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At least 181 records · Page 10Linked to original sources

Formation of ferromanganese crusts on northwest intertropical Pacific seamounts: Electron photomicrography and microprobe chemistry

Seven ferromanganese crusts from the northwest intertropical Pacific seamounts were analyzed for photomicroscopic growth structures, microprobe chemistry, and ages based on Co-chronometer growth rate. The crusts on the Marshall Islands seamounts are thick and ale divided into phosphatized lower older and nonphosphatized upper younger growth generations: the older crust consists of compact laminations and columns impregnated with carbonate fluoapatite (CFA), whereas the younger crust is characterized by porous botryoids and columns of ??-MnO2 and Fe oxyhydroxide. The crusts on the Federated States of Micronesia (FSM) and Palau Islands seamounts are thin and are often incorporated with inorganic opal-A in the uppermost part, comprising the younger generation. Some crusts show scours and fractures. Although the growth of crusts has been often interrupted by mass failure of slope sediments, the crusts on the Marshall Islands seamounts are estimated to have grown at rate of about 3 mm/Ma since the middle Eocene and to have been phosphatized in the late Oligocene during the host seamounts were located beneath the equatorial zone of high productivity. Prolonged infiltration of the oxygen minimum zone (OMZ) water into shallower water older crusts redistributed crust composition by precipitating CFA, enriching subsequent amounts of Mn and Ni, and removing some Co. The younger crust has formed at slower rate (about 2 mm/Ma) under the stronger influence of bottom-water circulation in the north of the equatorial zone, concentrating abundant Co. In the uppermost part of some crusts, siliceous skeletons transform with burial to inorganic opal-A and Si-rich Fe oxyhydroxide, suggesting that biosilica diagenesis can enhance crust growth. (C) 2000 Elsevier Science B.V.

Marine Geology

Changes in stream chemistry in the east-central Adirondack region of New York State, 2010–2018

Decreased acidic deposition occurred through the 2010s, extending the long-term decrease begun in the early 1980s. The overall decline has resulted in rates of acidic deposition in the Adirondack region that are similar to those estimated for the early 1900s. This achievement increased attention on the issue of acidic deposition recovery and raised the question of how the low deposition levels of the 2010s were affecting the Adirondack region of New York State, where past acidic deposition effects were among the highest in the United States. This report presents stream resampling results of the East-Central Adirondack Stream Survey (ECASS), the Adirondack high-elevation stream sampling program, and the first five years of stream chemistry measurements in the Boreas River Long-Term Monitoring Watersheds. In addition, a regional comparison of stream chemistry between ECASS and the Western Adirondack Stream Survey (WASS) is presented. The primary objective of these stream resampling programs was to evaluate changes in stream chemistry during the 2010s to evaluate ongoing recovery of acidic deposition within the Adirondack region. Streams in the ECASS region (19,658 km 2 ) were sampled during spring snowmelt in 2011, 2017, and 2018; summer baseflow in 2010 and 2017; and late autumn in 2011 and 2017. ECASS stream sampling results for snowmelt in 2018 are also compared with WASS stream sampling results during snowmelt of the same year to provide a spatial assessment of stream chemistry for the entire Adirondack region. In addition, high-elevation streams were sampled in 2010-2011 and 2017 during spring snowmelt and summer baseflow, and three streams in the Boreas River watershed were sampled biweekly from 2014 through 2019. Streams were selected for sampling from the approximately 200 streams sampled originally in both the ECASS and WASS. The original ECASS and WASS streams were randomly selected from the populations of accessible streams within their respective regions. For the study reported here, subsets of streams were selected from the two original groups using a random stratified design based on the stream chemistry of the original ECASS and WASS. ECASS data are presented only for streams that were sampled in each of the seasonal surveys, which was 59, 48, and 61 streams for spring snowmelt, summer baseflow, and autumn surveys, respectively. WASS data are presented for 60 streams and high-elevation data are presented for 11 streams sampled during summer baseflow and 12 streams sampled during spring snowmelt. Overall, mean values of chemical measurements did not indicate large changes between 2010-2011 and 2017-2018 in the ECASS snowmelt, summer baseflow, or autumn surveys. Minimal acidification was observed in mean values measured in any of the surveys. Mean values of acid-neutralizing capacity (ANC) remained above 80 microequivalents per liter (µeq L -1 ), mean pH remained above 6.37, and inorganic monomeric aluminum (Al i ) remained below 1.0 micromoles per liter (µmol L -1 ), with the exception of the mean value of 1.2 µmol L -1 in the 2017 autumn survey. However, in the 2017 and 2018 snowmelt samplings 15% and 10% of the streams, respectively, had Al i concentrations above 1.0 µmol L 1 , the concentration above which is toxic to fish. Based on the estimated total length of headwater streams in the ECASS region of 11,494 km, the 10% of ECASS streams that experienced harmful Al i concentrations (Al i >1.0 µmol L -1 ) during the 2018 snowmelt survey equated to a total length of 1,091 km of headwater stream length in the region. During both summer baseflow and snowmelt sampling, high-elevation streams were less acidic in 2017 than in 2010-2011. However, in 2017 the mean Al i concentration during snowmelt was 2.6 µmol L -1 , a value that reflected low to moderate toxicity to brook trout. Concentrations of Al i in 9 out of the 12 streams were above 1.5 µmol L -1 , which exceeds the value which impairs fish communities. Greater dilution of calcium (Ca 2+ ) concentrations than sulfate (SO 4 2- ) concentrations during snowmelt was a contributing factor to the more acidic stream water measured during snowmelt than summer baseflow. Comparison of 2018 ECASS and WASS snowmelt chemistry under the current low levels of acidic deposition indicated that the spatial pattern of acidification effects on stream chemistry is largely driven by inherent Ca 2+ availability tied to spatial variations in geologic factors that control acid buffering more effectively in the ECASS region than the WASS region. The higher degree of acidification in the WASS region than the ECASS region is likely to extend into the future as a result of the relatively high dissolved organic carbon (DOC) concentrations in the WASS. Pronounced increasing trends in DOC and similarly pronounced decreasing trends in Ca 2+ and nitrate (NO 3 - ) were observed in the streams of all three Boreas River watersheds. These strong increasing DOC trends occurred in streams during a period with little or no indication of further chemical recovery from acidic deposition. The strong DOC trends in Durgin Brook and Balsam Brook, which are streams that are unlikely to have ever experienced more than minimal acidification, suggest the need for further investigation to expand our understanding of the mechanisms behind the increasing DOC trends.

