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At least 271 records · Page 15Linked to original sources

Organic-carbon sequestration in soil/sediment of the Mississippi River deltaic plain — Data; landscape distribution, storage, and inventory; accumulation rates; and recent loss, including a post-Katrina preliminary analysis

Soil/sediment of the Mississippi River deltaic plain (MRDP) in southeastern Louisiana is rich in organic carbon (OC). The MRDP contains about 2 percent of all OC in the surface meter of soil/sediment in the Mississippi River Basin (MRB). Environments within the MRDP differ in soil/sediment organic carbon (SOC) accumulation rate, storage, and inventory. The focus of this study was twofold: (1) develop a database for OC and bulk density for MRDP soil/sediment; and (2) estimate SOC storage, inventory, and accumulation rates for the dominant environments (brackish, intermediate, and fresh marsh; natural levee; distributary; backswamp; and swamp) in the MRDP. Comparative studies were conducted to determine which field and laboratory methods result in the most accurate and reproducible bulk-density values for each marsh environment. Sampling methods included push-core, vibracore, peat borer, and Hargis1 sampler. Bulk-density data for cores taken by the "short push-core method" proved to be more internally consistent than data for samples collected by other methods. Laboratory methods to estimate OC concentration and inorganic-constituent concentration included mass spectrometry, coulometry, and loss-on-ignition. For the sampled MRDP environments, these methods were comparable. SOC storage was calculated for each core with adequate OC and bulk-density data. SOC inventory was calculated using core-specific data from this study and available published and unpublished pedon data linked to SSURGO2 map units. Sample age was estimated using isotopic cesium ( 37 Cs), lead ( 210 Pb), and carbon ( 14 C), elemental Pb, palynomorphs, other stratigraphic markers, and written history. SOC accumulation rates were estimated for each core with adequate age data. Cesium-137 profiles for marsh soil/sediment are the least ambiguous. Levee and distributary 137 Cs profiles show the effects of intermittent allochthonous input and/or sediment resuspension. Cesium-137 and 210 Pb data gave the most consistent and interpretable information for age estimations of soil/sediment deposited during the 1900s. For several cores, isotopic 14 C and 137 Cs data allowed the 1963-64 nuclear weapons testing (NWT) peak-activity datum to be placed within a few-centimeter depth interval. In some cores, a too old 14 C age (when compared to 137 Cs and microstratigraphic-marker data) is the probable result of old carbon bound to clay minerals incorporated into the organic soil/sediment. Elemental Pb coupled with Pb source-function data allowed age estimation for soil/sediment that accumulated during the late 1920s through the 1980s. Exotic pollen (for example, Vigna unguiculata and Alternanthera philoxeroides ) and other microstratigraphic indicators (for example, carbon spherules) allowed age estimations for marsh soil/sediment deposited during the settlement of New Orleans (1717-20) through the early 1900s. For this study, MRDP distributary and swamp environments were each represented by only one core, backswamp environment by two cores, all other environments by three or more cores. MRDP core data for the surface meter soil/sediment indicate that (1) coastal marshes, abandoned distributaries, and swamps have regional SOC-storage values >16 kg m -2 ; (2) swamps and abandoned distributaries have the highest SOC storage values (swamp, 44.8 kg m -2 ; abandoned distributary, 50.9 kg m -2 ); (3) fresh-to-brackish marsh environments have the second highest site-specific SOC-storage values; and (4) site-specific marsh SOC storage values decrease as the salinity of the environment increases (fresh-marsh, 36.2 kg m -2 ; intermediate marsh, 26.2 kg m -2 ; brackish marsh, 21.5 kg m -2 ). This inverse relation between salinity and SOC storage is opposite the regional systematic increase in SOC storage with increasing salinity that is evident when SOC storage is mapped by linking pedon data to SSURGO map units (fresh marsh, 47 kg m -2 ; intermediate marsh, 67 kg m -2 ; brackish marsh, 75 kg m -2 ; and salt marsh, 80 kg m -2 ). MRDP core data for this study also indicate that levees and backswamp have regional SOC-storage values <16 kg m -2 . Group-mean SOC storage for cores from these environments are natural levee (17.0 kg m -2 ) and backswamp (14.1 kg m -2 ). An estimate for the SOC inventory in the surface meter of soil/sediment in the MRDP can be made using the SSURGO mapped portion of the coastal-marsh vegetative-type map (13,236 km 2 , land-only area) published by the Louisiana Department of Wildlife and Fisheries and U.S. Geological Survey (1997). This area has a SOC inventory (surface meter) of 677 Tg (slightly more than 2 percent of the 30,289 Tg SOC inventory for the MRB). The MRDP (6,180 km2, land-only area) has an estimated SOC inventory of 397 Tg. Most of the MRDP is located within the SSURGO mapped coastal marshlands. The entire MRDP, including water, has an area of about 10,800 km 2 . Using the ratio of total MRDP area to SSURGO mapped MRDP area as an adjustment, the MRDP SOC inventory is estimated at 694 Tg. This larger estimate of 694 Tg for the SOC inventory is probably more realistic, because it is reasonable to assume that the marsh sediments overlain by shallow water have comparable SOC storage to that of the adjacent land areas. MRDP core data for this study indicate that there is some variability in long-term SOC mass-accumulation rates for centuries and millennia and that this variability may indicate important geologic changes or changes in land use. However, the consistency of the range in rates of SOC accumulation through time suggests a remarkable degree of marsh sustainability throughout the Holocene, including the recent period of significant marsh modification/channelization for human use. One example of marsh sustainability is its present ability to function as a SOC sink even with Louisiana's large-scale coastal land loss during the last several decades. With coastal-marsh restoration efforts, this sink potential will increase. Looking to the future, a total of 1,101 g m -2 yr -1 SOC is projected to be lost from all of coastal Louisiana (U.S. Army Corps of Engineers, Louisiana Coastal Area (LCA) subprovinces 1-4; not just the MRDP) through coastal erosion from year 2000 to 2050. This translates to a projected SOC-loss rate of about 0.20 percent per year. The recent Hurricanes Katrina and Rita, which devastated the Louisiana coast during late August and late September 2005, transformed about 259 km 2 (100 mi 2 ) of marsh to open water (U.S. Geological Survey, 2005). To the extent that some or all of this land loss is permanent, this result equates to a SOC loss of about 15 Tg. This estimate is based on the year-2000 15,153-km 2 land area for the LCA study area that includes LCA subprovince 4. Using the year-2000 land area, the LCA study area had an estimated SOC inventory of 858 Tg. The estimated 15 Tg SOC loss attributable to Hurricanes Katrina and Rita is 1.7 percent of the year-2000 LCA inventory and 2.3 percent of the year-2000 MRDP inventory. If this SOC loss is included in the projection for the year 2050, then the MRDP would either remain a source with a net SOC loss of 3 Tg or become a weak sink with a net SOC gain of 4 Tg. These estimates are lower bounds for potential SOC flux because they are only for the surface meter of landmass.

