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Tungstorhenate heteropolyanions. 2. Synthesis and characterization of enneatungstorhenates(V), -(VI), and -(VII)

The tungstorhenate(V) heteropolyanion [W 9 ReO 32 ] 5 - has been isolated as guanidinium and cesium salts from reaction of [ReO 2 (PPh 3 )(py) 3 ] + with sodium tungstate. Crystallographic analysis of black Cs 5 [W 9 ReO 32 ]·3H 2 O [triclinic, P 1 or P 1̄; a = 10.194(1), b = 11.503(2), c = 9.682(1) Å; α = 100.55(1), β = 115.81(1), γ = 99.13(1)°; Z = 1], based on 3743 reflections, shows the anion to be isostructural with decatungstate, [W 10 O 32 ] 4 - . Refinement in P 1̄ led to reliability indices R = 0.084, R w = 0.046. Electrochemical investigation revealed the existence of Re VI and Re VII analogues, which were hydrolytically unstable in aqueous solution but which were isolated as crystalline tetra- n -butylammonium and tetra- n -heptylammonium salts, respectively, from nonaqueous solvents. The tetra- n -butylammonium salts of [W 9 Re VI O 32 ] 4 - and [W 10 O 32 ] 4 - were shown to be isomorphous by X-ray powder diffraction. Simulation of the Q-band ESR spectrum of [W 9 Re VI O 32 ] 4 - (polycrystalline solid solution in [W 10 O 32 ] 4 - ) gave g x = 1.69(1), g y = 1.66(1), g z = 1.730(2) and 10 4 A x ( 185,187 Re, I = 5 / 2 ) = (−)252(10), 10 4 A y = (−)398(10), 10 4 A z = (−)653(5) cm - 1 . The orthorhombic ESR spectrum proves that the Re atom occupies one of the eight equivalent “equatorial” sites in the decatungstate structure.

Inorganic Chemistry↗

Baseline monitoring of the western Arctic Ocean estimates 20% of the Canadian Basin surface waters are undersaturated with respect to aragonite

Marine surface waters are being acidified due to uptake of anthropogenic carbon dioxide, resulting in surface ocean areas of undersaturation with respect to carbonate minerals, including aragonite. In the Arctic Ocean, acidification is expected to occur at an accelerated rate with respect to the global oceans, but a paucity of baseline data has limited our understanding of the extent of Arctic undersaturation and of regional variations in rates and causes. The lack of data has also hindered refinement of models aimed at projecting future trends of ocean acidification. Here, based on more than 34,000 data records collected in 2010 and 2011, we establish a baseline of inorganic carbon data (pH, total alkalinity, dissolved inorganic carbon, partial pressure of carbon dioxide, and aragonite saturation index) for the western Arctic Ocean. This data set documents aragonite undersaturation in ~20% of the surface waters of the combined Canada and Makarov basins, an area characterized by recent acceleration of sea ice loss. Conservative tracer studies using stable oxygen isotopic data from 307 sites show that while the entire surface of this area receives abundant freshwater from meteoric sources, freshwater from sea ice melt is most closely linked to the areas of carbonate mineral undersaturation. These data link the Arctic Ocean’s largest area of aragonite undersaturation to sea ice melt and atmospheric CO 2 absorption in areas of low buffering capacity. Some relatively supersaturated areas can be linked to localized biological activity. Collectively, these observations can be used to project trends of ocean acidification in higher latitude marine surface waters where inorganic carbon chemistry is largely influenced by sea ice meltwater.

PLoS ONE↗

Carbonate chemistry and carbon sequestration driven by inorganic carbon outwelling from mangroves and saltmarshes

Mangroves and saltmarshes are biogeochemical hotspots storing carbon in sediments and in the ocean following lateral carbon export (outwelling). Coastal seawater pH is modified by both uptake of anthropogenic carbon dioxide and natural biogeochemical processes, e.g., wetland inputs. Here, we investigate how mangroves and saltmarshes influence coastal carbonate chemistry and quantify the contribution of alkalinity and dissolved inorganic carbon (DIC) outwelling to blue carbon budgets. Observations from 45 mangroves and 16 saltmarshes worldwide revealed that >70% of intertidal wetlands export more DIC than alkalinity, potentially decreasing the pH of coastal waters. Porewater-derived DIC outwelling (81 ± 47 mmol m −2 d −1 in mangroves and 57 ± 104 mmol m −2 d −1 in saltmarshes) was the major term in blue carbon budgets. However, substantial amounts of fixed carbon remain unaccounted for. Concurrently, alkalinity outwelling was similar or higher than sediment carbon burial and is therefore a significant but often overlooked carbon sequestration mechanism.

