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Diagenetic fate of organic contaminants on the Palos Verdes Shelf, California

Municipal wastes discharged through deepwater submarine outfalls since 1937 have contaminated sediments of the Palos Verdes Shelf. A site approximately 6–8 km downcurrent from the outfall system was chosen for a study of the diagenetic fate of organic contaminants in the waste-impacted sediments. Concentrations of three classes of hydrophobic organic contaminants (DDT+metabolites, polychlorinated biphenyls (PCBs), and the long-chain alkylbenzenes) were determined in sediment cores collected at the study site in 1981 and 1992. Differences between the composition of effluent from the major source of DDT (Montrose Chemical) and that found in sediments suggests that parent DDT was transformed by hydrolytic dehydrochlorination during the earliest stages of diagenesis. As a result, p , p ′-DDE is the dominant DDT metabolite found in shelf sediments, comprising 60–70% of ΣDDT. The p , p -DDE/ p , p ′-DDMU concentration ratio decreases with increasing sub-bottom depth in sediment cores, indicating that reductive dechlorination of p , p ′-DDE is occurring. Approximately 9–23% of the DDE inventory in the sediments may have been converted to DDMU since DDT discharges began ca. 1953. At most, this is less than half of the decline in p , p ′-DDE inventory that has been observed at the study site for the period 1981–1995. Most of the observed decrease is attributable to remobilization by processes such as sediment mixing coupled to resuspension, contaminant desorption, and current advection. Existing field data suggest that the in situ rate of DDE transformation is 10 2 –10 3 times slower than rates determined in recent laboratory microcosm experiments (Quensen, J.F., Mueller, S.A., Jain, M.K., Tiedje, J.M., 1998. Reductive dechlorination of DDE to DDMU in marine sediment microcosms. Science, 280, 722–724.). This explains why the DDT composition (i.e. o , p ′-, p , p ′-isomers of DDE, DDD, DDT) of sediments from this site have not changed significantly since at least 1972. Congener-specific PCB compositions in shelf sediments are highly uniform and show no evidence of diagenetic transformation. Apparently, the agents/factors responsible for reductive dechlorination of DDE are not also effecting alteration of the PCBs. Two types of long-chain alkylbenzenes were found in the contaminated sediments. Comparison of chain length and isomer distributions of the linear alkylbenzenes in wastewater effluent and surficial sediment samples indicate that these compounds undergo biodegradation during sedimentation. Further degradation of the linear alkylbenzenes occurs after burial despite relatively invariant isomer compositions. The branched alkylbenzenes are much more persistent than the linear alkylbenzenes, presumably due to extensive branching of the alkyl side chain. Based on these results, p , p ′-DDE, PCBs, and selected branched alkylbenzenes are sufficiently persistent for use in molecular stratigraphy. The linear alkylbenzenes may also provide information on depositional processes. However, their application as quantitative molecular tracers should be approached with caution.

California↗

Hydrochemical facies and ground-water flow patterns in northern part of Atlantic Coastal Plain

The part of the Atlantic Coastal Plain that extends from New Jersey through Virginia was selected as a suitable field model in which to study the relationships between geology, hydrology, and chemical character of ground water. The ground-water flow pattern is the principal hydrologic control on the chemical character of the water. Within the Coastal Plain sediments, the proportions of clay, glauconitic sand, and calcareous material are the principal lithologic controls over the chemistry of the water. A subsurface body of salt water extends from southern New Jersey through southern Virginia and occupies the deposits deeper than about 500 feet below land surface in the eastern part of the Coastal Plain. The position of its top is determined by the relative head, which in turn is influenced by topography, drainage density, and the thickness and permeability of the Coastal Plain sediments. Hydrochemical facies is a term used in this paper to denote the diagnostic chemical aspect of ground-water solutions occurring in hydrologic systems. The facies reflect the response of chemical processes operating within the lithologic framework and also the pattern of flow of the water. The distribution of these facies is shown in trilinear diagrams and isometric fence diagrams and on maps showing isopleths of chemical constituents within certain formations. The occurrence of the various facies within one formation or within a group of formations of uniform mineralogy indicates that the ground-water flow through the aquifer system modifies the distribution of the facies. Flow patterns of fresh ground water shown on maps and in cross sections have been deduced from available water-level data. These patterns are controlled by the distribution of the higher landmasses and by the depth to either bedrock or to the salt-water interface. The mapping of hydrochemical facies shows that at shallow depths within the Coastal Plain (less than about 200 ft) the calcium-magnesium cation facies generally predominates. The bicarbonate anion facies occurs within more of the shallow Coastal Plain sediments than does the sulfate or the chloride facies. In deeper formations, the sodium chloride character predominates. The lower dissolved-solids content of the ground water in New Jersey indicates less upward vertical leakage than in Maryland and Virginia, where the shallow formations contain solutions of higher concentration.

