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John A. Izbicki

Publications and source records attributed to John A. Izbicki.

At least 37 records · Page 2Linked to original sources

Natural and man-made hexavalent chromium, Cr(VI), in groundwater near a mapped plume, Hinkley, California—study progress as of May 2017, and a summative-scale approach to estimate background Cr(VI) concentrations

This report describes (1) work done between January 2015 and May 2017 as part of the U.S. Geological Survey (USGS) hexavalent chromium, Cr(VI), background study and (2) the summative-scale approach to be used to estimate the extent of anthropogenic (man-made) Cr(VI) and background Cr(VI) concentrations near the Pacific Gas and Electric Company (PG&E) natural gas compressor station in Hinkley, California. Most of the field work for the study was completed by May 2017. The summative-scale approach and calculation of Cr(VI) background were not well-defined at the time the USGS proposal for the background Cr(VI) study was prepared but have since been refined as a result of data collected as part of this study. The proposed summative scale consists of multiple items, formulated as questions to be answered at each sampled well. Questions that compose the summative scale were developed to address geologic, hydrologic, and geochemical constraints on Cr(VI) within the study area. Each question requires a binary (yes or no) answer. A score of 1 will be assigned for an answer that represents data consistent with anthropogenic Cr(VI); a score of –1 will be assigned for an answer that represents data inconsistent with anthropogenic Cr(VI). The areal extent of anthropogenic Cr(VI) estimated from the summative-scale analyses will be compared with the areal extent of anthropogenic Cr(VI) estimated on the basis of numerical groundwater flow model results, along with particle-tracking analyses. On the basis of these combined results, background Cr(VI) values will be estimated for “Mojave-type” deposits, and other deposits, in different parts of the study area outside the summative-scale mapped extent of anthropogenic Cr(VI).

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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.

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Four-dimensional isotopic approach to identify perchlorate sources in groundwater: Application to the Rialto-Colton and Chino subbasins, southern California (USA)

Perchlorate (ClO 4 − ) in groundwater can be from synthetic or natural sources. Natural sources include ClO 4 − associated with historical application of imported natural nitrate fertilizer from the Atacama Desert of Chile, and indigenous ClO 4 − that accumulates locally in arid regions from atmospheric deposition. The Rialto-Colton groundwater subbasin, 80 km east of Los Angeles, California, includes two mapped ClO 4 − plumes from known military/industrial sources. Larger areas downgradient from those plumes, and in the Chino subbasin to the southwest, also contain ClO 4 − . Perchlorate from wells was analyzed for chlorine and oxygen stable isotope ratios (δ 37 Cl, δ 18 O, Δ 17 O) and radioactive chlorine-36( 36 Cl) isotopic abundance, along with other geochemical, isotopic, and hydrogeologic data. Isotopic data show that synthetic ClO 4 − was the dominant source within the mapped plumes. Downgradient from the mapped plumes, and in the Chino subbasin, the dominant source of ClO 4 − was related to past agricultural use of Chilean (Atacama) nitrate fertilizer. The 36 Cl and δ 18 O data indicate that wells having predominantly synthetic or Atacama ClO 4 − also contained small fractions of indigenous ClO 4 − . Little or no differences were observed in isotopic composition or ClO 4 − source with depth in depth-dependent data from selected wells. Indigenous ClO 4 − was most evident in upgradient wells having ClO 4 − concentrations <1 μg/L, consistent with its occurrence as a background constituent throughout the region. Stable isotope ratios of chlorine and oxygen and 36 Cl isotopic abundance data provided relatively unambiguous discrimination of synthetic and Atacama sources in most wells having ClO 4 − concentrations greater than 1 μg/L.

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Selected techniques for monitoring water movement through unsaturated alluvium during managed aquifer recharge

Managed aquifer recharge is used to augment natural recharge to aquifers. It can be used to replenish aquifers depleted by pumping or to store water during wetter years for withdrawal during drier years. Infiltration from ponds is a commonly used, inexpensive approach for managed aquifer recharge. At some managed aquifer-recharge sites, the time when infiltrated water arrives at the water table is not always clearly shown by water-level data. As part of site characterization and operation, it can be desirable to track downward movement of infiltrated water through the unsaturated zone to identify when it arrives at the water table.