Nature↗

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

“Clumped-isotope” thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13 C and 18 O isotopes bound to each other within carbonate minerals in 13 C 18 O 16 O 2 2- groups (heavy isotope “clumps”). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals. We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13 C- 18 O bond ordering (Δ 47 ) and δ 18 O of CO 3 2- and HCO 3 - molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13 C- 18 O bond abundances and δ 18 O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ 47 and δ 18 O compositions of CO 3 2- and HCO 3- ions are significantly different from each other. Experiments constrain the Δ 47- δ 18 O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ 47- δ 18 O slope of 0.011 ± 0.003, consistent with a pH effect. Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ 47 and δ 18 O are intermediate between HCO 3 − and CO 3 2− . We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ 47 and δ 18 O values consistent with lattice equilibrium. Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral–solution interface, have the potential to influence clumped-isotope signatures and the δ 18 O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO 3 − ) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO 3 - dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

Geochimica et Cosmochimica Acta↗

Inorganic and organic ground-water chemistry in the Canal Creek area of Aberdeen Proving Ground, Maryland

Groundwater chemical data were collected from November 1986 through April 1987 in the first phase of a 5-year study to assess the possibility of groundwater contamination in the Canal Creek area of Aberdeen Proving Ground, Maryland. Water samples were collected from 87 observation wells screened in Coastal Plain sediments; 59 samples were collected from the Canal Creek aquifer, 18 from the overlying surficial aquifer, and 10 from the lower confined aquifer. Dissolved solids, chloride, iron, manganese, fluoride, mercury, and chromium are present in concentrations that exceed the Federal maximum contaminant levels for drinking water. Elevated chloride and dissolved-solids concentrations appear to be related from contaminant plumes but also could result from brackish-water intrusion. Excessive concentrations of iron and manganese were the most extensive water quality problems found among the inorganic constituents and are derived from natural dissolution of minerals and oxide coatings in the aquifer sediments. Volatile organic compounds are present in the Canal Creek and surficial aquifers, but samples from the lower confined aquifer do not show any evidence of contamination by inorganic or organic chemicals. The volatile organic contaminants detected in the groundwater and their maximum concentrations (in micrograms/L) include 1,1,2,2- tetrachloroethane (9,000); carbon tetrachloride (480); chloroform (460); 1,1,2-trichloroethane (80); 1,2-dichloroethane (990); 1,1-dichloroethane (3.1); tetrachloroethylene (100); trichloroethylene (1,800); 1,2-trans- dichloroethylene (1,200); 1,1-dichloroethylene (4.4); vinyl chloride (140); benzene (70); and chlorobenzene (39). On the basis of information on past activities in the study area, some sources of the volatile organic compounds include: (1) decontaminants and degreasers; (2) clothing-impregnating operations; (3) the manufacture of impregnite material; (4) the manufacture of tear gas; and (5) fuels used in garages and at the air-field. The high density of most of the detected organic compounds in free-product form would have aided their movement into the aquifers by vertical sinking. The outcrop area of the upper confining unit and an area cut by a paleochannel are most susceptible to contamination because a near-surface impermeable layer is not present. (USGS)

Water-Resources Investigations Report↗

Organic and inorganic composition and microbiology of produced waters from Pennsylvania shale gas wells