Louisiana

Ground-water flow direction, water quality, recharge sources, and age, Great Sand Dunes National Monument, south-central Colorado

Great Sand Dunes National Monument is located in south-central Colorado along the eastern edge of the San Luis Valley. The Great Sand Dunes National Monument contains the tallest sand dunes in North America; some rise up to750 feet. Important ecological features of the Great Sand Dunes National Monument are palustrine wetlands associated with interdunal ponds and depressions along the western edge of the dune field. The existence and natural maintenance of the dune field and the interdunal ponds are dependent on maintaining ground-water levels at historic elevations. To address these concerns, the U.S. Geological Survey conducted a study, in collaboration with the National Park Service, of ground-water flow direction, water quality, recharge sources, and age at the Great Sand Dunes National Monument. A shallow unconfined aquifer and a deeper confined aquifer are the two principal aquifers at the Great Sand Dunes National Monument. Ground water in the unconfined aquifer is recharged from Medano and Sand Creeks near the Sangre de Cristo Mountain front, flows underneath the main dune field, and discharges to Big and Little Spring Creeks. The percentage of calcium in ground water in the unconfined aquifer decreases and the percentage of sodium increases because of ionic exchange with clay minerals as the ground water flows underneath the dune field. It takes more than 60 years for the ground water to flow from Medano and Sand Creeks to Big and Little Spring Creeks. During this time, ground water in the upper part of the unconfined aquifer is recharged by numerous precipitation events. Evaporation of precipitation during recharge prior to reaching the water table causes enrichment in deuterium (2H) and oxygen-18 (18O) relative to waters that are not evaporated. This recharge from precipitation events causes the apparent ages determined using chlorofluorocarbons and tritium to become younger, because relatively young precipitation water is mixing with older waters derived from Medano and Sand Creeks. Major ion chemistry of water from sites completed in the confined aquifer is different than water from sites completed in the unconfined aquifer, but insufficient data exist to quantify if the two aquifers are hydrologically disconnected. Radiocarbon dating of ground water in the confined aquifer indicates it is about 30,000 years old (plus or minus 3,000 years). The peak of the last major ice advance (Wisconsin) during the ice age occurred about 20,000 years before present; ground water from the confined aquifer is much older than that. Water quality and water levels of the interdunal ponds are not affected by waters from the confined aquifer. Instead, the interdunal ponds are affected directly by fluctuations in the water table of the unconfined aquifer. Any lowering of the water table of the unconfined aquifer would result in an immediate decrease in water levels of the interdunal ponds. The water quality of the interdunal ponds probably results from several factors, including the water quality of the unconfined aquifer, evaporation of the pond water, and biologic activity within the ponds.

Colorado

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

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

Scientific Investigations Report

Potential for formation of disinfection by-products from storage of chlorinated surface water in the Basalt aquifer near Fallon, Nevada

Increased pumpage from a basalt aquifer near Fallon, Nevada, has caused its water levels to decline and has induced changes in the quality of water pumped from the basalt. The aquifer is the sole source of water for municipal supply to the city of Fallon, the Naval Air Station Fallon, and the Fallon Paiute-Shoshone Tribe. These changes may be mitigated by storage of surface water in the basalt for subsequent use. Because chlorination of the surface water may be required for storage, the U.S. Geological Survey, in cooperation with the Fallon Paiute-Shoshone Tribe, made laboratory tests using laboratory carbon-organic-free water, surface-water, ground-water, and basaltic-rock samples to determine the potential for formation of disinfection by-products. Experiments with water samples only (no rock and no chlorine) indicated no change in dissolved-organic-carbon (DOC) concentrations over a 20-day reaction period; whereas, all experiments using rock, water, and no chlorine indicated an increase in DOC concentrations. The greatest increase in DOC concentrations for all three water samples occurred in experiments with the rock samples from outcrops on Rattlesnake Hill. Experiments with water only and chlorine yielded a total trihalomethane (THM) concentration of 97.4 ?g/L for the ground-water sample and 347 ?g/L for the surface-water sample. Experiments with mixtures of water, rocks, and chlorine indicated that reactions with the rock consumed chlorine and released significant amounts of organic carbon from the rock, increasing the DOC concentration in the water. The organic carbon in the rocks likely is associated with the secondary clay minerals that line vesicles and fractures in the rocks. THM concentrations were greatest, from 335 to 909 ?g/L, for surface water equilibrated with rock samples from Rattlesnake Hill. However, the concentration of chlorine required to produce these high THM concentrations ranged from 18 to 84 mg/L. The results of the experiments suggest that the amount of organic carbon released from the rocks during successive cycles of recharge, storage, and recovery of chlorinated surface water may be relatively small. The chlorine demand of the rocks is so large that all of the free chlorine in the entire volume of recharged water likely would be consumed by only a very small volume of the aquifer surrounding an injection well, or beneath an infiltration bed. The majority of the volume of the aquifer filled by the stored water likely would never come in contact with free chlorine, and the increases in concentration of DOC observed in these experiments likely would occur in a very small volume of the stored water. For this reason, increases in concentration of THMs for the entire volume of water stored also likely would be considerably less than those measured in these experiments. To test this hypothesis, additional laboratory experiments using varying levels of chlorination, varying lengths of reaction periods, and repeated cycles of chlorination would be useful. A field experiment made at a small scale in an isolated part of the basalt aquifer would aid in the design of an operational system.

