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Simultaneous determination of Cr(iii) and Cr(vi) using reversed-phased ion-pairing liquid chromatography with dynamic reaction cell inductively coupled plasma mass spectrometry

A method for the simultaneous determination of Cr(iii) and Cr(vi) species in waters, soil leachates and synthetic bio-fluids is described. The method uses reversed-phase ion-pairing liquid chromatography to separate the chromium species and a dynamic reaction cell (DRC??) equipped ICP-MS for detection of chromium. Separation of the chromium species is carried out in less than 2 min. Cr(iii) is complexed with ethylenediaminetetraacetic acid (EDTA) prior to separation by mixing samples with the mobile phase containing 2.0 mM tetrabutylammonium hydroxide (TBAOH), 0.5 mM EDTA (dipotassium salt), and 5% (vol/vol) methanol, adjusted to pH 7.6. The interfering 40Ar 12C+ background peak at mass 52 was reduced by over four orders of magnitude to less than 200 cps by using 0.65 mL min-1 ammonia as a reaction gas and an RPq setting on the DRC of 0.75. Method detection limits (MDLs) of 0.09 ??g L-1 for Cr(iii) and 0.06 ??g L-1 for Cr(vi) were obtained based on peak areas at mass 52 for 50 ??L injections of low level spikes. Reproducibility at 2 ??g L-1 was 3% RSD for 5 replicate injections. The tolerance of the method to various levels of common cations and anions found in natural waters and to matrix constituents found in soil leachates and simulated gastric and lung fluids was tested by performing spike recovery calculations for a variety of samples. ?? The Royal Society of Chemistry.

Journal of Analytical Atomic Spectrometry↗

Factors contributing to the formation of ferromanganese nodules in Oneida Lake, New York

Oneida Lake is a large, shallow, eutrophic lake situated in the Ontario lowlands of central New York State. It contains the most concentrated deposit of freshwater ferromanganese nodules (in terms of amount per unit area) yet reported in the literature. The mineralogy and bulk chemistry of these saucer-shaped nodules are similar to the mineralogy and bulk chemistry of deep-sea ferromanganese nodules, but the nodules in Oneida Lake contain considerably lower concentrations of trace metals, especially cobalt, nickel, and copper. Budgets for iron and manganese in waters from Oneida Lake and its tributaries indicate that approximately 122 t (metric tons) of iron and 23 t of manganese are lost each year from the lake waters, presumably by incorporation into sediments and ferromanganese nodules. Estimates based on nodule abundance and age of the lake suggest that iron and manganese are being incorporated into ferromanganese nodules at rates of 13 and 22 t/yr, respectively. Most iron lost from the lake waters is apparently incorporated into sediments, which contain an average of 10 times more iron than manganese. Most manganese lost from the lake waters is apparently incorporated into ferromanganese nodules, which contain an average of 1.7 times more manganese than iron. In Oneida Lake, very high rates of phytoplankton productivity, combined with almost continuous wind mixing to the bottom, provide high-pH and high-Eh conditions in most of the lake. Algae also provide an effective means of concentrating and transporting iron and manganese and thereby aid in the extensive development of ferromanganese nodule deposits.

New York↗

Modelling streamwater chemistry as a mixture of soilwater end-members - An application to the Panola Mountain catchment, Georgia, U.S.A.

Streamwater chemistry at Panola Mountain research catchment, Georgia, U.S.A., is explained as a mixture of representative soilwater solutions that are considered to be temporally invariant to a first approximation. The selection of three end-members from all sampled soil waters is evaluated by comparing the observed and predicted streamwater concentration of six solutes (alkalinity, sulfate, sodium, magnesium, calcium and dissolved silica), which are assumed to mix conservatively, and by assessing the consistency of the implied hydrograph separation with the hydrological mechanisms that are believed to be operating in this catchment. The percentage of variation in the streamwater solute concentrations explained by the end-member mixing analysis (EMMA) ranges from 82 to >97%, and the hydrograph separation is, intuitively, physically reasonable. If the correct end-members have been identified, the streamwater chemical response to different levels of acidic deposition can be predicted by examining the change in each end-member under different loads; no hydrological model is required. If a traditional hydrochemical model, which is driven by rainfall quantity and quality, is desired, this analysis provides an indication of the model structure that would be necessary to reproduce both streamwater and soilwater chemistry.