Hydraulically fractured shales are becoming an increasingly important source of natural gas production in the United States. This process has been known to create up to 420 gallons of produced water (PW) per day, but the volume varies depending on the formation, and the characteristics of individual hydraulic fracture. PW from hydraulic fracturing of shales are comprised of injected fracturing fluids and natural formation waters in proportions that change over time. Across the state of Pennsylvania, shale gas production is booming; therefore, it is important to assess the variability in PW chemistry and microbiology across this geographical span. We quantified the inorganic and organic chemical composition and microbial communities in PW samples from 13 shale gas wells in north central Pennsylvania. Microbial abundance was generally low (66–9400 cells/mL). Non-volatile dissolved organic carbon (NVDOC) was high (7–31 mg/L) relative to typical shallow groundwater, and the presence of organic acid anions (e.g., acetate, formate, and pyruvate) indicated microbial activity. Volatile organic compounds (VOCs) were detected in four samples (∼1 to 11.7 μg/L): benzene and toluene in the Burket sample, toluene in two Marcellus samples, and tetrachloroethylene (PCE) in one Marcellus sample. VOCs can be either naturally occurring or from industrial activity, making the source of VOCs unclear. Despite the addition of biocides during hydraulic fracturing, H 2 S-producing, fermenting, and methanogenic bacteria were cultured from PW samples. The presence of culturable bacteria was not associated with salinity or location; although organic compound concentrations and time in production were correlated with microbial activity. Interestingly, we found that unlike the inorganic chemistry, PW organic chemistry and microbial viability were highly variable across the 13 wells sampled, which can have important implications for the reuse and handling of these fluids

Pennsylvania↗

Water quality and evaluation of pesticides in lakes in the Ridge Citrus region of central Florida

Water chemistry, including major inorganic constituents, nutrients, and pesticide compounds, was compared between seven lakes surrounded by citrus agriculture and an undeveloped lake on the Lake Wales Ridge (herein referred to as the Ridge) in central Florida. The region has been recognized for its vulnerability to the leaching of agricultural chemicals into the subsurface due to factors including soils, climate, and land use. About 40 percent of Florida's citrus cultivation occurs in 'ridge citrus' areas characterized by sandy well drained soils, with the remainder in 'flatwoods citrus' characterized by high water tables and poorly drained soils. The lakes on the Ridge are typically flow-through lakes that exchange water with adjacent and underlying aquifer systems. This study is the first to evaluate the occurrence of pesticides in lakes on the Ridge, and also represents one of the first monitoring efforts nationally to focus on regional-scale assessment of current-use pesticides in small- to moderate-sized lakes (5 to 393 acres). The samples were collected between December 2003 and September 2005. The lakes in citrus areas contained elevated concentrations of major inorganic constituents (including alkalinity, total dissolved solids, calcium, magnesium, sodium, potassium, chloride, and sulfate), total nitrogen, pH, and pesticides compared to the undeveloped lake. Nitrate (as N) and total nitrogen concentrations were typically elevated in the citrus lakes, with maximum values of 4.70 and 5.19 mg/L (milligrams per liter), respectively. Elevated concentrations of potassium, nitrate, and other inorganic constituents in the citrus lakes likely reflect inputs from the surficial ground-water system that originated predominantly from agricultural fertilizers, soil amendments, and inorganic pesticides. A total of 20 pesticide compounds were detected in the lakes, of which 12 compounds exceeded the standardized reporting level of 0.06 ug/L (microgram per liter). Those most frequently detected above the 0.06-ug/L level were aldicarb sulfoxide, diuron, simazine degradates hydroxysimazine and didealkylatrazine (DDA), bromacil, norflurazon, and demethyl norflurazon which occurred at detection rates ranging from 25 to 86 percent of samples, respectively. Typically, pesticide concentrations in the lake samples were less than 1 microgram per liter. The number of targeted pesticide compounds detected per lake in the citrus areas ranged from 9 to 14 compared to 3 compounds detected at trace levels in the undeveloped lake. Consistent detections of parents and degradates in quarterly samples indicated the presence of pesticide compounds in the lakes many months or years (for example, bromacil) after their application, signaling the persistence of some pesticide compounds in the lakes and/or ground-water systems. Pesticide degradate concentrations frequently exceeded parent concentrations in the lakes. This study was the first in the Ridge citrus region to analyze for glyphosate - widely used in citrus - and its degradate aminomethylphosphonic acid (AMPA), neither of which were detected, as well as a number of triazine degradates, including hydroxysimazine, which were detected. The lake pesticide concentrations did not exceed current Federal aquatic-life benchmarks, available for 10 of the 20 detected pesticide compounds. Limited occurrences of bromacil, diuron, or norflurazon concentrations were within about 10 to 90 percent of benchmark guidelines for acute effects on nonvascular aquatic plants in one or two of the lakes. The lake pesticide concentrations for several targeted pesticides were relatively high compared to corresponding national stream-water percentiles, which is consistent with this region's vulnerability for pesticide leaching into water resources. Several factors were evaluated to gain insight into the processes controlling pesticide transport and fate, and to assess their utility for estimating th

