Preparation, certification and interlaboratory analysis of workplace air filters spiked with high-fired beryllium oxide

Occupational sampling and analysis for multiple elements is generally approached using various approved methods from authoritative government sources such as the National Institute for Occupational Safety and Health (NIOSH), the Occupational Safety and Health Administration (OSHA) and the Environmental Protection Agency (EPA), as well as consensus standards bodies such as ASTM International. The constituents of a sample can exist as unidentified compounds requiring sample preparation to be chosen appropriately, as in the case of beryllium in the form of beryllium oxide (BeO). An interlaboratory study was performed to collect analytical data from volunteer laboratories to examine the effectiveness of methods currently in use for preparation and analysis of samples containing calcined BeO powder. NIST SRM(?) 1877 high-fired BeO powder (1100 to 1200 °C calcining temperature; count median primary particle diameter 0.12 μm) was used to spike air filter media as a representative form of beryllium particulate matter present in workplace sampling that is known to be resistant to dissolution. The BeO powder standard reference material was gravimetrically prepared in a suspension and deposited onto 37 mm mixed cellulose ester air filters at five different levels between 0.5 μg and 25 μg of Be (as BeO). Sample sets consisting of five BeO-spiked filters (in duplicate) and two blank filters, for a total of twelve unique air filter samples per set, were submitted as blind samples to each of 27 participating laboratories. Participants were instructed to follow their current process for sample preparation and utilize their normal analytical methods for processing samples containing substances of this nature. Laboratories using more than one sample preparation and analysis method were provided with more than one sample set. Results from 34 data sets ultimately received from the 27 volunteer laboratories were subjected to applicable statistical analyses. The observed performance data show that sample preparations using nitric acid alone, or combinations of nitric and hydrochloric acids, are not effective for complete extraction of Be from the SRM 1877 refractory BeO particulate matter spiked on air filters; but that effective recovery can be achieved by using sample preparation procedures utilizing either sulfuric or hydrofluoric acid, or by using methodologies involving ammonium bifluoride with heating. Laboratories responsible for quantitative determination of Be in workplace samples that may contain high-fired BeO should use quality assurance schemes that include BeO-spiked sampling media, rather than solely media spiked with soluble Be compounds, and should ensure that methods capable of quantitative digestion of Be from the actual material present are used.     

In vitro methane removal by volcanic pumice soil biofilter columns over one year

Soil methane (CH(4)) biofilters, containing CH(4)-oxidizing bacteria (methanotrophs), are a promising technology for mitigating greenhouse gas emissions. However, little is known about long-term biofilter performance. In this study, volcanic pumice topsoils (0-10 cm) and subsoils (10-50 cm) were tested for their ability to oxidize a range of CH(4) fluxes over 1 yr. The soils were sampled from an 8-yr-old and a 2-yr-old grassed landfill cover and from a nearby undisturbed pasture away from the influence of CH(4) generated by the decomposing refuse. Methane was passed through the soils in laboratory chambers with fluxes ranging from 0.5 g to 24 g CH(4) m(-3) h(-1). All topsoils efficiently oxidized CH(4). The undisturbed pasture topsoil exhibited the highest removal efficiency (24 g CH(4) m(-3) h(-1)), indicating rapid activation of the methanotroph population to the high CH(4) fluxes. The subsoils were less efficient at oxidizing CH(4) than the topsoils, achieving a maximum rate oxidation rate of 7 g CH(4) m(-3) h(-1). The topsoils exhibited higher porosities; moisture contents; surface areas; and total C, N, and available-P concentrations than the subsoils, suggesting that these characteristics strongly influence growth and activity of the CH(4)-oxidizing bacteria. Soil pH values and available-P levels gradually declined during the trial, indicating a need to monitor chemical parameters closely so that adjustments can be made when necessary. However, other key soil physicochemical parameters (moisture, total C, total N) increased over the course of the trial. This study showed that the selected topsoils were capable of continually sustaining high CH(4) removal rates over 1 yr, which is encouraging for the development of biofilters as a low-maintenance greenhouse gas mitigation technology.     

CH4/CO2 ratios indicate highly efficient methane oxidation by a pumice landfill cover-soil

Landfills that generate too little biogas for economic energy recovery can potentially offset methane (CH₄) emissions through biological oxidation by methanotrophic bacteria in cover soils. This study reports on the CH₄ oxidation efficiency of a 10-year old landfill cap comprising a volcanic pumice soil. Surface CH₄ and CO₂ fluxes were measured using field chambers during three sampling intervals over winter and summer. Methane fluxes were temporally and spatially variable (?0.36 to 3044 mg CH₄ m^?2 h^?1); but were at least 15 times lower than typical literature CH₄ fluxes reported for older landfills in 45 of the 46 chambers tested. Exposure of soil from this landfill cover to variable CH₄ fluxes in laboratory microcosms revealed a very strong correlation between CH₄ oxidation efficiency and CH₄/CO₂ ratios, confirming the utility of this relationship for approximating CH₄ oxidation efficiency. CH₄/CO₂ ratios were applied to gas concentrations from the surface flux chambers and indicated a mean CH₄ oxidation efficiency of 72%. To examine CH₄ oxidation with soil depth, we collected 10 soil depth profiles at random locations across the landfill. Seven profiles exhibited CH₄ removal rates of 70–100% at depths <60 cm, supporting the high oxidation rates observed in the chambers. Based on a conservative 70% CH₄ oxidation efficiency occurring at the site, this cover soil is clearly offsetting far greater CH₄ quantities than the 10% default value currently adopted by the IPCC.     

