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USGS2009

Systematic approaches to comprehensive analyses of natural organic matter

The more that is learned of the chemistry of aquatic natural organic matter (NOM) the greater is the scientific appreciation of the vast complexity of this subject. This complexity is due not only to a multiplicity of precursor molecules in any environment but to their associations with each other and with other components of local environments such as clays, mineral acids and dissolved metals. In addition, this complex system is subject to constant change owing to environmental variables and microbial action. Thus, there is a good argument that no two NOM samples are exactly the same even from the same source at nearly the same time. When ubiquity of occurrence, reaction with water treatment chemicals, and subsequent human exposure are added to the list of NOM issues, one can understand the appeal that this subject holds for a wide variety of environmental scientists.

Annals of Environmental Science↗

USGS2021

Weathering of slags

Weathering is a natural process causing the transformation of minerals, rocks, and related materials like glass under near-surface conditions. Although metallurgical slags are human-made materials, they also undergo natural weathering processes. As base metal slags weather, the released solutions may contain contaminants that could pose an environmental risk. On the other hand, weathering of ferrous slags is important because of the common reuse of the slags. This chapter summarizes factors that affect rates of slag weathering as well as defining and characterizing the two stages of weathering (incipient and advanced) as they are observed in a wide variety of individual phases and slags. We conclude that slags weather at different scales and rates depending on their chemistry and phase composition as well as the external conditions. Furthermore, weathering of slags is a process that is not perfectly reflected by natural processes because these materials are complex (in terms of texture, composition, and disequilibrium with surficial conditions) and not always analogous to rocks. Therefore, some information in this chapter on weathering is applicable to all slag types, some is relevant to only specific slag types, and some aspects require additional study.

Book chapter↗

USGS2026

PFAS mixture composition and internal exposure profiles shape biological responses under field-realistic exposure

Per- and polyfluoroalkyl substances (PFAS) occur as complex mixtures, yet mixture-dependent biological effects under environmentally realistic exposure conditions remain poorly understood. We conducted multiyear (2018, 2019, 2021) continuous-flow, field-based exposures of male fathead minnows ( Pimephales promelas ) using a low-PFAS reference well (REF; sum of measured PFAS (∑PFAS) 0.1–0.2 μg L –1 ) and PFAS-contaminated groundwater from a fire-training area (FTA) at Joint Base Cape Cod, Massachusetts. Dilution treatments enabled separation of concentration and mixture effects. Groundwater from well FTA1 was perfluorooctanesulfonate (PFOS) dominated (∑PFAS 10–31 μg L –1 ), whereas groundwater from well FTA2 had higher concentrations and was enriched in perfluorooctanoate (PFOA) and diverse precursors (∑PFAS ∼ 80 μg L –1 ). Despite comparable plasma ∑PFAS and PFOS in FTA1–100% and FTA2–50% on day-7, cumulative mortality reached approximately 35% in FTA2–50% and 17% in FTA2–100%, and secondary sex trait expression was reduced by approximately 65–80% relative to REF, whereas sperm motility effects were mixture- and time-dependent. Plasma PFAS profiles were dominated by perfluorohexanesulfonate (PFHxS), PFOS, and sulfonamide precursors. Liver transcriptomics from REF-acclimated fish revealed robust disruption of metabolic, mitochondrial, and endocrine pathways that link PFAS mixture chemistry and internal exposure profiles to organismal outcomes, and testis transcriptomics provided complementary insight into reproductive impairment. These results indicate that PFAS mixture composition and internal exposure profiles, including precursor-associated differences, are important determinants of ecotoxicological outcomes under field-realistic conditions.

Massachusetts↗

USGS2023

Groundwater chemistry and hexavalent chromium

Water samples collected by the U.S. Geological Survey from more than 100 wells between March 2015 and November 2017 in Hinkley and Water Valleys, in the Mojave Desert 80 miles northeast of Los Angeles, California, were analyzed for field parameters, major ions, nutrients, and selected trace elements, including hexavalent chromium, Cr(VI). Water from most wells was alkaline and oxic. The pH ranged from 6.9 in water-table wells near recharge areas along the Mojave River to 9.4 in deeper wells farther downgradient in the northern subarea. Hexavalent chromium concentrations measured by ion chromatography using U.S. Environmental Protection Agency Method 218.6 and a version of that method used for detection of Cr(VI) concentrations as low as 0.06 micrograms per liter (μg/L), produced results comparable to field speciation with subsequent analyses by graphite furnace atomic absorption spectroscopy (coefficient of determination, R 2 , of 0.97). Hexavalent chromium concentrations ranged from less than the study reporting level of 0.10 to 2,500 μg/L. The highest concentrations were within the October–December 2015 (Q4 2015) regulatory Cr(VI) plume downgradient from the Hinkley compressor station. Hexavalent chromium concentrations outside the Q4 2015 regulatory Cr(VI) plume were as high as 11 μg/L. Hexavalent chromium concentrations in water from most wells were distributed in a narrow redox potential and pH band within the overlapping chromate ion, CrO 4 2− (aqueous) , and manganese-3, Mn(III) (solid) , stability fields. The redox potential of water from some wells completed in carbonate-rich mudflat/playa deposits approached the more oxic manganese-4, Mn(IV) (solid) , stability field. However, Cr(VI) concentrations in porewater pressure-extracted from Mn(IV)-containing deposits in the eastern subarea did not exceed 3.3 μg/L, and porewater does not appear to be a source of Cr(VI) concentrations greater than this concentration in water from wells in the eastern subarea. On the basis of comparison with California-wide data, Cr(VI) concentrations at the measured pH were higher than expected for uncontaminated water from wells (1) within the Q4 2015 regulatory Cr(VI) plume, (2) within the eastern subarea nominally crossgradient from the Hinkley compressor station and upgradient from the Q4 2015 regulatory Cr(VI) plume, and (3) from shallow wells in the northern subarea downgradient from the leading edge of the Q4 2015 regulatory Cr(VI) plume. Hexavalent chromium concentrations in alkaline water from wells in the northern subarea of Hinkley Valley and in Water Valley were within ranges expected for uncontaminated water elsewhere in California given their pH and trace-element composition. Hexavalent chromium concentrations were higher than expected on the basis of selected trace-element concentrations that co-occur with Cr(VI) in water from wells within the Q4 2015 regulatory Cr(VI) plume and from wells in the eastern and northern subareas near the plume margins. Hexavalent chromium concentrations did not exceed 4 μg/L in water from domestic wells sampled in Hinkley and Water Valleys and were generally within ranges expected for uncontaminated groundwater given their pH and trace-element composition. Interpretations derived from Cr(VI) and pH, and from Cr(VI) and selected trace-element concentrations collected between March 2015 and November 2017 were used within a summative-scale analysis to determine the Cr(VI) plume extent (chapter G). However, Cr(VI) background concentrations (chapter G) were calculated from regulatory data collected from selected wells between April 2017 and January 2018.

