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Trace elements in coal: Environmental and health significance

Trace elements can have profound adverse effects on the health of people burning coal in homes or living near coal deposits, coal mines, and coal-burning power plants. Trace elements such as arsenic emitted from coal-burning power plants in Europe and Asia have been shown to cause severe health problems. Perhaps the most widespread health problems are caused by domestic coal combustion in developing countries where millions of people suffer from fluorosis and thousands from arsenism. Better knowledge of coal quality characteristics may help to reduce some of these health problems. For example, information on concentrations and distributions of potentially toxic elements in coal may help delineate areas of a coal deposit to be avoided. Information on the modes of occurrence of these elements and the textural relations of the minerals in coal may help to predict the behavior of the potentially toxic trace metals during coal cleaning, combustion, weathering, and leaching.

Biological Trace Element Research

Selenium: Mercury molar ratios in freshwater fish in the Columbia River Basin: Potential applications for specific fish consumption advisories

Fish provide a valuable source of beneficial nutrients and are an excellent source of low fat protein. However, fish are also the primary source of methylmercury exposure in humans. Selenium often co-occurs with mercury and there is some evidence that selenium can protect against mercury toxicity yet States issue fish consumption advisories based solely on the risks that methylmercury pose to human health. Recently, it has been suggested the selenium: mercury molar ratio be considered in risk management. In order for agencies to utilize the ratio to set consumption guidelines, it is important to evaluate the variability in selenium and mercury in different fish species. We examined 10 different freshwater fish species found within the Columbia River Basin in order to determine the inter- and intra-specific variability in the selenium: mercury molar ratios and the selenium health benefit values. We found significant variation in selenium: mercury molar ratios. The mean molar ratios for each species were all above 1:1, ranging from 3.42:1 in Walleye to 27.2:1 in Chinook salmon. There was a positive correlation between both mercury and selenium with length for each fish species apart from yellow perch and rainbow trout. All species had health benefit values greater than 2. We observed considerable variability in selenium: mercury molar ratios within fish species collected in the Columbia River Basin. Although incorporating selenium: mercury molar ratios into fish consumption holds the potential for refining advisories and assessing the risk of methylmercury exposure, the current understanding of how these ratios apply is insufficient, and further understanding of drivers of variability in the ratios is needed.

Biological Trace Element Research

Mammalian sensitivity to elemental gold (Au?)

There is increasing documentation of allergic contact dermatitis and other effects from gold jewelry, gold dental restorations, and gold implants. These effects were especially pronounced among females wearing body-piercing gold objects. One estimate of the prevalence of gold allergy worldwide is 13%, as judged by patch tests with monovalent organogold salts. Eczema of the head and neck was the most common response of individuals hypersensitive to gold, and sensitivity can last for at least several years. Ingestion of beverages containing flake gold can result in allergic-type reactions similar to those seen in gold-allergic individuals exposed to gold through dermal contact and other routes. Studies with small laboratory mammals and injected doses of colloidal gold showed increased body temperatures, accumulations in reticular cells, and dose enhancement in tumor therapy; gold implants were associated with tissue injuries. It is proposed that Au? toxicity to mammals is associated, in part, with formation of the more reactive Au+ and Au3+ species.

Biological Trace Element Research

Stable isotopes of transition and post-transition metals as tracers in environmental studies

The transition and post-transition metals, which include the elements in Groups 3–12 of the Periodic Table, have a broad range of geological and biological roles as well as industrial applications and thus are widespread in the environment. Interdisciplinary research over the past decade has resulted in a broad understanding of the isotope systematics of this important group of elements and revealed largely unexpected variability in isotope composition for natural materials. Significant kinetic and equilibrium isotope fractionation has been observed for redox sensitive metals such as iron, chromium, copper, molybdenum and mercury, and for metals that are not redox sensitive in nature such as cadmium and zinc. In the environmental sciences, the isotopes are increasingly being used to understand important issues such as tracing of metal contaminant sources and fates, unraveling metal redox cycles, deciphering metal nutrient pathways and cycles, and developing isotope biosignatures that can indicate the role of biological activity in ancient and modern planetary systems.