Effects of Riparian Vegetation and Watershed Urbanization on Fishes in Streams of the Mid‐Atlantic Piedmont (USA)1

Abstract: The joint influences of riparian vegetation and urbanization on fish assemblages were analyzed by depletion sampling in paired forested and nonforested reaches of 25 small streams along an urbanization gradient. Nonforested reaches were narrower than their forested counterparts, so densities based on surface area differ from linear densities (based on reach length). Linear densities (based on number or biomass of fish) of American eel, white sucker and tesselated darter, and the proportion of biomass of benthic invertivores were significantly higher in nonforested reaches, while linear densities of margined madtom and the number of pool species were significantly higher in forested reaches. Observed riparian effects may reflect differences in habitat and algal productivity between forested and nonforested reaches. These results suggest that relatively small‐scale riparian restoration projects can affect local geomorphology and the abundance of fish. Dense vegetative cover in riparian zones and similar or analogous habitats in both forested and nonforested reaches, the relatively small scale of the nonforested reaches, and the low statistical power to detect differences in abundance of rare species may have limited the observed differences between forested and nonforested reaches. There was a strong urbanization gradient, with reductions of intolerant species and increases of tolerant species and omnivores with increasing urbanization. Interactions between riparian vegetation type and urbanization were found for blacknose dace, creek chub, tesselated darter, and the proportion of biomass of lithophilic spawners. The study did not provide consistent support for the hypotheses that responses of fish to riparian vegetation would be overwhelmed by urban degradation or insignificant at low urbanization.     

Dehalogenation of polychlorinated biphenyls and polybrominated diphenyl ethers using a hybrid bioinorganic catalyst

The environmentally prevalent polybrominated diphenyl ether (PBDE) #47 and polychlorinated biphenyls (PCBs) #28 and #118 were challenged for 24 hours with a novel biomass-supported Pd catalyst (Bio-Pd(0)). Analysis of the products via GC-MS revealed the Bio-Pd(0) to cause the challenged compounds to undergo stepwise dehalogenation with preferential loss of the least sterically hindered halogen atom. A mass balance for PCB #28 showed that it is degraded to three dichlorobiphenyls (33.9%), two monochlorobiphenyls (12%), and biphenyl (30.7%). The remaining mass was starting material. In contrast, while PCB #118 underwent degradation to yield five tetra- and five trichlorinated biphenyls, no less chlorinated products or biphenyl were detected, and the total mass of degraded products was 0.3%. Although the Bio-Pd(0) material was developed for treatment of PCBs, a mass balance for PBDE #47 showed that the biocatalyst could prove a potentially useful method for treatment of PBDEs. Specifically, 10% of PBDE #47 was converted to identifiable lower brominated congeners, predominantly the tribrominated PBDE #17 and the dibrominated PBDE #4, 75% remained intact, while 15% of the starting mass was unaccounted for.     

Relationships between organic matter, black carbon and persistent organic pollutants in European background soils: Implications for sources and environmental fate

Black carbon (BC) and total organic carbon (TOC) contents of UK and Norwegian background soils were determined and their relationships with persistent organic pollutants (HCB, PAHs, PCBs, co-planar PCBs, PBDEs and PCDD/Fs) investigated by correlation and regression analyses, to assess their roles in influencing compound partitioning/retention in soils. The 52 soils used were high in TOC (range 54-460 mg/g (mean 256)), while BC only constituted 0.24-1.8% (0.88%) of the TOC. TOC was strongly correlated (p < 0.001) with HCB, PCBs, co-PCBs and PBDEs, but less so with PCDD/Fs (p < 0.05) and PAHs. TOC explained variability in soil content, as follows: HCB, 80%; PCBs, 44%; co-PCBs, 40%; PBDEs, 27%. BC also gave statistically significant correlations with PBDEs (p < 0.001), co-PCBs (p < 0.01) and PCBs, HCB, PCDD/F (p < 0.05); TOC and BC were correlated with each other (p < 0.01). Inferences are made about possible combustion-derived sources, atmospheric transport and air-surface exchange processes for these compounds.     

Using environmental analytical data to estimate levels of community consumption of illicit drugs and abused pharmaceuticals

A solid phase extraction (SPE) method has been developed and applied in conjunction with a previously reported liquid chromatography tandem mass spectrometry (LC-MS-MS) procedure for the determination of illicit drugs and abused pharmaceuticals in treated wastewater and surface water samples at the ng L(-1) level. A full method validation was also performed and determined levels of analytical sensitivity were found to lie in the 1-10 ng L(-1) range using river water as a test sample matrix and a sample size of 500 mL. The developed procedure was successfully applied for the determination of the chosen analytes in wastewater treatment plants in Dublin, Ireland and rapidly expanding commuter towns in the surrounding counties. Cocaine was detected in 70% of the collected samples in the range of 25-489 ng L(-1), its primary metabolite, benzoylecognine (BZE) was also detected in the range of 22-290 ng L(-1). Other substances detected included morphine, Tempazepam and the primary metabolite of methadone.