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Elemental analysis using a handheld X-Ray fluorescence spectrometer

The U.S. Geological Survey is collecting geologic samples from local stream channels, aquifer materials, and rock outcrops for studies of trace elements in the Mojave Desert, southern California. These samples are collected because geologic materials can release a variety of elements to the environment when exposed to water. The samples are to be analyzed with a handheld X-ray fluorescence (XRF) spectrometer to determine the concentrations of up to 27 elements, including chromium.

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A plan for study of hexavalent chromium, CR(VI) in groundwater near a mapped plume, Hinkley, California, 2016

The Pacific Gas and Electric Company (PG&E) Hinkley compressor station, in the Mojave Desert 80 miles northeast of Los Angeles, is used to compress natural gas as it is transported through a pipeline from Texas to California. Between 1952 and 1964, cooling water used at the compressor station was treated with a compound containing chromium to prevent corrosion. After cooling, the wastewater was discharged to unlined ponds, resulting in contamination of soil and groundwater in the underlying alluvial aquifer (Lahontan Regional Water Quality Control Board, 2013). Since 1964, cooling-water management practices have been used that do not contribute chromium to groundwater. In 2007, a PG&E study of the natural background concentrations of hexavalent chromium, Cr(VI), in groundwater estimated average concentrations in the Hinkley area to be 1.2 micrograms per liter (μg/L), with a 95-percent upper-confidence limit of 3.1 μg/L (CH2M-Hill, 2007). The 3.1 μg/L upper-confidence limit was adopted by the Lahontan Regional Water Quality Control Board (RWQCB) as the maximum background concentration used to map the plume extent. In response to criticism of the study’s methodology, and an increase in the mapped extent of the plume between 2008 and 2011, the Lahontan RWQCB (Lahontan Regional Water Quality Control Board, 2012) agreed that the 2007 PG&E background-concentration study be updated. The purpose of the updated background study is to evaluate the presence of natural and man-made Cr(VI) near Hinkley, Calif. The study also is to estimate natural background Cr(VI) concentrations in the aquifer upgradient and downgradient from the mapped Cr(VI) contamination plume, as well as in the plume and near its margins. The study was developed by the U.S. Geological Survey (USGS) in collaboration with a technical working group (TWG) composed of community members, the Independent Review Panel (IRP) Manager (Project Navigator, Ltd.), the Lahontan RWQCB, PG&E, and consultants for PG&E.&E.

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Sources of high-chloride water and managed aquifer recharge in an alluvial aquifer in California, USA

As a result of pumping in excess of recharge, water levels in alluvial aquifers within the Eastern San Joaquin Groundwater Subbasin, 130 km east of San Francisco (California, USA), declined below sea level in the early 1950s and have remained so to the present. Chloride concentrations in some wells increased during that time and exceeded the US Environmental Protection Agency&rsquo;s secondary maximum contaminant level of 250 mg/L, resulting in removal of some wells from service. Sources of high-chloride water include irrigation return in 16 % of sampled wells and water from delta sediments and deeper groundwater in 50 % of sampled wells. Chloride concentrations resulting from irrigation return commonly did not exceed 100 mg/L, although nitrate concentrations were as high as 25 mg/L as nitrogen. Chloride concentrations ranged from less than 100&ndash;2,050 mg/L in wells affected by water from delta sediments and deeper groundwater. Sequential electromagnetic logs show movement of high-chloride water from delta sediments to pumping wells through permeable interconnected aquifer layers. &delta;D and &delta;18O data show most groundwater originated as recharge along the front of the Sierra Nevada, but tritium and carbon-14 data suggest recharge rates in this area are low and have decreased over recent geologic time. Managed aquifer recharge at two sites show differences in water-level responses to recharge and in the physical movement of recharged water with depth related to subsurface geology. Well-bore flow logs also show rapid movement of water from recharge sites through permeable interconnected aquifer layers to pumping wells.