California↗

USGS1983

Effects of specific land uses on nonpoint sources of suspended sediment, nutrients, and herbicides, Pequea Creek basin, Pennsylvania, 1979-80

The Susquehanna River Basin Commission and the U.S. Environmental Protection Agency cooperated with the U.S. Geological Survey in a study to quantify nonpoint-source loadings from an agricultural area in Pennsylvania. Pequea Creek, a tributary to the Susquehanna River, drains a 154-square mile agricultural area in Lancaster County, Pennsylvania. Previous studies defined the Pequea Creek basin as a contributor of sediment, nutrients, and pesticides from nonpoint sources to the Susquehanna River. The purpose of this intensive watershed investigation was to determine the effects of various land uses on water quality of receiving streams. Streamflow was measured and monthly base-flow samples and water-weighted composite storm samples were analyzed for suspended sediment, nutrients, organic carbon, and triazine herbicides. Constituent loadings were calculated to quantify their discharge from the entire Pequea Creek basin and from four specific subbasins: forest, cornfield, rural residential, and pasture. Soil samples were analyzed for nutrients and selected herbicides, and land use and application data were collected to determine the source of loadings. Precipitation amounts and chemistry were also measured. Precipitation and streamflow were below average for much of the investigation period, May 1979 to December 1980. The annual precipitation for 1980 was 10 inches below normal, with drought conditions the last half of the year. During base flow, the highest concentrations of individual constituents generally observed were: 4.0 milligrams per liter total organic nitrogen and 1.4 milligrams per liter total phosphorus from the downstream pasture site; 24 milligrams per liter total nitrate nitrogen and 3.9 micrograms per liter total atrazine from the cornfield site; and 0.5 micrograms per liter total prometone, and 2.3 micrograms per liter total simazine from the residential site. Nearly all total nitrate nitrogen concentrations from the cornfield site during base flow were about double the U.S. Environmental Protection Agency (1977) criterion of 10 milligrams per liter. The highest constituent concentrations found in composite storm samples were nearly all in samples from the cornfield site. The highest concentrations found were: 16,000 milligrams per liter suspended sediment, 54 milligrams per liter total organic nitrogen, 41 milligrams per liter total nitrate nitrogen, 19 milligrams per liter total phosphorus, and 200 micrograms per liter total atrazine. The highest concentrations found in composite storm samples for total prometone was 6.4 micrograms per liter at the residential site and for total simazine was 4.8 micrograms per liter at the downstream pasture site. Generally, concentrations of all the constituents, except nitrate, were higher during storms than during base flow at all sites. Total concentrations of the constituents increase during storms predominantly due to increases in suspended concentrations. The highest storm concentrations of most constituents occurred at the cornfield site. Fertilizer and herbicide applications increase the available sources of nutrients and herbicides for transport to the stream. The highest phosphorus, atrazine, and suspended-sediment concentrations at the cornfield site occurred during intense storms soon after application and planting. Constituent yields (tons per square mile) from storms, about evenly distributed throughout the basin, were compared from the other specific land-use sites to the forest site, which represents a relatively undisturbed land use. During storms, yields for suspended sediment, total organic nitrogen, and total phosphorus were highest for the pasture and lowest for the forest site. Total nitrate-nitrogen yields were highest for the cornfield and about the same for the forest and residential sites. Yields of total organic carbon were about the same for the cornfield and residential sites, which were both slightly higher than the forest

Water-Resources Investigations Report↗

USGS2011

Hydrogeology and water quality of the Floridan aquifer system and effects of Lower Floridan aquifer pumping on the Upper Floridan aquifer at Fort Stewart, Georgia