Georgia↗

Fluorine

Fluorine compounds are essential in numerous chemical and manufacturing processes. Fluorspar is the commercial name for fluorite (isometric CaF 2 ), which is the only fluorine mineral that is mined on a large scale. Fluorspar is used directly as a fluxing material and as an additive in different manufacturing processes. It is the source of fluorine in the production of hydrogen fluoride or hydrofluoric acid, which is used as the feedstock for numerous organic and inorganic chemical compounds. The United States was the world’s leading producer of fluorspar until the mid-1950s. In the mid-1970s, the U.S. fluorspar mining industry began to decline because of foreign competition. By 1982, there was essentially only a single U.S. producer left, and that company ceased mining in 1996. Consumption of fluorspar in the United States peaked in the early 1970s, which was also the peak period of U.S. steel production. Since then, U.S. fluorspar consumption has decreased substantially; the United States has nonetheless increased its imports of downstream fluorine compounds, such as, in order of tonnage imported, hydrofluoric acid, aluminum fluoride, and cryolite. This combination of no U.S. production (until recently) and high levels of consumption has made the United States the world’s leading fluorspar-importing country, in all its various forms. The number of fluorspar-exporting countries has decreased substantially in recent decades, and, as a result, the United States has become dependent on just a few countries to supply its needs. In 2013, the United States imported the majority of its fluorspar from three countries, which were, in descending order of the amount imported, Mexico, China, and South Africa. Geologically, in igneous systems, fluorine is one of a number of elements that are “incompatible.” These incompatible elements become concentrated in the residual magma while the common silicates crystallize upon magma ascent and cooling, leading to relatively high fluorine concentrations in the more evolved or differentiated igneous rocks and in hydrothermal deposits associated with those evolved igneous rocks. In sedimentary rocks, fluorine’s highest concentrations are found in phosphorites because fluorine substitutes for hydroxyl ions in apatite, which leads to fluorine concentrations of, typically, from 2 to 4 weight percent in phosphorites. Because of the presence of fluorine, phosphate fertilizer manufacturers can produce a fluorosilicic acid byproduct. Most deposits mined for fluorine are hydrothermal, however, and consist of fluorine minerals that precipitated from hot water. Magmatic brines and brines from deep within sedimentary basins that have high concentrations of dissolved fluoride are the mineralizing fluids for various types of hydrothermal fluorspar deposits. Relatively dilute hydrothermal fluids that formed in some volcanic rocks can also transport sufficient fluoride to form a high-grade fluorspar deposit. Fluorite has low solubility in a common range of hydrothermal temperatures, particularly from about 160 degrees Celsius (°C) down to 60 °C. The increasing fluorite solubility below 60 °C partly explains why some water with exceptionally high levels of dissolved fluorine are found even at ambient temperatures in evaporitic lake basins in some East African Rift valleys in Kenya and Tanzania. The geologic conditions that led to the high concentrations there are known to exist in a number of other places in the world as well, including, perhaps, places in the Basin and Range province of the United States. Eight minerals or mineral groups have sufficient fluorine in their structures to be considered as possible ores of the element; they are bastnaesite (also spelled bastnäsite; and other fluorocarbonates), cryolite, sellaite, villiaumite, fluorite, fluorapatite (in phosphorites), various phyllosilicates, and topaz. Fluorite is currently the only mineral that is mined for fluorine, and nomineral except fluorite is likely to become a source of commercially produced fluorine as a primary product as long as supplies from relatively thick and high-grade fluorite deposits continue to be available. At least seven classes (which include one subclass) of hydrothermal fluorite deposits are recognized; they are classified according to their tectonic and (or) magmatic settings, as follows: (1) carbonatite-related fluorspar deposits; (2) alkaline-intrusion-related fluorspar deposits; (3) alkaline-volcanic-related epithermal fluorspar deposits; (4) Mississippi Valley-type fluorspar deposits (and a subclass of salt-related carbonate-hosted fluorspar deposits); (5) fluorspar deposits related to strongly differentiated granites; (6) subalkaline-volcanic-related epithermal fluospar