Quantifying uranium complexation by groundwater dissolved organic carbon using asymmetrical flow field-flow fractionation

The long-term mobility of actinides in groundwaters is important for siting nuclear waste facilities and managing waste-rock piles at uranium mines. Dissolved organic carbon (DOC) may influence the mobility of uranium, but few field-based studies have been undertaken to examine this in typical groundwaters. In addition, few techniques are available to isolate DOC and directly quantify the metals complexed to it. Determination of U-organic matter association constants from analysis of field-collected samples compliments laboratory measurements, and these constants are needed for accurate transport calculations. The partitioning of U to DOC in a clay-rich aquitard was investigated in 10 groundwater samples collected between 2 and 30 m depths at one test site. A positive correlation was observed between the DOC (4-132 mg/L) and U concentrations (20-603 microg/L). The association of U and DOC was examined directly using on-line coupling of Asymmetrical Flow Field-Flow Fractionation (AsFlFFF) with UV absorbance (UVA) and inductively coupled plasma-mass spectrometer (ICP-MS) detectors. This method has the advantages of utilizing very small sample volumes (20-50 microL) as well as giving molecular weight information on U-organic matter complexes. AsFlFFF-UVA results showed that 47-98% of the DOC (4-136 mg C/L) was recovered in the AsFlFFF analysis, of which 25-64% occurred in the resolvable peak. This peak corresponded to a weight-average molecular weight of about 900-1400 Daltons (Da). In all cases, AsFlFFF-ICP-MS suggested that相似文献   

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.     

Interaction Between Scientists and Nonscientists in Community-Based Watershed Management: Emergence of the Concept of Stream Naturalization

The authors' personal experience in watershed planning and decision making in the agricultural Midwest is described to illustrate how: (1) formalization of the process of community-based management is not sufficient to guarantee that local people will meaningfully consider scientific information and opinion when making decisions about watersheds, and (2) genuine social interaction between scientists and nonscientists requires a considerable investment of time and energy on the part of the scientist to develop personal relationships with nonscientists based on trust and mutual exchange of information. This experience provides the basis for developing a general conceptual model of the interaction between scientists and nonscientists in community-based watershed management in the agricultural Midwest. An important aspect of integrating science effectively into community-based decision making is the need to revise existing concepts to accommodate place-based contexts. Stream naturalization is introduced as an alternative to stream restoration and rehabilitation, which are viewed as inappropriate management strategies in human-dominated environments. Stream naturalization seeks to establish sustainable, morphologically and hydraulically varied, yet dynamically stable fluvial systems that are capable of supporting healthy, biologically diverse aquatic ecosystems. This general goal is consistent with the types of stream-management practices emerging from community-based decision making in human-dominated, agricultural landscapes. Further research on the linkages between geomorphological and ecological dynamics of human-modified agricultural streams over multiple spatial and temporal scales is needed to provide a sound scientific framework for stream naturalization.     

RUNOFF AND EROSION RESPONSE OF SIMULATED WASTE BURIAL COVERS IN A SEMI-ARID ENVIRONMENT1

ABSTRACT: Control of runoff (reducing infiltration) and erosion at shallow land burials is necessary in order to assure environmentally safe disposal of low-level radioactive-waste and other waste products. This study evaluated the runoff and erosion response of two perennial grass species on simulated waste burial covers at Idaho National Engineering and Environmental Laboratory (INEEL). Rainfall simulations were applied to three plots covered by crested wheatgrass [Agropyron desertorum(Fischer ex Link) Shultes], three plots covered by streambank wheatgrass [Elymus lanceolatus(Scribner and Smith) Gould spp. lanceolaus], and one bare plot. Average total runoff for rainfall simulations in 1987, 1989, and 1990 was 42 percent greater on streambank wheatgrass plots than on crested wheatgrass plots. Average total soil loss for rainfall simulations in 1987 and 1990 was 105 percent greater on streambank wheatgrass plots than on crested wheatgrass plots. Total runoff and soil loss from natural rainfall and snowmelt events during 1987 were 25 and 105 percent greater, respectively, on streambank wheatgrass plots than on crested wheatgrass plots. Thus, crested wheatgrass appears to be better suited in revegetation of waste burial covers at INEEL than streambank wheatgrass due to its much lower erosion rate and only slightly higher infiltration rate (lower runoff rate).     