Scientific Investigations Report

Vertical gradients in water chemistry and age in the Northern High Plains Aquifer, Nebraska, 2003

The northern High Plains aquifer is the primary source of water used for domestic, industrial, and irrigation purposes in parts of Colorado, Kansas, Nebraska, South Dakota, and Wyoming. Despite the aquifer’s importance to the regional economy, fundamental ground-water characteristics, such as vertical gradients in water chemistry and age, remain poorly defined. As part of the U.S. Geological Survey’s National Water-Quality Assessment Program, water samples from nested, short-screen monitoring wells installed in the northern High Plains aquifer were analyzed for major ions, nutrients, trace elements, dissolved organic carbon, pesticides, stable and radioactive isotopes, dissolved gases, and other parameters to evaluate vertical gradients in water chemistry and age in the aquifer. Chemical data and tritium and radiocarbon ages show that water in the aquifer was chemically and temporally stratified in the study area, with a relatively thin zone of recently recharged water (less than 50 years) near the water table overlying a thicker zone of older water (1,800 to 15,600 radiocarbon years). In areas where irrigated agriculture was an important land use, the recently recharged ground water was characterized by elevated concentrations of major ions and nitrate and the detection of pesticide compounds. Below the zone of agricultural influence, major-ion concentrations exhibited small increases with depth and distance along flow paths because of rock/water interactions. The concentration increases were accounted for primarily by dissolved calcium, sodium, bicarbonate, sulfate, and silica. In general, the chemistry of ground water throughout the aquifer was of high quality. None of the approximately 90 chemical constituents analyzed in each sample exceeded primary drinking-water standards. Mass-balance models indicate that changes in groundwater chemistry along flow paths in the aquifer can be accounted for by small amounts of feldspar and calcite dissolution; goethite and clay-mineral precipitation; organic-carbon and pyrite oxidation; oxygen reduction and denitrification; and cation exchange. Mixing with surface water affected the chemistry of ground water in alluvial sediments of the Platte River Valley. Radiocarbon ages in the aquifer, adjusted for carbon mass transfers, ranged from 1,800 to 15,600 14C years before present. These results have important implications with respect to development of ground-water resources in the Sand Hills. Most of the water in the aquifer predates modern anthropogenic activity so excessive removal of water by pumping is not likely to be replenished by natural recharge in a meaningful timeframe. Vertical gradients in ground-water age were used to estimate long-term average recharge rates in the aquifer. In most areas, the recharge rates ranged from 0.02 to 0.05 foot per year. The recharge rate was 0.2 foot per year in one part of the aquifer characterized by large downward hydraulic gradients. Nitrite plus nitrate concentrations at the water table were 0.13 to 3.13 milligrams per liter as nitrogen, and concentrations substantially decreased with depth in the aquifer. Dissolved-gas and nitrogen-isotope data indicate that denitrification in the aquifer removed 0 to 97 percent (average = 50 percent) of the nitrate originally present in recharge. The average amount of nitrate removed by denitrification in the aquifer north of the Platte River (Sand Hills) was substantially greater than the amount removed south of the river (66 as opposed to 0 percent), and the extent of nitrate removal appears to be related to the presence of thick deposits of sediment on top of the Ogallala Group in the Sand Hills that contained electron donors, such as organic carbon and pyrite, to support denitrification. Apparent rates of dissolved-oxygen reduction and denitrification were estimated on the basis of decreases in dissolved-oxygen concentrations and increases in concentrations of excess nitrogen gas and ground-water ages along flow paths from the water table to deeper wells. Median rates of dissolved-oxygen reduction and denitrification south of the Platte River were at least 10 times smaller than the median rates north of the river in the Sand Hills. The relatively large denitrification rates in the Sand Hills indicate that the aquifer in that area may have a greater capacity to attenuate nitrate contamination than the aquifer south of the river, depending on rates of ground-water movement in the two areas. Small denitrification rates south of the river indicate that nitrate contamination in that part of the aquifer would likely persist for a longer period of time.

Nebraska

Ground-Water Temperature, Noble Gas, and Carbon Isotope Data from the Espanola Basin, New Mexico

Ground-water samples were collected from 56 locations throughout the Espanola Basin and analyzed for general chemistry (major ions and trace elements), carbon isotopes (delta 13C and 14C activity) in dissolved inorganic carbon, noble gases (He, Ne, Ar, Kr, Xe, and 3He/4He ratio), and tritium. Temperature profiles were measured at six locations in the southeastern part of the basin. Temperature profiles suggest that ground water generally becomes warmer with distance from the mountains and that most ground-water flow occurs at depths <250 m below ground surface. The two dominant water types in the basin are Ca/CO3+HCO3 and Na/CO3+HCO3, followed by mixed-cation/CO3+HCO3. Waters generally evolve from Ca/CO3+HCO3 to Na/CO3+HCO3 with increasing residence time through Ca-Na cation exchange with clay minerals. Basin ground water can be divided into four hydrochemical zones based on chemical and isotopic composition: West, Southeast, Northeast, and Central Deep. Hydrochemical zone boundaries are roughly correlated with contacts between geologic units or lithosome transitions within the Tesuque Formation. Geochemical mass-transfer modeling was performed using NETPATH and 14C ages were adjusted accordingly. Isotopic input parameters were varied within reasonable limits to assess uncertainty in the adjusted 14C ages. For each sample, a preferred adjusted age was selected from multiple possible adjusted ages based primarily on the fit between measured and modeled delta 13C values. The range of possible age adjustments for most samples is about 6,000 years or less, indicating that the preferred adjusted age for most samples has a total range of uncertainty of <6,000 years. Preferred adjusted ages range from 0 to 35,400 years. First-order trends in the age distribution include older ages generally occurring farther from rivers on the east side of the basin and farther from the mountains, consistent with both mountain-front recharge and recharge on the basin floor in the form of stream-loss and arroyo recharge. Ages also increase with depth in the Southeast zone, the only area where discrete-depth samples could be collected. Recharge temperatures derived from noble gas concentrations were used in conjunction with an empirically derived local relationship between recharge temperature and elevation to constrain recharge elevation and to estimate fractions of mountain-block recharge (MBR) in sampled waters of Holocene age. Noble gas recharge temperatures indicate that ground water in the Southeast zone contains a significant fraction of MBR, commonly 20-50 percent or more. The same is apparently true for the Northeast zone, though only two data points could be used to evaluate the MBR fraction in this area. Recharge temperatures indicate that the upper 30 m of the regional aquifer on the Pajarito Plateau typically contain little or no MBR. Tritium concentrations and apparent 3H/3He ages indicate that water in the mountain block is dominantly <50 years old, and water in the basin-fill is dominantly >50 years old, consistent with the 14C ages. Terrigenic He (Heterr) concentrations in ground water are high (log Delta Heterr of 2 to 5) throughout much of the basin. High Heterr concentrations are probably caused by in situ production in the Tesuque Formation from locally high concentrations of U-bearing minerals (Northeast zone only), or by upward diffusive/advective transport of crustal- and mantle-sourced He possibly enhanced by basement piercing faults, or by both. The 3He/4He ratio of Heterr (Rterr) is commonly high (Rterr/Ra of 0.3-2.0, where Ra is the 3He/4He ratio in air) suggesting that Espanola Basin ground water commonly contains mantle-sourced He. The 3He/4He ratio of Heterr is generally the highest in the western and southern parts of the basin, closest to the western border fault system and the Quaternary to Miocene volcanics of the Jemez Mountains and Cerros del Rio.

