Evaluation of geochemical associations as a screening tool for identifying anthropogenic trace metal contamination

Geochemical association plots are used as a screening tool for environmental site assessments and use empirical log–log relationships between total trace metal concentrations and concentrations of a major (i.e., reference) soil metal constituent, such as iron (Fe), to discern sites with naturally elevated trace metal levels from sites with anthropogenic contamination. Log–log relationships have been consistently observed between trace metal and reference metal concentrations and are often considered constant. Consequently, we used a regional geochemistry data set to evaluate background trace metal/Fe log–log associations across soils with highly diverse composition. Our results indicate that, although geochemical associations may be proportional, they significantly differ across predominant United States Department of Agriculture (USDA) soil orders. This suggests that highly complex interactions between soil-forming factors and variable secondary clay mineral composition affect the ratio of trace metals to Fe concentrations in soils. Also, intra-order variability in trace metal/Fe ratios generally ranged multiple orders of magnitude which suggest that the order level of the USDA soil taxonomic system is insufficient to reasonably classify background trace metal concentrations. Consequently, geochemical association plots are a useful screening tool for environmental site assessments, but ubiquitous application of generic background metal data sets could result in erroneous conclusions. Because significantly different ratios were observed across predominant USDA soil orders, an agglomerative clustering technique was used to elucidate hierarchical patterns of association. We present these results as a mechanism to aid environmental assessors in screening candidate background metal data sets for their applicability to site-specific soil composition; although site-specific background metal data should be utilized if ample pristine reference sites with similar (i.e., sub-order) soil composition can be identified and sampled.     

Managing scuba divers to meet ecological goals for coral reef conservation

Marine protected areas increasingly are challenged to maintain or increase tourism benefits while adequately protecting resources. Although carrying capacity strategies can be used to cope with use-related impacts, there is little understanding of divers themselves, their management preferences, and how preferences relate to conservation goals. By using a stated preference choice modeling approach, we investigated the choices divers make in selecting diving trips to marine protected areas as defined by use level, access, level of supervision, fees, conservation education, and diving expectations. Logit models showed that divers preferred a more restrictive management scenario over the status quo. Divers favored reductions in the level of site use and increased levels of conservation education. Divers did not favor fees to access protected areas, having less access to the resource, or extensive supervision. Finally, divers were much more willing to accept increasingly restrictive management scenarios when they could expect to see increased marine life.     

Effects of environmental methylmercury on the health of wild birds, mammals, and fish

Wild piscivorous fish, mammals, and birds may be at risk for elevated dietary methylmercury intake and toxicity. In controlled feeding studies, the consumption of diets that contained Hg (as methylmercury) at environmentally realistic concentrations resulted in a range of toxic effects in fish, birds, and mammals, including behavioral, neurochemical, hormonal, and reproductive changes. Limited field-based studies, especially with certain wild piscivorous bird species, e.g., the common loon, corroborated laboratory-based results, demonstrating significant relations between methylmercury exposure and various indicators of methylmercury toxicity, including reproductive impairment. Potential population effects in fish and wildlife resulting from dietary methylmercury exposure are expected to vary as a function of species life history, as well as regional differences in fish-Hg concentrations, which, in turn, are influenced by differences in Hg deposition and environmental methylation rates. However, population modeling suggests that reductions in Hg emissions could have substantial benefits for some common loon populations that are currently experiencing elevated methylmercury exposure. Predicted benefits would be mediated primarily through improved hatching success and development of hatchlings to maturity as Hg concentrations in prey fish decline. Other piscivorous species may also benefit from decreased Hg exposure but have not been as extensively studied as the common loon.     