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Cr(VI) occurrence and geochemistry in water from public-supply wells in California

Hexavalent chromium, Cr(VI), in 918 wells sampled throughout California between 2004 and 2012 by the Groundwater Ambient Monitoring and Assessment-Priority Basin Project (GAMA-PBP) ranged from less than the study reporting limit of 1 microgram per liter (μg/L) to 32 μg/L. Statewide, Cr(VI) was reported in 31 percent of wells and equaled or exceeded the recently established (2014) California Maximum Contaminant Level (MCL) for Cr(VI) of 10 μg/L in 4 percent of wells. Cr(VI) data collected for regulatory purposes overestimated Cr(VI) occurrence compared to spatially-distributed GAMA-PBP data. Ninety percent of chromium was present as Cr(VI), which was detected more frequently and at higher concentrations in alkaline (pH ≥ 8), oxic water; and more frequently in agricultural and urban land uses compared to native land uses. Chemical, isotopic (tritium and carbon-14), and noble-gas data show high Cr(VI) in water from wells in alluvial aquifers in the southern California deserts result from long groundwater-residence times and geochemical reactions such as silicate weathering that increase pH, while oxic conditions persist. High Cr(VI) in water from wells in alluvial aquifers along the west-side of the Central Valley results from high-chromium in source rock eroded to form those aquifers, and areal recharge processes (including irrigation return) that can mobilize chromium from the unsaturated zone. Cr(VI) co-occurred with oxyanions having similar chemistry, including vanadium, selenium, and uranium. Cr(VI) was positively correlated with nitrate, consistent with increased concentrations in areas of agricultural land use and mobilization of chromium from the unsaturated zone by irrigation return.

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Storage and mobilization of natural and septic nitrate in thick unsaturated zones, California

Mobilization of natural and septic nitrate from the unsaturated zone as a result of managed aquifer recharge has degraded water quality from public-supply wells near Yucca Valley in the western Mojave Desert, California. The effect of nitrate storage and potential for denitrification in the unsaturated zone to mitigate increasing nitrate concentrations were investigated. Storage of water extractable nitrate in unsaturated alluvium up to 160 meters (m) thick, ranged from 420 to 6600 kilograms per hectare (kg/ha) as nitrogen (N) beneath undeveloped sites, from 6100 to 9200 kg/ha as N beneath unsewered sites. Nitrate reducing and denitrifying bacteria were less abundant under undeveloped sites and more abundant under unsewered sites; however, &delta; 15 N&ndash;NO 3 , and &delta; 18 O&ndash;NO 3 data show only about 5&ndash;10% denitrification of septic nitrate in most samples&mdash;although as much as 40% denitrification occurred in some parts the unsaturated zone and near the top of the water table. Storage of nitrate in thick unsaturated zones and dilution with low-nitrate groundwater are the primary attenuation mechanisms for nitrate from septic discharges in the study area. Numerical simulations of unsaturated flow, using the computer program TOUGH2, showed septic effluent movement through the unsaturated zone increased as the number and density of the septic tanks increased, and decreased with increased layering, and increased slope of layers, within the unsaturated zone. Managing housing density can delay arrival of septic discharges at the water table, especially in layered unsaturated alluvium, allowing time for development of strategies to address future water-quality issues.

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Hydrogeologic data and water-quality data from a thick unsaturated zone at a proposed wastewater-treatment facility site, Yucca Valley, San Bernardino County, California, 2008-11