Scientific Investigations Report

Extending the turbidity record: making additional use of continuous data from turbidity, acoustic-Doppler, and laser diffraction instruments and suspended-sediment samples in the Colorado River in Grand Canyon

Turbidity is a measure of the scattering and absorption of light in water, which in rivers is primarily caused by particles, usually sediment, suspended in the water. Turbidity varies significantly with differences in the design of the instrument measuring turbidity, a point that is illustrated in this study by side-by-side comparisons of two different models of instruments. Turbidity also varies with changes in the physical parameters of the particles in the water, such as concentration, grain size, grain shape, and color. A turbidity instrument that is commonly used for continuous monitoring of rivers has a light source in the near-infrared range (860±30 nanometers) and a detector oriented 90 degrees from the incident light path. This type of optical turbidity instrument has a limited measurement range (depending on pathlength) that is unable to capture the high turbidity levels of rivers that carry high suspended-sediment loads. The Colorado River in Grand Canyon is one such river, in which approximately 60 percent of the range in suspended-sediment concentration during the study period had unmeasurable turbidity using this type of optical instrument. Although some optical turbidimeters using backscatter or other techniques can measure higher concentrations of suspended sediment than the models used in this study, the maximum turbidity measurable using these other turbidimeters may still be exceeded in conditions of especially high concentrations of suspended silt and clay. In Grand Canyon, the existing optical turbidity instruments remain in use in part to provide consistency over time as new techniques are investigated. As a result, during these periods of high suspended-sediment concentration, turbidity values that could not be measured with the optical turbidity instruments were instead estimated from concurrent acoustic attenuation data collected using side-looking acoustic-Doppler profiler (ADP) instruments. Extending the turbidity record to the full range of sediment concentrations in the study area using data from the ADP instruments is particularly useful for biological studies. In Grand Canyon, turbidity has been correlated with food availability for aquatic organisms (gross primary production) as well as with fish behavior specific to predator-prey interactions. On the basis of the complete “extended” turbidity record and the relation between suspended-sediment concentration and turbidity, levels were higher before the construction of Glen Canyon Dam by a factor of approximately 2,000 at the Lees Ferry monitoring station (15 miles downstream from the dam) and by a factor of approximately 20 at the monitoring station 87 miles downstream from Lees Ferry (102 miles downstream from the dam). A comparison of turbidity data with data from Laser In-Situ Scattering and Transmissometry (LISST) laser-diffraction instruments, suspended-sediment concentration data, and ADP data shows the influence of the physical properties of suspended sediment. Apparent outliers in relations between turbidity, ADP, and suspended-sediment data during two events within the study period, a 2007 tributary flood from a watershed altered by a recent wildfire and a 2008 experimental controlled-flood release from Glen Canyon Dam, are explained in part by atypical grain sizes, shapes, densities, colors, and (or) clay mineral assemblages of suspended sediment occurring in the Colorado River during these two events. These analyses demonstrate the value of using multiple data-collection strategies for turbidity and sediment-transport studies and of continuous monitoring for capturing the full range and duration of turbidity and sediment-transport conditions, identifying the provenance of the sediment causing turbidity, and detecting physical and chemical processes that may be important for management of critical physical and biological resources.