New York

Ground-Water Quality Data in the Coachella Valley Study Unit, 2007: Results from the California GAMA Program

Ground-water quality in the approximately 820 square-mile Coachella Valley Study Unit (COA) was investigated during February and March 2007 as part of the Priority Basin Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basin Project was developed in response to the Groundwater Quality Monitoring Act of 2001, and is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). The study was designed to provide a spatially unbiased assessment of raw ground water used for public-water supplies within the Coachella Valley, and to facilitate statistically consistent comparisons of ground-water quality throughout California. Samples were collected from 35 wells in Riverside County. Nineteen of the wells were selected using a spatially distributed, randomized grid-based method to provide statistical representation of the study unit (grid wells). Sixteen additional wells were sampled to evaluate changes in water chemistry along selected ground-water flow paths, examine land use effects on ground-water quality, and to collect water-quality data in areas where little exists. These wells were referred to as 'understanding wells'. The ground-water samples were analyzed for a large number of organic constituents (volatile organic compounds [VOC], pesticides and pesticide degradates, pharmaceutical compounds, and potential wastewater-indicator compounds), constituents of special interest (perchlorate and 1,2,3-trichloropropane [1,2,3-TCP]), naturally occurring inorganic constituents (nutrients, major and minor ions, and trace elements), radioactive constituents, and microbial indicators. Naturally occurring isotopes (uranium, tritium, carbon-14, and stable isotopes of hydrogen, oxygen, and boron), and dissolved noble gases (the last in collaboration with Lawrence Livermore National Laboratory) also were measured to help identify the source and age of the sampled ground water. A quality-control sample (blank, replicate, or matrix spike) was collected at approximately one quarter of the wells, and the results for these samples were used to evaluate the quality of the data for the ground-water samples. Assessment of the quality-control information resulted in V-coding less than 0.1 percent of the data collected. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, and (or) blended with other waters to maintain acceptable water quality. Regulatory thresholds apply to treated water that is supplied to the consumer, not to raw ground water. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and the California Department of Public Health (CDPH) and thresholds established for aesthetic purposes (secondary maximum contaminant levels, SMCL-CA) by CDPH. Most constituents detected in ground-water samples were at concentrations below drinking-water thresholds. Volatile organic compounds, pesticides, and pesticide degradates were detected in less than one-third of the grid well samples collected. All VOC and pesticide concentrations measured were below health-based thresholds. Potential waste-water indicators were detected in less than half of the wells sampled, and no detections were above health-based thresholds. Perchlorate was detected in seven grid wells; concentrations from two wells were above the CDPH maximum contaminant level (MCL-CA). Most detections of trace elements in samples collected from COA Study Unit wells were below water-quality thresholds. Exceptions include five samples of arsenic that were above the USEPA maximum contaminant level (MCL-US), two detections of boron above the CDPH notification level (NL-CA), and two detections of mol

Data Series

Variations in pore-water quality, mineralogy, and sedimentary texture of clay-silts in the lower Miocene Kirkwood Formation, Atlantic City, New Jersey

Properties of and pore-water solute chemistry in confining units in the New Jersey Coastal Plain were studied to determine whether leakage of solute-enriched pore water from confining units affects regional aquifer-water chemistry, which ultimately may result in aquifer waters with high sodium and bicarbonate concentrations. Pore-water samples collected from a continuously cored borehole in the lower Miocene Kirkwood Formation at Atlantic City, NJ, were analyzed: 15 samples were obtained from clay-silt confining-unit sediments, and four samples were from silt interbeds in the sand of the major confined aquifer in the region, the Atlantic City 800-ft sand. The samples were analyzed to assess interrelations among mineralogy, texture, fluidretention properties, sediment chemistry, and pore-water chemistry, and to document the scale of variation in these properties. Linear regressions were developed to describe the relations of constituents dissolved in 14 pore-water samples collected from the lower confining unit overlying the Atlantic City 800-ft sand and from the silt interbeds in the upper sand unit of the Atlantic City 800-ft sand. The regressions were for concentrations of magnesium and calcium (m = 0.27, R2 = 0.99); concentrations of sodium and the sum of calcium and magnesium (m = 0.17, R 2 = 0.92); concentrations of sulfate and the sum of calcium and magnesium (m = 1.14, R 2 = 0.99); and concentrations of sodium and sulfate (m = 0.14, R 2 = 0.89). The percentage of fine sand was greatest in the shallowest sampled interval, where pore-water concentrations of calcium, magnesium, and sulfate were greatest. The pore-water samples were of three distinct water-quality types (hydrogeochemical facies): a calcium-sulfate type, a mixed calcium-sodium-sulfate-chloride-bicarbonate type, and a sodium-sulfate-bicarbonate-chloride type. The first two types were found only in the lower confining unit; the third type was found only in the composite confining unit underlying the Atlantic City 800-ft sand. Each of these hydrogeochemical facies generally is found within distinct intervals over a range of tens of feet in the core. Krige estimates of pore-water–constituent variations with depth were made by using only the analytical results for the 14 samples from the lower confining unit overlying the Atlantic City 800-ft sand and the silt interbeds in the upper sand unit of the Atlantic City 800-ft sand. Geostatistical analysis of the pore-water–quality data generally resulted in two types of semivariograms. One semivariogram type best fits concentration trends with depth for calcium, magnesium, strontium, sodium, sulfate, and specific conductance; lithium and chloride may also fit this semivariogram type. The other semivariogram type best fits concentration trends with depth for silica, cation exchange capacity, and dissolved inorganic carbon. The scale of variation of the concentrations and properties is indicated by the maximum lag autocorrelation distance of the theoretical semivariograms (the range) and ranged from 44 to 110 ft (13.4–33.5 m). The scale of variation of pore-water major-ion concentrations of sulfate, chloride, calcium, and magnesium alone is on the order of 65–70 ft (19.8–21.3 m). The semivariograms for all pore-water constituents except silica have significant variance at the smallest lag distance, indicating that the constituent concentration varied over a larger scale than the sampling interval. The dominant exchangeable cation in the sediment is calcium. Cation exchange reactions do not appear to be the dominant process in the sediments of the lower confining unit above the Atlantic City 800-ft sand, because a linear correlation exists between the concentration of sodium and the sum of calcium and magnesium concentrations in the pore water; concentrations of all these constituents increase in the upward flow direction, and the ratio of sodium to chloride in the pore water is about 1.0. Two significant principal components explained 82.5% of the total variation in pore-water solute chemistry. Principal component 1 represents about 53% of the variation in pore-water quality and includes calcium, magnesium, sulfate, strontium, and lithium. Coupled chemical processes in the confining units, such as incongruent dissolution of carbonate and other mineral phases or redox transformations of sulfur, likely explain the covariance of these constituents. Principal component 2 represents about 30% of the variation and includes sodium, dissolved inorganic carbon, and chloride. Covariance of sodium and chloride probably is caused by the presence of residual seawater.

New Jersey

Short-term effects of salinity reduction and drainage on salt-marsh biogeochemical cycling and Spartina (cordgrass) production

To assess the biogeochemical effects of tidal restrictions on salt-marsh sulfur cycling and plant growth, cores of short-form Spartina alterniflora peat were desalinated and kept either waterlogged or drained in greenhouse microcosms. Changes in net Spartina production, and porewater and solid phase chemistry of treated cores were compared to natural conditions in the field collection site over a 21-mo period. Net production among treatments increased significantly in drained and waterlogged peat compared to field conditions during the first growing season. Constantly high sulfide in waterlogged cores accompanied reduced plant growth. Aeration invigorated growth in draimed cores but led to oxidization of sulfide minerals and to lowered pH. During the second growing season, growth declined in the drained treatment, probably because of acidification and decreased dissolved inorganic nitrogen. Results are pertinent to the success of current wetland protection and restoration activities in the coastal zone.