deposits; and (7) fluorspar deposits that appear to be conformable within tuffaceous limy lacustrine sediments. An eighth class (not hydrothermal) is that of fluorspar deposits concentrated in soils and weathered zones; that is, residual fluorspar deposits. Generally, fluorspar deposits related to strongly differentiated granites have larger tonnages and lower grades than carbonatite-related fluorspar deposits, which, in turn, have larger tonnages and lower grades than fluorspar vein deposits from various other classes. The United States has a few identified resources of fluorspar, most notably the Klondike II property in the Illinois- Kentucky fluorspar district located about 8 kilometers southwest of Salem, Kentucky, which has a large vein that contains at least 1.6 million metric tons at a grade of 60 percent CaF 2 (Feytis, 2009). Additional fluorspar resources of lower grade but larger tonnage have been identified at Hicks Dome in the Illinois-Kentucky fluorspar district and at Lost River near the western tip of the Seward Peninsula in Alaska, along with a couple of dozen smaller, higher grade resources. Internationally, new mines that either opened before the beginning of 2013 or were scheduled to open soon after that time include the Nui Phao tungsten-fluorspar-bismuth-copper-gold deposit in northern Vietnam; the St. Lawrence project in Newfoundland, Canada, which is located in a well-known fluorspar district; the Bamianshan deposit, which is related to a strongly differentiated granite in northwestern Zhejiang Province, China, near some of that Province’s large, subalkaline-volcanic-related epithermal veins; and the Nokeng project in South Africa, which is also related to a strongly differentiated granite. Other deposits in northwestern Australia, Nevada (United States), Norway, South Africa, and Sweden have been identified and could be put into production within just a few years. Among undiscovered resources, an interesting possibility might be to produce a fluorine product from evaporitic, high-fluorine, high-pH sodium-carbonate brines like Lake Magadi (Kenya) and Lake Natron (Tanzania) in Africa’s Eastern Rift Valley. In addition, apparently conformable fluorspar deposits in tuffaceous limy lacustrine sediments, such as those in Italy, are likely to occur in similar young alkalic volcanic settings elsewhere in the world. Modern geophysical and geochemical exploration techniques have typically not been brought to bear in exploration for new fluorspar deposits, although such techniques are likely to be used in future exploration. The tendency for fluorine to dissolve in significant concentrations in water at low temperature allows both surface water and groundwater to be used as sampling media in geochemical exploration. Evolved granite-related fluorspar deposits may be particularly susceptible to geophysical exploration methods because crystalline rocks that form a basement to sedimentary sections can be approximately defined with gravity and magnetic methods, and magnetite-bearing skarns can be directly detected with magnetic surveys. Environmental considerations of fluorine mining focus especially on drinking water, where high fluorine concentrations can lead to tooth decay; dental and skeletal fluorosis; and bone and cartilage conditions, including genu valgum, which is the crippling bone deformity more commonly known as knock knee. Trace amounts of other elements in fluorspar ores are a concern at some deposits; for example, high beryllium concentrations in alkaline-volcanic-related epithermal deposits or high cadmium concentrations associated with Mississippi Valley-type and salt-related carbonate-hosted fluorspar deposits. Future research might include testing whether fluorine can be extracted economically from high-pH, sodium-carbonate brines and exploring for new occurrences of apparently conformable fluorspar deposits in tuffaceous limy lacustrine sediments outside of the Latium Region of Italy. Other promising new areas of research could be studies of fluorspar deposit fluid inclusion compositions by quadrupole mass spectrometry, by noble gas mass spectrometry on irradiated fluid inclusions, or by chlorine isotopes, while also measuring the chemistry of the same fluid inclusions either by bulk crush-and-leach methods or by laser ablation-inductively coupled plasma mass spectrometry. Advanced studies of fluid inclusion chemistry could be applied beneficially to some of the enigmatic large epithermal fluorspar veins at various places in the world, where they might determine those deposits’ possible relationships to igneous intrusions, or to dissolved salt, or to heated meteoric water in volcanic sections, or perhaps to all three. This knowledge could help focus new exploration.

