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Geochemical investigations of selected Eastern United States watersheds affected by acid deposition

The effects of acid deposition on surface waters in eastern United States watersheds having similar size, physiography, climate and land use are related to the composition of the underlying bedrock. Watersheds developed on greenstone, calcareous shale, sandstone, granite, and schist differ in their ability to neutralize acid deposition. Surface waters in watersheds developed on greenstone and calcareous shale are not discernably affected by acidification. Wastersheds developed on sand-stone have little capacity to neutralize acid rain; consequently, stream acidity is similar to that of precipitation. Watersheds developed on granite and schist are intermediate in their capacity to neutralize acid deposition. Bedrock composition appears to be the major property controlling surface-water chemistry in these systems; hydrologic flow paths and the nature of surficial materials and vegetation also influence chemical responses to acid deposition in watersheds.

Journal of the Geological Society

Prioritizing US Geological Survey science on salinization and salinity in candidate and selected priority river basins

The US Geological Survey (USGS) is selecting and prioritizing basins, known as Integrated Water Science basins, for monitoring and intensive study. Previous efforts to aid in this selection process include a scientifically defensible and quantitative assessment of basins facing human-caused water resource challenges (Van Metre et al. in Environmental Monitoring and Assessment , 192(7), 458 2020). In the present work, we explore this ranking process based on water quality considerations, specifically salinity and salinization. We selected top candidate basins to study salinity and salinization issues in 18 hydrologic regions that include 163 candidate basins. Our prioritization is based on quantitative assessment of sources of salinity, drivers of change, and receptors that must respond to those sources and drivers. Source terms represented in the prioritization include geology, depth to brackish groundwater, stream conductivity, chloride in precipitation, urban and agricultural land use, application of road salt as a deicer, and irrigation. Drivers represented in prioritization include changes in chemical weathering as a result of changes in rainwater chemistry. Receptors include measures of water stress, measurements of stream ecological health, and socioeconomic factors. In addition, we present research activities for the USGS on salinity and salinization that can be pursued in these basins including assessment of sources, pathways, and loadings; predicting and understanding changes in sources, peaks, and trends; understanding the components of salinity and mobilization of contaminants; understanding the relationship between salinization and changing ecosystems; and developing knowledge on the causes and distribution of groundwater salinity, brackish water resources, and challenges related to desalination.

Enviornmental Monitoring and Assessment

Sources of terrestrially-derived organic carbon in lower Mississippi River and Louisiana shelf sediments: Implications for differential sedimentation and transport at the coastal margin

In this study, we examined the temporal and spatial variability of terrestrial organic carbon sources in lower Mississippi River and Louisiana shelf sediments (during 11 cruises over a 22-month period) to further understand the sorting dynamics and selective transport of vascular plant materials within the primary dispersal system of the river. Bulk ??13C values in lower river sediments ranged from -21.90??? to -24.64??? (mean=-23.20??1.09???), these values were generally more depleted than those found in shelf sediments (-22.5??? to -21.2???). The ??8 (??8 = sum of vanillyl, syringyl and cinnamyl phenols produced from the oxidation of 100 mg of organic carbon) values in the lower river ranged from 0.71 to 3.74 (mean = 1.78??0.23). While there was no significant relationship between ??8 and river discharge (p>0.05), the highest value occurred during peak discharge in April 1999-which corresponded to the highest observed C/N value of 17.41. The ??8 values on the shelf ranged from 0.68 to 1.36 (mean = 0.54??0.30) and were significantly lower (p <0.05) than the average value for lower river sediments. The range of S/V (syringyl/vanillyl) and C/V (cinnamyl/vanillyl) ratios on the shelf, 0.11 to 0.95 and 0.01 to 0.08, respectively, were similar to that found in the lower river. These low C/V ratios are indicative a mixture of woody and non-woody carbon sources. Recent work by Goni et al. [Nature 389 (1997) 275; Geochim. Cosmochim. Acta 62 (1998) 3055], which did not include sampling transects within the primary dispersal system of the Mississippi River, showed a non-woody vascular plant signature on the Louisiana shelf. This suggests that riverine-derived woody tissues preferentially settle out of the water column, in the lower river and inner shelf, prior to the selective dispersal of C3 versus C4 non-woody materials in other regions the shelf and slope. This works further demonstrates the importance of differential settlement of particles, sampling location within the dispersal system, and river discharge, when examining biogeochemical cycles in river-dominated margins. ?? 2002 Elsevier Science B.V. All rights reserved.