Massachusetts

Ground-water quality data in the coastal Los Angeles Basin study unit, 2006: Results from the California GAMA Program

Ground-water quality in the approximately 860 square-mile Coastal Los Angeles Basin study unit (CLAB) was investigated from June to November of 2006 as part of the Statewide Basin Assessment Project of the Ground-Water Ambient Monitoring and Assessment (GAMA) Program. The GAMA Statewide Basin Assessment was developed in response to the Ground-Water Quality Monitoring Act of 2001, and is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). The Coastal Los Angeles Basin study was designed to provide a spatially unbiased assessment of raw ground-water quality within CLAB, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from 69 wells in Los Angeles and Orange Counties. Fifty-five of the wells were selected using a spatially distributed, randomized grid-based method to provide statistical representation of the study area (?grid wells?). Fourteen additional wells were selected to evaluate changes in ground-water chemistry or to gain a greater understanding of the ground-water quality within a specific portion of the Coastal Los Angeles Basin study unit ('understanding wells'). Ground-water samples were analyzed for: a large number of synthetic organic constituents [volatile organic compounds (VOCs), gasoline oxygenates and their degradates, pesticides, polar pesticides, and pesticide degradates, pharmaceutical compounds, and potential wastewater-indicators]; constituents of special interest [perchlorate, N-nitrosodimethylamine (NDMA), 1,4-dioxane, and 1,2,3-trichloropropane (1,2,3-TCP)]; inorganic constituents that can occur naturally [nutrients, major and minor ions, and trace elements]; radioactive constituents [gross-alpha and gross-beta radiation, radium isotopes, and radon-222]; and microbial indicators. Naturally occurring isotopes [stable isotopic ratios of hydrogen and oxygen, and activities of tritium and carbon-14] and dissolved noble gases also were measured to help identify the sources and ages of the sampled ground water. Quality-control samples (blanks, replicates, and samples for matrix spikes) were collected at approximately one-fourth of the wells, and the results for these samples were used to evaluate the quality of the data for the ground-water samples. Field blanks rarely contained detectable concentrations of any constituent, suggesting that contamination was not a significant source of bias. Differences between replicate samples were within acceptable ranges, indicating acceptably low variability. Matrix spike recoveries were within acceptable ranges for most compounds. Assessment of the quality-control information resulted in applying ?V? codes to approximately 0.1 percent of the data collected for ground-water samples (meaning a constituent was detected in blanks as well as the corresponding environmental data). This study did not attempt to evaluate the quality of drinking water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, and (or) blended with other waters to maintain acceptable drinking-water quality. Regulatory thresholds are applied to the treated drinking water that is served to the consumer, not to raw ground water. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with regulatory and non-regulatory health-based thresholds established by the U.S. Environmental Protection Agency (USEPA), California Department of Public Health (CDPH, formerly California Department of Health Services [CADHS]) and thresholds established for aesthetic concerns (secondary maximum contaminant levels, SMCL-CA) by CDPH. Comparisons between data collected for this study and drinking-water thresholds are for illustrative purposes only, and are not indicative of compliance or non-compliance with those thresholds. VOCs were detected in alm

California

How can present and future satellite missions support scientific studies that address ocean acidification?

Space-based observations offer unique capabilities for studying spatial and temporal dynamics of the upper ocean inorganic carbon cycle and, in turn, supporting research tied to ocean acidification (OA). Satellite sensors measuring sea surface temperature, color, salinity, wind, waves, currents, and sea level enable a fuller understanding of a range of physical, chemical, and biological phenomena that drive regional OA dynamics as well as the potentially varied impacts of carbon cycle change on a broad range of ecosystems. Here, we update and expand on previous work that addresses the benefits of space-based assets for OA and carbonate system studies. Carbonate chemistry and the key processes controlling surface ocean OA variability are reviewed. Synthesis of present satellite data streams and their utility in this arena are discussed, as are opportunities on the horizon for using new satellite sensors with increased spectral, temporal, and/or spatial resolution. We outline applications that include the ability to track the biochemically dynamic nature of water masses, to map coral reefs at higher resolution, to discern functional phytoplankton groups and their relationships to acid perturbations, and to track processes that contribute to acid variation near the land-ocean interface.

Oceanography

Effects of forest harvesting on ecosystem health in the headwaters of the New York City Water Supply, Catskill Mountains, New York

The effects of forest clearcutting and selective harvesting on forest soils, soil and stream water chemistry, forest regrowth, and aquatic communities were studied in four small headwater catchments. This research was conducted to identify the sensitivity of forested ecosystems to forest disturbance in the northeastern United States. The study area was in the headwaters of the Neversink Reservoir watershed, part of the New York City water supply system, in the Catskill Mountains of southeastern New York. Two sub-catchments of the Shelter Creek watershed were selectively harvested, one in its northern half and one more heavily in its southern half in 1995?96, the Dry Creek watershed was clearcut in the winter of 1996?97, and the Clear Creek watershed was left undisturbed and monitored as a control site. Monitoring was conducted from 4 years before the harvests until 4 years after the harvests. Clearcutting caused a large release of nitrate (NO3-) from watershed soils and a concurrent release of inorganic monomeric aluminum (Alim), which is toxic to some aquatic biota. The increased soil NO3- concentrations measured after the harvest could be completely accounted for by the decrease in nitrogen (N) uptake by watershed trees, rather than an increase in N mineralization and nitrification. The large increase in stream water NO3- and Alim concentrations caused 100-percent mortality of caged brook trout (Salvelinus fontinalis) during the first year after the clearcut and adversely affected macroinvertebrate communities for 2 years after the harvest. Nutrient uptake and biomass accumulation increased in uncut mature trees after the two selective harvests. There was no increase in stream-water NO3- or Alim concentrations, and so there were no adverse affects on macroinvertebrate or trout communities. The amount of tree biomass that can be removed without causing a sharp increase in stream-water NO3- and Alim stream-water concentrations is unknown, but probably depends on the history of forest-disturbance and acid deposition and the level of soil acidification. Results of this study indicate that macroinvertebrate and brook trout communities were sensitive to clearcutting and that deer browsing may affect water quality by suppressing forest regeneration and nutrient uptake. Further studies of selective harvests could identify the harvesting threshold below which changes in water quality and soil chemistry are minimized, and nutrient retention is maximized, thus reducing the damage that logging can inflict on stream and aquatic communities.

New York

Carbonate control of H 2 and CH 4 production in serpentinization systems at elevated P-Ts

Serpentinization of forsteritic olivine results in the inorganic synthesis of molecular hydrogen (H 2 ) in ultramafic hydrothermal systems (e.g., mid-ocean ridge and forearc environments). Inorganic carbon in those hydrothermal systems may react with H 2 to produce methane (CH 4 ) and other hydrocarbons or react with dissolved metal ions to form carbonate minerals. Here, we report serpentinization experiments at 200°C and 300 bar demonstrating Fe 2+ being incorporated into carbonates more rapidly than Fe 2+ oxidation (and concomitant H 2 formation) leading to diminished yields of H 2 and H 2 -dependent CH 4 . In addition, carbonate formation is temporally fast in carbonate oversaturated fluids. Our results demonstrate that carbonate chemistry ultimately modulates the abiotic synthesis of both H 2 and CH 4 in hydrothermal ultramafic systems and that ultramafic systems present great potential for CO 2 -mineral sequestration.