Book

Modeling potential impacts of the Garrison Diversion Unit project on Sand Lake and Arrowwood National Wildlife Refuges: a feasibility analysis

The Garrison Diversion Unit (GDU) of the Pick-Sloan Missouri Basin program was authorized in 1965, with the purpose of diverting Missouri River water to the James River for irrigation, municipal and industrial water supply, fish and wildlife habitat, recreation, and flood control. The project was reauthorized in 1986, with the specification that comprehensive studies be conducted to address a variety of issues. One of these ongoing studies addresses potential impacts of GDU construction and operation on lands of the National Wildlife Refuge (NWR) system, including Arrowwood and Sand Lake Refuges (the Refuges) on the James River. A number of concerns at these Refuges have been identified; the primary concerns addressed in this report include increased winter return flows, which would limit control of rough fish; increased turbidity during project construction, which would decrease production of sago pondweed; and increased water level fluctuations in the late spring and early summer, which would destroy the nests of some over-water nesting birds. The facilitated workshop described in this report was conducted February 18-20, 1987, under the joint sponsorship of the U.S. Bureau of Reclamation, the U.S. Fish and Wildlife Service, and the North Dakota Game and Fish Department. The primary objectives of the workshop were to evaluate the feasibility of using simulation modeling techniques to estimate GDU impacts on Arrowwood and Sand Lake Refuges and to suggest enhancements to the James River Refuge monitoring program. The workshop was structured around the formulation of four submodels: a Hydrology and Water Quality submodel to simulate changes in Refuge pool elevations, turnover rates, and water quality parameters (e.g., total dissolved solids, turbidity, dissolved oxygen, nutrients, water temperature, pesticides) due to GDU construction and operation; a Vegetation submodel to simulate concomitant changes in wetland communities (e.g., sago pondweed, wet meadows, deep and shallow marsh); a Fish submodel to estimate changes in abundance or biomass of rough fish (carp, buffalo) and sportfish (northern pike); and a Wildlife submodel to calculate indices of waterfowl abundance or habitat suitability (e.g., for mallards, western grebes, migrating diving ducks, white-faced ibis, egrets, over-water nesters). Submodels considered weekly to monthly changes in pools within a Refuge over a time horizon of 30-50 years. Based on workshop discussions and past experience with impact analysis modeling, a phased modeling approach was recommended for the James River Refuges analysis. The first phase would involve two modeling efforts. The existing Sand Lake hydrology model, and a similar one developed for Arrowwood NWR, would be validated and used to predict changes on pool elevations and winter inflows to each pool for a variety of GDU alternatives. Outputs from simulations would then be evaluated in terms of potential fish and wildlife impacts. For example, the models could generate indices comparing the magnitude and timing of winter inflows for pre- and postproject conditions; fisheries biologists could then use these indices to better quantify their concerns relative to potential changes in the frequency of rough-fish control. The other modeling effort in the first phase would involve developing a sago pondweed growth model to integrate Refuge monitoring data and existing literature and perhaps to address some questions concerning turbidity impacts. A second phase of simulation modeling would be undertaken only if the initial analyses of hydrologic outputs indicated significant potential problems and if monitoring and research projects had clarified some of the biological and physical processes that cannot be modeled reliably at the present time (e.g., resuspension of sediments by carp, immigration and winter mortality of fish, loss of waterfowl nests due to wave action). The second phase would attempt to develop an integrated impact assessment model. In order to address some of the biological and physical processes that presently are not well understood, a number of studies and enhancements to the Refuge monitoring program were suggested. The Hydrology and Water Quality workgroup recommended increasing turbidity and dissolved oxygen sampling, dropping expensive analysis of some trace elements, adding more pesticide analysis (including some biological monitoring), and developing better area-capacity data for the Sand Lake hydrology model. The Vegetation workgroup suggested expanding the number of monitoring stations, monitoring photosynthetically active radiation by depth, and modifying the biomass sampling procedure and schedule. Also suggested were additional analyses of existing Refuge monitoring data and additional field studies concerning sago growth under a variety of environmental conditions and effects of rough fish density on sago. A careful examination of Refuge narrative reports was recommended by the Fish workgroup to characterize conditions that led to various rates of winter-kill. Monitoring enhancement related to a better understanding of fish population dynamics included increasing dissolved oxygen monitoring, continuing present monitoring of fish movement upstream from Jamestown Reservoir into Arrowwood NWR, initiating similar efforts for upstream movement into Sand Lake NWR and downstream movements into both Refuges, and augmenting the present gillnetting program (or replacing it) with sampling for population and age/size structure estimates. The Wildlife workgroup suggested estimating the relative density of mallard nests in over-water and wet meadow nesting areas, estimating the number of western grebe nests lost due to wave action, delineating wet meadows on the Refuge vegetation maps, estimating annual tuber consumption by birds, and monitoring insect/macroinvertebrate abundance. The workgroup also suggested research studies to better understand the relationships between food supplies and the growth and survival of ducklings and young grebes. the workshop discussions also helped identify some suggestions for modifying project features that, if feasible from an engineering and operational standpoint, would reduce impacts on Refuge lands. These suggestions included: designing drains with control structures or small "reregulation" reservoirs to hold winter return flows that might adversely affect rough fish control, spreading construction activities over a number of years to reduce potential impacts of turbidity on sago pondweed in any single year, scheduling construction to occur after the spring sprouting and elongation growth stages to reduce impacts on sago pondweed, and installing "quick acting" control structures at Arrowwood NWR to reduce pool level fluctuations that might destroy nests of some over-water nesting waterfowl.