Marine Chemistry

ChemCam activities and discoveries during the nominal mission of the Mars Science Laboratory in Gale crater, Mars

At Gale crater, Mars, ChemCam acquired its first laser-induced breakdown spectroscopy (LIBS) target on Sol 13 of the landed portion of the mission (a Sol is a Mars day). Up to Sol 800, more than 188 000 LIBS spectra were acquired on more than 5800 points distributed over about 650 individual targets. We present a comprehensive review of ChemCam scientific accomplishments during that period, together with a focus on the lessons learned from the first use of LIBS in space. For data processing, we describe new tools that had to be developed to account for the uniqueness of Mars data. With regard to chemistry, we present a summary of the composition range measured on Mars for major-element oxides (SiO 2 , TiO 2 , Al 2 O 3 , FeO T , MgO, CaO, Na 2 O, K 2 O) based on various multivariate models, with associated precisions. ChemCam also observed H, and the non-metallic elements C, O, P, and S, which are usually difficult to quantify with LIBS. F and Cl are observed through their molecular lines. We discuss the most relevant LIBS lines for detection of minor and trace elements (Li, Rb, Sr, Ba, Cr, Mn, Ni, and Zn). These results were obtained thanks to comprehensive ground reference datasets, which are set to mimic the expected mineralogy and chemistry on Mars. With regard to the first use of LIBS in space, we analyze and quantify, often for the first time, each of the advantages of using stand-off LIBS in space: no sample preparation, analysis within its petrological context, dust removal, sub-millimeter scale investigation, multi-point analysis, the ability to carry out statistical surveys and whole-rock analyses, and rapid data acquisition. We conclude with a discussion of ChemCam performance to survey the geochemistry of Mars, and its valuable support of decisions about selecting where and whether to make observations with more time and resource-intensive tools in the rover's instrument suite. In the end, we present a bird's-eye view of the many scientific results: discovery of felsic Noachian crust, first observation of hydrated soil, discovery of manganese-rich coatings and fracture fills indicating strong oxidation potential in Mars' early atmosphere, characterization of soils by grain size, and wide scale mapping of sedimentary strata, conglomerates, and diagenetic materials.

Journal of Analytical Atomic Spectrometry

Experimental translocation of a rare Hawaiian tree reveals disparity between remnant and potential habitat

Translocation is implemented worldwide as a conservation strategy for rare and endangered plant species, yet the factors that influence long-term success remain poorly understood. Remnant wild populations are often used as indicators to model habitat preference and select translocation sites, but such populations may be refugia from past biological or anthropogenic stressors and represent sub-optimal habitat conditions for focal taxa. To test assumptions about habitat preferences of rare species, we conducted a four-year experimental translocation of the Critically Endangered Hawaiian tree, ‘ohe mauka, Polyscias bisattenuata (Araliaceae), planting 3,700 saplings across eleven sites spanning diverse environmental conditions both within and beyond the species’ extant range. We measured seventeen predictor variables at the site and individual plant level in categories of climate, surrounding vegetation, soil chemistry, and genetic provenance. We used linear mixed effects models to assess relative effects of predictors on translocated plant survival, growth, and vigor. The factors which influenced plant performance shifted across ontogeny. The height of surrounding vegetation showed an initial negative relationship with two-year survival, but later showed a positive relationship with four-year growth. Four-year growth demonstrated a strong positive relationship with site annual mean temperature. Successful translocation sites were lower in elevation and warmer in temperature than conditions represented by remnant wild populations. Results demonstrate that basing translocation sites solely on limited extant wild occurrences can lead to suboptimal restoration practices, and experimental outplanting across broad conditions may help identify rare species' contemporary habitat preferences.