Professional Paper↗

Field and laboratory evaluation of the influence of copper-diquat on apple snails in southern Florida

The recent decline of apple snail ( Pomacea paludosa ) populations in canals surrounding Loxahatchee National Wildlife Refuge in southern Florida coincided with the use of copper-diquat for the control of the aquatic weed hydrilla ( Hydrilla verticillata ). Field and laboratory studies were designed to assess the effects of copper-diquat on apple snails, which are the primary food of the endangered snail kite Rostrhamus sociabilis (formerly known as the Everglade kite). Acute toxicities (96-h LC 50 values) of Cutrine-Plus and Komeen (chelated formulations of copper) to immature apple snails were 22 and 24 μg/L, respectively. Diquat was toxic at a concentration of 1,800 μg/L and did not increase the toxicity of copper when the chemicals were used in combination. Evaluation of field samples indicated that copper concentrations were higher in detritus than in water, plants and mud, and that there was a gradient of copper concentration from the canal to the interior, the highest residues being in samples from the canal. Copper associated with detritus (up to 150 μg/g) had no effect on growth or survival of apple snails in field cage and tank studies. Also, field applications of copper-diquat to hydrilla had no effect on survival of caged adult and immature snails. Copper from field applications was rapidly taken out of solution by plants and organic material in the water and subsequently incorporated into the bottom detritus. Although the effects of repeated applications of copper-diquat and high body burdens of copper (accumulated during exposure to herbicidal treatment) on survival and reproduction of apple snails are not known, the information available indicates that treatment of hydrilla with copper-diquat was probably not responsible for the decline in the apple snail population. Application at recommended rates should pose no threat to these snails in the organically rich waters of southern Florida.

Environmental Toxicology and Chemistry↗

Contaminant sensitivity of threatened and endangered fishes compared to standard surrogate species

Standard environmental assessment procedures are designed to protect terrestrial and aquatic species. However, it is not known if endangered species are adequately protected by these procedures. At present, toxicological data obtained from studies with surrogate test fishes are assumed to be applicable to endangered fish species, but this assumption has not been validated. Static acute toxicity tests were used to compare the sensitivity of rainbow trout, fathead minnows, and sheepshead minnows to several federally listed fishes (Apache trout, Lahontan cutthroat trout, greenback cutthroat trout, bonytail chub, Colorado pikeminnow, razorback sucker, Leon Springs pupfish, and desert pupfish). Chemicals tested included carbaryl, copper, 4-nonylphenol, pentachlorophenol, and permethrin. Results indicated that the surrogates and listed species were of similar sensitivity. In two cases, a listed species had a 96-h LC50 (lethal concentration to 50% of the population) that was less than one half of its corresponding surrogate. In all other cases, differences between listed and surrogate species were less than twofold. A safety factor of two would provide a conservative estimate for listed cold-water, warm-water, and euryhaline fish species.

Environmental Toxicology and Chemistry↗

Application of mixed-mode, solid-phase extraction in environmental and clinical chemistry. Combining hydrogen-bonding, cation-exchange and Van der Waals interactions

Silica- and styrene-divinylbenzene-based mixed-mode resins that contain C8, C18 and sulphonated cation-exchange groups were compared for their efficiency in isolation of neutral triazine compounds from water and of the basic drug, benzoylecgonine, from urine. The triazine compounds were isolated by a combination of Van der Waals and hydrogen-bonding interactions, and benzoylecgonine was isolated by Van der Waals interactions and cation exchange. All analytes were eluted with a polar organic solvent contaning 2% ammonium hydroxide. Larger recoveries (95%) were achieved on copolymerized mixed-mode resins where C18 and sulfonic acid are in closer proximity than on 'blended' mixed-mode resins (60-70% recovery).

Journal of Chromatography A↗

Trace metal seasonal variations in Texas marine sediments

Trace elements in coastal environments are derived from three major sources: (1) the bordering watershed; (2) the offshore marine environment; and (3) industrial and/or urban effluent. The site of deposition, however, is controlled by physical and chemical processes in the coastal zone. In many cases, these processes are controlled by climate and can vary seasonally. In the harbor at Corpus Christi, Texas, the summer climate creates an oxygen-poor environment in the water column near the sediment-water interface. This causes chalcophilic metals to precipitate from the water, resulting in high concentrations in the sediments near the source. During the winter, turbulence created by strong winds causes the entire water mass to become aerated and oxidizing, and remobilization of some metals results. In addition, this turbulence accelerates circulation which transports the metal-enriched waters from the harbor. On the outer continental shelf of south Texas, the infaunal activity varies seasonally with bottom water temperatures. As this infaunal activity has an effect on the chemical environment within the sediment near the sediment-water interface, the observed trace metal content at the interface also appears to change with the seasons.