Report

Prospects for reconstructing paleoenvironmental conditions from organic compounds in polar snow and ice

Polar ice cores provide information about past climate and environmental changes over periods ranging from a few years up to 800,000 years. The majority of chemical studies have focused on determining inorganic components, such as major ions and trace elements as well as on their isotopic fingerprint. In this paper, we review the different classes of organic compounds that might yield environmental information, discussing existing research and what is needed to improve knowledge. We also discuss the problems of sampling, analysis and interpretation of organic molecules in ice. This review highlights the great potential for organic compounds to be used as proxies for anthropogenic activities, past fire events from different types of biomass, terrestrial biogenic emissions and marine biological activity, along with the possibility of inferring past temperature fluctuations and even large-scale climate variability. In parallel, comprehensive research needs to be done to assess the atmospheric stability of these compounds, their ability to be transported long distances in the atmosphere, and their stability in the archive in order to better interpret their fluxes in ice cores. In addition, specific decontamination procedures, analytical methods with low detection limits (ng/L or lower), fast analysis time and low sample requests need to be developed in order to ensure a good time resolution in the archive.

Quaternary Science Reviews

A Synopsis of Technical Issues of Concern for Monitoring Trace Elements in Highway and Urban Runoff

Trace elements, which are regulated for aquatic life protection, are a primary concern in highway- and urban-runoff studies because stormwater runoff may transport these constituents from the land surface to receiving waters. Many of these trace elements are essential for biological activity and become detrimental only when geologic or anthropogenic sources exceed concentrations beyond ranges typical of the natural environment. The Federal Highway Administration and State Transportation Agencies are concerned about the potential effects of highway runoff on the watershed scale and for the management and protection of watersheds. Transportation agencies need information that is documented as valid, current, and scientifically defensible to support planning and management decisions. There are many technical issues of concern for monitoring trace elements; therefore, trace-element data commonly are considered suspect, and the responsibility to provide data-quality information to support the validity of reported results rests with the data-collection agency. Paved surfaces are fundamentally different physically, hydraulically, and chemically from the natural surfaces typical of most freshwater systems that have been the focus of many traceelement- monitoring studies. Existing scientific conceptions of the behavior of trace elements in the environment are based largely upon research on natural systems, rather than on systems typical of pavement runoff. Additionally, the logistics of stormwater sampling are difficult because of the great uncertainty in the occurrence and magnitude of storm events. Therefore, trace-element monitoring programs may be enhanced if monitoring and sampling programs are automated. Automation would standardize the process and provide a continuous record of the variations in flow and water-quality characteristics. Great care is required to collect and process samples in a manner that will minimize potential contamination or attenuation of trace elements and other sources of bias and variability in the sampling process. Trace elements have both natural and anthropogenic sources that may affect the sampling process, including the sample-collection and handling materials used in many trace-element monitoring studies. Trace elements also react with these materials within the timescales typical for collection, processing and analysis of runoff samples. To study the characteristics and potential effects of trace elements in highway and urban runoff, investigators typically sample one or more operationally defined matrixes including: whole water, dissolved (filtered water), suspended sediment, bottom sediment, biological tissue, and contaminant sources. The sampling and analysis of each of these sample matrixes can provide specific information about the occurrence and distribution of trace elements in runoff and receiving waters. There are, however, technical concerns specific to each matrix that must be understood and addressed through use of proper collection and processing protocols. Valid protocols are designed to minimize inherent problems and to maximize the accuracy, precision, comparability, and representativeness of data collected. Documentation, including information about monitoring protocols, quality assurance and quality control efforts, and ancillary data also is necessary to establish data quality. This documentation is especially important for evaluation of historical traceelement monitoring data, because trace-element monitoring protocols and analysis methods have been constantly changing over the past 30 years.