Geophysical Research Letters

Hydrogeology, Water Chemistry, and Factors Affecting the Transport of Contaminants in the Zone of Contribution of a Public-Supply Well in Modesto, Eastern San Joaquin Valley, California

Ground-water chemistry in the zone of contribution of a public-supply well in Modesto, California, was studied by the U.S. Geological Survey National Water Quality Assessment (NAWQA) Program's topical team for Transport of Anthropogenic and Natural Contaminants (TANC) to supply wells. Twenty-three monitoring wells were installed in Modesto to record baseline hydraulic information and to collect water-quality samples. The monitoring wells were divided into four categories that represent the chemistry of different depths and volumes of the aquifer: (1) water-table wells were screened between 8.5 and 11.7 m (meter) (28 and 38.5 ft [foot]) below land surface (bls) and were within 5 m (16 ft) of the water table; (2) shallow wells were screened between 29 and 35 m (95 and 115 ft) bls; (3) intermediate wells were screened between 50.6 and 65.5 m (166 and 215 ft) bls; and (4) deep wells are screened between 100 to 106 m (328 and 348 ft) bls. Inorganic, organic, isotope, and age-dating tracers were used to characterize the geochemical conditions in the aquifer and understand the mechanisms of mobilization and movement of selected constituents from source areas to a public-supply well. The ground-water system within the study area has been significantly altered by human activities. Water levels in monitoring wells indicated that horizontal movement of ground water was generally from the agricultural areas in the northeast towards a regional water-level depression within the city in the southwest. However, intensive pumping and irrigation recharge in the study area has caused large quantities of ground water to move vertically downward within the regional and local flow systems. Analysis of age tracers indicated that ground-water age varied from recent recharge at the water table to more than 1,000 years in the deep part of the aquifer. The mean age of shallow ground water was determined to be between 30 and 40 years. Intermediate ground water was determined to be a mixture of modern (Post-1950) and old (Pre-1950) ground water. As a result, concentrations of age tracers were detectable but diluted by older ground water. Deep ground water generally represented water that was recharged under natural conditions and therefore had much older ages. Ground water reaching the public-supply well was a mixture of older intermediate and deep ground water and young shallow ground water that has been anthropogenically-influenced to a greater extent than intermediate ground water. Uranium and nitrate pose the most significant threat to the quality of water discharged from the public-supply well. Although pesticides and VOCs were present in ground water from the public-supply well and monitoring wells, currently concentrations of these contaminants are generally less than one-hundredth the concentration of drinking water standards. In contrast, both uranium and nitrate were above half the concentration of drinking water standards for public-supply well samples, and were above drinking water standards for several water-table and shallow monitoring wells. Shallow ground water contributes roughly 20 percent of the total flow to the public-supply well and was the entry point of most contaminants reaching the public-supply well. Naturally-occurring uranium, which is commonly adsorbed to aquifer sediments, was mobilized by oxygen-rich, high-alkalinity water, causing concentrations in some monitoring wells to be above the drinking-water standard of 30 ug/L (microgram per liter). Adsorption experiments, sediment extractions, and uranium isotopes indicated uranium in water-table and shallow ground water was leached from aquifer sediments. Uranium is strongly correlated to bicarbonate concentrations (as measured by alkalinity) in ground water. Bicarbonate can effectively limit uranium adsorption to sediments. As a result, continued downward movement of high-alkalinity, oxygen-rich ground water will likely lead to larger portions of the aquifer having

Scientific Investigations Report

Morphology-dependent water budgets and nutrient fluxes in arctic thaw ponds

Thaw ponds on the Arctic Coastal Plain of Alaska are productive ecosystems, providing habitat and food resources for many fish and bird species. Permafrost in this region creates unique pond morphologies: deep troughs, shallow low-centred polygons (LCPs) and larger coalescent ponds. By monitoring seasonal trends in pond volume and chemistry, we evaluated whether pond morphology and size affect water temperature and desiccation, and nitrogen (N) and phosphorus (P) fluxes. Evaporation was the largest early-summer water flux in all pond types. LCPs dried quickly and displayed high early-summer nutrient concentrations and losses. Troughs consistently received solute-rich subsurface inflows, which accounted for 12 to 42 per cent of their volume and may explain higher P in the troughs. N to P ratios increased and ammonium concentrations decreased with pond volume, suggesting that P and inorganic N availability may limit ecosystem productivity in older, larger ponds. Arctic summer temperatures will likely increase in the future, which may accelerate mid-summer desiccation. Given their morphology, troughs may remain wet, become warmer and derive greater nutrient loads from their thawing banks. Overall, seasonal- to decadal-scale warming may increase ecosystem productivity in troughs relative to other Arctic Coastal Plain ponds.

Alaska

Bottom-sediment chemistry in Devil's Lake, northeast North Dakota

Devils Lake is a 200 km 2 terminal lake that contains sodium sulfate type water. Dissolved solids concentrations range from about 3,500 mg/L to 10,000 mg/L depending on location To investigate geochemical processes in the bottom sediments of Devils Lake, sediment cores were collected at two sites in the western half of the lake during a period of bottom water oxygen depletion. The upper 10 cm of the sediments consist of about 60 weight percent silicates (quartz, feldspar, and clays) 35 weight percent carbonates and 5 weight percent organic material. At depths between 1 and 3 cm in the sediments bacterial sulfate reduction and associated degradation of organic material cause minima in sulfate concentrations and δ 13 C values of dissolved inorganic carbon and maxima in alkalinity, ammonia, phosphate, and sulfide concentrations and δ 34 S values of dissolved sulfate. Downward increases of sodium, magnesium, potassium, and calcium concentrations result from upward diffusion of ions from saline pore water and dissolving sulfate minerals below 30 cm depth in the sediments. High magnesium calcite 8 mole percent MgCO 3 is the most abundant carbonate at the sediment surface. With increasing depth abundances of high magnesium carbonate decrease and abundances of low magnesium calcite aragonite and dolomite increase. Carbon isotope compositions of bulk carbonates range from δ 13 C = -0.7 to +0.5%. These values are close to equilibrium with dissolved inorganic carbon in lake water ( δ 13 C = -2%) but far from equilibrium with dissolved inorganic carbon in pore water ( δ 13 C = -16.3- -10/0%). Disequilibrium between pore water and carbonates suggests that the carbonates did not recrystallize substantially in the presence of pore water. Therefore the change of carbonate mineral proportions with depth in the sediments is due mainly to temporal changes in the proportions of endogenic, detrital, and biologic carbonates that were deposited on the lake bottom rather than postdepositional carbonate diagenesis.

