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Study and interpretation of the chemical characteristics of natural water

The chemical composition of natural water is derived from many different sources of solutes, including gases and aerosols from the atmosphere, weathering and erosion of rocks and soil, solution or precipitation reactions occurring below the land surface, and cultural effects resulting from human activities. Broad interrelationships among these processes and their effects can be discerned by application of principles of chemical thermodynamics. Some of the processes of solution or precipitation of minerals can be closely evaluated by means of principles of chemical equilibrium, including the law of mass action and the Nernst equation. Other processes are irreversible and require consideration of reaction mechanisms and rates. The chemical composition of the crustal rocks of the Earth and the composition of the ocean and the atmosphere are significant in evaluating sources of solutes in natural freshwater. The ways in which solutes are taken up or precipitated and the amounts present in solution are influenced by many environmental factors, especially climate, structure and position of rock strata, and biochemical effects associated with life cycles of plants and animals, both microscopic and macroscopic. Taken together and in application with the further influence of the general circulation of all water in the hydrologic cycle, the chemical principles and environmental factors form a basis for the developing science of natural-water chemistry. Fundamental data used in the determination of water quality are obtained by the chemical analysis of water samples in the laboratory or onsite sensing of chemical properties in the field. Sampling is complicated by changes in the composition of moving water and by the effects of particulate suspended material. Some constituents are unstable and require onsite determination or sample preservation. Most of the constituents determined are reported in gravimetric units, usually milligrams per liter or milliequivalents per liter. More than 60 constituents and properties are included in water analyses frequently enough to provide a basis for consideration of the sources from which each is generally derived, the most probable forms of elements and ions in solution, solubilitycontrols, expected concentration ranges, and other chemical factors. Mechanisms that control concentrations of elements commonly present in amounts less than a few tens of micrograms per liter cannot always be easily ascertained, but present information suggests that many are controlled by solubility of their hydroxides or carbonates or by sorption on solid particles. Many dissolved organic compounds can now be specifically determined. Chemical analyses may be grouped and statistically evaluated by means, medians, frequency distributions, or ion correlations to summarize large volumes of data. Graphing of analyses or of groups of analyses aids in showing chemical relationships among water, probable sources of solutes, areal water-quality regimen, temporal and spatial variation, and water-resources evaluation. Graphs may show water type based on chemical composition, relationships among ions, or groups of ions in individual waters or many waters considered simultaneously. The relationships of water quality to hydrogeologic characteristics, such as stream discharge rate or ground-water flow patterns, can be shown by mathematical equations, graphs, and maps. About 80 water analyses selected from the literature are tabulated to illustrate the relationships described, and some of these, along with many others that are not tabulated, are also used in demonstrating graphing and mapping techniques. Relationships of water composition to source rock type are illustrated by graphs of some of the tabulated analyses. Human activities may modify water composition extensively through direct effects of pollution and indirect results of water development, such as intrusion of seawater in groundwater aquifers. Water-quality standards for domestic, agricultural, and industrial use have been published by various agencies. Irrigation project requirements for water quality are particularly intricate. Fundamental knowledge of processes that control natural-water composition is required for rational management of water quality.

Water Supply Paper↗

Reconnaissance of ground-water quality in the Papio-Missouri River Natural Resources District, eastern Nebraska, July through September 1992

A reconnaissance of ground-water quality was conducted in the Papio-Missouri River Natural Resources District of eastern Nebraska. Sixty-one irrigation, municipal, domestic, and industrial wells completed in the principal aquifers--the unconfined Elkhorn, Missouri, and Platte River Valley alluvial aquifers, the upland area alluvial aquifers, and the Dakota aquifer--were selected for water-quality sampling during July, August, and September 1992. Analyses of water samples from the wells included determination of dissolved nitrate as nitrogen and triazine and acetanilide herbicides. Waterquality analyses of a subset of 42 water samples included dissolved solids, major ions, metals, trace elements, and radionuclides. Concentrations of dissolved nitrate as nitrogen in water samples from 2 of 13 wells completed in the upland area alluvial aquifers exceeded the U.S. Environmental Protection Agency Maximum Contaminant Level for drinking water of 10 milligrams per liter. Thirty-nine percent of the dissolved nitrate-as-nitrogen concentrations were less than the detection level of 0.05 milligram per liter. The largest median dissolved nitrate-as-nitrogen concentrations were in water from the upland area alluvial aquifers and the Dakota aquifer. Water from all principal aquifers, except the Dakota aquifer, had detectable concentrations of herbicides. Herbicides detected included alachlor (1 detection), atrazine (13 detections), cyanazine (5 detections), deisopropylatrazine (6 detections), deethylatrazine (9 detections), metolachlor (6 detections), metribuzin (1 detection), prometon (6 detections), and simazine (2 detections). Herbicide concentrations did not exceed U.S. Environmental Protection Agency Maximum Contaminant Levels for drinking water. In areas where the hydraulic gradient favors loss of surface water to ground water, the detection of herbicides in water from wells along the banks of the Platte River indicates that the river could act as a line source of herbicides. Water from the alluvial and bedrock aquifers generally was a calcium bicarbonate type and was hard. Two of nine water samples collected from the Dakota aquifer contained calcium sulfate type water. Results of analyses of 42 groundwater samples for major ions, metals, trace elements, and radionuclide constituents indicated that statistically at least one principal aquifer had significant differences in its water chemistry. In general, the water chemistry of the Dakota aquifer was similar to the water chemistry of the upland area alluvial aquifers in areas where there was a hydraulic connection. The water from the Dakota aquifer had large dissolved-solids, calcium, sulfate, chloride, iron, lithium, manganese, and strontium concentrations in areas where the aquifer is thought not to be in hydraulic connection with the Missouri River Valley and upland area alluvial aquifers. Ground-water quality in the Papio-MissouriRiver Natural Resources District is generally suitable for most uses. However, the numerous occurrences of herbicides in water of the Elkhorn and Platte River Valley alluvial aquifers, especially near the Platte River, are of concern because U.S. Environmental Protection Agency Maximum Contaminant Levels could be exceeded. Concentrations in three of nine water samples collected from wells completed in the Dakota aquifer exceeded the U.S. Environmental Protection Agency Maximum Contaminant Levels or Secondary Maximum Contaminant Levels for gross alpha activity, radon-222 activity, dissolved solids, sulfate, or iron. Also of concern are the exceedances of the U.S Environmental Protection Agency proposed Maximum Contaminant Level for radon-222 activity.