Open-File Report

Metals, trace elements, and organochlorine compounds in bottom sediment of Tuttle Creek Lake, Kansas, U.S.A.

Bottom-sediment cores were used to investigate the occurrence of 44 metals and trace elements, and 15 organochlorine compounds in Tuttle Creek Lake, a reservoir with an agricultural basin in northeast Kansas, U.S.A. On the basis of U.S. Environmental Protection Agency sediment-quality guidelines, concentrations of Ag, As, Cr, Cu, Ni, and Zn frequently or typically exceeded the threshold-effects levels for toxic biological effects. Organochlorine compounds either were not detected or were detected at concentrations generally below the threshold-effects levels. Statistically significant positive depositional trends were determined for several elements. However, because the vertical profiles of element concentrations typically indicated a bimodal distribution and much of the variability could be attributable to analytical variance, the statistical trends may not represent actual trends. DDE concentrations reflected the history of DDT use. Substantial increases in grain corn and soybean production, irrigated land, and hog production in the basin have not had a discernible effect on sediment quality in the reservoir. Future research focused on small impoundments throughout the basin may enhance understanding of the effects of human activity on sediment quality within the Tuttle Creek Lake system and elsewhere.

Conference Paper

Phytoplankton bloom dynamics in coastal ecosystems: A review with some general lessons from sustained investigation of San Francisco Bay, California

Phytoplankton blooms are prominent features of biological variability in shallow coastal ecosystems such as estuaries, lagoons, bays, and tidal rivers. Long-term observation and research in San Francisco Bay illustrates some patterns of phytoplankton spatial and temporal variability and the underlying mechanisms of this variability. Blooms are events of rapid production and accumulation of phytoplankton biomass that are usually responses to changing physical forcings originating in the coastal ocean (e.g., tides), the atmosphere (wind), or on the land surface (precipitation and river runoff). These physical forcings have different timescales of variability, so algal blooms can be short-term episodic events, recurrent seasonal phenomena, or rare events associated with exceptional climatic or hydrologic conditions. The biogeochemical role of phytoplankton primary production is to transform and incorporate reactive inorganic elements into organic forms, and these transformations are rapid and lead to measurable geochemical change during blooms. Examples include the depletion of inorganic nutrients (N, P, Si), supersaturation of oxygen and removal of carbon dioxide, shifts in the isotopic composition of reactive elements (C, N), production of climatically active trace gases (methyl bromide, dimethylsulfide), changes in the chemical form and toxicity of trace metals (As, Cd, Ni, Zn), changes in the biochemical composition and reactivity of the suspended particulate matter, and synthesis of organic matter required for the reproduction and growth of heterotrophs, including bacteria, zooplankton, and benthic consumer animals. Some classes of phytoplankton play special roles in the cycling of elements or synthesis of specific organic molecules, but we have only rudimentary understanding of the forces that select for and promote blooms of these species. Mounting evidence suggests that the natural cycles of bloom variability are being altered on a global scale by human activities including the input of toxic contaminants and nutrients, manipulation of river flows, and translocation of species. This hypothesis will be a key component of our effort to understand global change at the land-sea interface. Pursuit of this hypothesis will require creative approaches for distinguishing natural and anthropogenic sources of phytoplankton population variability, as well as recognition that the modes of human disturbance of coastal bloom cycles operate interactively and cannot be studied as isolated processes.