The Hi-Desert Water District, in the community of Yucca Valley, California, is considering constructing a wastewater-treatment facility and using the reclaimed water to recharge the aquifer system through surface spreading. The Hi-Desert Water District is concerned with possible effects of this recharge on water quality in the underlying groundwater system; therefore, an unsaturated-zone monitoring site was constructed by the U.S. Geological Survey (USGS) to characterize the unsaturated zone, monitor a pilot-scale recharge test, and, ultimately, to monitor the flow of reclaimed water to the water table once the treatment facility is constructed. In June and July 2008, a borehole (YVUZ-5) was drilled by the USGS through the unsaturated zone in the vicinity of the proposed wastewater-treatment facility site by using an overburden drilling method. In addition to a variety of unsaturated-zone instrumentation, an observation well screened near the water table was installed in the borehole. The drilling procedures, lithologic and geophysical data, construction details, physical properties of unsaturated alluvial deposits, and instrumentation installed in YVUZ-5 are described in this report. Core material was analyzed for bulk-density, porosity, effective porosity, volumetric water content, residual water content, saturation, effective saturation, matric-potential, and saturated hydraulic conductivity. Concentrations of soluble anions, including bromide, chloride, fluoride, sulfate, nitrate, nitrite, phosphate, and orthophosphate, in unsaturated-zone sediment and dissolved in unsaturated-zone water were determined by analyzing water extracted from drill-cutting material. A 0.1-acre pilot-scale infiltration pond was constructed in the vicinity of YVUZ-5. Water was applied to the pond over a period of about 8 months and allowed to infiltrate into the underlying unsaturated zone. Data were collected on chemical and isotopic composition of the groundwater, unsaturated-zone water, and infiltration pond water before, during, and after infiltration of water from the constructed pond. Selected drill cuttings and core samples collected during drilling were analyzed for the presence or absence of denitrifying and nitrate-reducing bacteria. Water levels in the observation well ranged from about 367 to 370 feet below land surface during the period of the study. Measured saturated hydraulic conductivity of core material ranged from 2.1 to 11.0 feet per day. Average vertical infiltration rates in the pilot-scale infiltration pond ranged from 0.7 to 2.4 feet per day. Both denitrifying and nitrate-reducing bacteria were present in drill cutting material in most probable numbers ranging from below detection limits to 2,400,000 for denitrifying and to 93,000 for nitrate-reducing bacteria.

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In-situ arsenic removal during groundwater recharge through unsaturated alluvium