Texas↗

Downhole measurements and fluid chemistry of a castle rock steam well, the Geysers, Lake County, California

Wellbore and reservoir processes in a steam well in the Castle Rock field of The Geysers have been studied by means of down-hole pressure and temperature measurements and analyses of ejected water and steam produced under bleed and full flow. Down-hole measurements show that below a vapor zone there is liquid water in the well in pressure equilibrium with reservoir steam at a depth of 2290 m. The progressive decreases, from 1973 to 1977, of pressure and temperature in the vapor zone indicate that wellbore heat loss is high enough to condense a large fraction of the steam inflow. The chemical composition of water ejected from the well is consistent with an origin from wellbore condensation of steam. Calculations using the differences in gas and isotopic compositions between bleed and full-flow steam show that about half of the full-flow steam originated as liquid water in the reservoir and that about 30% of the steam entering the well under bleed was condensed in the wellbore and drained downward. Heat loss calculations are also consistent with this amount of condensation.

Geothermics↗

Potassium bromide method of infrared sampling

In the preparation of potassium bromide pressed windows for use in the infrared analysis of solids, severe grinding of the potassium bromide powder may produce strong absorption bands that could interfere seriously with the spectra of the sample. These absorption bands appear to be due to some crystal alteration of the potassium bromide as a result of the grinding process. They were less apt to occur when the coarser powder, which had received a relatively gentle grinding, was used. Window blanks prepared from the coarser powders showed smaller adsorbed water peaks and generally higher over-all transmittance readings than windows pressed from the very fine powders.

Analytical Chemistry↗

The effects of ultraviolet-B radiation on the toxicity of fire-fighting chemicals

The interactive effects of ultraviolet (UV) and fire-retardant chemicals were evaluated by exposing rainbow trout (Oncorhyncus mykiss) juveniles and tadpoles of southern leopard frogs (Rana sphenocephala) to six fire-retardant formulations with and without sodium ferrocyanide (yellow prussiate of soda [YPS]) and to YPS alone under three simulated UV light treatments. Yellow prussiate of soda is used as a corrosion inhibitor in some of the fire-retardant chemical formulations. The underwater UV intensities measured were about 2 to 10% of surface irradiance measured in various aquatic habitats and were within tolerance limits for the species tested. Mortality of trout and tadpoles exposed to Fire-Trol?? GTS-R, Fire-Trol 300-F, Fire-Trol LCA-R, and Fire-Trol LCA-F was significantly increased in the presence of UV radiation when YPS was present in the formulation. The boreal toad (Bufo boreas), listed as endangered by the state of Colorado (USA), and southern leopard frog were similar in their sensitivity to these chemicals. Photoenhancement of fire-retardant chemicals can occur in a range of aquatic habitats and may be of concern even when optical clarity of water is low; however, other habitat characteristics can also reduce fire retardant toxicity.

Environmental Toxicology and Chemistry↗

Seasonal/yearly salinity variations in San Francisco Bay

The ability of resource agencies to manage fish, wildlife and freshwater supplies of San Francisco Bay estuary requires an integrated knowledge of the relations between the biota and their physical environment. A key factor in these relations is the role of salinity in determining both the physical and the biological character of the estuary. The saltiness of the water, and particularly its seasonal and interannual patterns of variability, affects which aquatic species live where within the estuary. Salinity also determines where water can and cannot be diverted for human consumption and irrigated agriculture, and plays a role in determining the capacity of the estuary to cleanse itself of wastes. In short, salinity is a fundamental property of estuarine physics and chemistry that, in turn, determines the biological characteristics of each estuary. Freshwater is a major control on estuarine salinity. Most freshwater supplied to the Bay is from river flow through the Delta, which is primarily runoff from the Sierra Nevada. Most contaminants in San Francisco Bay are from the Sacramento/San Joaquin Valley and the local watershed around the Bay rather than the sea or atmosphere. Land is the primary source of freshwater and freshwater serves as a tracer of land-derived substances such as the trace metals (copper, lead and selenium), pesticides and plant nutrients (nitrate and phosphate). The U.S. Geological Survey is collaborating with other agencies and institutions in studying San Francisco Bay salinity using field observations and numerical simulations to define the physical processes that control salinity. The issues that arise from salinity fluctuations, however, differ in the northern and southern parts of the bay. In North Bay we need to know how salinity responds to freshwater flow through the Sacramento/San Joaquin Delta; this knowledge will benefit water managers who determine how much delta flow is needed a) to protect freshwater supplies for municipal water use and b) modulate salinity for a healthy estuary. In South Bay we need to know where the freshwater comes from (the distant Delta or local streams) to sort out the sources of a) contamination or b) dilution.