Delaware, Maryland, New Jersey, Pennsylvania, Virg↗

Identifying calcium sources at an acid deposition-impacted spruce forest: A strontium isotope, alkaline earth element multi-tracer approach

Depletion of calcium from forest soils has important implications for forest productivity and health. Ca is available to fine feeder roots from a number of soil organic and mineral sources, but identifying the primary source or changes of sources in response to environmental change is problematic. We used strontium isotope and alkaline earth element concentration ratios of trees and soils to discern the record of Ca sources for red spruce at a base-poor, acid deposition-impacted watershed. We measured 87 Sr/ 86 Sr and chemical compositions of cross-sectional stemwood cores of red spruce, other spruce tissues and sequential extracts of co-located soil samples. 87 Sr/ 86 Sr and Sr/Ba ratios together provide a tracer of alkaline earth element sources that distinguishes the plant-available fraction of the shallow organic soils from those of deeper organic and mineral soils. Ca/Sr ratios proved less diagnostic, due to within-tree processes that fractionate these elements from each other. Over the growth period from 1870 to 1960, 87 Sr/ 86 Sr and Sr/Ba ratios of stemwood samples became progressively more variable and on average trended toward values that considered together are characteristic of the uppermost forest floor. In detail the stemwood chemistry revealed an episode of simultaneous enhanced uptake of all alkaline earth elements during the growth period from 1930 to 1960, coincident with reported local and regional increases in atmospheric inputs of inorganic acidity. We attribute the temporal trends in stemwood chemistry to progressive shallowing of the effective depth of alkaline earth element uptake by fine roots over this growth period, due to preferential concentration of fine roots in the upper forest floor coupled with reduced nutrient uptake by roots in the lower organic and upper mineral soils in response to acid-induced aluminum toxicity. Although both increased atmospheric deposition and selective weathering of Ca-rich minerals such as apatite provide possible alternative explanations of aspects of the observed trends, the chemical buffering capacity of the forest floor-biomass pool limits their effectiveness as causal mechanisms.

Biogeochemistry↗

Aqueous geochemical data from the analysis of stream-water samples collected in June and July 2005 — Taylor Mountains 1:250,000 scale quadrangle, Alaska

We report on the chemical analysis of water samples collected from the Taylor Mountains 1:250,000-scale quadrangle. Parameters for which data are reported include pH, conductivity, water temperature, major cation and anion concentrations, trace-element concentrations, and dissolved organic-carbon concentrations. Samples were collected as part of a multiyear U.S. Geological Survey project "Geologic and Mineral Deposit Data for Alaskan Economic Development." Data presented here are from samples collected in June and July of 2005. The data are being released at this time with minimal interpretation. This is the second release of aqueous geochemical data from this project; 2004 aqueous geochemical data were published previously ( Wang and others, 2006 ). The data in this report augment but do not duplicate or supersede the previous data release. Site selection was based on a regional sampling strategy that focused on first- and second-order drainages. Water sample site selection was based on landscape parameters that included physiography, wetland extent, lithological changes, and a cursory field review of mineralogy from pan concentrates. Stream water in the Taylor Mountians quadrangle is dominated by bicarbonate (HCO 3- ), though in a few samples more than 50 percent of the anionic charge can be attributed to sulfate (SO 4 2- ). The major-cation chemistry ranges from Ca 2+ /Mg 2+ dominated to a mix of Ca 2+ /Mg 2+ /Na + +K + . In general, good agreement was found between the major cations and anions in the duplicate samples. Many trace elements in these samples were at or near the analytical method detection limit, but good agreement was found between duplicate samples for elements with detectable concentrations. With the exception of a total mercury concentration of 0.33 ng/L detected in a field blank, field blank major-ion and trace-elements concentrations were below detection.

Alaska↗

Aqueous geochemical data from the analysis of stream-water samples collected in June and August 2008—Taylor Mountains 1:250,000- and Dillingham D-4 1:63,360-scale quadrangles, Alaska