Water-Resources Investigations Report↗

Results of mineral, chemical, and sulfate isotopic analyses of water, soil, rocks, and soil extracts from the Pariette Draw Watershed, Uinta Basin, Utah

In 2010, Utah Department of Environmental Quality (DEQ) Division of Water Quality (UDWQ, 2010) determined that water quality in Pariette Draw was in violation of Federal and State water quality criteria for total dissolved solids (TDS), selenium (Se), and boron (B). The measure of total dissolved solids is the sum of all the major ion concentrations in solution and in this case, the dominant ions are sodium (Na) and sulfate (SO4), which can form salts like thenardite (Na2SO4) and mirabilite (Na2SO4⋅H2O). The Utah Department of Environmental Quality (2010) classified the contamination as natural background and from nonpoint sources related to regional lithology and irrigation practices. Although the daily loads of the constituents of concern and water chemistry have been characterized for parts of the watershed, little is known about the controls that bedrock and soil mineralogy have on salt, Se, and B storage and the water-rock interactions that influence the mobility of these components in ground and surface waters. Studies in the Uncompahgre River watershed in Colorado by Tuttle and others (2014a, 2014b) show that salt derived from weathering of shale in a semiarid climate is stored in a variety of minerals that contribute solutes to runoff and surface waters based on a complex set of conditions such as water availability, geomorphic position (for example, topography controls the depth of salt accumulation in soils), water-table fluctuations, redox conditions, mineral dissolution kinetics, ion-exchange reactions, and secondary mineral formation. Elements like Se and B commonly reside in soluble salt phases, so knowledge of the behavior of salt minerals also sheds light on the behavior of associated contaminants. The goal of this study was to establish a process-based understanding of salt, Se, and B behavior to address whether these contaminants can be better managed, or if uncontrollable natural processes will overwhelm any attempts to bring Pariette Draw into compliance with respect to recently established total maximum daily limits (TMDLs). We collected data to refine our knowledge about the role of rock weathering and soil formation in the transport and storage of salt in the watershed and to show how salt is cycled under irrigated and natural conditions. Our approach was to sample rock, soils, and sediment on irrigated and natural terrain for mineralogical analysis to determine the residence of salt and associated Se and B, classify minerals as primary (related to rock formation) or secondary weathering products, and characterize mineral dissolution kinetics. Mineral and chemical analyses and selective extractions of rocks and soils provide useful information in understanding solute movement and mineral dissolution/ formation. The resulting data are critical in determining residence of salt, Se, and B in weathered rock and soil and understanding the mobility during water-rock-soil interactions. This report summarizes our methods for sample and data collection and tabulates the mineral, chemical, and isotopic data collected.