Florida↗

An important biogeochemical link between organic and inorganic carbon cycling: Effects of organic alkalinity on carbonate chemistry in coastal waters influenced by intertidal salt marshes

Organic acid charge groups in dissolved organic carbon (DOC) contribute to total alkalinity (TA), i.e. organic alkalinity (OrgAlk). Its effect is often ignored or treated as a calculation uncertainty in many aquatic CO2 studies. This study evaluated the variability, sources, and characteristics of OrgAlk in estuarine waters exchanged tidally with a groundwater-influenced salt marsh in the northeast USA. Importantly, OrgAlk was found to serve as a biogeochemical medium linking organic and inorganic carbon cycling through its effects on pH, CO2 system speciation, and buffering capacity (H = -(∂pH/∂[H+])-1). Both the concentrations and characteristics of the identified organic acid charge groups, as well as water pH, influenced the magnitude and sign of the OrgAlk effects. The two main charge groups identified include carboxylic and phenolic or amine groups, with concentrations and pK values varying across tides and seasons. OrgAlk and DOC in the tidal creek were highly variable over tidal and seasonal cycles, and may be sourced from both terrestrial groundwater and in situ production in salt marsh sediments. OrgAlk seems to be more preserved over DOC in groundwater, although DOC and OrgAlk largely covaried in marsh tidal water, but with variable OrgAlk:DOC ratios. This highlights the insufficiency of using a fixed proportion of DOC to account for organic acid charge groups. OrgAlk was found to affect H+ concentrations by ~ 1 – 40 nmol kg-1 (equivalent to a pH change of ~ 0.03 – 0.26), pCO2 by ~ 30 – 1590 atm and buffering capacity by ~ 0.00 – 0.14 mmol kg-1 at relative OrgAlk contributions of 0.9 – 4.3% of TA observed in the marsh-influenced tidal water. Thus OrgAlk may have a significant influence on coastal inorganic carbon cycling. Further theoretical calculations confirm that these concentrations of OrgAlk would have sizable impacts on both carbonate speciation and, ultimately, air-sea CO2 fluxes in different coastal environments, ranging from estuarine to shelf waters. A new conceptual model linking organic and inorganic carbon cycling for coastal waters is proposed to highlight the sources and sinks of organic acid charge groups, as well as their biogeochemical behaviors and mechanistic control on the CO2 system.

Geochimica et Cosmochimica Acta↗

Geophysical logs and water-quality data collected for boreholes Kimama-1A and -1B, and a Kimama water supply well near Kimama, southern Idaho