North Dakota

The mobilization of aluminum in a natural soil system: Effects of hydrologic pathways

A two-component soil water flow model was used in conjunction with an equilibrium speciation model WATEQF to study aluminum mobility in soils of a forested watershed, White Oak Run, in the Shenandoah National Park, Virginia. Soil solution samples, taken from the O, E, B, C 1 , and C 2 horizons, were collected from zero-tension lysimeters designed to collect faster gravitational macropore flow and tension lysimeters designed to collect slower capillary micropore flow. Dissolved aluminum was fractionated into acid-soluble, inorganic monomeric, and organic monomeric aluminum. Soil water aluminum concentrations decreased with depth indicating that the deep soil is a sink for aluminum. All waters contained significant concentrations of acid-soluble aluminum and exhibited a negative correlation between p H and the inorganic monomeric aluminum concentrations. Water in the shallow soil showed distinctly different chemical compositions for the two flow types, while C horizon micropore and macropore waters were more similar. Because of its shorter residence time, water flowing in deep soil macropores underwent less extensive neutralization and immobilization of aqueous aluminum than micropore water. The O horizon macropore waters were undersaturated for all hydroxide, silicate, and sulfate mineral phases considered. The C horizon samples from both flow types were near equilibrium with respect to kaolinite and synthetic gibbsite, indicating that mineral solubility controls water chemistry in the deep soil, while organic substances are the key control in the shallow macropore waters.

Water Resources Research

Spatial and temporal variation of stream chemistry associated with contrasting geology and land-use patterns in the Chesapeake Bay watershed—Summary of results from Smith Creek, Virginia; Upper Chester River, Maryland; Conewago Creek, Pennsylvania; and Difficult Run, Virginia, 2010–2013