California

Identifying recruitment sources across trophic levels in a large river food web

Assemblages are connected through the movement of physical and biological resources including recruits. Identifying recruitment sources for predators and their prey could help us understand how assemblages use connectivity across multiple trophic levels and whether predator and prey recruitment is coupled. Recruitment sources of organisms across multiple trophic levels can be quantified by trace element analysis of stomach contents. We used trace element analysis of otoliths to determine recruitment contributions from tributaries of predatory largemouth bass ( Micropterus salmoides ) and bowfin ( Amia calva ) and their consumed prey collected from Pools 4, 8, and 13 of the Upper Mississippi River. We used laser ablation inductively coupled mass spectrometry to quantify strontium:calcium of the core of each otolith and classified each fish to a natal origin (i.e., tributary or potential resident). We compared patterns of natal origin across study reaches, collection years, and species and with previously published origins of independently sampled prey fish. Predator and prey assemblages across all study reaches recruited from tributaries. More prey (44%) than predators (17%) recruited from tributaries. Of fishes originating from tributaries, individuals recruited from various rivers including the large Minnesota and Wisconsin Rivers and several small tributaries. Patterns in natal origin were similar among predators and prey families and among reaches, across sampling years, and between consumed prey and independently sampled prey. Tributaries consistently contributed recruits to both prey and predator fishes, leading to a coupling of predator and prey recruitment sources across space and time. Predators directly and indirectly used tributaries for recruitment and persistence through their own and their prey's recruitment. We further highlighted the utility of using consumed prey to simultaneously study the ecology of prey and predator assemblages, thereby reducing research sampling needs.

Illinois, Iowa, Minnesota, Wisconsin

Davis Pond freshwater prediversion biomonitoring study: freshwater fisheries and eagles