Utah↗

Toxic effects of dietary methylmercury on immune function and hematology in American kestrels (Falco sparverius)

Fifty-nine adult male American kestrels ( Falco sparverius ) were assigned to one of three diet formulations including 0 (control), 0.6, and 3.9 &mu;g/g (dry wt) methylmercury (MeHg). Kestrels received their diets daily for 13 weeks to assess the effects of dietary MeHg on immunocompetence. Immunotoxic endpoints included assessment of cell-mediated immunity (CMI) using the phytohemagglutinin (PHA) skin-swelling assay and primary and secondary antibody-mediated immune responses (IR) via the sheep red blood cell (SRBC) hemagglutination assay. Select hematology and histology parameters were evaluated to corroborate the results of functional assays and to assess immunosuppression of T and B cell-dependent components in spleen tissue. Kestrels in the 0.6 and 3.9 &mu;g/g MeHg groups exhibited suppression of CMI, including lower PHA stimulation indexes ( p = 0.019) and a 42 to 45% depletion of T cell-dependent splenic lymphoid tissue ( p = 0.006). Kestrels in the 0.6 &mu;g/g group exhibited suppression of the primary IR to SRBCs ( p = 0.014). MeHg did not have a noticeable effect on the secondary IR ( p = 0.166). Elevation of absolute heterophil counts ( p < 0.001), the heterophil to lymphocyte ratio ( p < 0.001), and total white blood cell counts ( p = 0.003) was apparent in the 3.9 &mu;g/g group at week 12. Heterophilia, or the excess of heterophils in peripheral blood above normal ranges, was apparent in seven of 17 (41%) kestrels in the 3.9 &mu;g/g group and was indicative of an acute inflammatory response or physiological stress. This study revealed that adult kestrels were more sensitive to immunotoxic effects of MeHg at environmentally relevant dietary concentrations than they were to reproductive effects as previously reported.

Environmental Toxicology and Chemistry↗

Regional ground-water flow and geochemistry in the midwestern Basins and Arches aquifer system in parts of Indiana, Ohio, Michigan, and Illinois

This report synthesizes information on the regional ground-water flow and geochemistry in the Midwestern Basins and Arches aquifer system in parts of Indiana, Ohio, Michigan, and Illinois. Aquifers that compose this water-table aquifer system include glacial aquifers and an underlying, areally extensive carbonate-rock aquifer. Water within the aquifers is most commonly a Ca-Mg-HCO 3 type or a Ca-Mg-SO 4 type. In general, the distribution of hydrochemical facies within the aquifer system is controlled by the mineralogy of the aquifer material, rather than by a chemical evolution of water along general directions of regional ground-water flow. Some ground-water flow systems within the aquifer system provide base flow to streams in response to ground-water recharge events. Other (often deeper) ground-water flow systems respond minimally to variations in ground-water recharge from precipitation and provide a fairly constant supply of water to streams. Streamflow hydrographs and base-flow duration curves were used to estimate such components of base flow in selected streams for long-term steady-state conditions in the aquifer system. Mean sustained ground-water discharge (discharge from fairly stable ground-water flow systems) ranges from 3 to 50 percent of mean ground-water discharge (discharge from all ground-water flow systems) to the selected stream reaches. These percentages indicate that 50 to 97 percent of base flow in the streams within the study area can be attributed to transient ground-water flow systems, which typically have a major component of local-scale flow. Because ground-water flow across the external boundaries of the aquifer system is minimal, such percentages indicate that most ground-water flow in the aquifer system is associated with seasonally transient local flow systems. Results of a ground-water flow model that was calibrated by use of regression methods and that simulates regional flow systems within the aquifer system (approximately 10 percent of total ground-water flow in the aquifer system) indicate that most water (99 percent) in simulated regional flow systems is from recharge at the water table. Most water (78 percent) discharges from simulated regional flow systems to the principal streams. Less than 3 percent of water in simulated regional flow systems discharges to the Ohio River, Lake Erie, or downdip areas in the Illinois (structural) Basin. Simulations also indicate that most of the Midwestern Basins and Arches aquifer system is characterized by alternating regional recharge and discharge areas at intervals of less than every 10 miles along the dominant regional trends of the potentiometric surfaces in the aquifers. Such alternating regional recharge and discharge areas result in the absence of long flow paths from the very highest regional potentiometric levels to the very lowest regional potentiometric levels. The presence of tritiated ground water (less than 50 years old) across most of the aquifer system also indicates that the aquifer system receives recharge across most of the study area. The northeastern part of the aquifer system near Lake Erie differs from the rest of the system with respect to regional ground-water flow and chemistry. Specifically, part of the northeastern part of the aquifer system can be characterized as a broad area (tens of miles) of weak regional discharge (less than 0.5 inch per year). Results of the regional ground-water flow model indicate that regional flow systems have a limited ability to carry ground water away from this area; thus precipitation is prevented from recharging the regional flow systems in this part of the aquifer system. Some ground water recharged during Pleistocene glaciation was found in this area.