Arizona

Baseline assessment of groundwater quality in Wayne County, Pennsylvania, 2014

The Devonian-age Marcellus Shale and the Ordovician-age Utica Shale, geologic formations which have potential for natural gas development, underlie Wayne County and neighboring counties in northeastern Pennsylvania. In 2014, the U.S. Geological Survey, in cooperation with the Wayne Conservation District, conducted a study to assess baseline shallow groundwater quality in bedrock aquifers in Wayne County prior to potential extensive shale-gas development. The 2014 study expanded on previous, more limited studies that included sampling of groundwater from 2 wells in 2011 and 32 wells in 2013 in Wayne County. Eighty-nine water wells were sampled in summer 2014 to provide data on the presence of methane and other aspects of existing groundwater quality throughout the county, including concentrations of inorganic constituents commonly present at low levels in shallow, fresh groundwater but elevated in brines associated with fluids extracted from geologic formations during shale-gas development. Depths of sampled wells ranged from 85 to 1,300 feet (ft) with a median of 291 ft. All of the groundwater samples collected in 2014 were analyzed for bacteria, major ions, nutrients, selected inorganic trace constituents (including metals and other elements), radon-222, gross alpha- and gross beta-particle activity, selected man-made organic compounds (including volatile organic compounds and glycols), dissolved gases (methane, ethane, and propane), and, if sufficient methane was present, the isotopic composition of methane. Results of the 2014 study show that groundwater quality generally met most drinking-water standards, but some well-water samples had one or more constituents or properties, including arsenic, iron, pH, bacteria, and radon-222, that exceeded primary or secondary maximum contaminant levels (MCLs). Arsenic concentrations were higher than the MCL of 10 micrograms per liter (µg/L) in 4 of 89 samples (4.5 percent) with concentrations as high as 20 µg/L; arsenic concentrations were higher than the Health Advisory level of 2 µg/L in 27 of 89 samples (30 percent). Total iron concentrations exceeded the secondary maximum contaminant level (SMCL) of 300 µg/L in 9 of 89 samples (10 percent). The pH ranged from 5.4 to 9.3 and did not meet the SMCL range of greater than 6.5 to less than 8.5 in 27 samples (30 percent); 22 samples had pH values less than 6.5, and 5 samples had pH values greater than 8.5. Total coliform bacteria were detected in 22 of 89 samples (25 percent); Escherichia coli were detected in only 2 of those 22 samples. Radon-222 activities ranged from 25 to 7,400 picocuries per liter (pCi/L), with a median of 2,120 pCi/L, and exceeded the proposed drinking-water standard of 300 pCi/L in 86 of 89 samples (97 percent); radon-222 activities were higher than the alternative proposed standard of 4,000 pCi/L in 12 of 89 samples (13.5 percent). Water from 8 of the 89 wells (9 percent) had concentrations of methane greater than the reporting level of 0.24 milligrams per liter (mg/L) with the detectable methane concentrations ranging from 0.74 to 9.6 mg/L. Of 16 replicate samples submitted to another laboratory with a lower reporting level of 0.0002 mg/L, 15 samples had detectable methane concentrations that ranged from 0.0011 to 9.7 mg/L. Of these 15 samples, low levels of ethane (0.00032 to 0.0017 mg/L) were detected in 6 of 7 samples with methane concentrations greater than 0.75 mg/L. The isotopic composition of methane in 6 of 8 samples with sufficient dissolved methane (about 1 mg/L) for isotopic analysis is consistent with a predominantly thermogenic methane source (sample carbon isotopic ratio δ13C CH4 values ranging from -56.36 to -45.97 parts per thousand (‰) and hydrogen isotopic ratio δD CH4 values ranging from -233.1 to -141.1 ‰). However, the low levels of ethane relative to methane indicate that the methane may be of microbial origin and subsequently underwent oxidation. Isotopic compositions indicated a possibly mixed thermogenic and microbial source (carbon dioxide reduction process) for the methane in 1 of the 8 samples (δ 13 C CH4 of -63.72 and δD CH4 of -192.3 ‰) and potential oxidation of microbial and (or) thermogenic methane in the remaining sample (δ 13 C CH4 of -46.56 and δD CH4 of -79.7 ‰). Groundwater samples with relatively elevated methane concentrations (near or greater than 1 mg/L) had a chemical composition that differed in some respects (pH, selected major ions, and inorganic trace constituents) from groundwater with relatively low methane concentrations (less than 0.75 mg/L). The seven well-water samples with the highest methane concentrations (from about 1 to 9.6 mg/L) also had among the highest pH values (8.1 to 9.3, respectively) and the highest concentrations of sodium, lithium, boron, fluoride, arsenic, and bromide. Relatively elevated concentrations of some other constituents, such as barium, strontium, and chloride, commonly were present in, but not limited to, those well-water samples with elevated methane. Groundwater samples with the highest methane concentrations had chloride/bromide ratios that indicate mixing with a small amount of brine (0.02 percent or less, by volume) similar in composition to that reported for gas and oil well brines in Pennsylvania. Most other samples with low methane concentrations (less than about 1 mg/L) had chloride/bromide ratios that indicate predominantly man-made sources of chloride, such as road salt, septic systems, and (or) animal waste. Although naturally occurring brines may originate from deeper parts of the aquifer system, the man-made sources are likely to affect shallow groundwater. Geochemical modeling showed that the water chemistry of samples with elevated pH, sodium, lithium, bromide, and alkalinity could result from dissolution of calcite (calcium carbonate) combined with cation exchange and mixing with a small amount of brine. Through cation exchange reactions (which are equivalent to processes in a water softener) calcium ions released by calcite dissolution are exchanged for sodium ions on clay minerals. The spatial distribution of groundwater compositions generally shows that (1) relatively dilute, slightly acidic, oxygenated, calcium-carbonate type waters tend to occur in the uplands along the western border of Wayne County; (2) waters of near neutral pH with the highest amounts of hardness (calcium and magnesium) generally occur in areas of intermediate altitudes; and (3) waters with pH values greater than 8, low oxygen concentrations, and the highest arsenic, sodium, lithium, bromide, and methane concentrations can occur in deep wells in uplands but most frequently occur in stream valleys, especially at low elevations (less than about 1,200 ft above North American Vertical Datum of 1988) where groundwater may be discharging regionally, such as to the Delaware River. Thus, the baseline assessment of groundwater quality in Wayne County prior to gas-well development shows that shallow (less than about 1,000 ft deep) groundwater is generally of good quality, but methane and some constituents present in high concentrations in brine (and produced waters from gas and oil wells) may be present at low to moderate concentrations in some parts of Wayne County.