We report on the chemical analysis of water samples collected from the Taylor Mountains 1:250,000- and Dillingham D-4 1:63,360-scale quadrangles, Alaska. Reported parameters include pH, conductivity, water temperature, major cation and anion concentrations, and trace-element concentrations. We collected the samples as part of a multiyear U.S. Geological Survey project entitled "Geologic and Mineral Deposit Data for Alaskan Economic Development." Data presented here are from samples collected in June and August 2008. Minimal interpretation accompanies this data release. This is the fourth release of aqueous geochemical data from this project; data from samples collected in 2004, 2005, and 2006 were published previously. The data in this report augment but do not duplicate or supersede the previous data releases. Site selection was based on a regional sampling strategy that focused on first- and second-order drainages. Water sample sites were selected on the basis of landscape parameters that included physiography, wetland extent, lithological changes, and a cursory field review of mineralogy from pan concentrates. Stream water in the study area is dominated by bicarbonate (HCO 3 - ), although in a few samples more than 50 percent of the anionic charge can be attributed to sulfate (SO 4 2- ). The major-cation chemistry of these samples ranges from Ca 2+ -Mg 2+ dominated to a mix of Ca 2+ -Mg 2+ -Na + +K 2+ . In most cases, analysis of duplicate samples showed good agreement for the major cation and major anions with the exception of the duplicate samples at site 08TA565. At site 08TA565, Ca, Mg, Cl, and CaCO 3 exceeded 25 percent and the concentrations of trace elements As, Fe and Mn also exceeded 25 percent in this duplicate pair. Chloride concentration varied by more than 25 percent in 5 of the 11 duplicated samples. Trace-element concentrations in these samples generally were at or near the detection limit for the method used and, except for Co at site 08TA565, generally good agreement was determined between duplicate samples for elements with detectable concentrations. Major-ion concentrations were below detection limits in all field blanks, and the trace-element concentrations also were generally below detection limits; however, Co, Mn, Na, Zn, Cl, and Hg were detected in one or more field blank samples.

Alaska↗

Influence of soil chemistry on metal and bioessential element concentrations in nymphal and adult periodical cicadas (Magicicada spp.)

Metal and bioessential element concentrations were measured in three species of 17-year periodical cicadas (Magicicada spp.) to determine how cicada tissue chemistry is affected by soil chemistry, measure the bioavailability of metals from both uncontaminated and lead-arsenate-pesticide contaminated soils, and assess the potential risks of observed metal contamination for wildlife. Periodical cicada nymphs feed on root xylem fluids for 13 or 17??years of underground development. The nymphs then emerge synchronously at high densities, before leaving their nymphal keratin exoskeleton and molting into their adult form. Cicadas are an important food source for birds and animals during emergence events, and influence nutrient cycles in woodland ecosystems. Nymphal exoskeletons and whole adult cicadas were sampled in Clarke and Frederick Counties, Virginia and Berkeley and Jefferson Counties, West Virginia during the Brood X emergence in May and June, 2004. Elements, such as Al, Fe, and Pb, are strongly enriched in the nymphal exoskeleton relative to the adult body; Cu and Zn are enriched in bodies. Concentrations of Fe and Pb, when normalized to relatively inert soil constituents such as Al and Ce, are similar in both the molt exoskeleton and their host soil, implying that passive assimilation through prolonged soil contact (adhesion or adsorption) might control these metal concentrations. Normalized concentrations of bioessential elements, such as S, P, K, Ca, Mn, Cu, Zn, and Mo, and chalcophile (sulfur-loving) elements, such as As, Se, and Au, indicate strong enrichment in cicada tissues relative to soil, implying selective absorption and retention by xylem fluids, the cicada nymphs themselves, or both. Element enrichment patterns in cicada tissues are similar to enrichment patterns observed in xylem fluids from tree roots. Chalcophile elements and heavy metals accumulate in keratin-rich tissues and may bind to sulfhydryl groups. Metal concentrations in the nymphal exoskeleton show a positive correlation with soil metal concentrations, with Au exhibiting particularly strong enrichment in the exoskeleton relative to soil concentrations. Metal concentrations in adult bodies do not correlate with soil chemistry. Bioessential elements S, Ca, Mn, Fe, and Zn differed by sex in adults, whereas Na, Mg, K, Ca, Mn, Fe, Zn, and As differed by species. Body concentrations of Ca differed by site conditions (orchard or reference setting). The high Pb contents of orchard soils contaminated by arsenical pesticide residues might inhibit Ca uptake by cicada nymphs. The adult cicadas contain concentrations of metals similar to, or less than, other invertebrates, such as earthworms. There does not appear to be a dietary threat to birds or other consumers of adult cicadas based on Maximum Tolerable Dietary Level (MTDL) Guidelines developed for agricultural animals.

Science of the Total Environment↗

Questa baseline and pre-mining ground-water quality investigation 22 — Groundwater budget for the Straight Creek drainage basin, Red River Valley, New Mexico, with a section on Sulphur Gulch water budget