In September 2010, a research consortium led by scientists from Utah State University began drilling the first of three continuously cored boreholes on the Snake River Plain in southern Idaho. The goals of this effort, the Snake River Scientific Drilling Project, are to study the interaction between the Earth's crust and mantle, to identify potential geothermal energy sources, and to track the evolution of the Yellowstone hotspot on the Snake River Plain. The first borehole, located near Kimama, Idaho, is about 50 miles southwest of the U.S. Department of Energy's Idaho National Laboratory. Because geohydrologic data are scarce for that area of the central Snake River Plain, the Kimama borehole, completed in January 2011, provided a unique opportunity to collect geophysical and water-chemistry data from the eastern Snake River Plain aquifer system, downgradient of the laboratory. Therefore, in conjunction with the Snake River Scientific Drilling Project, scientists from the U.S. Geological Survey's Idaho National Laboratory Project Office conducted geophysical logging and collected water samples at the Kimama site. Wireline geophysical logs were collected for the diverging borehole, Kimama-1A and -1B, from land surface to 976 and 2,498 feet below land surface (BLS), respectively. Water samples were collected from Kimama-1A at depths near 460 and 830 feet BLS, and from the Kimama Water Supply (KWS) well located about 75 feet away. Geophysical log data included a composite of natural gamma, neutron, gamma-gamma dual density, and gyroscopic analysis for boreholes Kimama-1A and -1B. Geophysical logs depicted eight sediment layers (excluding surficial sediment) ranging from 4 to 60 feet in thickness. About 155 individual basalt flows were identified, ranging from less than 3 feet to more than 175 feet in thickness (averaging 15 feet) for borehole Kimama-1B (0 to 2,498 feet BLS). Sediment and basalt contacts were selected based on geophysical traces and were confirmed with visual inspection of core photographs. Temperature logs from the water table surface (about 260 feet BLS) to the bottom of borehole Kimama-1B (2,498 feet BLS) were nearly isothermal, ranging from about 62 to 64 degrees Fahrenheit. Gyroscopic data revealed that borehole Kimama-1B begins to separate from borehole Kimama-1A near a depth of 676 feet BLS. Drillhole azimuth and horizontal deviation at total logged depth for boreholes Kimama-1A and -1B were 172.6 and 188.3 degrees and 25.9 and 82.0 feet, respectively. Water samples were collected and analyzed for common ions; selected trace elements; nutrients; isotopes of hydrogen, oxygen, and carbon; and selected radionuclides. One set of water samples was collected from the KWS well and the two other sample sets were collected from borehole Kimama-1A near 460 and 830 feet BLS. With one exception, data for all three zones sampled near Kimama generally indicated that the water chemistry was similar. The exception was found in the deepest zone in borehole Kimama-1A (830 feet BLS) where concentrations probably were affected by the drilling mud. A comparison of the inorganic, organic, and stable chemistry data between the KWS well and the 460-foot zone in borehole Kimama-1A indicated similar chemistry of the aquifer water, except for some variability with nitrate plus nitrite, orthophosphate, iron, zinc, and carbon-14. Radionuclide concentrations were either less than reporting levels or at background levels for the eastern Snake River Plain aquifer.

Idaho↗

Completion summary for boreholes USGS 148, 148A, and 149 at the Materials and Fuels Complex, Idaho National Laboratory, Idaho

In 2019, the U.S. Geological Survey (USGS), in cooperation with the U.S. Department of Energy, drilled and constructed boreholes USGS 148A and USGS 149 for stratigraphic framework analyses and long-term groundwater monitoring of the eastern Snake River Plain aquifer at the Idaho National Laboratory (INL) in southeastern Idaho. Initially, boreholes USGS 148A and USGS 149 were continuously cored to allow the USGS and INL subcontractor to collect select geophysical and seismic data and evaluate properties of recovered core material. The USGS geophysical data and descriptions of core material are described in this report; however, data collected by the INL contractor, including seismic data, are not included as part of the report. The unsaturated zone at both borehole locations is relatively thick, depth to water was measured at approximately 663.6 feet (ft) below land surface (BLS) in USGS 148A, and at approximately 654.1 ft BLS at USGS 149. On completion of coring and data collection, both boreholes (USGS 148A and USGS 149) were repurposed as monitoring wells. Well USGS 148A was constructed to a depth of 759 ft BLS and instrumented with a dedicated submersible pump and measurement line; well USGS 149 was constructed to a depth of 974 ft BLS and instrumented with a multilevel monitoring system (Westbay TM ). Geophysical data, collected by the USGS, were used to characterize the subsurface geology and aquifer conditions. Natural gamma log measurements were used to assess sediment-layer thickness and location. Neutron and gamma-gamma source logs were used to confirm fractured and vesicular basalt identified for aquifer testing and multilevel monitoring well zone testing. Acoustic televiewer logs, collected for well USGS 149, were used to identify fractures and assess groundwater movement when compared with neutron measurements. Furthermore, gyroscopic deviation measurements were used to measure horizontal and vertical displacement for the constructed boreholes USGS 148A and USGS 149. A single-well aquifer test was done in well USGS 148A during November 6–7, 2019, to provide estimates of transmissivity and hydraulic conductivity. Estimates for transmissivity and hydraulic conductivity were 6.34×10 3 feet squared per day and 3.17 feet per day, respectively. The aquifer test was run overnight (21.3 hours) and measured drawdown was relatively small (0.09 ft) at sustained pumping rates ranging from 15.7 to 16.1 gallons per minute. The transmissivity estimates for well USGS 148A were slightly lower than those determined from previous aquifer tests for wells near the Materials and Fuels Complex, but well within range of other aquifer tests done at the INL. Water-quality samples, collected from well USGS 148A and from four zones in well USGS 149, were analyzed for cations, anions, metals, nutrients, volatile organic compounds, stable isotopes, and radionuclides. Water samples for most of the inorganic constituents showed similar chemistry in USGS 148A and all four zones in USGS 149. Water samples for stable isotopes of oxygen and hydrogen indicated some possible influence of irrigation on the water quality. Nitrate plus nitrite concentrations indicated influence from anthropogenic sources. The volatile organic compound and radiochemical data indicated that wastewater disposal practices at the Materials and Fuels Complex or from drilling had no detectable influence on these wells.