Hawaii

Summer runoff generation in foothill catchments of the Colorado Front Range

Climatic shifts, disturbances, and land-use change can alter hydrologic flowpaths, water quality, and water supply to downstream communities. Prior research investigating streamflow generation processes in mountainous areas has largely focused on high-elevation alpine and subalpine catchments; less is known about these processes in lower-elevation foothills and montane catchments. In these lower-elevation ecoregions, precipitation shifts seasonally from snow to rain, which can result in differing seasonal flowpaths. We analyzed stream water for electrical conductivity, SiO 2 , Ca, Mg, Na, Cl, SO 4 , K, and dissolved organic carbon on both a weekly and storm event basis from April to August 2018 in three small (<10 km 2 ) foothill catchments, and one larger (63.2 km 2 ) catchment extending from the foothills to the subalpine ecoregions, in the Colorado Front Range. Using two end-member hydrograph separations and concentration-runoff relationships, we inferred the dominant catchment-scale flowpaths of precipitation to the streams. We selected catchments with varying land use to investigate the relationship between these characteristics and hydrologic flowpaths. We observed that concentrations of lithogenic constituents generally increased and dissolved organic carbon decreased as seasonal runoff decreased in the three foothill catchments, reflecting a transition from shallow subsurface flowpaths to deeper subsurface flowpaths. Elevated SO 4 and Cl concentrations during low-flow periods in two of our catchments suggest that historical or current anthropogenic activities, such as mining, application of road salt, and/or near-stream septic systems, affect local stream and groundwater chemistry. In a foothill catchment with anthropogenic and geologic impervious surfaces, streamflow during storm responses was sourced from faster, surficial flowpaths compared to a less disturbed neighboring catchment, highlighting the influence of anthropogenic land-use on runoff generation. This study provides insight into the fundamental hydrology of foothill catchments and how they may function in the future with human development, precipitation shifts and disturbances.

Colorado

Carbon chemistry of intact versus chronically drained peatlands in the southeastern USA

The Great Dismal Swamp (GDS) is a large temperate swamp in Virginia/North Carolina with peat soils historically resistant to microbial decomposition. However, this peatland has been subject to ~200 years of disturbance during which extensive drainage, fire suppression, and wide-spread logging have increased decomposition and dramatically decreased the distribution of Atlantic white cedar (AWC). The purpose of this study was to determine the impact of long-term drainage and AWC loss on the carbon chemistry of GDS peats. Peat cores were collected from three drained GDS vegetation communities (pocosin, AWC, and red maple-black gum) and compared to cores collected from an intact, undrained AWC peatland at the Alligator River National Wildlife Refuge (AR) in North Carolina, USA. The AR peats had higher lignin content in the deeper peat intervals, and lignin content and % organic carbon were largely invariant with depth compared to the GDS peats. The concentrations of syringyl group phenols were greater in the surface layers of GDS peats, likely reflecting the selective removal of AWC and transition from gymnosperms to angiosperms. Acid to aldehyde ratios for vanillyl and syringyl group phenols indicated that the GDS peats were more decomposed, particularly at depth, and that this occurred under aerobic conditions. Moreover, solid state 13C NMR confirmed a coincident loss of carbohydrates and increase in recalcitrant byproducts of carbohydrate degradation with depth. These data indicate that long-term drainage has accelerated the decomposition of peat at the GDS, reducing the capacity and stability of the carbon sink.

Virginia, North Carolina

Mining-impacted sources of metal loading to an alpine stream based on a tracer-injection study, Clear Creek County, Colorado

Base flow water in Leavenworth Creek, a tributary to South Clear Creek in Clear Creek County, Colorado, contains copper and zinc at levels toxic to aquatic life. The metals are predominantly derived from the historical Waldorf mine, and sources include an adit, a mine-waste dump, and mill-tailings deposits. Tracer-injection and water-chemistry synoptic studies were conducted during low-flow conditions to quantify metal loads of mining-impacted inflows and their relative contributions to nearby Leavenworth Creek. During the 2-year investigation, the adit was rerouted in an attempt to reduce metal loading to the stream. During the first year, a lithium-bromide tracer was injected continuously into the stream to achieve steady-state conditions prior to synoptic sampling. Synoptic samples were collected from Leavenworth Creek and from discrete surface inflows. One year later, synoptic sampling was repeated at selected sites to evaluate whether rerouting of the adit flow had improved water quality. The largest sources of copper and zinc to the creek were from surface inflows from the adit, diffuse inflows from wetland areas, and leaching of dispersed mill tailings. Major instream processes included mixing between mining- and non-mining-impacted waters and the attenuation of iron, aluminum, manganese, and othermetals by precipitation or sorption. One year after the rerouting, the Zn and Cu loads in Leavenworth Creek from the adit discharge versus those from leaching of a large volume of dispersed mill tailings were approximately equal to, if not greater than, those before. The mine-waste dump does not appear to be a major source of metal loading. Any improvement that may have resulted from the elimination of adit flow across the dump was masked by higher adit discharge attributed to a larger snow pack. Although many mine remediation activities commonly proceed without prior scientific studies to identify the sources and pathways of metal transport, such strategies do not always translate to water-quality improvements in the stream. Assessment of sources and pathways to gain better understanding of the system is a necessary investment in the outcome of any successful remediation strategy.