Test drilling, field investigations, and digital modeling were completed at Fort Stewart, GA, during 2009?2010, to assess the geologic, hydraulic, and water-quality characteristics of the Floridan aquifer system and evaluate the effect of Lower Floridan aquifer (LFA) pumping on the Upper Floridan aquifer (UFA). This work was performed pursuant to the Georgia Environmental Protection Division interim permitting strategy for new wells completed in the LFA that requires simulation to (1) quantify pumping-induced aquifer leakage from the UFA to LFA, and (2) identify the equivalent rate of UFA pumping that would produce the same maximum drawdown in the UFA that anticipated pumping from LFA well would induce. Field investigation activities included (1) constructing a 1,300-foot (ft) test boring and well completed in the LFA (well 33P028), (2) constructing an observation well in the UFA (well 33P029), (3) collecting drill cuttings and borehole geophysical logs, (4) collecting core samples for analysis of vertical hydraulic conductivity and porosity, (5) conducting flowmeter and packer tests in the open borehole within the UFA and LFA, (6) collecting depth-integrated water samples to assess basic ionic chemistry of various water-bearing zones, and (7) conducting aquifer tests in new LFA and UFA wells to determine hydraulic properties and assess interaquifer leakage. Using data collected at the site and in nearby areas, model simulation was used to assess the effects of LFA pumping on the UFA. Borehole-geophysical and flowmeter data indicate the LFA at Fort Stewart consists of limestone and dolomitic limestone between depths of 912 and 1,250 ft. Flowmeter data indicate the presence of three permeable zones at depth intervals of 912-947, 1,090-1,139, and 1,211?1,250 ft. LFA well 33P028 received 50 percent of the pumped volume from the uppermost permeable zone, and about 18 and 32 percent of the pumped volume from the middle and lowest permeable zones, respectively. Chemical constituent concentrations increased with depth, and water from all permeable zones contained sulfate at concentrations that exceeded the U.S. Environmental Protection Agency secondary maximum contaminant level of 250 milligrams per liter. A 72-hour aquifer test pumped LFA well 33P028 at 740 gallons per minute (gal/min), producing about 39 ft of drawdown in the pumped well and about 0.4 foot in nearby UFA well 33P029. Simulation using the U.S. Geological Survey finite-difference code MODFLOW was used to determine long-term, steady-state flow in the Floridan aquifer system, assuming the LFA well was pumped continuously at a rate of 740 gal/min. Simulated steady-state drawdown in the LFA was identical to that observed in pumped LFA well 33P028 at the end of the 72-hour test, with values larger than 1 ft extending 4.4 square miles symmetrically around the pumped well. Simulated steady-state drawdown in the UFA resulting from pumping in LFA well 33P028 exceeded 1 ft within a 1.4-square-mile circular area, and maximum drawdown in the UFA was 1.1 ft. Leakage from the UFA through the Lower Floridan confining unit contributed about 98 percent of the water to the well; lateral flow from specified-head model boundaries contributed about 2 percent. About 80 percent of the water supplied to LFA well 33P028 originated from within 1 mile of the well, and 49 percent was derived from within 0.5 mile of the well. Vertical hydraulic gradients and vertical leakage are progressively higher near the LFA pumped well which results in a correspondingly higher contribution of water from the UFA to the pumped well at distances closer to the pumped well. Simulated pumping-induced interaquifer leakage from the UFA to the LFA totaled 725 gal/min (1.04 million gallons per day), whereas simulated pumping at 205 gal/min (0.3 million gallons per day) from UFA well 33P029 produced the equivalent maximum drawdown as pumping LFA well 33P028 at 740 gal/min during the aquifer test. This equivalent pumpin

Georgia↗

USGS2013

Residence time control on hot moments of net nitrate production and uptake in the hyporheic zone

The retention capacity for biologically available nitrogen within streams can be influenced by dynamic hyporheic zone exchange, a process that may act as either a net source or net sink of dissolved nitrogen. Over 5 weeks, nine vertical profiles of streambed chemistry (NO 3 - and NH 4 + ) were collected above two beaver dams along with continuous high-resolution vertical hyporheic flux data. The results indicate a non-linear relation of net NO 3 - production followed by net uptake in the hyporheic zone as a function of residence time. This Lagrangian-based relation is consistent through time and across varied morphology (bars, pools, glides) above the dams, even though biogeochemical and environmental factors varied. The empirical continuum between net NO 3 - production and uptake and residence time is useful for identifying two crucial residence time thresholds: the transition to anaerobic respiration, which corresponds to the time of peak net nitrate production, and the net sink threshold, which is defined by a net uptake in NO 3 - relative to streamwater. Short-term hyporheic residence time variability at specific locations creates hot moments of net production and uptake, enhancing NO 3 - production as residence times approach the anaerobic threshold, and changing zones of net NO 3 - production to uptake as residence times increase past the net sink threshold. The anaerobic and net sink thresholds for beaver-influenced streambed morphology occur at much shorter residence times (1.3 h and 2.3 h, respectively) compared to other documented hyporheic systems, and the net sink threshold compares favorably to the lower boundary of the anaerobic threshold determined for this system with the new oxygen Damkohler number. The consistency of the residence time threshold values of NO 3 - cycling in this study, despite environmental variability and disparate morphology, indicates that NO 3 - hot moment dynamics are primarily driven by changes in physical hydrology and associated residence times.