Idaho↗

Hydrogeologic and chemical data for the O-Field area, Aberdeen Proving Ground, Maryland

O-Field, located at the Edgewood area of Aberdeen Proving Ground , Maryland, was periodically used for disposal of munitions, waste chemicals, and chemical-warfare agents from World War II through the 1950' s. This report includes various physical, geologic, chemical, and hydrologic data obtained from well-core, groundwater, surface water, and bottom-sediment sampling sites at and near the O-Field disposal area. The data are presented in tables and hydrographs. Three site-location maps are also included. Well-core data include lithologic logs for 11 well- cluster sites, grain-size distributions, various chemical characteristics, and confining unit characteristics. Groundwater data include groundwater chemistry, method blanks for volatile organic carbon, available data on volatile and base/neutral organics, and compilation of corresponding method blanks, chemical-warfare agents, explosive-related products, radionuclides, herbicides, and groundwater levels. Surface-water data include field-measured characteristics; concentrations of various inorganic constituents including arsenic; selected organic constituents with method blanks; detection limits of organics; and a compilation of information on corresponding acids, volatiles, and semivolatiles. Bottom- sediment data include inorganic properties and constituents; organic chemistry; detection limits for organic chemicals; a compilation of information on acids, volatiles, and semivolatiles; and method blanks corresponding to acids, volatiles, and semivolatiles. A set of 15 water- level hydrographs for the period March 1986 through September 1987 also is included in the report. (USGS)

Open-File Report↗

Completion summary for boreholes TAN-2271 and TAN‑2272 at Test Area North, Idaho National Laboratory, Idaho