In January 2001, the construction of the Davis Pond freshwater diversion structure was completed by the U.S. Army Corps of Engineers. The diversion of freshwater from the Mississippi River is intended to mitigate saltwater intrusion from the Gulf of Mexico and to lessen the concomitant loss of wetland areas. In addition to the freshwater inflow, Barataria Bay basin would receive nutrients, increased flows of sediments, and water-borne and sediment-bound compounds. The purpose of this biomonitoring study was, therefore, to serve as a baseline for prediversion concentrations of selected contaminants in bald eagle ( Haliaeetus leucocephalus ) nestlings (hereafter referred to as eaglets), representative freshwater fish, and bivalves. Samples were collected from January through June 2001. Two similarly designed postdiversion studies, as described in the biological monitoring program, are planned. Active bald eagle nests targeted for sampling eaglet blood (n = 6) were generally located southwest and south of the diversion structure. The designated sites for aquatic animal sampling were at Lake Salvador, at Lake Cataouatche, at Bayou Couba, and along the Mississippi River. Aquatic animals representative of eagle prey were collected. Fish were from three different trophic levels and have varying feeding strategies and life histories. These included herbivorous striped mullet ( Mugil cephalus ), omnivorous blue catfish ( Ictalurus furcatus ), and carnivorous largemouth bass ( Micropterus salmoides ). Three individuals per species were collected at each of the four sampling sites. Freshwater Atlantic rangia clams ( Rangia cuneata ) were collected at the downstream marsh sites, and zebra mussels ( Dreissena spp.) were collected on the Mississippi River. The U.S. Geological Survey (USGS) Biomonitoring of Environmental Status and Trends (BEST) protocols served as guides for fish sampling and health assessments. Fish are useful for monitoring aquatic ecosystems because they accumulate pesticides and other contaminants. Biomarker data on individual fish, generated at the USGS National Wetlands Research Center (Lafayette, La.), included percent white blood cells in whole blood, spleen weight to body weight ratio, liver weight to body weight ratio, condition factor, splenic macrophage aggregates, and liver microsomal 7-ethoxyresorufin-o-deethylase (EROD) activity. Fish age was estimated by comparing total lengths with values from the same species in the Southeast United States as determined from the literature. Contaminant analyses were coordinated by the U.S. Fish and Wildlife Service (USFWS) Analytical Control Facility (Laurel, Md.), where residues of organochlorine (OC) pesticides, total polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons (AHs), and trace elements were determined. The organic contaminant data were generated at the Mississippi State University Chemical Lab (Mississippi State, Miss.), and the inorganic contaminant data were generated by the Texas A&M University Geochemical and Environmental Research Group (College Station, Tex.). Statistical tests were performed to assess relationships among contaminants, fish age, fish species, and collection sites. Trends in interspecific differences among fish in concentrations of contaminants were noted. Striped mullet (hereafter mullet) frequently displayed the highest chemical concentrations. Levels of contaminants were generally higher in samples obtained from the Mississippi River than in those collected from the diversion area and were higher in mussels and clams (hereafter bivalves) than in fish. Because the Mississippi River sampling site for mullet and largemouth bass was downriver of the structure and south of New Orleans and the catfish site was upriver, the downriver data may not be directly reflective of the results from the receiving waters at the Davis Pond structure. Compared to the Caernarvon freshwater prediversion study in 1990 that assessed possible influx of contaminants with the freshwater diversion, contaminant levels in fishes and bivalves in this study were generally lower, yet three nontoxic inorganic elements in Davis Pond fish samples exhibited ranges of concentrations that were more than two times higher than did those from Caernarvon. Levels in bivalves were different between diversions but about equal in the numbers of trace elements showing high levels per location. Contaminant values were compared to those listed in various literature and agency sources, both regional and national, including the National Contaminant Biomonitoring Program (NCBP), in which the 85th percentile and above represents what is considered to be an elevated contaminant concentration and cause for concern. Generally, bivalves were at the high end of their ranges for both organic and inorganic contaminants. In this study, OCs were detectable in 67 percent of fish from the Mississippi River site, ranging from 0.15 to 1.09 μg/g wet weight (ww) or fresh weight (fw), and in 11 percent of the fish from the marsh sites, ranging from 0.06 to 0.612 μg/g ww. Bivalves from the Mississippi River had OC levels of 0.096 μg/g ww, whereas none were detectable in bivalves at the marsh sites. In this study, p,p ’-dichlorodiphenyldichloroethylene ( p,p’ -DDE) (a biodegradation product of DDT [dichlorodiphenyl trichloroethane]) and total PCBs were the most frequently detected OCs and were primarily from the Mississippi River. For total OC content, using adjusted least squares means, some significant interactions were noted between fish species and sites. PAHs were detected in aquatic animals at all sites (range of 0.017–17.534 μg/g ww), as were AHs (range of 0.423–4.549 μg/g ww); the highest levels of PAHs and AHs were found in bivalves from the Mississippi River. When analysis of variance (α = 0.05) was performed with data from aquatic animals, there were only two significant relationships between PAHs, AHs, and OCs between species, site, and age or the interaction among these variables. There was an interaction between fish species and n-decane (an AH) in that mullet and largemouth bass had significantly higher levels than did catfish ( P = 0.0175). When general linear means were