Colorado

Dissolved pesticide and organic carbon concentrations detected in surface waters, northern Central Valley, California, 2001-2002

Field and laboratory studies were conducted to determine the effects of pesticide mixtures on Chinook salmon under various environmental conditions in surface waters of the northern Central Valley of California. This project was a collaborative effort between the U.S. Geological Survey (USGS) and the University of California. The project focused on understanding the environmental factors that influence the toxicity of pesticides to juvenile salmon and their prey. During the periods January through March 2001 and January through May 2002, water samples were collected at eight surface water sites in the northern Central Valley of California and analyzed by the USGS for dissolved pesticide and dissolved organic carbon concentrations. Water samples were also collected by the USGS at the same sites for aquatic toxicity testing by the Aquatic Toxicity Laboratory at the University of California Davis; however, presentation of the results of these toxicity tests is beyond the scope of this report. Samples were collected to characterize dissolved pesticide and dissolved organic carbon concentrations, and aquatic toxicity, associated with winter storm runoff concurrent with winter run Chinook salmon out-migration. Sites were selected that represented the primary habitat of juvenile Chinook salmon and included major tributaries within the Sacramento and San Joaquin River Basins and the Sacramento?San Joaquin Delta. Water samples were collected daily for a period of seven days during two winter storm events in each year. Additional samples were collected weekly during January through April or May in both years. Concentrations of 31 currently used pesticides were measured in filtered water samples using solid-phase extraction and gas chromatography-mass spectrometry at the U.S. Geological Survey's organic chemistry laboratory in Sacramento, California. Dissolved organic carbon concentrations were analyzed in filtered water samples using a Shimadzu TOC-5000A total organic carbon analyzer.

California

A geochemical and geophysical assessment of coastal groundwater discharge at select sites in Maui and O’ahu, Hawai’i

This chapter summarizes fieldwork conducted to derive new estimates of coastal groundwater discharge and associated nutrient loadings at select coastal sites in Hawai’i, USA. Locations for this work were typically identified based on pronounced, recent ecosystem degradation that may at least partially be attributable to sustained coastal groundwater discharge. Our suite of tools used to evaluate groundwater discharge included select U/Th series radionuclides, a broad spectrum of geochemical analytes, multi-channel electrical resistivity, and in situ oceanographic observations. Based on the submarine groundwater discharge tracer 222Rn, coastal groundwater discharge rates ranged from about 22–50 cm per day at Kahekili, a site in the Ka’anapali region north of Lahaina in west Maui, while at Black Point in Maunalua Bay along southern O’ahu, coastal groundwater discharge rates ranged up to 700 cm per day, although the mean discharge rate at this site was 60 cm per day. The water chemistry of the discharging groundwater can be dramatically different than ambient seawater at both coastal sites. For example, at Kahekili the average concentrations of dissolved inorganic nitrogen (DIN), dissolved silicate (DSi) and total dissolved phosphorus (TDP) were roughly 188-, 36-, and 106-times higher in the discharging groundwater relative to ambient seawater, respectively. Such data extend our basic understanding of the physical controls on coastal groundwater discharge and provide an estimate of the magnitude and physical forcings of submarine groundwater discharge and associated trace metal and nutrient loads conveyed by this submarine route.

Hawaii

Loparite, a rare-earth ore (Ce, Na, Sr, Ca)(Ti, Nb, Ta, Fe+3)O3

The mineral loparite (Ce, NA, Sr, Ca)(Ti, Nb, Ta, Fe+3)O3 is the principal ore of the light-group rare-earth elements (LREE) in Russia. The complex oxide has a perovskite (ABO3) structure with coupled substitutions, polymorphism, defect chemistry and a tendency to become metamict. The A site generally contains weakly bonded, easily exchanged cations of the LREE, Na and Ca. The B site generally contains smaller, highly charged cations of Ti, Nb or Fe+3. Mine production is from Russia's Kola Peninsula. Ore is beneficiated to produce a 95% loparite concentrate containing 30% rare-earth oxides. Loparite concentrate is refined by either a chlorination process or acid decomposition process to recover rare-earths, titanium, niobium and tantalum. Rare-earths are separated by solvent extraction and selective precipitation/dissolution. The concentrate is processed at plants in Russia, Estonia and Kazakstan.