Despite widespread and ongoing implementation of conservation practices throughout the Chesapeake Bay watershed, water quality continues to be degraded by excess sediment and nutrient inputs. While the Chesapeake Bay Program has developed and maintains a large-scale and long-term monitoring network to detect improvements in water quality throughout the watershed, fewer resources have been allocated for monitoring smaller watersheds, even though water-quality improvements that may result from the implementation of conservation practices are likely to be first detected at smaller watershed scales. In 2010, the U.S. Geological Survey partnered with the U.S. Environmental Protection Agency and the U.S. Department of Agriculture to initiate water-quality monitoring in four selected small watersheds that were targeted for increased implementation of conservation practices. Smith Creek watershed is an agricultural watershed in the Shenandoah Valley of Virginia that is dominated by cattle and poultry production, and the Upper Chester River watershed is an agricultural watershed on the Eastern Shore of Maryland that is dominated by row-cropping activities. The Conewago Creek watershed is an agricultural watershed in southeastern Pennsylvania that is characterized by mixed agricultural activities. The fourth watershed, Difficult Run, is a suburban watershed in northern Virginia that is dominated by medium density residential development. The objective of this study was to investigate spatial and temporal variations in water chemistry and suspended sediment in these four relatively small watersheds that represent a range of land-use patterns and underlying geology to (1) characterize current water-quality conditions in these watersheds, and (2) identify the dominant sources, sinks, and transport processes in each watershed. The general study design involved two components. The first included intensive routine water-quality monitoring at an existing streamgage within each study area (including continuous water-quality monitoring as well as discrete water-quality sampling) to develop a detailed understanding of the temporal and hydrologic variability in stream chemistry and sediment transport in each watershed. The second component involved extensive water-quality monitoring at various sites throughout each watershed to develop a detailed understanding of spatial patterns. Both components were used to improve understanding of sources and transport processes affecting stream chemistry, including nutrients and suspended sediments, and their implications for detecting long-term trends related to best management practices. This report summarizes the results of monitoring that was performed from April 2010 through September 2013. Individual Small Watershed Summaries Summaries for each of the four small watersheds are presented below. Each watershed has a more descriptive and detailed section in the report, but these summaries may be particularly useful for some watershed managers and stakeholders desiring slightly less technical detail. Smith Creek Smith Creek is a 105.39-mi 2 watershed within the Shenandoah Valley that drains to the North Fork Shenandoah River. The long-term Smith Creek base-flow index is 72.3 percent, indicating that on average, approximately 72 percent of Smith Creek flow was base flow, which suggests that Smith Creek streamflow is dominated by groundwater discharge rather than stormwater runoff. A series of cluster and principal components analyses demonstrated that the majority of the variability in Smith Creek water quality could be attributed to hydrologic and seasonal variability. Statistically significant positive correlations with flow were observed for turbidity, suspended sediments, total nitrogen, ammonium, orthophosphate, iron, total phosphorus, and the ratio of calcium to magnesium. Statistically significant inverse correlations with flow were observed for specific conductance, magnesium, δ 15 N of nitrate, pH, bicarbonate, calcium, and δ 18 O of nitrate. Of particular note, flow and nitrate were not statistically significantly correlated, likely because of the relatively complex concentration-discharge relationship observed in continuous and discrete datasets. Statistically significant seasonal patterns were observed for numerous water-quality constituents: water temperature, turbidity, orthophosphate, total phosphorus, suspended-sediment concentration, and silica were higher during the warm season, but pH, dissolved oxygen, and sulfate were higher during the cool season. Surrogate regression models were developed to compute sediment and nutrient loads in Smith Creek using the continuous water-quality monitors. The mean Smith Creek in-stream sediment load was approximately 6,900 tons per year, with nearly 90 percent of the sediment load over the 3-year study period contributed during the eight largest storm events during that period. The Smith Creek total phosphorus load was approximately 21,000 pounds of phosphorus per year, with the majority of the load contributed during stormflow periods, although a substantial phosphorus load still occurs during base-flow conditions. The Smith Creek total nitrogen load was approximately 400,000 pounds per year, with total nitrogen accumulation less dominated by stormflow contributions (as was the case for sediment and total phosphorus) and strongly affected by base-flow export of nitrogen from the basin. Extensive water-quality monitoring throughout the Smith Creek watershed revealed how the complex geology and hydrology interacted to result in variable water chemistry. During relatively dry and low base-flow periods, much of the discharge in Smith Creek was contributed by a single dominant spring—Lacey Spring. During wetter base-flow periods, the flows in Smith Creek were largely generated by a mixture of headwater springs and forested mountain tributaries with very different geochemical composition. The headwater springs generally issued from limestone bedrock and were characterized as having relatively high nitrate, specific conductance, calcium, and magnesium, as well as relatively low concentrations of phosphorus, ammonium, iron, and manganese. The undeveloped, high-gradient, forested mountain sites were generally characterized by low ionic strength waters with low nutrient concentrations. Nitrate isotope data from the limestone springs generally were consistent with manure-derived nitrogen sources (such as cattle and poultry), although the possibility of other mixed sources cannot be excluded. Nitrate isotope data from the undeveloped, high-gradient forested mountain sites were more consistent with nitrogen from undisturbed soils, atmospheric deposition, or nitrogen fixation. Regardless of the nitrogen source, oxygen isotope data indicate that the nitrate was largely a result of nitrification. Land-use data indicate that manure sources of nitrogen dominated watershed nitrogen inputs. Phosphorus sources were less well studied. The presence of a single point-source discharge near the town of New Market contributed the majority of the phosphorus to Smith Creek under base-flow conditions, but nonpoint sources of phosphorus dominated the loading to Smith Creek during stormflow periods. Implementation of conservation practices increased in the Smith Creek watershed during the study period, and even though a broad range of practice types was implemented, the most common practices included stream fencing (for cattle exclusion), the development of nutrient management plans, conservation crop rotation, and the planting of cover crops. While the implementation of these conservation practices is encouraging, results indicate small increases in nitrate concentrations at the streamgage over the last 29 years, concurrent with small decreases in nitrate fluxes. It will likely be years before the cumulative effect of these practices can be detected in the Smith Creek water quality, and the magnitude of the effect of these conservation practices detected in Smith Creek will depend largely on whether nutrient loading (of manure and commercial fertilizer) is reduced over time. Upper Chester River The Upper Chester River watershed includes the 36-square-mile (mi 2 ) watershed area around several nontidal tributaries that drain into the tidal Chester River. The streamgage is on Chesterville Branch, the largest nontidal tributary (approximately 6.12 mi 2 ) and is the site for continuous water-quality monitoring for this project. The base-flow index at Chesterville Branch is about 72 percent and indicates that, as in most of the Coastal Plain, groundwater is the greatest contributor to streamflow. As such, more than 90 percent of the nitrogen in the stream is in the form of nitrate from groundwater. Continuous and discrete data collected at Chesterville Branch show the effects of streamflow and season on water quality. Significantly positive correlations with flow were observed for ammonium, dissolved and total phosphorus, sediment, and turbidity as runoff carried these constituents from the land surface into Chesterville Branch. Other constituents that increased significantly with flow include potassium, sulfate, iron, and manganese, which are likely contributed from near-stream areas and ponds with high organic-matter content. Total nitrogen, pH, and specific conductance, along with chemical constituents associated with groundwater inputs including nitrate, calcium, ratio of calcium to magnesium, silica, bicarbonate, and sodium, were negatively correlated with flow because concentrations of these constituents were diluted by runoff. Seasonal differences in water chemistry, which are most likely related to increased biologic effects on the uptake and release of chemicals in the stream and near-stream areas, also were observed. Water temperature, orthophosphate, δ 15 N of nitrate, bicarbonate, sodium, and the ratio of sodium to chloride were higher during the warm season, and dissolved oxygen, total nitrogen, nitrate, magnesium, sulfate, and manganese were higher during the cool season. Surrogate-regression models developed by using continuous water-quality data showed that the annual sediment load for the 2013 water year was about 2,600 tons, with more than 90 percent of this sediment contributed during two storms. The total phosphorus load in 2013 was about 13,000 pounds with more than 90 percent contributed during the same two storms as sediment. The load of total nitrogen, 140,000 pounds, accumulated steadily throughout the 2013 water year as nitrate in groundwater continuously discharged into the stream. The same two large storms that contributed 90 percent of the suspended-sediment and total phosphorus load only contributed about 20 percent of the annual total nitrogen load. Extensive water-quality monitoring of stream base flow throughout the Upper Chester River watershed identified how differences in land use and hydrogeology affected water chemistry. In parts of the watershed with well-drained soil and thick sandy aquifer sediments, concentrations of nitrate and other chemicals associated with fertilizer and lime application increased in streams as agricultural land use increased. More than 90 percent of the nitrogen in streams from these areas was in the form of nitrate, and concentrations ranged from about 5 milligrams per liter (mg/L) to 8 mg/L as nitrogen in the two largest tributaries. Stream nitrate concentrations were about 1 mg/L as nitrogen where soils were more poorly drained, the surficial aquifer sediments were thinner, and forests and wetlands were more widespread than agriculture. Nitrate isotope data were consistent with inorganic fertilizers ± atmospheric deposition and N 2 fixation as sources of nitrogen, and with nitrification as the dominant nitrate-forming process. Nitrate reduction was indicated by elevated δ 15 N and δ 18 O values in some samples from streams draining watersheds with poorly drained soils. An analysis of land-use data and SPARROW modeling input data attributed almost 90 percent of the nitrogen sources in the Upper Chester River watershed to inorganic fertilizer and fixation of atmospheric nitrogen by legumes, which is in agreement with the isotopic characteristics of nitrate in this watershed. Local sources of manure are limited in this area. Total phosphorus concentrations during base flow ranged from below detection to about 0.2 mg/L. Stream phosphorus concentrations during base flow were generally lower than those measured during storms because most phosphorus transport likely occurs as phosphorus attached to sediment particles during runoff. Because manure is not widely used in this area, the major source of phosphorus is likely fertilizer. The implementation of conservation practices in the Upper Chester River watershed increased substantially during the study period, with a total implementation of 1,194 U.S. Department of Agriculture-compliant practices. The most frequently used practices were oriented towards nutrient and sediment control, including cover crops, nutrient management planning, conservation crop rotation, conservation tillage, and irrigation management. The current Chesapeake Bay model for this area predicts that implementation of best management practices should result in a 13-percent decrease in overall delivery of nitrogen to the Upper Chester River. Because most nitrogen travels through the groundwater system for years to decades before being discharged to streams, the time period of monitoring was not sufficient to see the effects of these practices on water quality. The magnitude of the effect that may eventually be detected will depend on the degree to which nitrate leaching into the groundwater system is reduced over time. Loadings of phosphorus and sediment are primarily transported during large runoff events and are difficult to control and analyze for trends because of their timing and episodic nature. Conewago Creek Conewago Creek has two primary monitoring locations—one near the middle of the 47-mi 2 watershed and the other near the outlet just upstream of the Susquehanna River. The base-flow index was 47.3 percent for 2012–2013, indicating that on average, approximately 53 percent of the streamflow in Conewago Creek exited the watershed as surface flow, which suggests that the stormwater runoff was somewhat greater than groundwater discharge (base flow). A series of cluster and principal components analyses demonstrated that the majority of the variability in the Conewago Creek water quality could be attributed to hydrologic and seasonal variability. Statistically significant positive correlations with flow were observed at both monitoring sites for ammonium, total phosphorus, orthophosphate, iron, and manganese; additionally, at the upstream monitoring station, total nitrogen demonstrated a statistically significant positive correlation with flow. Statistically significant inverse correlations with flow were observed at both sites for water temperature, specific conductance (at the downstream site only), sulfate, chloride, calcium, and magnesium. Statistically significant seasonal patterns were observed for several water-quality constituents. Water temperature, phosphorus (upstream site only), and orthophosphate were higher during the warm season, and nitrate and total nitrogen (upstream site only) were higher during the cool season. Surrogate regression models were developed to compute sediment and nutrient load in Conewago Creek by using the continuous water-quality monitors and water-quality samples. Conewago Creek sediment load was approximately 9,900 tons in 2012 and approximately 18,900 tons in 2013, with nearly 80 percent of the sediment load in 2013 contributed by the three largest storm events. Annual total nitrogen loads could not be estimated due to poor model performance. The addition of continued monitoring or a continuously recording nitrate sensor could improve estimates of total nitrogen loads. During 2012 and 2013, phosphorus loads in Conewago Creek were approximately 50,000 pounds in each year. Combining data from one high-flow synoptic sampling with the data from routine sampling revealed how the geology and hydrology interact to result in variable water chemistry throughout the Conewago Creek watershed. The areas above the upstream gage in the headwaters are generally underlain by forested non-carbonate bedrock and are characterized by relatively low nitrate, specific conductance, calcium, and magnesium, as well as relatively low concentrations of phosphorus, ammonium, iron, and manganese. The more developed, agricultural areas below the upstream site were generally characterized by higher ionic strength waters with higher nutrient and metal concentrations. An analysis of land-use data and SPAtially Referenced Regressions On Watershed (SPARROW) modeling data indicates that manure sources of nitrogen dominate the input of nitrogen to the watershed. Implementation of conservation practices increased in the Conewago Creek watershed during the study period, and while a broad range of practice types were implemented, the most common practices included residue and tillage management, cover crops, nutrient management, terracing, and stream fencing (for animal exclusion or bank restoration). While the implementation of these conservation practices is encouraging, the cumulative effects of these practices probably will not be detected in Conewago Creek water quality for several years. The magnitude of the effects of these conservation practices on water quality in Conewago Creek will depend largely on the extent to which nutrient loading (septic, manure, and commercial fertilizer) and sediment-producing activities are reduced over time. Difficult Run The Difficult Run watershed is a 57.82-mi 2 watershed that drains to the Potomac River. The long-term Difficult Run base-flow index (from 1936 to 2010) was 57.9, indicating that approximately 58 percent of streamflow exited the watershed as base flow and 42 percent as stormflow; however, with continued development and urbanization of the watershed, the base-flow index has decreased to 50 percent during the last 20 years. This base-flow index was less than those of the other watersheds evaluated in this study, likely because the Difficult Run watershed largely is underlain by crystalline piedmont metamorphic rocks and has a greater proportion of impervious urban land cover. A series of cluster and principal components analyses indicated that most of the variability in Difficult Run water quality could be attributed to hydrologic variability and seasonality. Statistically significant positive correlations with flow were observed for turbidity, dissolved oxygen, suspended sediments, ammonium, orthophosphate, iron, and total phosphorus. Statistically significant inverse correlations with flow were observed for water temperature, pH, specific conductance, bicarbonate, calcium, magnesium, nitrate, δ 15 N of nitrate, and silica. Statistically significant seasonal patterns were observed for numerous water-quality constituents: water temperature, ammonium, orthophosphate, and δ 15 N of nitrate were higher during the warm season, and dissolved oxygen, nitrate, and manganese were higher during the cool season. Surrogate regression models were developed to compute sediment and nutrient loading rates. The Difficult Run sediment load was approximately 8,000 tons per year, with greater than 95 percent of the sediment load in the 2013 water year contributed by the seven largest storm events. The total phosphorus load in Difficult Run was approximately 14,000 pounds of phosphorus per year, with the majority of the load contributed during stormflow periods. The total nitrogen load in Difficult Run is estimated to have been approximately 140,000 pounds per year, with total nitrogen accumulation less dominated by stormflow contributions than that of phosphorus and strongly affected by base-flow export of nitrogen from the basin. Extensive water-quality monitoring throughout the Difficult Run watershed revealed relatively uniform generation of flow per unit of watershed area, as well as spatial variation in water quality that is strongly related to land-use activities. Elevated nitrate concentrations were observed in a subset of monitoring sites that are inversely correlated with population density and positively correlated to the septic system density within each subwatershed. The majority of the elevated nitrate concentrations for these sites are hypothesized to be caused by nitrate leaching from septic systems, more so than homeowner fertilizer usage among these subwatersheds that have lower population densities than other parts of the watershed. Nitrate isotope data, temporal patterns in the water-quality data, mass-balance computations, and a separate land-use analysis all generally indicate that leachate from septic systems was the likely source of the elevated nitrate. Another group of water-quality sites have relatively low nitrogen concentrations, are located in areas that are served by city sewer lines, and have experienced stream restoration activities. A final group of sites drained the areas with the highest imperviousness and had strongly elevated specific conductance, chloride, and sodium, which were likely caused by a combination of road salting and other anthropogenic sources draining these urbanized areas in the watershed. A fourth group of sites represents a mixture of water sources and had water quality similar to that at the Difficult Run streamgage. Analysis of the nitrate isotope data generally indicates a broad range of composition indicative of mixed natural and anthropogenic nitrogen sources. Implementation of conservation practices increased in the Difficult Run watershed during the study period, and while a broad range of practice types was implemented, the most common practices included stream restoration. While the implementation of these conservation practices is encouraging, the cumulative effect of these practices probably will not be detected in Difficult Run water quality for several years.