used to investigate associations of inorganic contaminants among fish species, site, and age or any interactions among these variables, no significant results were noted for arsenic, cadmium, lead, beryllium, boron, molybdenum, or nickel. The range of mercury in fish in this study was 0.04–0.14 μg/g ww (0.14– 0.48 μg/g dry weight [dw]), with the most elevated levels detected in predatory largemouth bass at the sampling point farthest downstream from the structure and within the marsh area. Mercury was positively correlated with fish age ( P = 0.0152), where levels were estimated to increase 0.0253 parts per million (ppm) dw per year. In the Mississippi River, catfish showed significantly higher levels of mercury than did mullet or largemouth bass ( P = 0.00167). Among fish species, mullet displayed the highest levels in fish of aluminum, barium, manganese, and iron, all considered to have low toxicity in hydrologic systems. An interaction between fish and site was seen with aluminum ( P = 0.0031), where concentrations in mullet were significantly higher in the Mississippi River than at the other sites, as was also seen with barium ( P = 0.0009), chromium ( P = <0.0001), manganese ( P = 0.0004), strontium ( P = 0.0074), vanadium ( P = 0.0156), and zinc ( P = 0.0059). For iron ( P = 0.0.0001), mullet and largemouth bass at both the Mississippi River and Lake Salvador showed higher levels than did catfish, and these two species showed higher levels at two of the four sites. An interaction between fish and site was also seen with chromium ( P = <0.0001) in that concentrations in mullet were significantly higher in the Mississippi River than at the other sites, as was also seen with strontium ( P = 0.0074), vanadium ( P = 0.0156), and zinc ( P = 0.0059), metals for which deleterious effects have been demonstrated in other ecosystems. The NCBP program lists the 85th percentile for zinc at 34.2 μg/g fw (117.9 μg/g dw). In the Davis Pond prediversion biomonitoring study (hereafter the current study), one fish (MUL31RIVER, fish ID 8) showed values higher than that (125.4 μg/g dw or 37.54 μg/g ww), and the Mississippi River bivalve sample (MUSSRIVER) had a value of 140 μg/g dw (41.2 μg/g ww). In the current study, approximately 86 percent of the fish had measurable selenium levels, yet none reached the 85th percentile. The 85th percentile for selenium from the NCBP was 0.73 μg/g ww. Significantly higher levels of selenium were seen in mullet than in largemouth bass and catfish ( P = 0.0023). The NCBP 85th percentile for lead is 0.22 μg/g ww (0.76 μg/g dw). In the current study, the range of concentrations of lead was as much as 18.3 ppm dw (MUL31RIVER, fish ID 8), with the three most elevated values (range of 3.46–5.31 μg/g ww) coming from mullet from the Mississippi River. Biomarker data are measurable and directly reflect the condition of the animal, and measuring more than one biomarker in an individual increases confidence in health assessments. In the current study, biomarkers included macrophage aggregates (MAs), liver (hepatosomatic index [HSI]) and spleen (splenosomatic index [SSI]) weight to body weight ratios, percent white blood cells (WBCs) in whole blood, and condition factor. Few significant differences were noted with any of the biomarkers between sites, and there were no relationships between species and sites. For improved use of biomarker assessments, an increase in fish sample size would be useful for postdiversion sampling, as would comparisons of fish of the same sex and reproductive condition. During the current study, success for eagle nests in the diversion area and reference sites was similar as determined by numbers of nestlings fledged. When temperatures were below average during winter 2000, nests in both regions similarly failed. At each nest, the primary evidence of food items was small mammals. Eaglets (n = 6) generally appeared healthy, and whole blood concentrations of organic contaminants exceeded detection limits with three incidences of p,p’ -DDE (0.002–0.006 μg/L ww) and one incidence of oxychlordane (0.002 μg/L ww). The levels of p,p’ -DDE were well below those that have been inversely correlated with productivity and success rates of nesting bald eagles on a regional scale. The low values found in the whole blood samples for OC pesticides and PCBs were even lower when corrected for plasma volume. Aluminum values were 3.66 and 5.75 μg/L in two samples, zinc ranged from 5.21 to 6.77 μg/L ww in six samples, and silicon ranged from 1.7 to 4.6 μg/L in four samples. Selenium was detectable in each bird with the range at 0.332–0.566 μg/L ww, and strontium ranged from 0.0581 to 0.0975 μg/L ww. Mercury was detectable in blood samples from each bird and ranged from 0.0254 to 0.0845 μg/L ww, whereas lead was detectable in four samples and ranged from 0.0042 to 0.0136 μg/L ww. Although no detectable levels of total PCBs were found (also correlated with decreased reproductive productivity), 70 percent of the aquatic animals from the Mississippi River contained total PCBs (range 0.13–0.79 μg/L), whereas only about 7 percent of the aquatic animals sampled from the marsh area contained PCBs. Suggestions for postdiversion sampling include lowering the analytical detection limit for some metals, sampling aquatic animals over the course of a single season, obtaining a higher sample number of mature fish of one species (for example, blue catfish) within a range of total lengths for biomarker analyses, obtaining otoliths for estimating fish ages, assessing dioxins in eaglet blood, examining triazines in water, and obtaining all Mississippi River fish samples as close to the Davis Pond structure intake as possible. Because contaminants found in blood of eaglets reflect their prey species and because of the contaminant levels found in fish in the current study, eaglets may not be consuming primarily these species; therefore, obtaining juvenile nutria ( Myocastor coypus ) or turtle species for contaminant analyses might be considered, as well as collecting greater blood volume and using plasma to measure OCs and PCBs. Data obtained postdiversion will be compared with prediversion data to monitor changes.