Hydrological Processes↗

USGS2023

Environmental tracers of groundwater source, age, and geochemical evolution

Hexavalent chromium, Cr(VI), was discharged in cooling wastewater to unlined surface ponds from 1952 to 1964 and reached the underlying unconsolidated aquifer at the Pacific Gas and Electric Company (PG&E) Hinkley compressor station in the Mojave Desert, 80 miles northeast of Los Angeles, California. A suite of environmental tracers was analyzed in water samples collected from more than 100 wells to characterize the source, age, and geochemical evolution of groundwater within and near the Cr(VI) plume in Hinkley and Water Valleys. This information was used to help determine the extent of Cr(VI) associated with releases from the Hinkley compressor station and to identify Cr(VI) associated with natural sources. The source of water in most wells, indicated by stable oxygen and hydrogen isotope values for water, delta oxygen-18 and delta deuterium, was recharge by infiltration of intermittent surface flows in the Mojave River. With the exception of small flows in 1958, the Mojave River was largely dry between 1952 and 1969. This dry period spans the period of Cr(VI) releases from the Hinkley compressor station; 1952–69 also spans the period of high tritium levels in precipitation resulting from the atmospheric testing of nuclear weapons and, as a consequence, tritium concentrations in groundwater in Hinkley Valley were comparatively low. Groundwater ages (time since recharge) increased downgradient from the Mojave River and with depth. Tritium, measured by helium ingrowth with a study reporting level of 0.05 tritium unit, was detected in water from 51 percent of wells, with detectable tritium as far as 7 miles downgradient from the Mojave River. Tritium concentrations were higher, and tritium/helium-3 groundwater ages younger, in water from wells near the Mojave River and in water from shallower wells downgradient. Agricultural pumping has decreased groundwater levels as much as 60 feet since 1952. As a result of this pumping, some groundwater containing tritium, and presumably anthropogenic Cr(VI), has been removed from the aquifer. The distribution of wells having carbon-14 activities near or greater than 100-percent modern carbon, consistent with post-1952 recharge water, was similar to the distribution of wells containing detectable tritium. Carbon-14 activities as low as 8.9-percent modern carbon, with carbon-14 ages (unadjusted for reactions with aquifer materials) of almost 20,000 years before present (ybp), were sampled in water from some deep wells. Hexavalent chromium concentrations in older groundwater were as high as 11 micrograms per liter but did not exceed 3.6 micrograms per liter in older water from wells completed in “Mojave-type” deposits (composed of felsic Mojave River stream and near-shore lake deposits sourced from the Mojave River); this value may represent an upper limit on Cr(VI) concentrations in groundwater within Mojave-type deposits that likely approximates background Cr(VI) concentrations in the study area. Chlorofluorocarbons were released to the atmosphere and hydrologic cycle as a result of industrial activity beginning in the 1930s. Chlorofluorocarbon data were not generally suitable for groundwater-age dating in Hinkley and Water Valley because of nonatmospheric contributions from local sources. Strontium-87/86 isotope ratios and stable chromium isotopes, delta chromium-53, provide information on the geochemical evolution of groundwater in the aquifer. Highly radiogenic strontium-87/86 ratios greater than 0.71000 were present in water from wells completed in coarse-textured Mojave-type deposits having low chromium concentrations but were not diagnostic of these materials. Nonradiogenic strontium-87/86 ratios less than 0.70950 were diagnostic of weathered materials in the northern subarea of Hinkley and in Water Valley that were eroded from Miocene (23–5 million ybp) deposits east of the study area. Values for delta chromium-53 ranged from near 0 to 2.8 parts per thousand (‰) difference. The extent of reductive fractionation, mixing with native groundwater, and longitudinal dispersion within the October–December 2015 (Q4 2015) regulatory Cr(VI) plume can be estimated on the basis of the delta chromium-53 isotope composition of groundwater within the plume. Reduction of Cr(VI) to trivalent chromium, Cr(III), can occur in the presence of natural reductants in oxic groundwater. Although not diagnostic of anthropogenic chromium at the concentrations of interest near the Q4 2015 regulatory Cr(VI) plume margin, delta chromium-53 data indicate anthropogenic Cr(VI) within the plume is not conservative and has reacted with aquifer materials; these reactions have removed some anthropogenic Cr(VI) from groundwater. Environmental tracers, and the distribution of modern (post-1952) and premodern (pre-1952) groundwater, inform understanding of the extent of anthropogenic and naturally occurring Cr(VI) near the Q4 2015 regulatory Cr(VI) plume and the understanding of geochemical processes occurring in and near the margins of the Cr(VI) plume. The oxygen and hydrogen isotope compositions of water, tritium/helium-3 groundwater-age data, and carbon-14 data were used with mineralogy and chemistry data as part of a summative-scale analysis to determine the Cr(VI) plume extent later in this professional paper (chapter G).

California↗

USGS2010

Effects of urbanization on stream ecosystems along an agriculture-to-urban land-use gradient, Milwaukee to Green Bay, Wisconsin, 2003-2004

In 2003 and 2004, 30 streams near Milwaukee and Green Bay, Wisconsin, were part of a national study by the U.S. Geological Survey to assess urbanization effects on physical, chemical, and biological characteristics along an agriculture-to-urban land-use gradient. A geographic information system was used to characterize natural landscape features that define the environmental setting and the degree of urbanization within each stream watershed. A combination of land cover, socioeconomic, and infrastructure variables were integrated into a multi-metric urban intensity index, scaled from 0 to 100, and assigned to each stream site to identify a gradient of urbanization within relatively homogeneous environmental settings. The 35 variables used to develop the final urban intensity index characterized the degree of urbanization and included road infrastructure (road area and road traffic index), 100-meter riparian land cover (percentage of impervious surface, shrubland, and agriculture), watershed land cover (percentage of impervious surface, developed/urban land, shrubland, and agriculture), and 26 socioeconomic variables (U.S. Census Bureau, 2001). Characteristics examined as part of this study included: habitat, hydrology, stream temperature, water chemistry (chloride, sulfate, nutrients, dissolved and particulate organic and inorganic carbon, pesticides, and suspended sediment), benthic algae, benthic invertebrates, and fish. Semipermeable membrane devices (SPMDs) were used to assess the potential for bioconcentration of hydrophobic organic contaminants (specifically polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine and pyrethroid insecticides) in biological membranes, such as the gills of fish. Physical habitat measurements reflective of channel enlargement, including bankfull channel size and bank erosion, increased with increasing urbanization within the watershed. In this study, percentage of riffles and streambed substrate size were more strongly related to local geologic setting, slope, watershed topography, and river-engineering practices than to urbanization. Historical local river-engineering features such as channelization, bank stabilization, and grade controls may have confounded relations among habitat characteristics and urbanization. A number of hydrologic-condition metrics (including flashiness and duration of high flow during pre- or post-ice periods) showed strong relations to the urban intensity index. Hydrologic-condition metrics cannot be used alone to predict habitat or geomorphic change. Chloride and SPMD measures of potential toxicity and polycyclic aromatic hydrocarbon concentrations showed the strongest positive correlations to urbanization including increases in road infrastructure, percentage of impervious surface in the watershed, urban land cover, and land-distribution related to urban land cover. This suggests that automobiles and the infrastructure required to support automobiles are a significant source of these compounds in this study area. Chloride in spring and summer showed a significant positive correlation with the urban intensity index; concentrations increased with increasing road infrastructure, urban land cover, and a number of landscape variables related to urbanization. Spring concentrations of sulfate, prometon, and diazinon correlated to fewer urban characteristics than chloride, including increases in road infrastructure, percentage of impervious surface, and urban land cover. Changes in biological communities correlated to the urban intensity index or individual urban-associated variables. Decreased percentages of pollution-sensitive diatoms and diatoms requiring high dissolved-oxygen saturation correlated to increases in the percentage of developed urban land, total impervious surface, stream flashiness, population density, road-area density, and decreases in the percentage of wetland in the watershed. Invertebrate taxa richness and Coleop