Journal of Alloys and Compounds

Using fish communities to assess streams in Romania: Initial development of an index of biotic integrity

Multimetric biotic indices increasingly are used to complement physicochemical data in assessments of stream quality. We initiated development of multimetric indices, based on fish communities, to assess biotic integrity of streams in two physiographic regions of central Romania. Unlike previous efforts to develop such indices for European streams, our metrics and scoring criteria were selected largely on the basis of empirical relations in the regions of interest. We categorised 54 fish species with respect to ten natural-history attributes, then used this information to compute 32 candidate metrics of five types (taxonomic, tolerance, abundance, reproductive, and feeding) for each of 35 sites. We assessed the utility of candidate metrics for detecting anthropogenic impact based on three criteria: (a) range of values taken, (b) relation to a site-quality index (SQI), which incorporated information on hydrologic alteration, channel alteration, land-use intensity, and water chemistry, and (c) metric redundancy. We chose seven metrics from each region to include in preliminary multimetric indices (PMIs). Both PMIs included taxonomic, tolerance, and feeding metrics, but only two metrics were common to both PMIs. Although we could not validate our PMIs, their strong association with the SQI in each region suggests that such indices would be valuable tools for assessing stream quality and could provide more comprehensive assessments than the traditional approaches based solely on water chemistry.

Hydrobiologia

Age and source of water in springs associated with the Jacksonville Thrust Fault Complex, Calhoun County, Alabama

Water from wells and springs accounts for more than 90 percent of the public water supply in Calhoun County, Alabama. Springs associated with the Jacksonville Thrust Fault Complex are used for public water supply for the cities of Anniston and Jacksonville. The largest ground-water supply is Coldwater Spring, the primary source of water for Anniston, Alabama. The average discharge of Coldwater Spring is about 32 million gallons per day, and the variability of discharge is about 75 percent. Water-quality samples were collected from 6 springs and 15 wells in Calhoun County from November 2001 to January 2003. The pH of the ground water typically was greater than 6.0, and specific conductance was less than 300 microsiemens per centimeter. The water chemistry was dominated by calcium, carbonate, and bicarbonate ions. The hydrogen and oxygen isotopic composition of the water samples indicates the occurrence of a low-temperature, water-rock weathering reaction known as silicate hydrolysis. The residence time of the ground water, or ground-water age, was estimated by using analysis of chlorofluorocarbon, sulfur hexafluoride, and regression modeling. Estimated ground-water ages ranged from less than 10 to approximately 40 years, with a median age of about 18 years. The Spearman rho test was used to identify statistically significant covariance among selected physical properties and constituents in the ground water. The alkalinity, specific conductance, and dissolved solids increased as age increased; these correlations reflect common changes in ground-water quality that occur with increasing residence time and support the accuracy of the age estimates. The concentration of sodium and chloride increased as age increased; the correlation of these constituents is interpreted to indicate natural sources for chloride and sodium. The concentration of silica increased as the concentration of potassium increased; this correlation, in addition to the isotopic data, is evidence that silicate hydrolysis of clay minerals occurred. The geochemical modeling program NETPATH was used to investigate possible mixing scenarios that could yield the chemical composition of water collected from springs associated with the Jacksonville Thrust Fault Complex. The results of NETPATH modeling suggest that the primary source of water in Coldwater Spring is a deep aquifer, and only small amounts of rainwater from nearby sources are discharged from the spring. Starting with Piedmont Sports Spring and moving southwest along a conceptual ground-water flow path that parallels the Jacksonville Thrust Fault Complex, NETPATH simulated the observed water quality of each spring, in succession, by mixing rainwater and water from the spring just to the northeast of the spring being modeled. The percentage of rainwater and ground water needed to simulate the quality of water flowing from the springs ranged from 1 to 25 percent rainwater and 75 to 99 percent ground water.