OBJECTIVES The purpose of this study was to determine the feasibility and sustainability of in-situ removal of arsenic from water infiltrated through unsaturated alluvium. BACKGROUND Arsenic is naturally present in aquifers throughout the southwestern United States and elsewhere. In January 2006, the U.S. Environmental Protection Agency (EPA) lowered the Maximum Contaminant Level (MCL) for arsenic from 50 to 10 micrograms per liter (g/L). This raised concerns about naturally-occurring arsenic in groundwater. Although commercially available systems using sorbent iron or aluminum oxide resins are available to treat high-arsenic water, these systems are expensive to build and operate, and may generate hazardous waste. Iron and aluminum oxides occur naturally on the surfaces of mineral grains that compose alluvial aquifers. In areas where alluvial deposits are unsaturated, these oxides may sorb arsenic in the same manner as commercial resins, potentially providing an effective low-cost alternative to commercially engineered treatment systems. APPROACH The Antelope Valley within the Mojave Desert of southern California contains a shallow water-table aquifer with arsenic concentrations of 5 g/L, and a deeper aquifer with arsenic concentrations of 30 g/L. Water was pumped from the deep aquifer into a pond and infiltrated through an 80 m-thick unsaturated zone as part of field-scale and laboratory experiments to treat high-arsenic groundwater and recharge the shallow water table aquifer at the site. The field-scale recharge experiment included the following steps: 1) construction of a recharge pond 2) test drilling for sample collection and instrument installation adjacent to the pond 3) monitoring downward migration of water infiltrated from the pond 4) monitoring changes in selected trace-element concentrations as water infiltrated through the unsaturated zone Data from instruments within the borehole adjacent to the pond were supplemented with borehole and surface geophysical data to evaluate the lateral spreading of water as it moved downward through the unsaturated zone. Three laboratory studies were undertaken. Sequential extraction was used to evaluate the abundance of iron, aluminum, and manganese oxides and selected trace elements on operationally defined sites on the surfaces of mineral grains collected before and after infiltration from the pond. Secondly, radio-labeled arsenic-73 microcosm experiments evaluated the potential for incorporation of arsenic sorbed to exchange sites on mineral grains into less reactive crystalline mineral structures with time. Finally, column studies evaluated arsenic sorption and the pH dependence of sorption for selected unsaturated zone materials. RESULTS/CONCLUSIONS Between December 2010 and July 2012, more than 120,000 cubic meters (m3 ) (about 97 acre-feet) of high-arsenic groundwater was pumped from the deep aquifer into a 0.11 hectare (about 0.27 acres) pond and infiltrated though an 80-meter (about 260 feet) thick unsaturated zone to recharge a water-table aquifer. Arsenic concentrations were lowered from 30 to 2 g/L as water infiltrated though the unsaturated zone at the site. Some uranium, possibly associated with past agricultural land use at the site, was mobilized to concentrations as high as 66 g/L within the unsaturated zone during the experiment. Uranium was resorbed and the high uranium concentrations did not reach the water table at the site. Concentrations of other trace elements, including antimony, chromium, vanadium, and selenium were low throughout the study. Infiltration rates from the pond were as high as 0.4 meters per day (1.1 feet per day, ft/d), and the wetting front moved downward about 25 centimeters per day (cm/d) (0.8 ft/d) to a depth of about 50 m (about 165 feet). Clay layers at that depth slowed the downward movement of the wetting front to about 5 cm/d (0.16 ft/d). Lateral movement of the wetting front was monitored using sequential direct-current (DC) surface and sequential electromagnetic (EM) and DC borehole resistivity. Most lateral movement occurred on a clay layer about 50 m (about 165 feet) below land surface. Infiltrated water reached the water table in January 2013. At the water table, the “wetted footprint” of water infiltrated from the pond, indicated by surface resistivity data, was about 13 hectares (about 32 acres). On the basis of data collected at the site, there is enough sorbent material to operate this pond and treat groundwater having an arsenic concentration of 30 g/L to 2 g/L for about 500 years. Toxicity Characteristic Leaching Procedure (TCLP) data showed arsenic concentrations to be below hazardous levels beneath the pond after the experiment. Pond maintenance may be required to keep infiltration rates high, and prevent accumulation of organic material on the pond bottom, although organic material on the pond bottom may increase removal of other trace elements in infiltrated water including chromium, selenium, and vanadium. Laboratory results are consistent with the field data and show sorption of arsenic in 10 cm (0.3 feet) columns to about 2 g/L over a pH range of 6 to 8, and at influent arsenic concentrations as high as 300 g/L, without breakthrough in 50 pore volumes. Column results suggest that the insitu treatment may remove arsenic in a range of hydrogeologic settings, and would not necessarily be restricted to alkaline alluvial aquifers common throughout the southwestern United States. Radiolabeled arsenic-73 experiments show that although arsenic is initially weakly sorbed (and potentially mobile), with time arsenic is incorporated into amorphous materials. One year after sorption onto surface exchange sites, most sorbed arsenic is incorporated into crystalline oxide minerals on the surfaces of primary mineral grains and is less mobile. Results of the study suggest that long-term land use restrictions on sites used for in-situ treatment of arsenic may not be needed to control water applied to surface materials. This minimizes some regulatory concerns about future land use at sites used for in-situ arsenic treatment. However, future land uses that may alter reduction-oxidation conditions in the subsurface should be avoided, such as infiltration of stormwater recharge or recharge with other water having high organic carbon concentrations (including unsewered residential land use, dairy or other confined animal operations).