In April 2001, the U.S. Geological Survey (USGS) and the New Mexico Environment Department (NMED) began a cooperative study to infer the pre-mining ground-water chemistry at the Molycorp molybdenum mine site in the Red River Valley. The Molycorp mine has been in operation since the 1920s. Because ground-water conditions prior to mining are not available, sites analogous to the pre-mining conditions at the mine site must be studied to infer those pre-mining conditions. The Straight Creek drainage basin (watershed) was selected as the primary analog site for this study because of its similar terrain and geology to the mine site, accessibility, potential for well construction, and minimal anthropogenic activity. The purpose of this report is to present results of a water-budget analysis of the debris-flow aquifer in the Straight Creek watershed. The water budget is based on mean annual conditions and is assumed to be steady state. For this study, the Straight Creek watershed was divided into sub-watersheds on the basis of locations of seismic lines, which were used to calculate cross-section area through the Straight Creek debris-flow deposits and underlying fractured and weathered bedrock (regolith). Water-budget components were calculated for areas upstream from and between the seismic lines. Components of the water budget were precipitation, evapotranspiration, surface-water flow, and ground-water flow under a steady-state mean annual condition. Watershed yield, defined as precipitation minus evapotranspiration, was separated into surface-water flow, ground-water flow through the debris-flow deposits and regolith, and ground-water flow through fractured bedrock. The approach to this calculation was to use Darcy's Law to calculate the flow through the cross-section area of the saturated debris-flow deposits and underlying regolith as defined by the interpreted seismic data. The amount of watershed yield unaccounted for through this section then was attributed to either surface-water flow or the component of ground-water flow through fractured bedrock. The inflow to the watershed, calculated to be 701 gallons per minute, is from precipitation. The calculated outflow from the watershed at or upstream from seismic-line 5 (the downstream-most line in Straight Creek prior to entering the Red River Valley) is 540 gallons per minute of evapotranspiration in the watershed upstream from line 5 (77.0 percent of precipitation), 5 gallons per minute of surface-water flow (0.7 percent of precipitation), 122 gallons per minute of ground-water flow through the debris-flow deposits and underlying regolith defined by the seismic data (17.4 percent of precipitation), and 34 gallons per minute of ground-water flow through fractured bedrock below the defined seismic line (4.9 percent of precipitation). The ground-water flow through the alluvium and inter-tonguing debris-flow deposits of the Red River Valley was calculated to be 5,227 gallons per minute at seismic-line 7, the first seismic line in the Red River Valley downstream from Straight Creek. The water budget indicates the amount of ground-water flow that enters the Red River alluvium from the debris-flow deposits and regolith in Straight Creek is small (about 2.3 percent; 122 gallons per minute) compared to the volume of flow that moves through the Red River alluvium. The total amount of ground-water flow from Straight Creek (156 gallons per minute; 122 gallons per minute from debris-flow deposits and regolith plus 34 gallons per minute through fractured bedrock) is about 3.0 percent of the ground-water flow calculated at line 7 for the Red River alluvium.

New Mexico↗

Improvements in the use of aquatic herbicides and establishment of future research directions

Peer-reviewed literature over the past 20 years identifies significant changes and improvements in chemical control strategies used to manage nuisance submersed vegetation. The invasive exotic plants hydrilla (Hydrilla verticillata L.f. Royle) and Eurasian watermilfoil (Myriophyllum spicatum L.) continue to spread and remain the plant species of greatest concern for aquatic resource managers at the national scale. Emerging exotic weeds of regional concern such as egeria (Egeria densa Planch.), curlyleaf pondweed (Potamogeton crispus L.), and hygrophila (Hygrophila polysperma (Roxb.) T. Anders), as well as native plants such as variable watermilfoil (Myriophyllum heterophyllum Michx), and cabomba (Cabomba caroliniana Gray) are invasive outside their home ranges. In addition, there is always the threat of new plant introductions such as African elodea (Lagarosiphon major (Ridley) Moss) or narrow-leaf anacharis (Egeria najas Planchon). The registration of the bleaching herbicide fluridone in the mid 1980s for whole-lake and large-scale management stimulated numerous lines of research involving reduction of use rates, plant selectivity, residue monitoring, and impacts on fisheries. In addition to numerous advances, the specificity of fluridone for a single plant enzyme led to the first documented case of herbicide resistance in aquatic plant management. The resistance of hydrilla to fluridone has stimulated a renewed interest by industry and others in the registration of alternative modes of action for aquatic use. These newer chemistries tend to be enzyme-specific compounds with favorable non-target toxicity profiles. Registration efforts have been facilitated by increased cooperation between key federal government agencies that have aquatic weed control and research responsibilities, and regulators within the U.S. Environmental Protection Agency (USEPA). We reviewed past and current research efforts to identify areas in need of further investigation and to establish priorities for future research directions in chemical management of submersed plants. The priorities we identified include: (A) improving methods for evaluating non-target impacts of herbicides with an emphasis on threatened and endangered species, or species of special concern; (B) improving herbicide performance in flowing-water environments, including irrigation canals; (C) screening and developing new herbicides to supplement fluridone for large-scale or whole-lake management approaches; (D) screening and developing new organic algaecides to supplement the use of copper-based compounds; (E) developing risk assessment tools to educate the public on the risks of invasive species and chemical management options; (F) increasing cooperative research with ecologists and fisheries scientists to evaluate the long-term impacts of invasive species introductions and herbicide programs on native plant assemblages, water quality, and fish populations; and (G) improving the integration of chemical control technology with other aquatic plant management disciplines. While circumstances may dictate setting new priorities or dropping current ones, the list we have generated represents our vision of the needs that will require the greatest focus over the next several years.