Scientific Investigations Report

Riparian and Associated Habitat Characteristics Related to Nutrient Concentrations and Biological Responses of Small Streams in Selected Agricultural Areas, United States, 2003-04

Physical factors, including both in-stream and riparian habitat characteristics that limit biomass or otherwise regulate aquatic biological condition, have been identified by previous studies. However, linking the ecological significance of nutrient enrichment to habitat or landscape factors that could allow for improved management of streams has proved to be a challenge in many regions, including agricultural landscapes, where many ecological stressors are strong and the variability among watersheds typically is large. Riparian and associated habitat characteristics were sampled once during 2003-04 for an intensive ecological and nutrients study of small perennial streams in five contrasting agricultural landscapes across the United States to determine how biological communities and ecosystem processes respond to varying levels of nutrient enrichment. Nutrient concentrations were determined in stream water at two different sampling times per site and biological samples were collected once per site near the time of habitat characterization. Data for 141 sampling sites were compiled, representing five study areas, located in parts of the Delmarva Peninsula (Delaware and Maryland), Georgia, Indiana, Ohio, Nebraska, and Washington. This report examines the available data for riparian and associated habitat characteristics to address questions related to study-unit contrasts, spatial scale-related differences, multivariate correlation structure, and bivariate relations between selected habitat characteristics and either stream nutrient conditions or biological responses. Riparian and associated habitat characteristics were summarized and categorized into 22 groups of habitat variables, with 11 groups representing land-use and land-cover characteristics and 11 groups representing other riparian or in-stream habitat characteristics. Principal components analysis was used to identify a reduced set of habitat variables that describe most of the variability among the sampled sites. The habitat characteristics sampled within the five study units were compared statistically. Bivariate correlations between riparian habitat variables and either nutrient-chemistry or biological-response variables were examined for all sites combined, and for sites within each study area. Nutrient concentrations were correlated with the extent of riparian cropland. For nitrogen species, these correlations were more frequently at the basin scale, whereas for phosphorus, they were about equally frequent at the segment and basin scales. Basin-level extents of riparian cropland and reach-level bank vegetative cover were correlated strongly with both total nitrogen and dissolved inorganic nitrogen (DIN) among multiple study areas, reflecting the importance of agricultural land-management and conservation practices for reducing nitrogen delivery from near-stream sources. When sites lacking segment-level wetlands were excluded, the negative correlation of riparian wetland extent with DIN among 49 sites was strong at the reach and segment levels. Riparian wetland vegetation thus may be removing dissolved nutrients from soil water and shallow groundwater passing through riparian zones. Other habitat variables that correlated strongly with nitrogen and phosphorus species included suspended sediment, light availability, and antecedent water temperature. Chlorophyll concentrations in seston were positively correlated with phosphorus concentrations for all sites combined. Benthic chlorophyll was correlated strongly with nutrient concentrations in only the Delmarva study area and only in fine-grained habitats. Current velocity or hydraulic scour could explain correlation patterns for benthic chlorophyll among Georgia sites, whereas chlorophyll in seston was correlated with antecedent water temperature among Washington and Delmarva sites. The lack of any consistent correlation pattern between habitat characteristics and organic material density (ash-free dry mass)

Scientific Investigations Report

Hydrogeochemical survey of groundwater for selected areas in the Arabian Shield and in cover rocks, Kingdom of Saudi Arabia

In the spring of 1984, a hydrogeochemical survey was conducted in the Kingdom of Saudi Arabia to test ground water as a sampling medium in exploration for mineral deposits. Eighty-one water samples (mostly from wells) were collected. The samples were analysed for the presence and concentration of major cations and anions, as well as a suite of trace elements. Most of the water samples contained high concentrations of dissolved salts. The majority of the samples showed no significant amounts of the trace elements. A few well-water samples contained moderately anomalous concentrations of zinc, molybdenum, and uranium. These anomalies could be due to salinity effects, contamination, or the proximity of mineral sources. This survey has established some baseline water-chemistry data, especially for the trace metals, which to date have not been reported in ground water in the Kingdom of Saudi Arabia.