Scientific Investigations Report↗

USGS1998

The influence of extraction procedure on ion concentrations in sediment pore water

Sediment pore water has the potential to yield important information on sediment quality, but the influence of isolation procedures on the chemistry and toxicity are not completely known and consensus on methods used for the isolation from sediment has not been reached. To provide additional insight into the influence of collection procedures on pore water chemistry, anion (filtered only) and cation concentrations were measured in filtered and unfiltered pore water isolated from four sediments using three different procedures: dialysis, centrifugation, and vacuum. Peepers were constructed using 24-cell culture plates and cellulose membranes and vacuum extractors consisted of fused-glass air stones attached with airline tubing to 60-cc syringes. Centrifugation was accomplished at two speeds (2,500 and 10,000 g ) for 30 min in a refrigerated centrifuge maintained at 4°C. Only minor differences in chemical characteristics and cation and anion concentrations were found among the different collecting methods with differences being sediment-specific. Filtering of the pore water did not appreciably reduce major cation concentrations, but trace metals (Cu and Pb) were markedly reduced. Although the extraction methods evaluated produced pore waters of similar chemistries, the vacuum extractor provided the following advantages over the other methods: ease of extraction, volumes of pore water isolated, minimal preparation time, and least time required for extraction of pore water from multiple samples at one time.

Archives of Environmental Contamination and Toxico↗

USGS2005

Transport and fate of nitrate and pesticides: Hydrogeology and riparian zone processes

There is continuing concern over potential impacts of widespread application of nutrients and pesticides on ground- and surface-water quality. Transport and fate of nitrate and pesticides were investigated in a shallow aquifer and adjacent stream, Cow Castle Creek, in Orangeburg County, South Carolina. Pesticide and pesticide degradate concentrations were detected in ground water with greatest frequency and largest concentrations directly beneath and downgradient from the corn (Zea mays L.) field where they were applied. In almost all samples in which they were detected, concentrations of pesticide degradates greatly exceeded those of parent compounds, and were still present in ground waters that were recharged during the previous 18 yr. The absence of both parent and degradate compounds in samples collected from deeper in the aquifer suggests that this persistence is limited or that the ground water had recharged before use of the pesticide. Concentrations of NO3- in ground water decreased with increasing depth and age, but denitrification was not a dominant controlling factor. Hydrologic and chemical data indicated that ground water discharges to the creek and chemical exchange takes place within the upper 0.7 m of the streambed. Ground water had its greatest influence on surface-water chemistry during low-flow periods, causing a decrease in concentrations of Cl-, NO3-, pesticides, and pesticide degradates. Conversely, shallow subsurface drainage dominates stream chemistry during high-flow periods, increasing stream concentrations of Cl-, NO3-, pesticides, and pesticide degradates. These results point out the importance of understanding the hydrogeologic setting when investigating transport and fate of contaminants in ground water and surface water. ?? ASA, CSSA, SSSA.

Journal of Environmental Quality↗

USGS2010

Mineralogy and the release of trace elements from slag from the Hegeler Zinc smelter, Illinois (USA)

Slag from the former Hegeler Zn-smelting facility in Illinois (USA) is mainly composed of spinifex Ca-rich plagioclase, fine-grained dendritic or coarse-grained subhedral to anhedral clinopyroxenes, euhedral to subhedral spinels, spherical blebs of Fe sulfides, silicate glass, and less commonly fayalitic olivine. Mullite and quartz were also identified in one sample as representing remnants of the furnace lining. Secondary phases such as goethite, hematite and gypsum are significant in some samples and reflect surficial weathering of the dump piles or represent byproducts of roasting. A relatively rare Zn-rich material contains anhedral willemite, subhedral gahnite, massive zincite, hardystonite and a Zn sulfate (brianyoungite), among other phases, and likely represents the molten content of the smelting furnace before Zn extraction. The bulk major-element chemistry of most slag samples is dominated by SiO 2 , Al 2 O 3 , Fe 2 O 3 and CaO. The bulk composition of the slag suggests a high viscosity of the melt and the mineralogy suggests a high silica content of the melt. Bulk slag trace-element chemistry shows that the dominant metal is Zn with >28.4 wt.% in the Zn-rich material and between 212 and 14,900 mg/kg in the other slags. The concentrations of other trace elements reach the following: 45 mg/kg As, 1170 mg/kg Ba, 191 mg/kg Cd, 242 mg/kg Co, 103 mg/kg Cr, 6360 mg/kg Cu, 107 mg/kg Ni, and 711 mg/kg Pb. Zinc, as the dominant metal in the slags, is likely the most environmentally significant metal in these samples; Cd, Cu, and Pb are also of concern and their concentrations exceed US Environmental Protection Agency preliminary remediation goals for residential soils. Spinel was found to be the dominant concentrator of Zn for samples containing significant Zn (>1 wt.%); the silicate glass also contained relatively high concentrations of Zn compared to other phases. Zinc partitioned into the silicates and oxides in these samples is generally more resistant to weathering and therefore less leached when compared to the slag samples with lower bulk Zn concentrations where Zn is likely partitioned into volumetrically minor sulfides. This is confirmed by leachate tests that resulted in low leachate Zn concentrations for samples with Zn partitioned into spinel. In contrast, the concentrations of Zn and SO 4 are close to those expected from the dissolution of stoichiometric ZnS in leachates from samples in which the dominant host of Zn is suspected to be sulfides. The fact that Zn and other metals occur commonly as sulfides, which are more reactive than the silicates and oxides into which they dominantly partition according to other slag studies, indicates the Hegeler slag pile may be more of an environmental concern than other slag piles.