Illinois, Indiana, Michigan, Ohio↗

Estimates of groundwater recharge rates and sources in the East Mountain area, Eastern Bernalillo County, New Mexico, 2005-12

The U.S. Geological Survey, in cooperation with the Bernalillo County Public Works Division, has conducted a monitoring program in the East Mountain area of eastern Bernalillo County, New Mexico, since 2000 to better define the hydrogeologic characteristics of the East Mountain area and to provide scientific information that will assist in the sustainable management of water resources. This report presents estimates of groundwater recharge to the aquifers that supply water to a network of springs that discharged within the East Mountain area of eastern Bernalillo County during 2005&ndash;12. Chloride concentration, the mass ratio of chloride to bromide, and the stable isotope ratios of hydrogen and oxygen were used to estimate annual groundwater recharge rates and to identify the sources and timing of recharge to the aquifers in the East Mountain area. Groundwater recharge rates were estimated by using a chloride mass-balance (CMB) method applied to data from selected springs located in the study area. Eleven springs and four downgradient monitoring wells were sampled for this study. On the basis of chloride concentrations and the mass ratio of chloride to bromide, eight of the eleven sampled springs are considered representative of dilute groundwater recharged by meteoric water in the Sandia Mountains. Eight of the eleven springs sampled as part of this investigation are considered representative of dilute groundwater not influenced by nonmeteoric chloride sources on the basis of analysis of chloride concentrations and the mass ratio of chloride to bromide. Chloride concentrations at three of the sampled springs were likely affected by nonmeteoric chloride sources. Results of CMB calculations for the eight springs with Cl:Br ratios and chloride concentrations within the range of dilute groundwater (not influenced by nonmeteoric chloride sources) indicated that between about 5.5 and 23 percent of annual precipitation recharges the groundwater system. The variation in estimated recharge rates indicated that the mechanisms for recharge and groundwater movement in the East Mountain area are complex and that factors such as climate variability, the extent and interconnection of structural features such as faults and fractures, and potential solution enhancement of the aquifers all play important roles in the rates and timing of recharge. Stable isotope data from springs and snowpacks sampled in the East Mountain area were compared with local, regional, and global meteoric water lines and were analyzed along with values representing the stable isotope composition of winter precipitation and summer monsoonal rains. Results of the stable isotope analysis from springs in this study suggested that winter precipitation is the primary source of groundwater recharge to the aquifers supplying the springs, but there is a component of more isotopically enriched precipitation being recharged as well, likely from summer monsoonal rains. Specific conductance, groundwater-level hydrographs, snowpack chemistry, and snow-water equivalent data were used to inform the analyses and corroborate the findings of the CMB and stable isotope results.

New Mexico↗

Dislocation substructure of mantle-derived olivine as revealed by selective chemical etching and transmission electron microscopy

Cleaved and mechanically polished surfaces of olivine from peridotite xenoliths from San Carlos, Arizona, were chemically etched using the techniques of Wegner and Christie (1974). Dislocation etch pits are produced on all surface orientations and they tend to be preferentially aligned along the traces of subgrain boundaries, which are approximately parallel to (100), (010), and (001). Shallow channels were also produced on (010) surfaces and represent dislocations near the surface that are etched out along their lengths. The dislocation etch channel loops are often concentric, and emanate from (100) subgrain boundaries, which suggests that dislocation sources are in the boundaries. Data on subgrain misorientation and dislocation line orientation and arguments based on subgrain boundary energy minimization are used to characterize the dislocation structures of the subgrain boundaries. (010) subgrain boundaries are of the twist type, composed of networks of [100] and [001] screw dislocations. Both (100) and (001) subgrain boundaries are tilt walls composed of arrays of edge dislocation with Burgers vectors b=[100] and [001], respectively. The inferred slip systems are {001} ???100???, {100} ???001???, and {010} ???100??? in order of diminishing importance. Exploratory transmission electron microscopy is in accord with these identifications. The flow stresses associated with the development of the subgrain structure are estimated from the densities of free dislocations and from the subgrain dimensions. Inferred stresses range from 35 to 75 bars using the free dislocation densities and 20 to 100 bars using the subgrain sizes. ?? 1978 Springer-Verlag.

Physics and Chemistry of Minerals↗

Rapid toxicity assessment of sediments from estuarine ecosystems: A new tandem in vitro testing approach

Microtox® and Mutatox® were used to evaluate the acute toxicity and genotoxicity, respectively, of organic sediment extracts from Pensacola Bay and St. Andrew Bay, two estuaries that cover about 273 and 127 km 2 , respectively, along the Gulf coast of Florida, USA. The sensitivity and selectivity of these two bioluminescent toxicity assays were demonstrated in validation studies with over 50 pesticides, genotoxins, and industrial pollutants, both as single compounds and in complex mixtures. The 50% effective concentration (EC50) values of insecticides, petroleum products, and polychlorinated biphenyls determined by Microtox all tended to group around the mean EC50 value of 1.2 (0.8) mg/L. The polycyclic aromatic hydrocarbon sensitivity of Mutatox was in general similar to that reported in the Ames test. Surficial sediment samples were collected, extracted with dichloromethane, evaporated and concentrated under nitrogen, dissolved in dimethyl sulfoxide, assayed for acute toxicity and genotoxicity, and compared with reference sediments. Samples with low EC50 values, and determined to be genotoxic, were detected in Massalina Bayou, Watson Bayou, East Bay, and St. Andrew Bay–East in St. Andrew Bay as well as Bayou Grande, Bayou Chico, and Bayou Texar in Pensacola Bay. An overview of these data sets analyzed by Spearman rank correlation showed a significant correlation between acute toxicity and genotoxicity ( p < 0.05). Microtox and Mutatox in tandem was a sensitive, cost‐effective, and rapid (<24 h) screening tool that identified troublesome areas of pollution and assessed the potential sediment toxicity of lipophilic contaminants in aquatic ecosystems.