California↗

A Geochemical Mass-Balance Method for Base-Flow Separation, Upper Hillsborough River Watershed, West-Central Florida, 2003-2005 and 2009

Geochemical mass-balance (GMB) and conductivity mass-balance (CMB) methods for hydrograph separation were used to determine the contribution of base flow to total stormflow at two sites in the upper Hillsborough River watershed in west-central Florida from 2003-2005 and at one site in 2009. The chemical and isotopic composition of streamflow and precipitation was measured during selected local and frontal low- and high-intensity storm events and compared to the geochemical and isotopic composition of groundwater. Input for the GMB method included cation, anion, and stable isotope concentrations of surface water and groundwater, whereas input for the CMB method included continuous or point-sample measurement of specific conductance. The surface water is a calcium-bicarbonate type water, which closely resembles groundwater geochemically, indicating that much of the surface water in the upper Hillsborough River basin is derived from local groundwater discharge. This discharge into the Hillsborough River at State Road 39 and at Hillsborough River State Park becomes diluted by precipitation and runoff during the wet season, but retains the calcium-bicarbonate characteristics of Upper Floridan aquifer water. Field conditions limited the application of the GMB method to low-intensity storms but the CMB method was applied to both low-intensity and high-intensity storms. The average contribution of base flow to total discharge for all storms ranged from 31 to 100 percent, whereas the contribution of base flow to total discharge during peak discharge periods ranged from less than 10 percent to 100 percent. Although calcium, magnesium, and silica were consistent markers of Upper Floridan aquifer chemistry, their use in calculating base flow by the GMB method was limited because the frequency of point data collected in this study was not sufficient to capture the complete hydrograph from pre-event base-flow to post-event base-flow concentrations. In this study, pre-event water represented somewhat diluted groundwater. Streamflow conductivity integrates the concentrations of the major ions, and the logistics of acquiring specific conductance at frequent time intervals are less complicated than data collection, sample processing, shipment, and analysis of water samples in a laboratory. The acquisition of continuous specific conductance data reduces uncertainty associated with less-frequently collected geochemical point data.

Scientific Investigations Report↗

Hydrothermal alteration and diagenesis of terrestrial lacustrine pillow basalts: Coordination of hyperspectral imaging with laboratory measurements

We investigate an outcrop of ∼187 Ma lacustrine pillow basalts of the Talcott Formation exposed in Meriden, Connecticut, USA, focusing on coordinated analyses of one pillow lava to characterize the aqueous history of these basalts in the Hartford Basin. This work uses a suite of multidisciplinary measurements, including hyperspectral imaging, other spectroscopic techniques, and chemical and mineralogical analyses, from the microscopic scale up to the scale of an outcrop. The phases identified in the sample are albite, large iron oxides, and titanite throughout; calcite in vesicles; calcic clinopyroxene, aegirine, and Fe/Mg-bearing clay in the rind; and fine-grained hematite and pyroxenes in the interior. Using imaging spectroscopy, the chemistry and mineralogy results extend to the hand sample and larger outcrop. From all of the analyses, we suggest that the pillow basalts were altered initially after emplacement, either by heated lake water or magmatic fluids, at temperatures of at least 400-600°C, and the calcic clinopyroxenes and aegirine identified in the rind are a preserved record of that alteration. As the hydrothermal system cooled to slightly lower temperatures, clays formed in the rind, and, during this alteration, the sample oxidized to form hematite in the matrix of the interior and Fe 3+ in the pyroxenes in the rind. During the waning stages of the hydrothermal system, calcite precipitated in vesicles within the rind. Later, diagenetic processes albitized the sample, with albite replacing plagioclase, lining vesicles, and accreting onto the exterior of the sample. This albitization or Na-metasomatism occurred when the lake within the Hartford Basin evaporated during a drier past climatic era, resulting in Na-rich brines. As Ca-rich plagioclase altered to albite, Ca was released into solution, eventually precipitating as calcite in previously-unfilled vesicles, dominantly in the interior of the pillow. Coordinated analyses of this sample permit identification of the alteration phases and help synthesize the aqueous history of pillow lavas of the Talcott formation. These results are also relevant to Mars, where volcanically-resurfaced open basin lakes have been found, and this Hartford Basin outcrop may be a valuable analog for any potential volcano-lacustrine interactions. The results can also help to inform the utility and optimization of potentially complementary, synergistic, and uniquely-suited techniques for characterization of hydrothermally-altered terrains.