Pennsylvania

Hydrogeologic controls and geochemical indicators of groundwater movement in the Niles Cone and southern East Bay Plain groundwater subbasins, Alameda County, California

Beginning in the 1970s, Alameda County Water District began infiltrating imported water through ponds in repurposed gravel quarries at the Quarry Lakes Regional Park, in the Niles Cone groundwater subbasin, to recharge groundwater and to minimize intrusion of saline, San Francisco Bay water into freshwater aquifers. Hydraulic connection between distinct aquifers underlying Quarry Lakes allows water to recharge the upper aquifer system to depths of 400 feet below land surface, and the Deep aquifer to depths of more than 650 feet. Previous studies of the Niles Cone and southern East Bay Plain groundwater subbasins suggested that these two subbasins may be hydraulically connected. Characterization of storage capacities and hydraulic properties of the complex aquifers and the structural and stratigraphic controls on groundwater movement aids in optimal storage and recovery of recharged water and provides information on the ability of aquifers shared by different water management agencies to fulfill competing storage and extraction demands. The movement of recharge water through the Niles Cone groundwater subbasin from Quarry Lakes and the possible hydraulic connection between the Niles Cone and the southern East Bay Plain groundwater subbasins were investigated using interferometric synthetic aperture radar (InSAR), water-chemistry, and isotopic data, including tritium/helium-3, helium-4, and carbon-14 age-dating techniques. InSAR data collected during refilling of the Quarry Lakes recharge ponds show corresponding ground-surface displacement. Maximum uplift was about 0.8 inches, reasonable for elastic expansion of sedimentary materials experiencing an increase in hydraulic head that resulted from pond refilling. Sodium concentrations increase while calcium and magnesium concentrations in groundwater decrease along groundwater flowpaths from the Niles Cone groundwater subbasin through the Deep aquifer to the northwest toward the southern East Bay Plain groundwater subbasin. Residual effects of pre-1970s intrusion of saline water from San Francisco Bay, including high chloride concentrations in groundwater, are evident in parts of the Niles Cone subbasin. Noble gas recharge temperatures indicate two primary recharge sources (Quarry Lakes and Alameda Creek) in the Niles Cone groundwater subbasin. Although recharge at Quarry Lakes affects hydraulic heads as far as the transition zone between the Niles Cone and East Bay Plain groundwater subbasins (about 5 miles), the effect of recharged water on water quality is only apparent in wells near (less than 2 miles) recharge sources. Groundwater chemistry from upper aquifer system wells near Quarry Lakes showed an evaporated signal (less negative oxygen and hydrogen isotopic values) relative to surrounding groundwater and a tritium concentration (2 tritium units) consistent with recently recharged water from a surface-water impoundment. Uncorrected carbon-14 activities measured in water sampled from wells in the Niles Cone groundwater subbasin range from 16 to 100 percent modern carbon (pmC). The geochemical reaction modeling software NETPATH was used to interpret carbon-14 ages along a flowpath from Quarry Lakes toward the East Bay Plain groundwater subbasin. Model results indicate that changes in groundwater chemistry are controlled by cation exchange on clay minerals and weathering of primary silicate minerals. Old groundwater (lower carbon-14 activities) is characterized by high dissolved silica and pH. Interpreted carbon-14 ages ranged from 830 to more than 7,000 years before present and are less than helium-4 ages that range from 2,000 to greater than 11,000 years before present. The average horizontal groundwater velocity along the studied flowpath, as calculated using interpreted carbon-14 ages, through the Deep aquifer of the Niles Cone groundwater subbasin is between 3 and 12 feet per year. The groundwater velocity decreases near the boundary of the transition zone to the southern East Bay Plain groundwater subbasin to about 0.5 feet per year. These changes may result from water recharged from different sources converging in flowpaths north of the transition zone, or a boundary to flow between the Niles Cone and southern East Bay Plain groundwater subbasins, likely owing to changes in lithology caused by depositional patterns.

California

Carnotite resources of Club Mesa, Montrose County, Colorado

Club Mesa is 1 mile west of Uravan, Montrose County, Colo. About 200,000 short tons of carnotite ore containing an estimated 0.45 percent U 3 O 8 and 2.1 percent V 2 O 5 has been mined from the mesa. This production represents about one-fifth of the carnotite ore mined from the Colorado Plateau. All the principal deposits on the mesa are in the main ore-bearing sandstone which is in the top part of the Salt Wash sandstone member of the Jurassic Morrison formation. The deposits are in tabular masses of uneven thickness lying more or less parallel to the enclosing strata. The ore consists mainly of sandstone impregnated with carnotite and vanadiferous clay minerals. The sandstone near the deposits is generally over 30 feet in thickness, contains noticeable quantities of carbon, and vivid patches of limonite (?) stain. Also near ore deposits, the mudstone in contact with the sandstone is altered from red to gray or green through a thickness of 3 or 4 feet. Certain linear features of the ore bodies and of favorable parts of the main ore-bearing sandstone offer clues by their orientation to extensions of known ore bodies and of favorable ground. These features on Club Mesa trend mostly east to northeast. Between March 6, 1948, and January 22, 1952, the U.S. Geological Survey drilled 651 holes for a total of 167,495 feet. As a result of this drilling, 18 deposits were discovered and partly outlined. These range in size from 200 to 55,000 short tons of indicated ore reserves and are in layers 1 foot or more thick containing 0.10 percent or more U 3 O 8 or 1.0 percent or more V 2 O 5 . About 85 percent of this ore is in public land; the remainder is in claims owned by the United States Vanadium Co. Reserves in deposits known from drill holes or exposures are classed as indicated or inferred, and those in deposits that are predicted solely on geologic evidence are classed as potential. The tons of indicated and inferred reserves and the pounds of contained U 3 O 8 and V 2 O 5 are summarized in table 1. These reserves are subdivided also by thickness and grade cutoffs. At the higher grade cutoff, reserve figures express approximately the tonnage and grade of material that might actually be mined from these deposits under 1951 conditions. Indicated and inferred reserves of this type total 198,000 short tons, averaging 0.35 percent U 3 O 8 and 1.8 percent V 2 O 5, and contain 1,1,372,000 pounds of U 3 O 8 and 7,260,000 pounds of V 2 O 5. These reserves are based on Geological Survey drilling. Potential reserves are predicted to total about 40,000 short tons, averaging about 0.35 percent U 3 O 8 and 1.9 percent V 2 O 5 . No additional exploration on Club Mesa is planned by the Geological Survey, but exploration by private companies is recommended.