Illinois↗

USGS2015

Geochemical conditions and the occurrence of selected trace elements in groundwater basins used for public drinking-water supply, Desert and Basin and Range hydrogeologic provinces, 2006-11: California GAMA Priority Basin Project

The geochemical conditions, occurrence of selected trace elements, and processes controlling the occurrence of selected trace elements in groundwater were investigated in groundwater basins of the Desert and Basin and Range (DBR) hydrogeologic provinces in southeastern California as part of the Priority Basin Project (PBP) of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA PBP is designed to provide an assessment of the quality of untreated (raw) groundwater in the aquifer systems that are used for public drinking-water supply. The GAMA PBP is being conducted by the California State Water Resources Control Board in collaboration with the U.S. Geological Survey and the Lawrence Livermore National Laboratory. The DBR hydrogeologic provinces consist of 141 defined groundwater basins separated by mountain ranges, faults, and other features. This report presents analyses of data collected from nine study areas within the DBR hydrogeologic provinces: Antelope Valley, Borrego Valley, the Central Desert area, Coachella Valley, Colorado River, Indian Wells Valley, Low-Use Basins of the Mojave and Sonoran Deserts, the Mojave, and Owens Valley. Collectively, these nine study areas are referred to as the DBR study unit. The study unit covers approximately 7,000 square miles and includes the 63 groundwater basins in the DBR hydrogeologic provinces in which groundwater is used for public drinking-water supply. The vast majority of the 223 wells sampled for this study were long-screened production wells used primarily for public supply. Uncorrected carbon-14 ( 14 C) groundwater ages for samples collected in the DBR study unit ranged from less than (<) 100 to 33,700 years before present (BP). Sixty-six percent of sample ages were greater than (>) 100 years BP, and 40 percent were >3,800 years BP. Samples collected from wells located adjacent to mountain-front recharge areas or major surface-water features generally had younger groundwater ages than did samples collected from wells located away from mountain fronts or towards the distal ends of basin groundwater flow paths. Most groundwater sampled in the DBR study unit had alkaline pH: 89 percent of sample pH values ranged from 7.1 to 9.8, with 37 percent greater than or equal to (≥) 7.9. Groundwater age was significantly correlated (positively) with pH, likely because silicate weathering is a primary control on groundwater pH and is a slow process. The oxidation-reduction (redox) condition of the groundwater sampled in the DBR study unit was predominantly oxic (71 percent), except in the Colorado River study area where organic-rich fluvial aquifers provide the electron donors necessary to support iron-reducing (anoxic-Fe) redox processes. The cation type of 78 percent of the samples was either sodium- or mixed-type, and the anion type of 83 percent of the samples was either bicarbonate- or mixed-type. Sodium-type groundwaters generally were older and more alkaline than calcium-type groundwaters, consistent with the change in water chemistry expected from cation exchange between groundwater and aquifer sediments over long periods of time. Because of the correlation with young groundwater, calcium-type groundwater was predominantly from wells located adjacent to mountain-front recharge areas. Arsenic (As), boron (B), fluoride (F), molybdenum (Mo), strontium (Sr), uranium (U), and vanadium (V) were selected for assessment in this study because they occurred at concentrations greater than California Department of Public Health or U.S. Environmental Protection Agency regulatory or non-regulatory drinking-water-quality benchmarks in more than 2 percent of the 223 samples collected in the DBR study unit. As and F were detected most commonly (18 and 13 percent, respectively) at concentrations above associated water-quality benchmarks and Sr and V least frequently (both at 3 percent). Given that 14 C groundwater ages are predominantly >100 years BP, land use in the study unit is primarily undeveloped, and chemicals derived from anthropogenic sources, such as volatile organic compounds, were infrequently detected, high concentrations of these trace elements in groundwater were most likely the result of natural factors and not anthropogenic factors. As, F, Mo, and V concentrations showed significant positive correlations to groundwater age and to pH. This relation is partly due to the sources of trace elements likely being the weathering of primary minerals, such as silicate minerals, which is a slow process that takes place over hundreds to thousands of years. This relation also reflects the positive correlation between groundwater age and pH. Geochemical modeling predicted that the dominant species of As, Mo, and V in solution were oxyanions (HAsO 4 2– , MoO 4 2– , and H 2 VO 4– ), which are likely to be mobile in alkaline groundwater because mineral surfaces composing aquifer matrices have a predominantly negative surface charge under alkaline conditions. F also exists predominantly as a negatively charged ion (F – ). At pH values >7.5, saturation indices generated by the geochemical modeling program PHREEQC indicated that F solubility may be somewhat limited by the precipitation of the mineral fluorapatite [Ca 5 (PO 4 ) 3 F]. Speciation modeling of As in anoxic-Fe groundwater (iron-reducing conditions) showed that samples were supersaturated with orpiment (As 2 S 3 ), indicating that mineral precipitation may be responsible for low As concentrations observed in reducing groundwater. In contrast, U concentrations showed significant negative correlations to groundwater age and to pH. Higher U concentrations generally occurred in samples for which geochemical modeling indicated that the uncharged ternary complex Ca 2 UO 2 (CO 3 ) 3 was the dominant aqueous U species. This uncharged complex is not attracted to the charged surfaces of minerals and thus increases U solubility. Formation of Ca 2 UO 2 (CO 3 ) 3 was greater in younger groundwaters because calcium and uranium concentrations generally were lower in older groundwaters, likely due to cation-exchange processes and precipitation of the mineral calcite as groundwater pH increased. Co-precipitation of U with the calcite (CaCO 3 ) may remove U from the aqueous phase. Saturation indices indicated that the anoxic-Fe groundwaters from the Colorado River study area were supersaturated with the mineral uraninite (UO 2 ), suggesting that UO 2 precipitation may be responsible for the low concentrations of U observed in these samples. Concentrations of strontium, which exists primarily in a cationic form (Sr 2+ ), were not significantly correlated with either groundwater age or pH. Strontium concentrations showed a strong positive correlation with total dissolved solids (TDS). Dissolved constituents, such as Sr, that interact with mineral surfaces through outer-sphere complexation become increasingly soluble with increasing TDS concentrations of groundwater. Boron concentrations also showed a significant positive correlation with TDS, indicating the B may interact to a large degree with mineral surfaces through outer-sphere complexation.