Application of microbial hot spots enhances pesticide degradation in soils

Through transfer of an active, isoproturon degrading microbial community, pesticide mineralization could be successfully enhanced in various soils under laboratory and outdoor conditions. The microbes, extracted from a soil having high native ability to mineralize this chemical, were established on expanded clay particles and distributed to various soils in the form of microbial "hot spots". Both, diffusion controlled isoproturon mass flow towards these "hot spots" (6microg d(-1)) as well as microbial ability to mineralize the herbicide (approximately 5microg d(-1)) were identified as the main processes enabling a multiple augmentation of the native isoproturon mineralization even in soils with heavy metal contamination. Soil pH-value appears to exert an important effect on the sustainability of this process.     

Leaded electronic waste is a possible source material for lead-contaminated jewelry

Highly leaded jewelry, often imported from China, remains widely available in the United States. Leaded electronic waste is exported from the United States to several Asian countries where solder is recovered and circuit boards are stripped of parts in small workshops. To assess whether electronic waste is being recycled into the jewelry, lead, tin and copper content of highly leaded jewelry samples were determined by atomic absorption spectrometry. Sixteen jewelry items previously determined to contain 20-80% lead by weight were analyzed. Samples were digested in nitric acid for analysis of lead and copper, and in aqua regia for analysis of tin. Six samples contained significant amounts of tin, from 20.8% to 29.9% by weight. In addition, copper was a significant minor component of five of these samples (up to 4% by weight). Copper (present at 10-40% by weight in circuit boards) was shown to rapidly move into heated lead-tin solder. The combined lead-tin-copper content of these six items ranges from 93.5% to 100%, suggestive of a solder-based source material. These results are consistent with the hypothesis that recycled circuit board solders are being used to produce some of the heavily leaded imported jewelry sold in the United States. Should this hypothesis be substantiated, it suggests that environmental policies to protect children's health must address both proper recycling of source materials as well as restrictions of the lead content in consumer goods.     

Acetylcholinesterase-polyaniline biosensor investigation of organophosphate pesticides in selected organic solvents

The behavior of an amperometric organic-phase biosensor consisting of a gold electrode modified first with a mercaptobenzothiazole self-assembled monolayer, followed by electropolymerization of polyaniline in which acetylcholinesterase as enzyme was immobilized, has been developed and evaluated for organophosphorous pesticide detection. The voltammetric results have shown that the formal potential shifts anodically as the Au/MBT/PANI/AChE/PVAc thick-film biosensor responded to acetylthiocholine substrate addition under anaerobic conditions in selected organic solvent media containing 2% v/v 0.05 M phosphate buffer, 0.1 M KCl (pH 7.2) solution. Detection limits in the order of 0.147 ppb for diazinon and 0.172 ppb for fenthion in acetone-saline phosphate buffer solution, and 0.180 ppb for diazinon and 0.194 ppb for fenthion in ethanol-saline phosphate buffer solution has been achieved.     

Laboratory and field evaluation of crystallized DOW 704 oil on the performance of the Well Impactor Ninety-Six fFine particulate matter fractionator

Subsequent to the 1997 promulgation of the Federal Reference Method (FRM) for monitoring fine particulate matter (PM2.5) in ambient air, U.S. Environmental Protection Agency (EPA) received reports that the DOW 704 diffusion oil used in the method's Well Impactor Ninety-Six (WINS) fractionator would occasionally crystallize during field use, particularly under wintertime conditions. Although the frequency of occurrence on a nationwide basis was low, uncertainties existed as to whether crystallization of the DOW 704 oil may adversely affect a sampling event's data quality. In response to these concerns, EPA and the State of Connecticut Department of Environmental Protection jointly conducted a series of specialized tests to determine whether crystallized oil adversely affected the performance of the WINS fractionator. In the laboratory, an experimental setup used dry ice to artificially induce crystallization of the diffusion oil under controlled conditions. Using primary polystyrene latex calibration aerosols, standard size-selective performance tests of the WINS fractionator showed that neither the position nor the shape of the WINS particle size fractionation curve was substantially influenced by the crystallization of the DOW 704 oil. No large particle bounce from the crystallized impaction surface was observed. During wintertime field tests, crystallization of the DOW 704 oil did not adversely affect measured PM2.5 concentrations. Regression of measurements with crystallized DOW 704 versus liquid dioctyl sebacate (DOS) oil produced slope, intercept, and R2 values of 0.98, 0.1, and 0.997 microg/m3, respectively. Additional field tests validated the use of DOS as an effective impaction substrate. As a result of these laboratory and field tests, DOS oil has been approved by EPA as a substitute for DOW 704 oil. Since the field deployment of DOS oil in 2001, users of this alternative oil have not reported any operational problems associated with its use in the PM2.5 FRM. Limited field evaluation of the BGI very sharp cut cyclone indicates that it provides a viable alternative to the WINS fractionator.     