Colorado

Carnotite resources of Outlaw Mesa, Mesa County, Colorado

The U.S. Geological Survey explored Outlaw Mesa for carnotite deposits from 1949 through 1951 with 1,302 diamond-drill holes that totaled 222,150 feet. Total production from Outlaw Mesa from 1914 through 1951 was about 30,000 short tons of carnotite ore, having an estimated grade of about 0.40 percent U3O8 and 1.7 percent V205. The known carnotite deposits are in a number of sandstone lenses in the upper part of the Salt Wash sandstone member of the Jurassic Morrison formation. The deposits are mainly impregnations of sandstone by carnotite and vanadium-bearing clay minerals. Commonly, the deposits are irregular tabular layers or pod-like or crescentic masses ("rolls") connected by thin layers of mineralized rock. The deposits and rolls have a dominant northeasterly trend. Useful criteria for recognizing-sandstone that might contain mineralized rock are: (1) thick, light-brown sandstone, (2) gray mudstone at the base of and in this sandstone, and (3) abundant carbonaceous material. The indicated and inferred reserves of carnotite-bearing material, and the pounds of contained U308 and V205 are summarized in table 1. Potential reserves, whose existence is based on geologic evidence alone, are estimated to total about 80,000 short tones, averaging about 0.35 percent U308 and 1.5percent V205. No further exploration by the Geological Survey is planned; however, additional drilling by private operators is recommended, particularly in ground underlain by mineralized rock.

Colorado

Carnotite resources of the Dolores bench, Montrose County, Colorado

The Dolores bench is about 2 miles northwest of Uravan, Montrose County, Colo. From 1913 to November 1952 about 95,000 short tons of ore averaging 0.40 percent U 3 O 8 and 2.0 percent V 2 O 5 was mined from the Dolores bench. The production represents three periods of activity--1913-18, 1938-43, and 1948-52. The ore deposits are in broad sandstone lenses near the top of the Salt Wash member of the Jurassic Morrison formation. The deposits are mainly impregnations of sandstone by carnotite and vanadiferous clay minerals. The deposits are irregular tabular layers which occasionally include pod-like masses called “rolls”. The rolls as well as the mineralized areas enclosing them have a poorly defined northeast trend. Between December 4, 1951, and August 1, 1952, the U.S. Geological Survey diamond-drilled 183 holes totaling 53,654 feet. The indicated and inferred reserves of carnotite-bearing material, and the pounds of contained U 3 O 8 and V 2 O 5 area summarized in table 1. At the highest thickness and grade cutoffs (1 foot thick and 0.10 percent U 3 O 8 or 1.0 percent V 2 O 5 ), indicated and inferred ore reserves total 90,000 short tons, averaging 0.33 percent U 3 O 8 and 2.11 percent V 2 O 5 . These reserves include only those discovered by U.S. Geological Survey drilling. Potential reserves, whose existence is based on geologic evidence alone, are estimated to be about 10,000 short tons, averaging about 0.30 percent U 3 O 8 and 2.00 percent V 2 O 5 . No additional exploration of the Dolores bench is planned by the Geological Survey. Diamond drilling by claim owners is recommended in several parts of the area.

Colorado

Carnotite resources of the Spud Patch area, San Miguel County, Colorado

The Spud Patch area comprises about 8 square in T. 43 M., R. 18 and 19 W., San Miguel County, Colo., and is about 4 miles northeast of Egnar, Colo. Claims of the United States Vanadium Co. and the Vanadium Corp. of America cover about half the area. Claims of other owners, public land, and patented agricultural land, comprise the remainder of the area. The area is about 38 miles from the Government mill at Montecello, Utah, and 55 miles from the Vanadium Corp. of America mill at Naturita, Colo. Between 1940 and 1951, the Spud Patch area yielded about 24,000 short tons of carnotite ore that probably averaged 0.21 percent U 3 O 8 and 2.2 percent V 2 O 5 . The deposits are in a broad sandstone lens near the top of the Salt Wash member of the Jurassic Morrison formation. Although the deposits mined have been mainly impregnations of sandstone by carnotite and gray vanadium-bearing clay minerals, some of the richer deposits found by Geological Survey drilling have a finely disseminated black uranium mineral but no carnotite. The deposits commonly are thin irregular tabular layers, which locally thicken to form elongate masses called "rolls". These rolls have a dominant northeasterly trend. Geologic features found to be most useful as guides to ore are listed. From November 1949 to May 1952, the U.S. Geological Survey drilled 415 diamond-drill holes totaling 67,215 feet in the Spud Patch area. The purpose of this drilling was to find deposits that would make new mines and to appraise the reserves in the unexplored area. As a result of Geological Survey drilling, indicated and inferred reserves computed at the cutoff of 1 foot or more thick and 0.10 percent U 3 O 8 or 1.0 percent V 2 O 5 total 20,500 short tons, averaging 0.28 percent U 3 O 8 and 2.1 percent V 2 O 5 . These reserves and those computed at a lower grade cutoff of 0.05 percent U 3 O 8 or 0.50 percent V 2 O 5 and the pounds of contained metal are summarized in table 1. Potential reserves, whose existence is based on geologic evidence alone, are predicted to total about 42,000 short tons, averaging 0.25 percent U 3 O 8 and 2.0 percent V 2 O 5 . No additional exploratory-type drilling by the Geological Survey is planned in the Spud Patch area. Recommendations are offered for additional development-type drilling, preferably by claim owners or lessees in specific areas in the vicinity of deposits discovered by Geological Survey drilling.

Colorado

Chemical interactions of aluminum with aqueous silica at 25 degrees Celsius

Solutions containing from 10 -5 to 10 -2 moles per liter of aluminum and dissolved silica in various ratios were aged at pH levels between 4 and 10 at 25?C. A colloidal amorphous product having the composition of halloysite was produced in most solutions. It had a consistent and reversible equilibrium solubility equivalent to a standard free energy of formation of -8974 ? 1.0 kcal per mole for the formula A12Si2O5(OH)4. Some aging times were longer than 4 years, but most solutions gave consistent solubilities after only a few months of aging. Where silica concentrations were below about 10 -4 molar, microcrystalline gibbsite was formed below pH 6.0 and crystalline bayerite above pH 7.0, but only after much longer aging than was required for crystallization in silica-free solutions. Electron micrographs and diffraction patterns of the synthesized material indicate some crystallinity in the aluminosilicate, but no X-ray diffraction patterns could be obtained even in the material aged 4 years. Solubility relationships for solutions containing fluoride as well as silica and aluminum are explainable by using cryolite stabilities determined in previous work. Aluminum contents of 51 samples of water analyzed for other purposes are in reasonable agreement with the assumption of equilibrium with amorphous clay mineral species similar to the material synthesized in this work. Solubility calculations are summarized graphically for solutions of ionic strength of 0.01 and 0.10.