Environmental Toxicology and Chemistry↗

Quantifying solar spectral irradiance in aquatic habitats for the assessment of photoenhanced toxicity

The spectra and intensity of solar radiation (solar spectral irradiance [SSI]) was quantified in selected aquatic habitats in the vicinity of an oil field on the California coast. Solar spectral irradiance measurements consisted of spectral scans (280–700 nm) and radiometric measurements of ultraviolet (UV): UVB (280–320 nm) and UVA (320–400 nm). Solar spectral irradiance measurements were taken at the surface and at various depths in two marsh ponds, a shallow wetland, an estuary lagoon, and the intertidal area of a high-energy sandy beach. Daily fluctuation in SSI showed a general parabolic relationship with time; maximum structure–activity relationship (SAR) was observed at approximate solar noon. Solar spectral irradiance measurements taken at 10-cm depth at approximate solar noon in multiple aquatic habitats exhibited only a twofold variation in visible light and UVA and a 4.5-fold variation in UVB. Visible light ranged from 11,000 to 19,000 μW/cm 2 , UVA ranged from 460 to 1,100 μW/cm 2 , and UVB ranged from 8.4 to 38 μW/cm 2 . In each habitat, the attenuation of light intensity with increasing water depth was differentially affected over specific wavelengths of SSI. The study results allowed the development of environmentally realistic light regimes necessary for photoenhanced toxicity studies.

Environmental Toxicology and Chemistry↗

Simultaneous speciation of arsenic, selenium, and chromium: species, stability, sample preservation, and analysis of ash and soil leachates

An analytical method using high-performance liquid chromatography separation with inductively coupled plasma mass spectrometry (ICP-MS) detection previously developed for the determination of Cr(III) and Cr(VI) has been adapted to allow the determination of As(III), As(V), Se(IV), Se(VI), Cr(III), and Cr(VI) under the same chromatographic conditions. Using this method, all six inorganic species can be determined in less than 3 min. A dynamic reaction cell (DRC)-ICP-MS system was used to detect the species eluted from the chromatographic column in order to reduce interferences. A variety of reaction cell gases and conditions may be utilized with the DRC-ICP-MS, and final selection of conditions is determined by data quality objectives. Results indicated all starting standards, reagents, and sample vials should be thoroughly tested for contamination. Tests on species stability indicated that refrigeration at 10&deg; C was preferential to freezing for most species, particularly when all species were present, and that sample solutions and extracts should be analyzed as soon as possible to eliminate species instability and interconversion effects. A variety of environmental and geological samples, including waters and deionized water [leachates] and simulated biological leachates from soils and wildfire ashes have been analyzed using this method. Analytical spikes performed on each sample were used to evaluate data quality. Speciation analyses were conducted on deionized water leachates and simulated lung fluid leachates of ash and soils impacted by wildfires. These results show that, for leachates containing high levels of total Cr, the majority of the chromium was present in the hexavalent Cr(VI) form. In general, total and hexavalent chromium levels for samples taken from burned residential areas were higher than those obtained from non-residential forested areas. Arsenic, when found, was generally in the more oxidized As(V) form. Selenium (IV) and (VI) were present, but typically at low levels.

Analytical and Bioanalytical Chemistry↗

Development of soil radiocarbon profiles in a reactive transport framework

Today, there is a greater appreciation for the importance of the physical protection of carbon (C) through interactions with mineral surfaces, isolation from microbes, and the important role of transport in shaping soil properties and controlling moisture limitations on decomposition. As our paradigm for soil organic carbon (SOC) preservation changes, so too should our representation of the underlying processes in soil models. Reactive transport models (RTMs) provide a framework capable of assessing the interactive influence of soil chemistry and transport processes on the accumulation and turnover of SOC. In this study, we present new developments in the isotopically enabled RTM “CrunchTope,” which is capable of explicitly tracking the three isotopes of carbon ( 12 C, 13 C, and 14 C) and their fractionation between multiple coexisting and interacting solid, liquid and gas phases. This modeling framework opens the door to new applications of depth-resolved RTMs models in application to SOC and deeper subsurface carbon reservoirs. Here, we demonstrate SOC accumulation and radiocarbon aging for long-timescale models of soil development in CrunchTope. Our goal is to assess advantages and limitations of such an approach and to identify the type and complexity of reaction networks that are required to adequately apply this model to SOC dynamics. We assess the behavior of this model relative to a high-resolution dataset of SOC content, stable isotope composition, and radiocarbon ages as well as physical and hydrologic data measured from a chronosequence of soils located near Santa Cruz, California. Starting from a previously published model using a simplified reaction network with a single class of carbon, we sequentially incorporate multiple C reservoirs subject to both reactivity and transport pathways. Our results indicate that multiple SOC pools with different mean ages of C do not inherently emerge as a result of including reactions which are conventionally expected to provide a diversity of transit times, i.e., sorption and complexation of SOC on mineral surfaces. Instead, transit times emerge as a result of the timescales of the reactions represented in the reaction network. For mineral associated C, the RTM framework imposes dynamic equilibrium with the fluid phase dissolved organic C, such that no distinction in radiocarbon ages is achieved between these pools. Aged C can be produced by including a solid-phase C reservoir, with a rate-limited solubilization coefficient. Aging of SOC in this way is more akin to selective preservation than to mineral protection and, while such a mechanism may be at play in many soils, mineral protection is thought to be at least as important. As such, our results indicate that additional parameterization is required to reproduce the heterogeneity of carbon transit times that result from organo-mineral interactions. These efforts show the promise of a modeling approach where the varied transit time of soil C emerges from the dynamic physical and hydrologic properties of the model rather than from the a priori assignment of operationally defined pools.