Open-File Report

Detailed study of selenium and selected constituents in water, bottom sediment, soil, and biota associated with irrigation drainage in the San Juan River area, New Mexico, 1991-95

In response to increasing concern about the quality of irrigation drainage and its potential effects on fish, wildlife, and human health, the U.S. Department of the Interior began the National Irrigation Water Quality Program (NIWQP) to investigate these concerns at irrigation projects sponsored by the Department. The San Juan River area in northwestern New Mexico was one of the areas designated for study. Study teams composed of scientists from the U.S. Geological Survey, the U.S. Fish and Wildlife Service, the Bureau of Reclamation, and the Bureau of Indian Affairs collected water, bottom-sediment, soil, and biological samples at 61 sites in the San Juan River area during 1993-94. Supplemental data collection conducted during 1991-95 by the Bureau of Indian Affairs and its contractor extended the time period and sampling sites available for analysis. Analytical chemistry performed on samples indicated that most potentially toxic elements other than selenium generally were not high enough to be of concern to fish, wildlife, and human health. Element concentrations in some water, bottom-sediment, soil, and biological samples exceeded applicable standards and criteria suggested by researchers in current literature. Selenium concentrations in water samples from 28 sites in the study area exceeded the 2-microgramper-liter (lg/L) wildlife-habitat standard. Vanadium concentrations in water exceeded the 100-Kg/L standard for livestock-drinking water at one site. In biota, selenium and aluminum concentrations regularly equaled or exceeded avian dietary threshold concentrations. In bottom sediment and soil, element concentrations above the upper limit of the baseline range for western soils were: selenium, 24 exceedances; lead, 2 exceedances; molybdenum, 2 exceedances;strontium, 4 exceedances; and zinc, 4 exceedances. Concentrations of total selenium in bottom-sediment and soil samples were significantly greater for Cretaceous than for non-Cretaceous soil types in the study area and were generally similar for habitats within and outside irrigation-affected areas. Mean and median total-selenium concentrations in samples from areas with Cretaceous soil types were 4.6 and 2.2 micrograms per gram (ps/g), respectively. Mean and median total-selenium concentrations in samples from areas with non-Cretaceous soil types were 0.6 and 0.15 pg/g, respectively. Samples from the study area had low concentrations of organic constituents. Organochlorine pesticides and polychlorinated biphenyls were detected in a few biological samples at low concentrations. Polycyclic aromatic hydrocarbon (PAH) compounds were not detected in whole-water samples collected using conventional water-sampling techniques. In tests involving the use of semipermeable-membrane devices to supplement conventional water assays for PAH's, low concentrations of PAH's were found at several locations in the Hammond Irrigation Supply Canal, but were not detected in the Hammond ponds at the downstream reach of the Hammond irrigation service area. PAH compounds do not appear to reach the San Juan River through the Hammond Canal. Data indicate that water samples from irrigation-drainage-affected habitats had increased mean selenium concentrations compared with samples from irrigation-delivery habitat. The mean selenium concentration in water was greatest at seeps and tributaries draining irrigated land (17 μg/L); less in irrigation drains and in ponds on irrigated land (61.tg/L); and least in backwater, the San Juan River, and irrigation-supply water (0.5 - 0.6 μg/L). Statistical tests imply that irrigation significantly increases selenium concentrations in water samples when a Department of the Interior irrigation project is developed on selenium-rich sediments. Water samples from sites with Cretaceous soils had significantly greater selenium concentrations than water samples from sites with non-Cretaceous soils. Water samples from Department of the Interior project irrigation-drainage sites developed on Cretaceous soils contained a mean selenium concentration about 10 times greater than those in samples from Department of the Interior project sites developed on non-Cretaceous soils. Selenium was much less concentrated in water than in bottom sediment, soil, or biota in the study area. The range in concentrations of dissolved selenium in water was less than 1 ptg/L to 37 1.1g/L (less than 1 to 37 parts per billion). The range in concentrations of total selenium in bottom sediment and soil was less than 0.1 to 23lig/g (less than 100 to 23,000 parts per billion). The range in concentration of selenium in biota was less than 0.1 to 24.0 fig/g (less than 100 to 24,000 parts per billion). Data indicated that bioaccumulation and leaching from soil were the important processes at the study area that lead to elevated levels of selenium. Other processes examined included: (1) evapoconcentration of selenium; (2) atmospheric deposition of aerosols containing selenium; and (3) contamination of surface water by point-source or non-point-source discharges. Selenium concentrations in biological samples were evaluated by a number of variables including: (1) media sampled (emergent and submergent plants, nektonic and benthic invertebrates, omnivore/herbivore and carnivore fish, and terrestrial and aquatic amphibians); (2) habitat (San Juan River main-stem reaches, backwaters, tributary reaches, irrigation delivery or drainage canals, and ponds); (3) irrigation project area and reference sites; and (4) soil type (non-Cretaceous or Cretaceous soils). Graphical techniques and nonparametric statistical tests were applied to determine the influence of selected physiographic variables on selenium concentrations in biological samples collected in the San Juan River area. Species of sucker and of smaller fish contained significantly higher selenium concentrations in the upstream portion of the river where a productive community of plants and animals is found that is associated with warming, nutrient-rich waters discharged from an upstream reservoir. Selenium concentrations in algae, odonates, and mosquitofish collected from both irrigation-drain and pond habitats underlain by Cretaceous soils were significantly greater than in those collected from similar habitats underlain by non-Cretaceous soils. Investigators conclude that the major factor affecting the variability of selenium accumulation in biota at aquatic habitats was the presence of underlying Cretaceous soils. Median selenium concentrations were less than 2 lAg/g for plant samples, less than 7 μg/g for invertebrate samples, and less than 6 lAg/g for whole-fish samples collected from aquatic habitats underlain by non-Cretaceous soils. Similar samples collected from aquatic habitats underlain by Cretaceous soils contained median selenium concentrations two to five times greater. Leaching of selenium from Cretaceous soils in the San Juan River area increases the accumulation of selenium concentrations in the biota and thereby increases the exposure and potential health risks associated with selenium to migratory birds, fish, and other wildlife that use these aquatic habitats extensively. Aquatic habitats presenting the greatest average exposure to excess selenium concentrations in the diets of resident wildlife are from consumption of plants, invertebrates, and fish at irrigation-drain habitats underlain by Cretaceous soils. Of the irrigation projects evaluated in the San Juan River area, the highest median selenium concentrations in algae, cattail leaves, odonate nymphs, mosquitofish, and leopard frog samples from the study area were collected from the east hogback irrigation drain.

