas-phase carbonyls in indoor environments using PFBHA derivatization and solid-phase microextraction (SPME)

Solid-phase microextraction (SPME) was evaluated for the detection and quantification of the gas-phase carbonyls: citronellal, glyoxal, methylglyoxal, and beta-ionone. Prepared air samples containing the carbonyl compounds were collected at a flow rate of 2.8 L min(-1) in an impinger containing a 25% reagent water/75% methanol collection liquid. The aqueous samples were then derivatized with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA), extracted with a PDMS/DVB coated SPME fiber, and analyzed by GC-MS. Detection limits with a sample air volume of 76 L were calculated to be 0.03 ppbv, 0.34 ppbv, 0.12 ppbv, and 0.28 ppbv for citronellal, glyoxal, methylglyoxal, and beta-ionone, respectively.     

Phytoremediation of Atrazine by Poplar Trees: Toxicity,Uptake, and Transformation

Toxicity, uptake, and transformation of atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine] by three species of poplar tree were assessed. Poplar cuttings were grown in sealed flasks with hydrophonic solutions and exposed to various concentrations of atrazine for a period of two weeks. Toxicity effects were evaluated by monitoring transpiration and measuring poplar cutting mass. Exposure to higher atrazine concentrations resulted in decrease of biomass and transpiration accompanied by leaf chlorosis and abscission. However, poplar cuttings exposed to lower concentrations of atrazine grew well and transpired at a constant rate during experiment periods. Poplar cuttings could take up, hydrolyze, and dealkylate atrazine to less toxic metabolites. Metabolism of atrazine occurred in roots, stems, and leaves and became more complete with increased residence time in tissue. These results suggest that phytoremediation is a viable approach to removing atrazine from contaminated water and should be considered for other contaminants.