Connecticut↗

Tile drainage as karst: Conduit flow and diffuse flow in a tile-drained watershed

The similarity of tiled-drained watersheds to karst drainage basins can be used to improve understanding of watershed-scale nutrient losses from subsurface tile drainage networks. In this study, short-term variations in discharge and chemistry were examined from a tile outlet collecting subsurface tile flow from a 963 ha agricultural watershed. Study objectives were to apply analytical techniques from karst springs to tile discharge to evaluate water sources and estimate the loads of agricultural pollutants discharged from the tile with conduit, intermediate and diffuse flow regimes. A two-member mixing model using nitrate, chloride and specific conductance was used to distinguish rainwater versus groundwater inputs. Results indicated that groundwater comprised 75% of the discharge for a three-day storm period and rainwater was primarily concentrated during the hydrograph peak. A contrasting pattern of solute concentrations and export loads was observed in tile flow. During base flow periods, tile flow consisted of diffuse flow from groundwater sources and contained elevated levels of nitrate, chloride and specific conductance. During storm events, suspended solids and pollutants adhered to soil surfaces (phosphorus, ammonium and organic nitrogen) were concentrated and discharged during the rapid, conduit flow portion of the hydrograph. During a three-day period, conduit flow occurred for 5.6% of the time but accounted for 16.5% of the total flow. Nitrate and chloride were delivered primarily with diffuse flow (more than 70%), whereas 80-94% of total suspended sediment, phosphorus and ammonium were exported with conduit and intermediate flow regimes. Understanding the water sources contributing to tile drainage and the manner by which pollutant discharge occurs from these systems (conduit, intermediate or diffuse flow) may be useful for designing, implementing and evaluating non-point source reduction strategies in tile-drained landscapes. ?? 2007 Elsevier B.V. All rights reserved.

Journal of Hydrology↗

Geothermal system at 21°N, East Pacific Rise: physical limits on geothermal fluid and role of adiabatic expansion

Pressure-volume-temperature relations for water at the depth of the magma chamber at 21 ° N on the East Pacific Rise suggest that the maximum subsurface temperature of the geothermal fluid is about 420 ° C. Both the chemistry of the discharging fluid and thermal balance considerations indicate that the effective water/rock ratios in the geothermal system are between 7 and 16. Such low ratios preclude effective metal transport at temperatures below 350 ° C, but metal solubilization at 400 ° C and above is effective even at such low ratios. It is proposed that the 420 ° C fluid ascends essentially adiabatically and in the process expands, cools, and precipitates metal sulfides within the upper few hundred meters of the sea floor and on the sea floor itself.

Science↗

Characterization of Groundwater Quality Based on Regional Geologic Setting in the Piedmont and Blue Ridge Physiographic Provinces, North Carolina

A compilation of groundwater-quality data collected as part of two U.S. Geological Survey studies provides a basis for understanding the ambient geochemistry related to geologic setting in the Piedmont and Blue Ridge Physiographic Provinces (hereafter referred to as Piedmont and Mountains Provinces) of North Carolina. Although the geology is complex, a grouping of the sampled wells into assemblages of geologic units described as 'geozones' provides a basis for comparison across the region. Analyses of these two data sets provide a description of water-quality conditions in bedrock aquifers of the Piedmont and Mountains Provinces of North Carolina. Analyzed data were collected between 1997 and 2008 from a network of 79 wells representing 8 regional geozones distributed throughout the Piedmont and Mountains Provinces. This area has experienced high rates of population growth and an increased demand for water resources. Groundwater was used by about 34 percent of the population in the 65 counties of this region in 2005. An improved understanding of the quality and quantity of available groundwater resources is needed to plan effectively for future growth and development. The use of regional geologic setting to characterize groundwater-quality conditions in the Piedmont and Mountains Provinces is the focus of this investigation. Data evaluation included an examination of selected properties and the ionic composition of groundwater in the geozones. No major differences in overall ionic chemistry of groundwater among the geozones were evident with the data examined. Variability in the cationic and anionic composition of groundwater within a particular geozone appeared to reflect local differences in lithologic setting, hydrologic and geochemical conditions, and(or) land-use effects. The most common exceedances of the drinking-water criteria (in accordance with Federal and State water-quality standards) occurred for radon, pH, manganese, iron, and zinc. Radon had the most exceedances, with groundwater from 61 of the 69 sampled wells having activities higher than the U.S. Environmental Protection Agency's proposed maximum contaminant level of 300 picocuries per liter. Overall, the Milton and the Raleigh and Charlotte geozones had the greatest number, eight each, of water-quality properties or constituents that exceeded applicable drinking-water criteria in at least one well. The Eastern Blue Ridge and Felsic intrusive geozones each had seven properties or constituents that exceeded criteria, and the Carolina slate geozone had six. Based on limited data, initial results of statistical comparison tests identified statistically significant differences in concentrations of some groundwater constituents among the geozones. Statistically significant differences in median values of specific conductance and median concentrations of calcium, potassium, sodium, bicarbonate, chloride, silica, ammonia, aluminum, antimony, cadmium, and uranium were identified between one or more geozone pairs. Overall, the groundwater constituents appear to be influenced most significantly by the Inner Piedmont, Carolina slate, and Felsic intrusive geozones. The study data indicate that grouping and evaluating analytical data on the basis of regional geozone setting can be useful for characterizing water-quality conditions in bedrock aquifers of the Piedmont and Blue Ridge Provinces of North Carolina.