Water Supply Paper

Controls on phosphorus mobility in the Potomac River near the Blue Plains wastewater treatment plant

The Blue Plains wastewater treatment plant is the largest point source of phosphorus in the Potomac River basin, discharging an average of 2 metric tons of phosphorus into the river each day in 1980. An intensive study of the water and sediments in the vicinity of the treatment plant was conducted in 1979-80 in order to characterize the major factors controlling the mobility of effluent-derived phosphorus in the area. The transport of phosphorus near the treatment plant was found to be affected by the circulation regime, by inorganic adsorption reactions with sediments, and by metabolic uptake and release by phytoplankton. The effect of river discharge on the convective transport of phosphorus near the outfall is significantly reduced by a mid-river shoal area, which confines the flow path of the effluent to an embayment on the eastern side of the river for a distance of 4 kilometers below the outfall. This embayment appears to serve as a sediment trap, where protection from bottom scour during high-flow events has permitted fine-grained sediments to accumulate. Measurements of mean residence time indicate that the effluent leaves the embayment area 21? days after being discharged from the outfall. Measurements of the linear decay constant for the removal of dissolved phosphorus from the water column reveal a diurnal cycle corresponding to the metabolic utilization of phosphorus by phytoplankton. This cyclic removal is superimposed on a constant and noncyclic adsorption of phosphorus by inorganic phases. Forty-eight hour average values of the linear decay constant for dissolved phosphorus in the area range from 0.4 to 1.1 per day. Analyses of bottom sediments indicate that approximately 13 percent of the phosphorus discharged between September 1977 and August 1980 has been retained in the embayment. The primary inorganic phase responsible for phosphorus adsorption is amorphous iron (ferric oxy-hydroxides); amorphous aluminum and clay minerals appear to play secondary roles. The accumulation of sorbed phosphorus in the embayment has been promoted by the deposition of fine-grained sediments enriched in ferric oxy-hydroxides. Conversely, the absence of ferric oxy-hydroxides in coarse-grained sediments near the outfall has facilitated the precipitation of the ferrous phosphate mineral vivianite.

District of Columbia, Maryland, Virginia

A primer on trace metal-sediment chemistry

In most aquatic systems, concentrations of trace metals in suspended sediment and the top few centimeters of bottom sediment are far greater than concentrations of trace metals dissolved in the water column. Consequently, the distribution, transport, and availability of these constituents can not be intelligently evaluated, nor can their environmental impact be determined or predicted solely through the sampling and analysis of dissolved phases. This Primer is designed to acquaint the reader with the basic principles that govern the concentration and distribution of trace metals associated with bottom and suspended sediments. The sampling and analysis of suspended and bottom sediments are very important for monitoring studies, not only because trace metal concentrations associated with them are orders of magnitude higher than in the dissolved phase, but also because of several other factors. Riverine transport of trace metals is dominated by sediment. In addition, bottom sediments serve as a source for suspended sediment and can provide a historical record of chemical conditions. This record will help establish area baseline metal levels against which existing conditions can be compared. Many physical and chemical factors affect a sediment's capacity to collect and concentrate trace metals. The physical factors include grain size, surface area, surface charge, cation exchange capacity, composition, and so forth. Increases in metal concentrations are strongly correlated with decreasing grain size and increasing surface area, surface charge, cation exchange capacity, and increasing concentrations of iron and manganese oxides, organic matter, and clay minerals. Chemical factors are equally important, especially for differentiating between samples having similar bulk chemistries and for inferring or predicting environmental availability. Chemical factors entail phase associations (with such sedimentary components as interstitial water, sulfides, carbonates, and organic matter) and ways in which the metals are entrained by the sediments (such as adsorption, complexation, and within mineral lattices).

Water Supply Paper

Integrating surface and borehole geophysics in ground water studies: An example using electromagnetic soundings in south Florida

Time domain surface electromagnetic soundings, borehole induction logs, and other borehole logging techniques are used to construct a realistic model for the shallow subsurface hydraulic properties of unconsolidated sediments in south Florida. Induction logs are used to calibrate surface induction soundings in units of pore water salinity by correlating water sample specific electrical conductivity with the electrical conductivity of the formation over the sampled interval for a two‐layered aquifer model. Geophysical logs are also used to show that a constant conductivity layer model is appropriate for the south Florida study. Several physically independent log measurements are used to quantify the dependence of formation electrical conductivity on such parameters as salinity, permeability, and clay mineral fraction. The combined interpretation of electromagnetic soundings and induction logs was verified by logging three validation boreholes, confirming quantitative estimates of formation conductivity and thickness in the upper model layer, and qualitative estimates of conductivity in the lower model layer.

Journal of Environmental & Engineering Geophysics

Geochemical controls of vanadium accumulation in fossil fuels

High vanadium contents in petroleum and other fossil fuels have been attributed to organic-matter type, organisms, volcanic emanations, diffusion of sea water, and epigenetic enrichment. However, these factors are inadequate to account for the high abundance of vanadium in some fossil fuels and the paucity in others. By examining vanadium deposits in sedimentary rocks with sparse organic matter, constraints are placed on processes controlling vanadium accumulation in organic-rich sediments. Vanadium, as vanadate (V(V)), entered some depositional basins in oxidizing waters from dry, subaerial environments. Upon contact with organic matter in anoxic waters, V(V) is reduced to vanadyl (V(IV)), which can be removed from the water column by adsorption. H2S reduces V(IV) to V(III), which hydrolyzes and precipitates. The lack of V(III) in petroleum suggests that reduction of V(IV) to V(III) is inhibited by organic complexes. In the absence of strong complexing agents, V(III) forms and is incorporated in clay minerals.

Conference Paper