Louisiana

Applied Geochemistry Special Issue on Environmental geochemistry of modern mining

Environmental geochemistry is an integral part of the mine-life cycle, particularly for modern mining. The critical importance of environmental geochemistry begins with pre-mining baseline characterization and the assessment of environmental risks related to mining, continues through active mining especially in water and waste management practices, and culminates in mine closure. The enhanced significance of environmental geochemistry to modern mining has arisen from an increased knowledge of the impacts that historical and active mining can have on the environment, and from new regulations meant to guard against these impacts. New regulations are commonly motivated by advances in the scientific understanding of the environmental impacts of past mining. The impacts can be physical, chemical, and biological in nature. The physical challenges typically fall within the purview of engineers, whereas the chemical and biological challenges typically require a multidisciplinary array of expertise including geologists, geochemists, hydrologists, microbiologists, and biologists. The modern mine-permitting process throughout most of the world now requires that potential risks be assessed prior to the start of mining. The strategies for this risk assessment include a thorough characterization of pre-mining baseline conditions and the identification of risks specifically related to the manner in which the ore will be mined and processed, how water and waste products will be managed, and what the final configuration of the post-mining landscape will be. In the Fall 2010, the Society of Economic Geologists held a short course in conjunction with the annual meeting of the Geological Society of America in Denver, Colorado (USA) to examine the environmental geochemistry of modern mining. The intent was to focus on issues that are pertinent to current and future mines, as opposed to abandoned mines, which have been the focus of numerous previous short courses. The geochemical challenges of current and future mines share similarities with abandoned mines, but differences also exist. Mining and ore processing techniques have changed; the environmental footprint of waste materials has changed; environmental protection has become a more integral part of the mine planning process; and most historical mining was done with limited regard for the environment. The 17 papers in this special issue evolved from the Society of Economic Geologists’ short course. The relevant geochemical processes encompass the source, transport, and fate of contaminants related to the life cycle of a mine. Contaminants include metals and other inorganic species derived from geologic sources such as ore and solid mine waste, and substances brought to the site for ore processing, such as cyanide to leach gold. Factors, such as mine-waste mineralogy, hydrologic setting, mine-drainage chemistry, and microbial activity, that affect the hydrochemical risks from mining are reviewed by Nordstrom et al. In another paper, Nordstrom discusses baseline characterization at mine sites in a regulatory framework, and emphasizes the influence of mineral deposits in producing naturally elevated concentrations of many trace elements in surface water and groundwater. Surface water quality in mineralized watersheds is influenced by a number of processes that act on daily (diel) cycles and can produce dramatic variations in trace element concentrations as described by Gammons et al. Pre-mining baseline characterization studies should strive to capture the magnitude of these diel variations. Desbarats et al., using a case study of mine drainage from a gold mine, illustrate how elements that commonly occur as negatively charged species (anions) in solution, such as arsenic as arsenate, behave in an opposite fashion than most metals, which occur as positively charged species (cations). Significant improvement in the understanding of factors that influence the toxicity of metals to aquatic organisms in surface water has highlighted the importance of aqueous chemistry, particularly dissolved organic carbon, as described by Smith et al. Stream sediment contamination is another important pathway for affecting aquatic organisms, as reviewed by Besser et al. Understanding and predicting environmental consequences from mining begins with knowing the mineralogy and mineral reactivity of the ore, the wastes, and of secondary minerals formed later. Jamieson et al. review the importance of mineralogical studies in mine planning and remediation. A number of types of site-specific studies are needed to identify environmental risks related to individual mines. Lapakko reviews the general framework of mine waste characterization studies that are integral to the mine planning process. Hageman et al. present a comparative study of several static tests commonly used to characterize mine waste. The mining and ore processing practices employed at a specific mine site will vary on the basis of the commodities being targeted, the geology of the deposit, the geometry of the deposit, and the mining and ore processing methods used. Thus, these factors, in addition to the waste management practices used, can result in a variety of end-member mine waste features, each of which has its own set of challenges. Open pit mines and underground mines require waste rock to be removed to access ore. Waste rock presents unique problems because the rock is commonly mineralized at sub-economic grades and has not been processed to remove potentially problematic minerals, such as pyrite. Amos et al. examine the salient aspects of the geochemistry of waste rock. Mill tailings – the waste material after ore minerals have been removed – are a volumetrically important solid waste at many mine sites. Their fine grain size and the options for their management make their behavior in the environment distinct from that of waste rock. Lindsay et al. describe some of these differences through three case-study examples. Subaqueous disposal of tailings is another option described by Moncur et al. Cyanide leaching for gold extraction is a common method throughout the world. Johnson describes environmental aspects of cyanidation. Uranium mining presents unique environmental challenges, particularly since in-situ recovery has seen widespread use. Campbell et al. review the environmental geochemistry of uranium mining and current research on bioremediation. Ore concentrates from many types of metal mining undergo a pyrometallurgical technique known as smelting to extract the metal. Slag is the result of smelting, and it may be an environmental liability or a valuable byproduct, as described by Piatak et al. Finally, the open pits that result from surface mining commonly reach below the water table. At the end of mining, these pits may fill to form lakes that become part of the legacy of the mine. Castendyk et al., in two papers, review theoretical aspects of the environmental limnology of pit lakes. They also describe approaches that have been used to model pit lake water balance, wall-rock contributions to pit lake chemistry, pit lake water quality, and limnological processes, such as vertical mixing, through the use of three case studies.

Applied Geochemistry