Maryland, Pennsylvania, Virginia

Geochemistry of the Birch Creek Drainage Basin, Idaho

The U.S. Survey and Idaho State University, in cooperation with the U.S. Department of Energy, are conducting studies to describe the chemical character of ground water that moves as underflow from drainage basins into the eastern Snake River Plain aquifer (ESRPA) system at and near the Idaho National Engineering and Environmental Laboratory (INEEL) and the effects of these recharge waters on the geochemistry of the ESRPA system. Each of these recharge waters has a hydrochemical character related to geochemical processes, especially water-rock interactions, that occur during migration to the ESRPA. Results of these studies will benefit ongoing and planned geochemical modeling of the ESRPA at the INEEL by providing model input on the hydrochemical character of water from each drainage basin. During 2000, water samples were collected from five wells and one surface-water site in the Birch Creek drainage basin and analyzed for selected inorganic constituents, nutrients, dissolved organic carbon, tritium, measurements of gross alpha and beta radioactivity, and stable isotopes. Four duplicate samples also were collected for quality assurance. Results, which include analyses of samples previously collected from four other sites, in the basin, show that most water from the Birch Creek drainage basin has a calcium-magnesium bicarbonate character. The Birch Creek Valley can be divided roughly into three hydrologic areas. In the northern part, ground water is forced to the surface by a basalt barrier and the sampling sites were either surface water or shallow wells. Water chemistry in this area was characterized by simple evaporation models, simple calcite-carbon dioxide models, or complex models involving carbonate and silicate minerals. The central part of the valley is filled by sedimentary material and the sampling sites were wells that are deeper than those in the northern part. Water chemistry in this area was characterized by simple calcite-dolomite-carbon dioxide models. In the southern part, ground water enters the ESRPA. In this area, the sampling sites were wells with depths and water levels much deeper than those in the northern and central parts of the valley. The calcium and carbon water chemistry in this area was characterized by a simple calcite-carbon dioxide model, but complex calcite-silicate models more accurately accounted for mass transfer in these areas. Throughout the geochemical system, calcite precipitated if it was an active phase in the models. Carbon dioxide either precipitated (outgassed) or dissolved depending on the partial pressure of carbon dioxide in water from the modeled sites. Dolomite was an active phase only in models from the central part of the system. Generally the entire geochemical system could be modeled with either evaporative models, carbonate models, or carbonate-silicate models. In both of the latter types of models, a significant amount of calcite precipitated relative to the mass transfer to and from the other active phases. The amount of calcite precipitated in the more complex models was consistent with the amount of calcite precipitated in the simpler models. This consistency suggests that, although the simpler models can predict calcium and carbon concentrations in Birch Creek Valley ground and surface water, silicate-mineral-based models are required to account for the other constituents. The amount of mass transfer to and from the silicate mineral phases was generally small compared with that in the carbonate phases. It appears that the water chemistry of well USGS 126B represents the chemistry of water recharging the ESRPA by means of underflow from the Birch Creek Valley.