North Carolina↗

U/Th series radionuclides as coastal groundwater tracers

The study of coastal groundwater has recently surfaced as an active interdisciplinary area of research, driven foremost by its importance as a poorly quantified pathway for subsurface material transport into coastal ecosystems. Key issue in coastal groundwater research include a complete geochemical characterization of the groundwater(s); quantification of the kinetics of subsurface transport, including rock-water interactions; determination of groundwater ages; tracing of groundwater discharge into coastal waters using radiochemical fingerprints; and an assessment of the potential ecological impact of such subsurface flow to a reviving water body. For such applications, the isotopic systemics of select naturally occurring radionucludes in the U/Th series has proven to be particularly useful. These radionuclides (e.g., U, Th, Ram and Rn) are ubiquitous in all groundwaters ad are represented by several isotopes with widely different half-lives and chemistries (Figure 1). As a result, varied biogeochemical processes occurring over a broad range of time scales can be studied. In source rock, most U/Th series isotopes in secular equilibrium; that is, the rate of decay of a daughter isotope is equal to that of it radiogenic parent, and so will have equal activities (in this context, the specific activity is simply a measure of the amount of radioactivity per unit amount). In contrast, these nuclides exhibit strong fractionations within the surrounding groundwaters because of their respective physiochemical differences. Disequilibria in U/Th series radionuclides can thus be used to identify distinct water masses, quantify release rates from source rocks, assess groundwater migration rates, and assess groundwater discharge rates in coastal waters., Large isotopic variations also have the potential for providing precise fingerprints for groundwaters from specific aquifers and have been explored as a means for calculating groundwater ages and estuarine water mass transit times. The highly fractionated nature of U/Th series nuclides in groundwater is illustrated by the range in some measured activities. highest activities are typically observed for 222 Rn, reflecting the inert nature of this noble gas. Groundwater 222 Rn (t 1/2 =3.8) activities are thus controlled only by rapid in situ decay (Table 1) and production within host rocks, without the added complications of reversible removal via absorption or precipitation. Uranium, which is soluble as U(VI) in oxidizing waters, is present in intermediate activities in groundwaters that are moderated by redox-initiated removal onto aquifer rocks. The alkaline earth Ra and, to a greater extent, the less soluble actinide Th are readily removed from groundwater by water -- rock interactions and so are strongly depleted. Both of these elements have very short-lived as well as longer-lived isotopes, and so isotopes compositions reflect processes over a range of time scales. Many studies have evaluated and behavior of select radionuclides in groundwater and surface water systems. Recent advances in high-=precision mass spectrometry have opted new possibilities for more subtle interpretations in select long-lived U/Th series isotopes, such as U, Ra, Pa, and Th. However, these techniques have yet to be fully developed, ahns as a consequence, such data remain largely scarce and underutilized. Although many different approaches have been developed to study radionucluide behavior in groundwater, all are based on principles of radioactive production and decay and knowledge of source terms from weathering and recoil processes, as well as removal terms from the interaction with aquifer host rock surface by sorption and precipitation. This review is structured to present first a brief description of the background, driving forces, scales, and ecological significance of submarine groundwater discharge. Following this, a description of the geochemistry and behavior of select radionuclides in groundwater will be presented, and their application to tracing submarine groundwater discharge will be discussed.

Chemical Reviews↗