California↗

USGS1998

Assessing sediment toxicity from navigational pools of the Upper Mississippi River using a 28-day Hyalella azteca test

To assess the extent of sediment contamination in the Upper Mississippi River (UMR) system after the flood of 1993, sediment samples were collected from 24 of the 26 navigational pools in the river and from one site in the Saint Croix River in the summer of 1994. Whole-sediment tests were conducted with the amphipod Hyalella azteca for 28 days measuring the effects on survival, growth, and sexual maturation. Amphipod survival was significantly reduced in only one sediment (13B) relative to the control and reference sediments. Body length of amphipods was significantly reduced relative to the control and reference sediments in only one sample (26C). Sexual maturation was not significantly reduced in any treatment when compared to the control and reference sediments. No significant correlations were observed between survival, growth, and maturation to either the physical or chemical characteristics of the sediment samples from the river. When highly reliable effect range medians (ERMs) were used to evaluate sediment chemistry, 47 of 49 (96%) of the samples were correctly classified as nontoxic. These results indicate that sediment samples from the Upper Mississippi River are relatively uncontaminated compared to other areas of known contamination in the United States.

Archives of Environmental Contamination and Toxico↗

USGS2009

Bacterial and archaeal phylogenetic diversity of a cold sulfur-rich spring on the shoreline of Lake Erie, Michigan

Studies of sulfidic springs have provided new insights into microbial metabolism, groundwater biogeochemistry, and geologic processes. We investigated Great Sulphur Spring on the western shore of Lake Erie and evaluated the phylogenetic affiliations of 189 bacterial and 77 archaeal 16S rRNA gene sequences from three habitats: the spring origin (11-m depth), bacterial-algal mats on the spring pond surface, and whitish filamentous materials from the spring drain. Water from the spring origin water was cold, pH 6.3, and anoxic (H 2 , 5.4 nM; CH 4 , 2.70 ??M) with concentrations of S 2- (0.03 mM), SO 4 2- (14.8 mM), Ca 2+ (15.7 mM), and HCO 3 - (4.1 mM) similar to those in groundwater from the local aquifer. No archaeal and few bacterial sequences were >95% similar to sequences of cultivated organisms. Bacterial sequences were largely affiliated with sulfur-metabolizing or chemolithotrophic taxa in Beta-, Gamma-, Delta-, and Epsilonproteobacteria. Epsilonproteobacteria sequences similar to those obtained from other sulfidic environments and a new clade of Cyanobacteria sequences were particularly abundant (16% and 40%, respectively) in the spring origin clone library. Crenarchaeota sequences associated with archaeal-bacterial consortia in whitish filaments at a German sulfidic spring were detected only in a similar habitat at Great Sulphur Spring. This study expands the geographic distribution of many uncultured Archaea and Bacteria sequences to the Laurentian Great Lakes, indicates possible roles for epsilonproteobacteria in local aquifer chemistry and karst formation, documents new oscillatorioid Cyanobacteria lineages, and shows that uncultured, cold-adapted Crenarchaeota sequences may comprise a significant part of the microbial community of some sulfidic environments. Copyright ?? 2009, American Society for Microbiology. All Rights Reserved.

Applied and Environmental Microbiology↗

USGS1994

Quality of water and chemistry of bottom sediment in the Rillito Creek basin, Tucson, Arizona, 1986-92

Data were collected on physical properties and chemistry of 4 surface water, l4 ground water, and 4 bottom sediment sites in the Rillito Creek basin where artificial recharge of surface runoff is being considered. Concentrations of suspended sediment in streams generally increased with increases in streamflow and were higher during the summer. The surface water is a calcium and bicarbonate type, and the ground water is calcium sodium and bicarbonate type. Total trace ek=nents in surface water that exceeded the U.S. Environmental Protection Agency primary maximum contaminant levels for drinking-water standards were barium, beryllium, cadmium, chromium, lead, mercury and nickel. Most unfiltered samples for suspended gross alpha as uranium, and unadjusted gross alpha plus gross beta in surface water exceeded the U.S. Environmental Protection Agency and the State of Arizona drinking-water standards. Comparisons of trace- element concentrations in bottom sediment with those in soils of the western conterminous United States generally indicate similar concentrations for most of the trace elements, with the exceptions of scandium and tin. The maximum concentration of total nitrite plus nitrate as nitrogen in three ground- samples and total lead in one ground-water sample exceeded U.S. Environmental Protection Agency primary maximum contaminant levels for drinking- water standards, respectively. Seven organochlorine pesticides were detected in surface-water samples and nine in bottom-sediment samples. Three priority pollutants were detected in surface water, two were detected in ground water, and eleven were detected in bottom sediment. Low concentrations of oil and grease were detected in surface-water and bottom- sediment samples.