Geochimica et Cosmochimica Acta↗

Selected trace elements and organochlorines: some findings in blood and eggs of nesting common eiders ( Somateria mollissima ) from Finland

In 1997 and 1998, we collected blood samples from nesting adult female common eiders (Somateria mollissima) at five locations in the Baltic Sea near coastal Finland and analyzed them for lead, selenium, mercury, and arsenic. Eggs were collected from three locations in 1997 for analysis of selenium, mercury, arsenic, and 17 organochlorines (OCs). Mean blood lead concentrations varied by location and year and ranged from 0.02 ppm (residues in blood on wet weight basis) to 0.12 ppm, although one bird had 14.2 ppm lead in its blood. Lead residues in the blood of eiders were positively correlated with the stage of incubation, and lead inhibited the activity of the enzyme delta-aminolevulinic acid dehydratase (ALAD) in the blood. Selenium concentrations in eider blood varied by location, with means of 1.26 to 2.86 ppm. Median residues of selenium and mercury in eider eggs were 0.55 and 0.10 ppm (residues in eggs on fresh weight basis), respectively, and concentrations of both selenium and mercury in eggs were correlated with those in blood. Median concentrations of p,pa??-dichlorodiphenyldichloroethylene in eggs ranged from 13.1 to 29.6 ppb, but all other OCs were below detection limits. The residues of contaminants that we found in eggs were below concentrations generally considered to affect avian reproduction. The negative correlation of ALAD activity with blood lead concentrations is evidence of an adverse physiological effect of lead exposure in this population.

Coastal Areas↗

Effects of water temperature on the toxicity of 4-nitrophenol and 2,4-dinitrophenol to developing rainbow trout (Oncorhynchus mykiss)

Early-life-stage (ELS) toxicity tests were conducted to determine the effect of selected water temperatures on the toxicity of 4-nitrophenol and 2,4-dinitrophenol to rainbow trout ( Oncorhynchus mykiss ). NOECs were determined for growth and mortality at selected time intervals and water temperatures of 7, 12, and 17°C. As tests progressed, NOECs leveled to constant time-independent values that were similar for tests at each temperature. In 4-nitrophenol tests, the time-independent NOEC values at 7, 12, and 17°C, respectively, were 1.16, 1.20, and 1.16 mg/L for growth and 3.40, 3.38, and 2.20 mg/L for mortality. For 2,4-dinitrophenol, time-independent NOEC values at 7, 12, and 17°C, respectively, were 1.07, 0.50, and 0.80 mg/L for growth and 1.30, 1.89, and 1.60 mg/L for mortality. Temperature did, however, affect the rate at which time-independent NOECs were reached. More time was required to reach time-independent NOECs as temperature decreased. For example, the time-independent NOEC in 4-nitrophenol tests at 17°C was reached in 14 d, whereas it required 42 d at 7°C. The effect of temperature on toxicity must be considered in hazard assessment protocols to assess risk accurately and protect aquatic organisms adequately. Chronic toxicity tests are necessary to assess risk because acute toxicity tests cannot provide the information necessary to predict the long-term effects of factors such as temperature in natural environments.