Nutrient enrichment reduces constraints on material flows in a detritus-based food web

Most aquatic and terrestrial ecosystems are experiencing increased nutrient availability, which is affecting their structure and function. By altering community composition and productivity of consumers, enrichment can indirectly cause changes in the pathways and magnitude of material flows in food webs. These changes, in turn, have major consequences for material storage and cycling in the ecosystem. Understanding mechanisms and predicting consequences of nutrient-induced changes in material flows requires a quantitative food web approach that combines information on consumer energetics and consumer-resource stoichiometry. We examined effects of a whole-system experimental nutrient enrichment on the trophic basis of production and the magnitude and pathways of carbon (C), nitrogen (N), and phosphorus (P) flows in a detritus-based stream food web. We compared the response of the treated stream to an adjacent reference stream throughout the study. Dietary composition and elemental flows varied considerably among invertebrate functional feeding groups. During nutrient enrichment, increased flows of leaf litter and amorphous detritus to shredders and gatherers accounted for most of the altered flows of C from basal resources to consumers. Nutrient enrichment had little effect on patterns of material flows but had large positive effects on the magnitude of C, N, and P flows to consumers (mean increase of 97% for all elements). Nutrient-specific food webs revealed similar flows of N and P to multiple functional groups despite an order of magnitude difference among groups in consumption of C. Secondary production was more strongly related to consumption of nutrients than C, and increased material flows were positively related to the degree of consumer-resource C:P and C:N imbalances. Nutrient enrichment resulted in an increased proportion of detrital C inputs consumed by primary consumers (from -15% to 35%) and a decreased proportion of invertebrate prey consumed by predators (from -80% to 55%). Our results demonstrate that nutrient enrichment of detritus-based systems may reduce stoichiometric constraints on material flows, increase the contribution of consumers to C, N, and P cycling, alter the proportion of C inputs metabolized by consumers, and potentially lead to reduced ecosystem-level storage of C.     

Citizenship under pressure: What's a “good soldier” to do?

Organizational citizenship behaviors (OCBs) are typically defined as discretionary behaviors that contribute to the effective functioning of organizations. Prior research has generally focused on instances in which employees willingly engage in such behaviors; however, because OCBs are often informally encouraged and rewarded, workers may experience pressure to be “good soldiers” within their organizations. Using a sample of 245 employees, our findings indicate that citizenship pressure is related to increased levels of OCB, particularly among unmarried and less conscientious employees. However, there appear to be negative consequences associated with citizenship pressure, even when controlling for OCB and other job demands, such as role overload and hours worked. In particular, citizenship pressure is associated with work–family conflict, work–leisure conflict, job stress, and intentions to quit. Implications of this study and some directions for future research are also discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Four challenges to an effective national nature assessment

Comprehensive biodiversity assessments play an essential role in strengthening global and national conservation strategies. The recently announced first U.S. National Nature Assessment (NNA) provides an unparalleled opportunity to comprehensively review status and trends of biodiversity at all levels. This broad context can help in the coordination of actions to conserve individual species and ecosystems. The scientific assessments that informed the Kunming–Montreal Global Biodiversity Framework adopted at the 2022 Convention on Biological Diversity (CBD) conference of parties provide models for synthesizing information on trends at multiple levels of biodiversity, including decline in abundance and distribution of species, loss of populations and genetic diversity, and degradation and loss of ecosystems and their services. The assessments then relate these trends to data on drivers of biodiversity loss and pathways to their mitigation. The U.S. NNA can augment such global analyses and avoid the pitfalls encountered by previous U.S. efforts by ensuring policy-relevant design, data accessibility, and inclusivity in process and product and by incorporating spatial data relevant to national and subnational audiences. Although the United States is not formally a CBD party, an effective NNA should take full advantage of the global context by including indicators adopted at the 2022 meeting and incorporating an independent review mechanism that supports periodic stocktaking and ratcheting up of ambition in response to identified shortfalls in stemming biodiversity loss. The challenges to design of an effective U.S. assessment are relevant globally as nations develop assessments and reporting to support the new global biodiversity framework's targets. By considering and incorporating the diverse ways in which society values and benefits from nature, such assessments can help bridge the gap between research and conservation practice and communicate the extent of the biodiversity crisis to the public, fostering broad-based support for transformative change in humanity's relationship to the natural world.     