Water-Resources Investigations Report↗

USGS2024

Vulnerability assessment of groundwater influenced ecosystems in the Northeastern United States

Groundwater-influenced ecosystems (GIEs) are increasingly vulnerable due to groundwater extraction, land-use practices, and climate change. These ecosystems receive groundwater inflow as a portion of their baseflow or water budget, which can maintain water levels, water temperature, and chemistry necessary to sustain the biodiversity that they support. In some systems (e.g., springs, seeps, fens), this connection with groundwater is central to the system’s integrity and persistence. Groundwater management decisions for human use often do not consider the ecological effects of those actions on GIEs. This disparity can be attributed, in part, to a lack of information regarding the physical relationships these systems have with the surrounding landscape and climate, which may influence the environmental conditions and associated biodiversity. We estimate the vulnerability of areas predicted to be highly suitable for the presence of GIEs based on watershed (U.S. Geological Survey Hydrologic Unit Code 12 watersheds: 24–100 km 2 ) and pixel (30 m × 30 m pixels) resolution in the Atlantic Highlands and Mixed Wood Plains EPA Level II Ecoregions in the northeastern United States. We represent vulnerability with variables describing adaptive capacity (topographic wetness index, hydric soil, physiographic diversity), exposure (climatic niche), and sensitivity (aquatic barriers, proportion urbanized or agriculture). Vulnerability scores indicate that ~26% of GIEs were within 30 m of areas with moderate vulnerability. Within these GIEs, climate exposure is an important contributor to vulnerability of 40% of the areas, followed by land use (19%, agriculture or urbanized). There are few areas predicted to be suitable for GIEs that are also predicted to be highly vulnerable, and of those, climate exposure is the most important contributor to their vulnerability. Persistence of GIEs in the northeastern United States may be challenged as changes in the amount and timing of precipitation and increasing air temperatures attributed to climate change affect the groundwater that sustains these systems.

Connecticut, Delaware, District of Columbia, Maine↗

USGS2014

2011 Summary: Coastal wetland restoration research

The Great Lakes Restoration Initiative (GLRI) projects currently taking place in Great Lakes coastal wetlands provide a unique opportunity to study ecosystem response to management actions as practitioners strive to improve wetland function and increase ecosystem services. Through a partnership between the U.S. Geological Survey – Great Lakes Science Center (GLSC), U.S. Fish and Wildlife Service (USFWS), and Ducks Unlimited, a GLRI-funded project has reestablished the hydrologic connection between an intensively managed impounded wetland (Pool 2B) and Crane Creek, a small Lake Erie tributary, by building a water-control structure that was opened in the spring of 2011. The study site is located within the USFWS Ottawa National Wildlife Refuge (ONWR) and lies within the boundaries of the U.S. Environmental Protection Agency (EPA)-designated Maumee River Area of Concern. The broad objective of the project is to evaluate how hydrologically reconnecting a previously diked wetland impacts fish, mollusks, and other biota and affects nutrient transport, nutrient cycling, water quality, flood storage, and many other abiotic conditions. The results from this project suggest large system-wide benefits from sustainable reestablishment of lake-driven hydrology in this and other similar systems. We comprehensively sampled water chemistry, fish, birds, plants, and invertebrates in Crane Creek coastal wetlands, Pool 2A (a reference diked wetland), and Pool 2B (the reconnected wetland) in 2010 and 2011 to: 1) Characterize spatial and seasonal patterns for these parameters. 2) Examine ecosystem response to the opening of a water-control structure that allows fish passage Our sampling efforts have yielded data that reveal striking changes in water quality, hydrology, and fish assemblages in our experimental unit (2B). Prior to the reconnection, the water chemistry in pools 2A and 2B were very similar. Afterwards, we found that the water chemistry in reconnected Pool 2B was more similar to Crane Creek (e.g., greater turbidity, higher concentration of nitrogen). Sites closest to the structure showed the most creek influence with that influence decreasing with distance from the structure, suggesting that input water from Crane Creek is not mixing fully with the pool water. We also found that water level fluctuations were much greater in the reconnected wetland due to the influence of seiches in Lake Erie. We measured the nutrient concentrations of water flowing into and out of Pool 2B during seiche events and found that the phosphorous and nitrogen concentrations generally were drastically reduced after pulsing through the reconnected wetland. Fish response to the reconnection was equally striking. High-resolution sonar revealed extensive bidirectional movement of fish through the structure on a daily and seasonal basis. There also were significant increases in both the catch per unit effort (CPUE) and the species richness of all sites in Pool 2B from 2010 to 2011. Reconnecting the diked pool to the larger Crane Creek wetland complex, and therefore Lake Erie, has opened up rich new habitat for many fish species. Thirteen species of fish not previously found in the pool entered through the structure and actively used the reconnected wetland. We also found that the wetland functions as a productive spawning ground and nursery area with notable shifts in the predominant age-class of several species of fish, especially northern pike. We observed no negative effects of reconnection on the avian or vegetative communities. All sites within the connected pool had increases in diversity and abundance in the avian community and decreases in the species richness and Floristic Quality Assessment Index values for vegetative communities. After one year of study, data suggest that maintaining a hydrologic connection between diked and coastal wetlands in Lake Erie allows fishes to use vegetated habitats regularly, reduces the concentration of nutrients in coastal waters, and maintains productive habitats for birds and other biota. It will be important to continue to monitor the status of the reconnected wetland to determine the effect of long-term connection to Crane Creek and Lake Erie. If conditions degrade, periodic management actions involving hydrologic isolation of the rehabilitated coastal wetland could be used to mimic intermediate levels of disturbance and maintain wetland vegetation.

Report↗