Interlaboratory evaluation of trace element determination in workplace air filter samples by inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS) is becoming more widely used for trace elemental analysis in the occupational hygiene field, and consequently new ICP-MS international standard procedures have been promulgated by ASTM International and ISO. However, there is a dearth of interlaboratory performance data for this analytical methodology. In an effort to fill this data void, an interlaboratory evaluation of ICP-MS for determining trace elements in workplace air samples was conducted, towards fulfillment of method validation requirements for international voluntary consensus standard test methods. The study was performed in accordance with applicable statistical procedures for investigating interlaboratory precision. The evaluation was carried out using certified 37-mm diameter mixed-cellulose ester (MCE) filters that were fortified with 21 elements of concern in occupational hygiene. Elements were spiked at levels ranging from 0.025 to 10 μg filter(-1), with three different filter loadings denoted "Low", "Medium" and "High". Participating laboratories were recruited from a pool of over fifty invitees; ultimately twenty laboratories from Europe, North America and Asia submitted results. Triplicates of each certified filter with elemental contents at three different levels, plus media blanks spiked with reagent, were conveyed to each volunteer laboratory. Each participant was also provided a copy of the test method which each participant was asked to follow; spiking levels were unknown to the participants. The laboratories were requested to prepare the filters by one of three sample preparation procedures, i.e., hotplate digestion, microwave digestion or hot block extraction, which were described in the test method. Participants were then asked to analyze aliquots of the prepared samples by ICP-MS, and to report their data in units of μg filter(-1). Most interlaboratory precision estimates were acceptable for medium- and high-level spikes (RSD <25%), but generally yielded greater uncertainties than were anticipated at the outset of the study.     

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.     

Migration of acidic groundwater seepage from uranium-tailings impoundments, 2. Geochemical behavior of radionuclides in groundwater

In this second paper of a series on groundwater seepage from uranium tailings, the general geochemical behavior of radionuclides is described and then applied to data from the field site, Seepage Area A of the Nordic Main impoundment near Elliot Lake, Ontario. The delineation of radionuclide behavior requires (1) the calculation of total element concentration by the summation of concentrations of each element's isotopes (the isotopic concentrations are calculated from the isotopes' radioactivities), (2) the evaluation of solid-liquid interactions using total element concentrations, and (3), for particular isotopes, the evaluation of the extent to which parental geochemical behavior causes a deviation in the isotope's behavior from that of its total element. A computerized speciation program, WATRAD, is used to evaluate aqueous complexation and mineral saturation indices of radium, actinium, thorium, and uranium. Data from Seepage Area A on isotopes of these four elements plus ²¹⁰Pb show that the geochemical behavior of radionuclides can be best defined on an individual isotopic basis rather than on an elemental basis.     

Freshwater stress on small island developing states: population projections and aridity changes at 1.5 and 2 °C

Small island developing states (SIDS) face multiple threats from anthropogenic climate change, including potential changes in freshwater resource availability. Due to a mismatch in spatial scale between SIDS landforms and the horizontal resolution of global climate models (GCMs), SIDS are mostly unaccounted for in GCMs that are used to make future projections of global climate change and its regional impacts. Specific approaches are required to address this gap between broad-scale model projections and regional, policy-relevant outcomes. Here, we apply a recently developed methodology that circumvents the GCM limitation of coarse resolution in order to project future changes in aridity on small islands. These climate projections are combined with independent population projections associated with shared socioeconomic pathways (SSPs) to evaluate overall changes in freshwater stress in SIDS at warming levels of 1.5 and 2 °C above pre-industrial levels. While we find that future population growth will dominate changes in projected freshwater stress especially toward the end of the century, projected changes in aridity are found to compound freshwater stress for the vast majority of SIDS. For several SIDS, particularly across the Caribbean region, a substantial fraction (~?25%) of the large overall freshwater stress projected under 2 °C at 2030 can be avoided by limiting global warming to 1.5 °C. Our findings add to a growing body of literature on the difference in climate impacts between 1.5 and 2 °C and underscore the need for regionally specific analysis.     

Estimating willingness to pay for a threatened species within a threatened ecosystem

This study conducts a choice experiment to determine the willingness to pay for Palouse Prairie conservation. The giant Palouse earthworm (Driloleirus americanus), a rare species endemic to the Palouse region, is included as an attribute of conservation and serves as a method for determining the willingness to pay for protecting the species. This method evaluates the value of the earthworm as an attribute of an overall willingness to pay for threatened ecosystem preservation rather than a direct willingness to pay for protecting the species. This method is expected to yield a more accurate measure of willingness to pay for rare species. The annual willingness to pay per household for the giant Palouse earthworm is $20.45 based on the conditional logit model and $19.30 based on the mixed logit model. Ranking and relative importance are included as methods for representing a non-monetary value and importance of the giant Palouse earthworm.     

Ecosystem responses to climate change at a Low Arctic and a High Arctic long-term research site

Long-term measurements of ecological effects of warming are often not statistically significant because of annual variability or signal noise. These are reduced in indicators that filter or reduce the noise around the signal and allow effects of climate warming to emerge. In this way, certain indicators act as medium pass filters integrating the signal over years-to-decades. In the Alaskan Arctic, the 25-year record of warming of air temperature revealed no significant trend, yet environmental and ecological changes prove that warming is affecting the ecosystem. The useful indicators are deep permafrost temperatures, vegetation and shrub biomass, satellite measures of canopy reflectance (NDVI), and chemical measures of soil weathering. In contrast, the 18-year record in the Greenland Arctic revealed an extremely high summer air-warming of 1.3 °C/decade; the cover of some plant species increased while the cover of others decreased. Useful indicators of change are NDVI and the active layer thickness.     