New Mexico

Orthene® toxicity to little brown bats (Myotis lucifugus): Acetylcholinesterase inhibition, coordination loss, and mortality

The 24-h LD50 of Orthener̀ (active ingredient acephate, acetylphosphoramidothioic acid o,s -dimethyl ester, CAS 30560-19–1) to little brown bats (Myotis lucifugus) was high (> 1,500 mg acephate/kg) and at least several times greater than the LD50 for mice (Mus musculus) (720 mg/kg). Twenty-four hours after dosing, all surviving mice appeared behaviorally normal, but 9 of 30 surviving bats could not right themselves when placed on their backs. When dead and incapacitated bats were combined to calculate an ED50 (median effective dose), the resultant estimate (687 mg/kg) did not differ ( p > 0.05) from the LD50 for mice. Serum cholinesterase (ChE) activity in control bats was 3.2 times greater than in mice. The relationship between this naturally high level of ChE and the relative tolerance of bats to organophosphorus insecticides is unexplained. Toxicity of Orthene was clearly less than that reported elsewhere for methyl parathion (phosphorothioic acid o,o -dimethyl o-[4-nitrophenyl] ester, CAS 298–00-0). This finding may be useful in selection of a chemical for agricultural use, but conclusions about the safety of Orthene to this bat species, or to others, must remain tentative until confirmed by studies under field conditions. Because bats are long-lived with low reproductive rates and slow recruitment, any additional mortality in the wild could be critical to population survival.

Environmental Toxicology and Chemistry

Bayesian multimodel inference for dose-response studies

Statistical inference in dose-response studies is model-based: The analyst posits a mathematical model of the relation between exposure and response, estimates parameters of the model, and reports conclusions conditional on the model. Such analyses rarely include any accounting for the uncertainties associated with model selection. The Bayesian inferential system provides a convenient framework for model selection and multimodel inference. In this paper we briefly describe the Bayesian paradigm and Bayesian multimodel inference. We then present a family of models for multinomial dose-response data and apply Bayesian multimodel inferential methods to the analysis of data on the reproductive success of American kestrels (Falco sparveriuss) exposed to various sublethal dietary concentrations of methylmercury.

Environmental Toxicology and Chemistry