An international survey of decabromodiphenyl ethane (deBDethane) and decabromodiphenyl ether (decaBDE) in sewage sludge samples

Decabromodiphenyl ethane (deBDethane) is an additive flame retardant marketed as a replacement for decabromodiphenyl ether (decaBDE). The structures of the two chemicals are similar, and hence deBDethane may also become an environmental contaminant of concern. Environmental data on deBDethane are scarce. Since sewage sludge is an early indicator of leakage of these chemicals into the environment, an international survey of deBDethane and decaBDE levels in sludge was conducted. Samples were collected from 42 WWTPs in 12 different countries and analyzed with GC/LRMS. DeBDethane was present in sludge from all countries and may therefore be a worldwide concern. The levels of deBDethane in sludge samples from the Ruhr area of Germany were the highest so far reported in the literature (216 ng g⁻¹ d.wt.). The [deBDethane]/[decaBDE] quotient for the whole data set ranged from 0.0018 to 0.83. High ratios were found in and around Germany where deBDethane imports are known to have been high and substitution of decaBDE with deBDethane is likely to have occurred. Low ratios were found in the USA and the UK, countries that have traditionally been large users of decaBDE. An estimate of the flux of deBDEthane from the technosphere via WWTPs to the environment within the European Union gave 1.7 ± 0.34 mg annually per person. The corresponding value for decaBDE was 41 ± 22 mg annually per person.     

Development of a risk-based index for source water protection planning, which supports the reduction of pathogens from agricultural activity entering water resources

Source water protection planning (SWPP) is an approach to prevent contamination of ground and surface water in watersheds where these resources may be abstracted for drinking or used for recreation. For SWPP the hazards within a watershed that could contribute to water contamination are identified together with the pathways that link them to the water resource. In rural areas, farms are significant potential sources of pathogens. A risk-based index can be used to support the assessment of the potential for contamination following guidelines on safety and operational efficacy of processes and practices developed as beneficial approaches to agricultural land management. Evaluation of the health risk for a target population requires knowledge of the strength of the hazard with respect to the pathogen load (massxconcentration). Manure handling and on-site wastewater treatment systems form the most important hazards, and both can comprise confined and unconfined source elements. There is also a need to understand the modification of pathogen numbers (attenuation) together with characteristics of the established pathways (surface or subsurface), which allow the movement of the contaminant species from a source to a receptor (water source). Many practices for manure management have not been fully evaluated for their impact on pathogen survival and transport in the environment. A key component is the identification of potential pathways of contaminant transport. This requires the development of a suitable digital elevation model of the watershed for surface movement and information on local groundwater aquifer systems for subsurface flows. Both require detailed soils and geological information. The pathways to surface and groundwater resources can then be identified. Details of land management, farm management practices (including animal and manure management) and agronomic practices have to be obtained, possibly from questionnaires completed by each producer within the watershed. To confirm that potential pathways are active requires some microbial source tracking. One possibility is to identify the molecular types of Escherichia coli present in each hazard on a farm. An essential part of any such index is the identification of mitigation strategies and practices that can reduce the magnitude of the hazard or block open pathways.