Capacity building for food justice in England: the contribution of charity-led community food initiatives

This paper discusses the extent to which charity-led initiatives can contribute to capacity building for food justice in England. The paper draws on evaluations of two projects run by the charity Garden Organic: the Master Gardener Programme, operating a network of volunteers who mentor households, schools and community groups to support local food growing, and the Sowing New Seeds programme, which engages “Seed Stewards” to work with communities to encourage the growing and cooking of “exotic” crops. Based on qualitative data about peoples’ motivations for participation and the benefits that are experienced, we interpret these projects as examples of capacity building for food justice. We suggest that whilst currently depoliticised, the “quiet” process of reskilling and awareness raising that occurs through shared gardening projects could have transformative potential for people’s relationship with food. Finally, we use our findings to raise critical questions and propose future research about food justice concepts and practices.     

Seasonal influences on PCB retention and biotransformation in fish

There is extensive evidence that fish from waters with polychlorinated biphenyls (PCB)-contaminated sediments accumulate PCBs and related chemicals and that people who eat fish from contaminated waters have higher body burdens of PCBs and PCB metabolites than those who do not. PCBs and their metabolites are potentially toxic; thus, it is important to human health to understand the uptake, biotransformation, and elimination of PCBs in fish since these processes determine the extent of accumulation. The intestinal uptake of PCBs present in the diet of fish into fish tissues is a process that is influenced by the lipid composition of the diet. Biotransformation of PCBs in fish, as in mammals, facilitates elimination, although many PCB congeners are recalcitrant to biotransformation in fish and mammals. Sequential biotransformation of PCBs by cytochrome P450 and conjugation pathways is even less efficient in fish than in mammalian species, thus contributing to the retention of PCBs in fish tissues. A very important factor influencing overall PCB disposition in fish is water temperature. Seasonal changes in water temperature produce adaptive physiological and biochemical changes in fish. While uptake of PCBs from the diet is similar in fish acclimated to winter or summer temperatures, there is evidence that elimination of PCBs occurs much more slowly when the fish is acclimated at low temperatures than at warmer temperatures. Research to date suggests that the processes of elimination of PCBs are modulated by several factors in fish including seasonal changes in water temperature. Thus, the body burden of PCBs in fish from a contaminated location is likely to vary with season.     

The fate of recombinant plasmids during composting of organic wastes

Composting was investigated as a means for safe disposal of organic waste containing bacteria that carry transgenes in recombinant plasmids. To generate model recombinant plasmids, a mobile IncQ plasmid, RSF1010, and a non-mobile plasmid, pGFP, were genetically modified to carry a DNA segment encoding both green fluorescent protein and kanamycin resistance and were designated as RSF1010-GFPK and pGFPK. Escherichia coli (E. coli) C600 harboring these plasmids were inoculated into chicken manure specimens that were placed in compost at 20 and 60 cm from the bottom of a 1.0-m high compost bin. Control specimens were held at ambient temperature. By day 10, compost temperatures at the lower and upper levels of the bin had reached 45.3 and 61.5°C, respectively, and at both levels the target E. coli had been inactivated and the plasmids had lost their capacity to be transformed or mobilized. Furthermore, based on real time Polymerase chain reaction (PCR), the transgene fragments along with the host chromosomal DNA fragment from specimens at the upper level had been degraded beyond the detection limit. However, at the lower level where temperatures remained below 48°C these fragment persisted to day 21. At ambient temperatures (0–8°C), the E. coli, plasmids and the transgene fragments persisted in manure specimens throughout the 21 day test period. The study showed the potential for composting as a safe procedure for disposal of bacteria carrying transgenes in recombinant plasmids.     

Integrated Assessment Modeling of Atmospheric Pollutants in the Southern Appalachian Mountains. Part I: Hourly and Seasonal Ozone

Abstract

Recently, a comprehensive air quality modeling system was developed as part of the Southern Appalachians Mountains Initiative (SAMI) with the ability to simulate meteorology, emissions, ozone, size- and composition-resolved particulate matter, and pollutant deposition fluxes. As part of SAMI, the RAMS/EMS-95/URM-1ATM modeling system was used to evaluate potential emission control strategies to reduce atmospheric pollutant levels at Class I areas located in the Southern Appalachians Mountains. This article discusses the details of the ozone model performance and the methodology that was used to scale discrete episodic pollutant levels to seasonal and annual averages. The daily mean normalized bias and error for 1-hr and 8-hr ozone were within U.S. Environment Protection Agency guidance criteria for urban-scale modeling. The model typically showed a systematic overestimation for low ozone levels and an underestimation for high levels. Because SAMI was primarily interested in simulating the growing season ozone levels in Class I areas, daily and seasonal cumulative ozone exposure, as characterized by the W126 index, were also evaluated. The daily ozone W126 performance was not as good as the hourly ozone performance; however, the seasonal ozone W126 scaled up from daily values was within 17% of the observations at two typical Class I areas of the SAMI region. The overall ozone performance of the model was deemed acceptable for the purposes of SAMI’s assessment.