Conference Paper↗

Toxicity of sediment cores collected from the Ashtabula River in northeastern Ohio, USA, to the amphipod Hyalella azteca

This study was conducted to support a Natural Resource Damage Assessment and Restoration project associated with the Ashtabula River in Ohio. The objective of the study was to evaluate the chemistry and toxicity of 50 sediment samples obtained from five cores collected from the Ashtabula River (10 samples/core, with each 10-cm-diameter core collected to a total depth of about 150 cm). Effects of chemicals of potential concern (COPCs) measured in the sediment samples were evaluated by measuring whole-sediment chemistry and whole-sediment toxicity in the sediment samples (including polycyclic aromatic hydrocarbons [PAHs], polychlorinated biphenyls [PCBs], organochlorine pesticides, and metals). Effects on the amphipod Hyalella azteca at the end of a 28-day sediment toxicity test were determined by comparing survival or length of amphipods in individual sediment samples in the cores to the range of responses of amphipods exposed to selected reference sediments that were also collected from the cores. Mean survival or length of amphipods was below the lower limit of the reference envelope in 56% of the sediment samples. Concentrations of total PCBs alone in some samples or concentrations of total PAHs alone in other samples were likely high enough to have caused the reduced survival or length of amphipods (i.e., concentrations of PAHs or PCBs exceeded mechanistically based and empirically based sediment quality guidelines). While elevated concentrations of ammonia in pore water may have contributed to the reduced length of amphipods, it is unlikely that the reduced length was caused solely by elevated ammonia (i.e., concentrations of ammonia were not significantly correlated with the concentrations of PCBs or PAHs and concentrations of ammonia were elevated both in the reference sediments and in the test sediments). Results of this study show that PAHs, PCBs, and ammonia are the primary COPCs that are likely causing or substantially contributing to the toxicity to sediment-dwelling organisms. ?? 2009 US Government.

Archives of Environmental Contamination and Toxico↗

Study of multicomponent mixtures in solution with a vertical-axis transmission-type filter-fluorometer

Fluorescence intensity, sensitivity, and the effect of diverse ions are discussed in relation to chemical equilibrium and the general equation for fluorescence. High sensitivity is the common denominator in eliminating or reducing all types of interference and the general equation is the key for quickly selecting conditions that give maximum sensitivity. With a transmission-type fluorometer, experimental fluorescence intensities adhere to the general equation over a very wide range of light absorption. If the instrument has a vertical axis, solution depth can be adjusted so that the data fall on that portion of the theoretical curve which is essentially a straight line. When the fluorescence wavelength selected for measurement is not absorbed by the solution, the general equation reduces to a much simpler expression, and then, under proper circumstances, fluorescence values can be used for calculations as confidently and as easily as absorbance values.

Analytical Chemistry↗

Simulations of ground-water flow and particle pathline analysis in the zone of contribution of a public-supply well in Modesto, eastern San Joaquin Valley, California

Shallow ground water in the eastern San Joaquin Valley is affected by high nitrate and uranium concentrations and frequent detections of pesticides and volatile organic compounds (VOC), as a result of ground-water development and intensive agricultural and urban land use. A single public-supply well was selected for intensive study to evaluate the dominant processes affecting the vulnerability of public-supply wells in the Modesto area. A network of 23 monitoring wells was installed, and water and sediment samples were collected within the approximate zone of contribution of the public-supply well, to support a detailed analysis of physical and chemical conditions and processes affecting the water chemistry in the well. A three-dimensional, steady-state local ground-water-flow and transport model was developed to evaluate the age of ground water reaching the well and to evaluate the vulnerability of the well to nonpoint source input of nitrate and uranium. Particle tracking was used to compute pathlines and advective travel times in the ground-water flow model. The simulated ages of particles reaching the public-supply well ranged from 9 to 30,000 years, with a median of 54 years. The age of the ground water contributed to the public-supply well increased with depth below the water table. Measured nitrate concentrations, derived primarily from agricultural fertilizer, were highest (17 milligrams per liter) in shallow ground water and decreased with depth to background concentrations of less than 2 milligrams per liter in the deepest wells. Because the movement of water is predominantly downward as a result of ground-water development, and because geochemical conditions are generally oxic, high nitrate concentrations in shallow ground water are expected to continue moving downward without significant attenuation. Simulated long-term nitrate concentrations indicate that concentrations have peaked and will decrease in the public-supply well during the next 100 years because of the low nitrate concentrations in recharge beneath the urban area and the increasing proportion of urban-derived ground water reaching the well. The apparent lag time between peak input concentrations and peak concentrations in the well is about 20 to 30 years. Measured uranium concentrations were also highest (45 micrograms per liter) in shallow ground water, and decreased with depth to background concentrations of about 0.5 microgram per liter. Naturally-occurring uranium adsorbed to aquifer sediments is mobilized by oxygen-rich, high-alkalinity water. Alkalinity increased in shallow ground water in response to agricultural development. As ground-water pumping increased in the 1940s and 1950s, this alkaline water moved downward through the ground-water flow system, mobilizing the uranium adsorbed to aquifer sediments. Ground water with high alkalinity and high uranium concentrations is expected to continue to move deeper in the system, resulting in increased uranium concentrations with depth in ground water. Because alkalinity (and correspondingly uranium) concentrations were high in shallow ground water beneath both the urban and the agricultural land, long-term uranium concentrations in the public-supply well are expected to increase as the proportion of uranium-affected water contributed to the well increases. Assuming that the alkalinity near the water table remains the same, the simulation of long-term alkalinity in the public-supply well indicates that uranium concentrations in the public-supply well will likely approach the maximum contaminant level; however, the time to reach this level is more than 100 years because of the significant proportion of old, unaffected water at depth that is contributed to the public-supply well.