Environmental Toxicology and Chemistry↗

Aquatic dissipation of triclopyr in Lake Seminole, Georgia

A field study was conducted to evaluate the environmental dissipation of triclopyr herbicide under aquatic-use conditions. Three 4-h plots in Lake Seminole, Georgia, were selected for use: one control, one aerial plot, and one subsurface plot; both applications were at the maximum aquatic-use rate of 2.5 mg/L. Water, sediment, plants, fish, clams, and crayfish were all analyzed for residues, and water temperature, oxygen levels, pH, and conductivity were monitored. The half-life for aqueous-phase triclopyr ranged from 0.5 to 3.6 days, and the dissipation in surface and bottom waters was equivalent. The intermediate decay product of triclopyr, 3,5,6-trichloro-2-pyridinol (TCP), had an observed aquatic half-life of less than 1 day. No accumulation of triclopyr or TCP on sediment was observed. The half-life of triclopyr metabolized by aquatic plants averaged 4 days. Fish species did not exhibit any bioconcentration of triclopyr or TCP, with only trace amounts of either compound found in fish tissue. Both clams and crayfish contained detectable residues of triclopyr. The elimination of triclopyr from clam tissue was more rapid, with an observed half-life of 1.5 days, vs 12 days for crayfish; retention of triclopyr in the crayfish carcass (carapace, chelopeds, and gills) may have been an important mechanism. There was no detectable decline in water quality in either treatment plot. ?? 1993 American Chemical Society.

Journal of Agricultural and Food Chemistry↗

Chemical evolution and estimated flow velocity of water in the Trinity Aquifer, south-central Texas

Three permeable zones with varying lithology and water chemistry compose the Trinity aquifer, a principal source of water in the 5,500- square-mile study area in south-central Texas. The upper permeable zone locally yields small quantities of water to wells and was not included in this study. The middle permeable zone primarily is composed of limestone with minor amounts of dolostone. Terrigenous sand and marine limestone, with minor amounts of dolostone, are the principal lithologic units in the lower permeable zone. Dissolved solids concentrations range from 329 to 1,820 milligrams per liter in water samples from the middle permeable zone and from 518 to 3,030 milligrams per liter in water samples from the lower permeable zone. Principal hydrochemical facies in the middle permeable zone are calcium magnesium bicarbonate and calcium magnesium sulfate. Hydrochemical facies in ground-water samples from the lower permeable zone vary. Tritium concentrations as large as 5.3 tritium units in the southeastern part of the study area are indicative of relatively recent recharge. Results of a geochemical mass balance simulation along a flowpath in the middle permeable zone indicate a mass transfer of 4.25 millimoles per liter of dolomite dissolved, 5.74 millimoles per liter of gypsum dissolved, 0.46 millimole per liter of sodium chloride dissolved, 8.07 millimoles per liter of calcite precipitated, and 0.67 millimole per liter of calcium-for-sodium cation exchange between solid and aqueous phases. These results support dedolomitization as a principal chemical process in the middle permeable zone of the Trinity aquifer. Results of a simulation along a flowpath in the lower permeable zone indicate a mass transfer of 0.41 millimole per liter of dolomite dissolved, 0.001 millimole per liter of gypsum dissolved, 9.58 millimoles per liter of sodium chloride dissolved, 1.09 millimoles per liter of calcite precipitated, and 1.11 millimoles per liter of sodium-forcalcium cation exchange between solid and aqueous phases. Lower permeable zone processes indicate sodium chloride dissolution, dedolomitization, and cation exchange. Ground-water-flow velocities determined from adjusted carbon-14 ages, calculated using NETPATH, for selected flowpaths in the middle and lower permeable zones were about 1.7 feet per year and less than about 4.4 feet per year, respectively.

Texas↗

Immunological and reproductive health assessment in herring gulls and black-crowned night herons in the Hudson–Raritan Estuary

Previous studies have shown inexplicable declines in breeding waterbirds within western New York/New Jersey Harbor between 1996 and 2002 and elevated polychlorinated dibenzo- p -dioxins and polychlorinated biphenyls (PCBs) in double-crested cormorant ( Phalacrocorax auritus ) eggs. The present study assessed associations between immune function, prefledgling survival, and selected organochlorine compounds and metals in herring gulls ( Larus argentatus ) and black-crowned night herons ( Nycticorax nycticorax ) in lower New York Harbor during 2003. In pipping gull embryos, lymphoid cells were counted in the thymus and bursa of Fabricius (sites of T and B lymphocyte maturation, respectively). The phytohemagglutinin (PHA) skin response assessed T cell function in gull and heron chicks. Lymphocyte proliferation was measured in vitro in adult and prefledgling gulls. Reference data came from the Great Lakes and Bay of Fundy. Survival of prefledgling gulls was poor, with only 0.68 and 0.5 chicks per nest surviving to three and four weeks after hatch, respectively. Developing lymphoid cells were reduced 51% in the thymus and 42% in the bursa of gull embryos from New York Harbor. In vitro lymphocyte assays demonstrated reduced spontaneous proliferation, reduced T cell mitogen-induced proliferation, and increased B cell mitogen-induced proliferation in gull chicks from New York Harbor. The PHA skin response was suppressed 70 to 80% in gull and heron chicks. Strong negative correlations ( r = –0.95 to –0.98) between the PHA response and dioxins and PCBs in gull livers was strong evidence suggesting that these chemicals contribute significantly to immunosuppression in New York Harbor waterbirds.