Idaho

Changes in ground-water quality near two granular-iron permeable reactive barriers in a sand and gravel aquifer, Cape Cod, Massachusetts, 1997-2000

Two experimental permeable reactive barriers (PRBs) of granular zero-valent iron were emplaced in the path of a tetrachloroethene plume (the Chemical Spill-10 plume) at the Massachusetts Military Reservation, Cape Cod, Massachusetts, in June 1998. The goal of the field experiment was to achieve emplacement of a granular-iron PRB deeper than attempted before. The PRBs were expected to create a reducing environment and degrade the tetrachloroethene by reductive dechlorination. The goal of the work presented in this report was to observe temporary and sustained changes to the ground-water chemistry downgradient from the PRBs. A hydraulic-fracturing method involving injection of the granular iron with a guar-biopolymer and enzyme slurry was used to install the parallel 30- to 33-foot-wide wall-shaped barriers at a depth of 82 to 113 feet below land surface. An acetic acid and enzyme mixture was subsequently injected in wells near the barriers to degrade the guar biopolymer. Prior to the emplacement, tetrachloroethene concentrations in the Chemical Spill-10 plume at the study area were as high as 250 micrograms per liter. Other water properties in the plume generally were similar to the properties of uncontaminated ground water in the area, which typically has dissolved oxygen concentrations of 250 to 375 micromoles per liter, pH of 5.5 to 6.0, and specific conductance of 60 to 90 microsiemens per centimeter. Water-quality samples were collected periodically from monitoring wells near the PRBs to determine how the emplacement of the granular-iron walls altered the ground-water quality. In addition, an automated well-sampling device measured temperature, specific conductance, pH, and dissolved oxygen every 1–4 days for 16 months in a well downgradient from the two parallel PRBs. Temporary increases (lasting about 5 to 6 months) in specific conductance were observed downgradient from the PRBs as a result of the sodium chloride, potassium carbonate, and other salts included in the slurry and the acetic acid and enzyme mixture that was subsequently injected to degrade the guar biopolymer. Temporary increases in the concentrations of major cations (sodium, potassium, magnesium, and calcium) were observed downgradient from the PRBs, as were temporary but substantial increases in the dissolved and total organic carbon concentrations. Methane was detected, sulfate concentrations decreased temporarily, and concentrations of dissolved inorganic carbon increased in samples from wells downgradient from the PRBs. A sustained (longer than 12 months) reducing environment, in which dissolved oxygen concentrations decreased to zero, the pH increased to about 6.8, and dissolved iron concentrations increased substantially, developed as a result of the oxidation (corrosion) of the granular iron; this zone persisted at least 65 feet downgradient from the PRBs. The pH and dissolved iron concentrations increased with distance from the granular-iron walls. Concentrations of arsenic, cobalt, manganese, and phosphorus increased, and nitrate concentrations were reduced to below the detection limit downgradient from the walls. A sustained decrease of tetrachloroethene concentrations was not observed; however, reductive dechlorination products were observed at wells downgradient from the PRBs during several rounds of sampling. The emplacement of zero-valent iron in the aquifer to remove tetrachloroethene from the ground water caused changes in the water chemistry that persisted farther downgradient from the PRBs than has been observed at other sites because of the low chemical reactivity of the quartz-dominated aquifer sediments and the low ambient dissolved chemical concentrations in the ground water. The small transverse dispersion in the aquifer and the probable long-term persistence of the iron indicate that the chemically altered zone probably will extend a substantial distance downgradient from the PRBs for a substantial period of time (years); further investigation would be needed to determine this distance.

Massachusetts

Automated atomic absorption spectrometric determination of total arsenic in water and streambed materials

An automated method to determine both inorganic and organic forms of arsenic In water, water-suspended mixtures, and streambed materials Is described. Organic arsenic-containing compounds are decomposed by either ultraviolet radiation or by suHurlc acid-potassium persulfate digestion. The arsenic liberated, with Inorganic arsenic originally present, is reduced to arsine with sodium borohydrlde. The arable Is stripped from the solution with the aid of nitrogen and Is then decomposed In a tube furnace heated to 800 0176C which Is placed in the optical path of an atomic absorption spectrometer. Thirty samples per hour can be analyzed to levels of 1 μ g arsenic per liter.

Analytical Chemistry

Changes in the chemistry of shallow groundwater related to the 2008 injection of CO2 at the ZERT field site, Bozeman, Montana

Approximately 300 kg/day of food-grade CO 2 was injected through a perforated pipe placed horizontally 2–2.3 m deep during July 9–August 7, 2008 at the MSU-ZERT field test to evaluate atmospheric and near-surface monitoring and detection techniques applicable to the subsurface storage and potential leakage of CO 2 . As part of this multidisciplinary research project, 80 samples of water were collected from 10 shallow monitoring wells (1.5 or 3.0 m deep) installed 1–6 m from the injection pipe, at the southwestern end of the slotted section (zone VI), and from two distant monitoring wells. The samples were collected before, during, and following CO 2 injection. The main objective of study was to investigate changes in the concentrations of major, minor, and trace inorganic and organic compounds during and following CO 2 injection. The ultimate goals were (1) to better understand the potential of groundwater quality impacts related to CO 2 leakage from deep storage operations, (2) to develop geochemical tools that could provide early detection of CO 2 intrusion into underground sources of drinking water (USDW), and (3) to test the predictive capabilities of geochemical codes against field data. Field determinations showed rapid and systematic changes in pH (7.0–5.6), alkalinity (400–1,330 mg/l as HCO 3 ), and electrical conductance (600–1,800 μS/cm) following CO 2 injection in samples collected from the 1.5 m-deep wells. Laboratory results show major increases in the concentrations of Ca (90–240 mg/l), Mg (25–70 mg/l), Fe (5–1,200 ppb), and Mn (5–1,400 ppb) following CO 2 injection. These chemical changes could provide early detection of CO 2 leakage into shallow groundwater from deep storage operations. Dissolution of observed carbonate minerals and desorption-ion exchange resulting from lowered pH values following CO 2 injection are the likely geochemical processes responsible for the observed increases in the concentrations of solutes; concentrations generally decreased temporarily following four significant precipitation events. The DOC values obtained are 5 ± 2 mg/l, and the variations do not correlate with CO 2 injection. CO 2 injection, however, is responsible for detection of BTEX (e.g. benzene, 0–0.8 ppb), mobilization of metals, the lowered pH values, and increases in the concentrations of other solutes in groundwater. The trace metal and BTEX concentrations are all significantly below the maximum contaminant levels (MCLs). Sequential leaching of core samples is being carried out to investigate the source of metals and other solutes.

Montana