California↗

Natural attenuation of chlorinated volatile organic compounds in ground water at Area 6, Naval Air Station Whidbey Island, Washington

Natural attenuation is a viable alternative to pump and treat for meeting remediation objectives in the vicinity of the southern contaminant plume. The combination of historically low contaminant concentrations in ground water, a landfill cap that limits source area contributions, favorable conditions for degradation of VC, and a relatively long downgradient distance to potential receptors are all favorable for natural attenuation as a remediation alternative. Natural attenuation could effectively meet all but one remediation goal that extraction wells PW- 2, PW-4, PW-6, PW-7, PW-8 and PW-9 are currently being employed to meet. The goal of preventing migration of all VC across the site boundary could not be met by natural attenuation. Some VC would migrate south of the Navy boundary, but the potential for subsequent VC mineralization downgradient of the base and the existing institutional controls would result in minimal additional risk from using natural attenuation. In the western contaminant plume natural attenuation is not currently a viable alternative to pump and treat for meeting remediation objectives. There is a possibility that rates for reductive dechlorination of TCE and TCA could increase substantially if the plume was allowed to migrate beneath the Oak Harbor landfill, but there are not enough data to be certain of such an increase. TCA and TCE concentrations at the leading edge of the western plume need to be reduced to at least 25 and 40 µg/L, respectively, to be protective of potential downgradient receptors. Source area TCA and TCE concentrations have decreased substantially over the past ten years, and the extraction wells PW-3 and PW-5 in particular are removing a significant mass of contaminants from ground water, so natural attenuation may be a viable alternative for the western plume in the future. There would be some possible side benefits of using natural attenuation as an alternative to pump and treat in the southern contaminant plume. The first would be that the resulting decrease in the amount of treated water that would need to be recharged in the swale north of the landfill would result in less off-base migration of contamination across the western site boundary. The second benefit would be a substantial reduction in the amount of dissolved iron and manganese being extracted from the shallow aquifer and run through the treatment system. Removing that source of operation and maintenance problems would result in more effective containment and removal of contamination in the western contaminant plume. The most critical data gap identified in this evaluation is the paucity of contaminant chemistry information downgradient of the Navy boundary in the vicinity of the southern contaminant plume. Without such data, the behavior of the plume and the protectiveness of natural attenuation to downgradient receptors cannot be verified, and field attenuation rates for VC cannot be determined directly. The existing long-term monitoring plan would need to be reviewed and revised if natural attenuation is selected as a remedy for the contamination in the southern plume. In particular, additional performance monitoring wells may be required downgradient of the property.

Washington↗

Hydrogeology and selected water-quality aspects of the Hueco Bolson Aquifer at the Hueco Bolson Recharge Project area, El Paso, Texas

Samples of ground water and tertiary-treated water were evaluated to determine the distribution of injected water and trihalomethane compounds in the Hueco bolson aquifer near El Paso, Texas. Chloride and nitrate concentrations and oxygen-18/oxygen-16 (δ 18 O) values were used with end-member mixing analysis to estimate the fractional contributions of injected water, irrigation-affected water, saline ground water, and freshwater to ground-water chemistry. Several laterally continuous sand and gravel layers are the principal water-yielding lithologies in the aquifer. The potentiometric surface sloped toward the south and southwest during January 1990. Average linear ground-water velocities were as large as 1.4 feet per day near the zone of largest hydraulic conductivity and were substantially smaller farther south and east. Ground-water samples from as far as 2,900 feet from an injection well contained injectedwater tracers and trihalomethane compounds. Ground-water samples with injected-water tracers and no trihalomethane compounds may indicate infiltration from septic systems or oxidation ponds. Apparent breakthrough velocities of injected water in the aquifer ranged from 0.13 to 1.3 feet per day. Irrigation-affected water and saline water also were identified in water from several wells. Ground-water transport of bromoform and dibromochloromethane is attenuated relative to injected water, chloroform, and dichlorobromomethane. Microbial transformation of bromoform and dibromochloromethane probably was responsible for their disappearance from ground water. Chloroform and dichlorobromomethane concentrations were affected principally by advective and dispersive transport of injected water.