New Jersey, New York↗

A 1000-year sediment record of recurring hypoxia off the Mississippi River: The potential role of terrestrially-derived organic matter inputs

A suite of inorganic and organic geochemical tracers and a low-oxygen tolerant benthic faunal index ('PEB') were measured in a 14C-dated 2+??m long gravity core collected on the Louisiana shelf adjacent to the Mississippi River delta to study potential millennium-scale low-oxygen events. Periodic down-core excursions in the PEB index throughout the core suggest recurring, natural bottom water low-oxygen events that extend back ??? 1000??14C years. Select trace element and biomarker distributions in these same sediments were examined as potential tracers of past hypoxic events and to help distinguish between marine versus terrestrial processes involved in organic carbon production. In discrete sediment horizons where the PEB index was elevated, redox-sensitive vanadium concentrations were consistently depleted, excursions in sedimentary ??13C suggest periodic, preferential terrestrial inputs, and the concentrations of two sterol biomarkers (sitosterol and ??-stigmasterol) also showed concurrent enrichments. If the PEB index successfully records ??? 1000??14C year-scale low-oxygen events, then the distribution of these geochemical tracers can be interpreted to corroborate the view that naturally occurring low-oxygen bottom water conditions have existed on the inner Louisiana continental shelf, not only in recent times, but also over at least the last 1000??14C years. These data support the general hypothesis that historic, low-oxygen bottom water conditions on the Louisiana shelf are likely tied to periods of increased fluvial discharge and associated wetland export in the absence of modern river levees. Enhanced river discharge and associated material export would both stimulate enhanced in situ organic carbon production and foster water column stratification. Such periodic elevated river flows during the last millennium can be linked to climate fluctuations and tropical storm activity. ?? 2008 Elsevier B.V. All rights reserved.

Marine Chemistry↗

Developing integrated methods to address complex resource and environmental issues

Introduction This circular provides an overview of selected activities that were conducted within the U.S. Geological Survey (USGS) Integrated Methods Development Project, an interdisciplinary project designed to develop new tools and conduct innovative research requiring integration of geologic, geophysical, geochemical, and remote-sensing expertise. The project was supported by the USGS Mineral Resources Program, and its products and acquired capabilities have broad applications to missions throughout the USGS and beyond. In addressing challenges associated with understanding the location, quantity, and quality of mineral resources, and in investigating the potential environmental consequences of resource development, a number of field and laboratory capabilities and interpretative methodologies evolved from the project that have applications to traditional resource studies as well as to studies related to ecosystem health, human health, disaster and hazard assessment, and planetary science. New or improved tools and research findings developed within the project have been applied to other projects and activities. Specifically, geophysical equipment and techniques have been applied to a variety of traditional and nontraditional mineral- and energy-resource studies, military applications, environmental investigations, and applied research activities that involve climate change, mapping techniques, and monitoring capabilities. Diverse applied geochemistry activities provide a process-level understanding of the mobility, chemical speciation, and bioavailability of elements, particularly metals and metalloids, in a variety of environmental settings. Imaging spectroscopy capabilities maintained and developed within the project have been applied to traditional resource studies as well as to studies related to ecosystem health, human health, disaster assessment, and planetary science. Brief descriptions of capabilities and laboratory facilities and summaries of some applications of project products and research findings are included in this circular. The work helped support the USGS mission to “provide reliable scientific information to describe and understand the Earth; minimize loss of life and property from natural disasters; manage water, biological, energy, and mineral resources; and enhance and protect our quality of life.” Activities within the project include the following: Spanned scales from microscopic to planetary; Demonstrated broad applications across disciplines; Included life-cycle studies of mineral resources; Incorporated specialized areas of expertise in applied geochemistry including mineralogy, hydrogeology, analytical chemistry, aqueous geochemistry, biogeochemistry, microbiology, aquatic toxicology, and public health; and Incorporated specialized areas of expertise in geophysics including magnetics, gravity, radiometrics, electromagnetics, seismic, ground-penetrating radar, borehole radar, and imaging spectroscopy. This circular consists of eight sections that contain summaries of various activities under the project. The eight sections are listed below: Laboratory Facilities and Capabilities, which includes brief descriptions of the various types of laboratories and capabilities used for the project; Method and Software Development, which includes summaries of remote-sensing, geophysical, and mineralogical methods developed or enhanced by the project; Instrument Development, which includes descriptions of geophysical instruments developed under the project; Minerals, Energy, and Climate, which includes summaries of research that applies to mineral or energy resources, environmental processes and monitoring, and carbon sequestration by earth materials; Element Cycling, Toxicity, and Health, which includes summaries of several process-oriented geochemical and biogeochemical studies and health-related research activities; Hydrogeology and Water Quality, which includes descriptions of innovative geophysical, remote-sensing, and geochemical research pertaining to hydrogeology and water-quality applications; Hazards and Disaster Assessment, which includes summaries of research and method development that were applied to natural hazards, human-caused hazards, and disaster assessments; and Databases and Framework Studies, which includes descriptions of fundamental applications of geophysical studies and of the importance of archived data.

Circular↗