Use of Airborne γ-Ray Spectrometry for Environmental Assessment of the Rehabilitated Nabarlek Uranium Mine, Australia

This article describes an airborne γ survey of a 7 × 5 km region around the rehabilitated Nabarlek uranium mine in northern Australia. An unusually tight line spacing (100 m) and low aircraft height (50 m) were used, enabling the survey to distinguish man-made structures such as ponds and accommodation areas, as well as creek lines. Positive correlations between airborne data and ground-based readings enabled an estimation of the average absorbed dose rate arising from terrestrial γ radiation over large areas of the site to be derived. For the fenced minesite area this estimate was 0.31 μ Gy hr^{− 1}. The airborne survey data were found to be invaluable in helping to plan further ground-level investigations and showed promise as an assessment tool for rehabilitated minesites.     

A comparison of X-ray fluorescence and wet chemical analysis for lead on air filters from different personal samplers used in a secondary lead smelter/solder manufacturer

Portable X-ray fluorescence (XRF) technology may provide faster turn-around without compromising accuracy when assessing personal exposures to metals such as lead, but it has only been tested in limited field environments. This study is part of a series, where various types of sampler are used to collect airborne lead in different environments for presentation to a portable XRF analyzer. In this case personal samples were taken at a manufacturer of solder alloys consisting mainly of lead and tin, using the closed-face 37 mm cassette (CFC), the 37 mm GSP or "cone" sampler, the 25 mm Institute of Occupational Medicine (IOM) inhalable sampler, the 25 mm button sampler, and the open-face 25 mm cassette. Mixed cellulose-ester filters were used in all samplers. Following XRF analysis the samples were extracted with acid and analyzed by inductively coupled plasma optical emission spectroscopy (ICP). The internal surfaces of CFC's and 25 mm open-face cassettes were also wiped, and the wipes analyzed for lead to assess wall-losses in these two samplers. Analysis of all elements present is useful to ascertain contributions to matrix interference effects. In addition to lead, other metals such as tin, copper, iron, silver, cadmium and antimony were also detected in some or all of the samples by ICP analysis, but only copper and iron could be determined using the XRF analyzer under test. After the removal of a few outliers, all five samplers gave good correlations (r(2) > 0.9) between the two analytical methods over the entire range of found lead mass, which encompassed both the action level and the permissible exposure limit enforced in the USA by the Occupational Safety and Health Administration (OSHA). Linear regression on the results from most samplers gave almost 1 ratio 1 correlations without additional correction, indicating an absence of matrix effects, particularly from tin, which was the most common element after lead. The average of three XRF readings across filters from the GSP samplers gave the best results with 96.7% of results within +/-25% and 100% within +/-30% of the associated ICP values. Using the center reading only was almost as good with 90.0% of results within +/-25% and 96.7% within +/-30% of the associated ICP values, and results can be obtained faster with a single reading. The use of an algorithm developed by OSHA for three readings from the CFC filter samples gave the next best results with 93.3% of XRF results within +/-25% of the corresponding ICP values. However, analysis of wipes from the interior of the cassettes indicated a substantial loss of sample to the walls, and even larger wall-losses were encountered in the 25 mm open-face cassette. Neither this latter sampler nor the IOM or button sampler met the 95% criterion, even for +/-30% accuracy.     

Bioassessment in A Harsh Environment: A Comparison of Macroinvertebrate Assemblages at Reference and Assessment Sites in An Australian Inland River System

The Lachlan River system of inland New South Wales, which extends into semi-arid areas, is prone to natural extremes of climate and water quality and has been almost entirely modified since European settlement in Australia. We used this system as a proving ground for the mainly qualitative bioassessment metrics for river macroinvertebrates that are used widely in Australia – the EPT (Ephemeroptera, Plecoptera and Trichoptera) index, the SIGNAL (Stream Invertebrate Grade Number Average Level) biotic index and the AUSRIVAS O/E (Australian River Assessment System Observed over Expected) index – plus a recently developed qualitative index, the observed proportion of potential taxa (OPP). We tested these metrics on their ability to discriminate between sites judged to be less disturbed by human activities (reference sites) and sites selected by a semi-random process and therefore expected to have a higher average level of human disturbance (assessment sites). All metrics except the AUSRIVAS O/E index differed significantly between the two types of sites at higher altitudes, with SIGNAL showing the greatest discrimination. Assessment at these altitudes was more effective if based on composite data from multiple mesohabitats rather than data from single mesohabitats. No metric differentiated the two types of sites in the more arid, lowland, floodplain region of the river system. We suggest that Australia relies too heavily on bioassessment concepts developed to assess water pollution in well-watered regions of the Northern Hemisphere. Effective assessment of human impacts on macroinvertebrates in the rivers of inland Australia requires a better understanding of the roles of flow regimes, including flood and drought sequences, and of microhabitat structure and invasive alien species. Quantitative approaches may also be required.