Texas↗

Properties and chemical constituents in ground water from the middle Wilcox aquifer, Gulf Coast regional aquifer systems, south-central United States

The Gulf Coast Regional Aquifer-System Analysis is a study of regional aquifers composed of sediments of mostly Cenozoic age that underlie about 230,000 sq mi of the Gulf Coastal Plain. These regional aquifers are part of three aquifer systems: (1) the Mississippi Embayment Aquifer System, (2) the Texas Coastal Uplands Aquifer System, and (3) the Coastal Lowlands Aquifer System. The water chemistry of the Middle Wilcox Aquifer, which is part of the Mississippi Embayment Aquifer System and the Texas Coastal Uplands Aquifer System is presented by a series of maps. These maps show the area1 distribution of (1) the concentration of dissolved solids and temperature, (2) the primary water types and pH, (3) the concentration of major ions and silica, and (4) the milliequivalent ratios of selected ions. Dissolved constituents, pH, temperature, and ratios are based on the median values of all samples in each 100-sq-mi area. The concentration of dissolved solids in water from the Middle Wilcox Aquifer ranges from 26 mg/L in the northern part of the Mississippi Embayment Aquifer System to 125,500 mg/L in a down-dip area in southeastern Texas. The primary water types, which are based on the most frequently observed type in each 100-sq-mi area, are calcium bicarbonate in the outcrop in Missouri, Kentucky, Mississippi, and southern Texas; sodium bicarbonate in the remaining outcrop areas and all areas from outcrop to mid-dip; and sodium chloride in all down-dip areas. The concentrations of major ions in water from the Middle Wilcox Aquifer generally increase from the outcrop area to the down-dip limit of the data. The milliequivalent ratio of magnesium plus calcium to bicarbonate ranges from less than 0.01 to 158 and generally decreases from outcrop to mid-dip and increases from mid-dip to the down-dip limit of the data. From the Sabine Uplift eastward to southwestern Alabama the ratio of bicarbonate to chloride generally decreases from outcrop to down-dip in the area west of the Mississippi River and shows localized trends east of the Mississippi River.

Alabama, Arkansas, Kentucky, Louisiana, Mississipp↗

Design of the National Trends Network for monitoring the chemistry of atmospheric precipitation

Long-term monitoring (10 years minimum) of the chemistry of wet deposition will be conducted at National Trends Network (NTN) sites across the United States. Precipitation samples will be collected at sites that represent broad regional characteristics. Design of the NTN considered four basic elements during construction of a model to distribute 50, 75, 100, 125 or 150 sites. The modeling oriented design was supplemented with guidance developed during the course of the site selection process. Ultimately, a network of 151 sites was proposed. The basic elements of the design are: (1) Assurance that all areas of the country are represented in the network on the basis of regional ecological properties (96 sites); (2) Placement of additional sites east of the Rocky Mountains to better define high deposition gradients (27 sites); (3) Placement of sites to assure that potentially sensitive regions are represented (15 sites); (4) Placement of sites to allow for other considerations, such as urban area effects (5 sites), intercomparison with Canada (3 sites), and apparent disparities in regional coverage (5 sites). Site selection stressed areas away from urban centers, large point sources, or ocean influences. Local factors, such as stable land ownership, nearby small emission sources (about 10 km), and close-by roads and fireplaces (about 0.5 km) were also considered. All proposed sites will be visited as part of the second phase of the study.

Circular↗

Water-quality and bottom-material characteristics of Cross Lake, Caddo Parish, Louisiana, 1997-99