In 2015, the U.S. Geological Survey, in cooperation with the U.S. Department of Energy, drilled and constructed boreholes TAN-2271 and TAN-2272 for stratigraphic framework analyses and long-term groundwater monitoring of the eastern Snake River Plain aquifer at the Idaho National Laboratory in southeast Idaho. Borehole TAN-2271 initially was cored to collect continuous geologic data, and then re-drilled to complete construction as a monitor well. Borehole TAN-2272 was partially cored between 210 and 282 feet (ft) below land surface (BLS) then drilled and constructed as a monitor well. Boreholes TAN-2271 and TAN-2272 are separated by about 63 ft and have similar geologic layers and hydrologic characteristics based on geologic, geophysical, and aquifer test data collected. The final construction for boreholes TAN-2271 and TAN-2272 required 10-inch (in.) diameter carbon-steel well casing and 9.9-in. diameter open-hole completion below the casing to total depths of 282 and 287 ft BLS, respectively. Depth to water is measured near 228 ft BLS in both boreholes. Following construction and data collection, temporary submersible pumps and water-level access lines were placed to allow for aquifer testing, for collecting periodic water samples, and for measuring water levels. Borehole TAN-2271 was cored continuously, starting at the first basalt contact (about 33 ft BLS) to a depth of 284 ft BLS. Excluding surface sediment, recovery of basalt and sediment core at borehole TAN-2271 was better than 98 percent. Based on visual inspection of core and geophysical data, material examined from 33 to 211ft BLS primarily consists of two massive basalt flows that are about 78 and 50 ft in thickness and three sediment layers near 122, 197, and 201 ft BLS. Between 211 and 284 ft BLS, geophysical data and core material suggest a high occurrence of fractured and vesicular basalt. For the section of aquifer tested, there are two primary fractured aquifer intervals: the first between 235 and 255 ft BLS and the second between 272 and 282 ft BLS. Basalt texture for borehole TAN-2271 generally was described as aphanitic, phaneritic, and porphyritic. Sediment layers, starting near 122 ft BLS, generally were composed of fine-grained sand and silt with a lesser amount of clay. Basalt flows generally ranged in thickness from 2 to 78 ft and varied from highly fractured to dense with high to low vesiculation. Geophysical data and limited core material collected from TAN-2272 show similar lithologic sequences to those reported for TAN-2271. Geophysical and borehole video logs were collected during certain stages of the drilling and construction process at boreholes TAN-2271 and TAN-2272. Geophysical logs were examined synergistically with available core material to confirm geologic and hydrologic similarities and suggest possible fractured network interconnection between boreholes TAN-2271 and TAN-2272. Natural gamma log measurements were used to assess the completeness of the vapor port lines behind 10-in. diameter well casing. Electromagnetic flow meter results were used to identify downward flow conditions that exist for boreholes TAN-2271 and TAN-2272. Furthermore, gyroscopic deviation measurements were used to measure horizontal and vertical displacement at all depths in boreholes TAN-2271 and TAN-2272. After borehole construction was completed, single‑well aquifer tests were done within wells TAN-2271 and TAN ‑ 2272 to provide estimates of transmissivity and hydraulic conductivity. The transmissivity and hydraulic conductivity were estimated for the pumping well and observation well during the aquifer tests conducted on August 25 and August 27, 2015. Estimates for transmissivity range from 4.1 . 10 3 feet squared per day (ft 2 /d) to 8.1 . 10 3 ft 2 /d; estimates for hydraulic conductivity range from 5.8 to 11.5 feet per day (ft/d). Both TAN-2271 and TAN ‑ 2272 show sustained pumping rates of about 30 gallons per minute (gal/min) with measured drawdown in the pumping well of 1.96 ft and 1.14 ft, respectively. The transmissivity estimates for wells tested were within the range of values determined from previous aquifer tests in other wells near Test Area North. Groundwater samples were collected from both wells and were analyzed for cations, anions, metals, nutrients, volatile organic compounds, stable isotopes, and radionuclides. Groundwater samples for most of the inorganic constituents showed similar water chemistry in both wells. Groundwater samples for strontium-90, trichloroethene, and vinyl chloride exceeded maximum contaminant levels for public drinking water supplies in one or both wells.

Idaho↗

Source and fate of inorganic solutes in the Gibbon River, Yellowstone National Park, Wyoming, USA. II. Trace element chemistry

The Gibbon River in Yellowstone National Park receives inflows from several geothermal areas, and consequently the concentrations of many trace elements are elevated compared to rivers in non-geothermal watersheds. Water samples and discharge measurements were obtained from the Gibbon River and its major tributaries near Norris Geyser Basin under the low-flow conditions of September 2006 allowing for the identification of solute sources and their downstream fate. Norris Geyser Basin, and in particular Tantalus Creek, is the largest source of many trace elements (Al, As, B, Ba, Br, Cs, Hg, Li, Sb, Tl, W, and REEs) to the Gibbon River. The Chocolate Pots area is a major source of Fe and Mn, and the lower Gibbon River near Terrace Spring is the major source of Be and Mo. Some of the elevated trace elements are aquatic health concerns (As, Sb, and Hg) and knowing their fate is important. Most solutes in the Gibbon River, including As and Sb, behave conservatively or are minimally attenuated over 29 km of fluvial transport. Some small attenuation of Al, Fe, Hg, and REEs occurs but primarily there is a transformation from the dissolved state to suspended particles, with most of these elements still being transported to the Madison River. Dissolved Hg and REEs loads decrease where the particulate Fe increases, suggesting sorption onto suspended particulate material. Attenuation from the water column is substantial for Mn, with little formation of Mn as suspended particulates.

Wyoming↗