Cross Lake is a shallow, monomictic lake that was formed in 1926 by the impoundment of Cross Bayou. The lake is the primary drinking-water supply for the City of Shreveport, Louisiana. In recent years, the lakeshore has become increasinginly urbanized. In addition, the land use of the watershed contributing runoff to Cross Lake has changed. Changes in land use and urbanization could affect the water chemistry and biology of the Lake. Water-quality data were collected at 10 sites on Cross Lake from February 1997 to February 1999. Water-column and bottom-material samples were collected. The water-column samples were collected at least four times per year. These samples included physical and chemical-related properties such as water temperature, dissolved oxygen, pH, and specific conductance; selected major inorganic ions; nutrients; minor elements; organic chemical constituents; and bacteria. Suspended-sediment samples were collected seven times during the sampling period. The bottom-material samples, which were collected once during the sampling period, were analyzed for selected minor elements and inorganic carbon. Aside from the nutrient-enriched condition of Cross Lake, the overall water-quality of Cross Lake is good. No primary Federal or State water-quality criteria were exceeded by any of the water-quality constituents analyzed for this report. Concentrations of major inorganic constituents, except iron and manganese, were low. Water from the lake is a sodium-bicarbonate type and is soft. Minor elements and organic compounds were present in low concentrations, many below detection limits. Nitrogen and phosphorus were the nutrients occurring in the highest concentrations. Nutrients were evenly distributed across the lake with no particular water-quality site indicating consistently higher or lower nutrient concentrations. No water samples analyzed for nitrate exceeded the U.S. Environmental Protection Agency's Maximum Contaminant Level of 10 milligrams per liter. Based on nitrogen to phosphorus ratios calculated for Cross Lake, median values for all water-quality sites were within the nitrogen-limited range (less than or equal to 5). Historical Trophic State Indexes for Cross Lake classified the lake as eutrophic. Recent (1998-99) Trophic State Indexes classify Cross Lake as mesotrophic-eutrophic, which might indicate a recution in eutrophication. Sedimentation traps indicate that Cross Lake is filling at an average rate of 0.41 inches per year. Concentrations of fecal-coliform and streptococci bacteria generally were low. Fecal coliform was detected in higher concentrations than fecal streptococci. High bacterial concentrations were measured shortly after rainfall-runoff events, possibly washing bacteria from surrounding areas into the lake.

Louisiana↗

Relation between organic-wastewater compounds, groundwater geochemistry, and well characteristics for selected wells in Lansing, Michigan

In 2010, groundwater from 20 Lansing Board of Water and Light (BWL) production wells was tested for 69 organic-wastewater compounds (OWCs). The OWCs detected in one-half of the sampled wells are widely used in industrial and environmental applications and commonly occur in many wastes and stormwater. To identify factors that contribute to the occurrence of these constituents in BWL wells, the U.S. Geological Survey (USGS) interpreted the results of these analyses and related detections of OWCs to local characteristics and groundwater geochemistry. Analysis of groundwater-chemistry data collected by the BWL during routine monitoring from 1969 to 2011 indicates that the geochemistry of the BWL wells has changed over time, with the major difference being an increase in sodium and chloride. The concentrations of sodium and chloride were positively correlated to frequency of OWC detections. The BWL wells studied are all completed in the Saginaw aquifer, which consists of water-bearing sandstones of Pennsylvanian age. The Saginaw aquifer is underlain by the Parma-Bayport aquifer, and overlain by the Glacial aquifer. Two possible sources of sodium and chloride were evaluated: basin brines by way of the Parma-Bayport aquifer, and surficial sources by way of the Glacial aquifer. To determine if water from the underlying aquifer had influenced well-water geochemistry over time, the total dissolved solids concentration and changes in major ion concentrations were examined with respect to well depth, age, and pumping rate. To address a possible surficial source of sodium and chloride, 25 well, aquifer, or hydrologic characteristics, and 2 groundwater geochemistry variables that might influence whether, or the rate at which, water from the land surface could reach each well were compared to OWC detections and well chemistry. The statistical tests performed during this study, using available variables, indicated that reduced time of travel of water from the land surface to the well opening was significantly correlated with detections of OWCs. No specific well or aquifer characteristic was correlated with OWC detections; however, wells with detections tended to have less modeled confining material thickness (as simulated in the regional groundwater flow model), which is an estimate of the amount of clay or shale between the Glacial and Saginaw aquifers. Additional analyses and collection of other data would be required to more conclusively identify the source and to determine the potential vulnerability of other wells because each BWL well may have a somewhat unique set of characteristics that governs its response to pumping. Therefore, it is possible that a relevant explanatory variable was not included in this analysis. The current patterns of geochemistry, and the relation between these patterns and volume of pumpage for the BWL wells, indicates other wells may be susceptible to OWCs in the future.

Michigan↗

A modeling tool to evaluate regional coral reef responses to changes in climate and ocean chemistry

We developed a spreadsheet-based model for the use of managers, conservationists, and biologists for projecting the effects of climate change on coral reefs at local-to-regional scales. The COMBO (Coral Mortality and Bleaching Output) model calculates the impacts to coral reefs from changes in average SST and CO2 concentrations, and from high temperature mortality (bleaching) events. The model uses a probabilistic assessment of the frequency of high temperature events under a future climate to address scientific uncertainties about potential adverse effects. COMBO offers data libraries and default factors for three selected regions (Hawai'i, Great Barrier Reef, and Caribbean), but it is structured with user-selectable parameter values and data input options, making possible modifications to reflect local conditions or to incorporate local expertise. Preliminary results from sensitivity analyses and simulation examples for Hawai'i demonstrate the relative importance of high temperature events, increased average temperature, and increased CO2 concentration on the future status of coral reefs; Illustrate significant interactions among variables; and allow comparisons of past environmental history with future predictions. ?? 2008, by the American Society of Limnology and Oceanugraphy, Inc.

Limnology and Oceanography: Methods↗