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Evaluation of perchlorate sources in the Rialto-Colton and Chino California subbasins using chlorine and oxygen isotope ratio analysis

Perchlorate (ClO4-) in groundwater can be from synthetic or natural sources, the latter of which include both historical application of imported nitrate fertilizers from the Atacama Desert of Chile and naturally deposited ClO4- that forms atmospherically and accumulates in arid regions such as the southwestern US. The objective of this study was to evaluate the use of isotopic data to distinguish sources of ClO4- in groundwater in a specific region of the Rialto-Colton and Chino, CA groundwater subbasins (Study Area). This region includes two groundwater ClO4- plumes emanating from known military/industrial source areas, and a larger area outside of these plumes having measurable ClO4-. Perchlorate extracted from wells in this region was analyzed for chlorine and oxygen stable isotope ratios (δ37Cl, δ18O, δ17O) and radioactive chlorine-36 (36Cl) isotopic abundance, along with other geochemical, isotopic, and hydrogeologic data. Isotope data indicate synthetic, Atacama, and indigenous natural ClO4- were present in the Study Area. Stable isotope data from nearly all sampled wells within the contours of the two characterized plumes, including those located in a perched zone and within the regional groundwater aquifer, were consistent with a dominant synthetic ClO4- source. In wells downgradient from the synthetic plumes and in the Chino subbasin to the southwest, isotopic data indicate the dominant source of ClO4- largely was Atacama, presumably from historical application of nitrate fertilizer in this region. Past agricultural land use and historical records are consistent with this source being present in groundwater. The 36Cl and δ18O data indicate that wells having predominantly synthetic or Atacama ClO4- also commonly contained small fractions of indigenous natural ClO4-. The indigenous ClO4- was most evident isotopically in wells having the lowest overall ClO4- concentrations (< 1 μg/L), consistent with its occurrence as a low-level background constituent in the region. A small subset of wells outside the contours of the two synthetic plumes, including an upgradient well, had characteristics indicating small amounts of synthetic ClO4- mixed with one or both of the natural source types. Hydrogeologic data indicate synthetic ClO4- in the upgradient well may be from a source other than the identified plume sources, but it is not known whether this source might also be present in other wells at low concentrations. The stable isotope and 36Cl data provided relatively unambiguous discrimination of synthetic and Atacama ClO4- sources in most wells having relatively high concentrations, providing regional perspective on anthropogenic ClO4- contamination in the Rialto-Colton and Chino subbasins. Where indigenous natural ClO4- was indicated as a substantial component, total ClO4- concentrations were low and concentrations of anthropogenic components were near background levels.

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Groundwater movement, recharge, and perchlorate occurrence in a faulted alluvial aquifer in California (USA)

Perchlorate from military, industrial, and legacy agricultural sources is present within an alluvial aquifer in the Rialto-Colton groundwater subbasin, 80 km east of Los Angeles, California (USA). The area is extensively faulted, with water-level differences exceeding 60 m across parts of the Rialto-Colton Fault separating the Rialto-Colton and Chino groundwater subbasins. Coupled well-bore flow and depth-dependent water-quality data show decreases in well yield and changes in water chemistry and isotopic composition, reflecting changing aquifer properties and groundwater recharge sources with depth. Perchlorate movement through some wells under unpumped conditions from shallower to deeper layers underlying mapped plumes was as high as 13 kg/year. Water-level maps suggest potential groundwater movement across the Rialto-Colton Fault through an overlying perched aquifer. Upward flow through a well in the Chino subbasin near the Rialto-Colton Fault suggests potential groundwater movement across the fault through permeable layers within partly consolidated deposits at depth. Although potentially important locally, movement of groundwater from the Rialto-Colton subbasin has not resulted in widespread occurrence of perchlorate within the Chino subbasin. Nitrate and perchlorate concentrations at the water table, associated with legacy agricultural fertilizer use, may be underestimated by data from long-screened wells that mix water from different depths within the aquifer.

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Fate of nutrients in shallow groundwater receiving treated septage, Malibu, CA

Treated wastewater discharged from more than 400 onsite wastewater treatment systems (OWTS) near the Civic Center area of Malibu, California, 40 km west of downtown Los Angeles, composes 28% of the recharge to a 3.4 km 2 alluvial aquifer. On the basis of &delta; 18 O and &delta;D data, the fraction of wastewater in some samples was >70%. Ammonium and nitrate concentrations in water from 15 water-table wells sampled in July 2009 and April 2010 ranged from <0.01 to 12 milligrams per liter as nitrogen (mg/L as N), and from <0.01 to 11 mg/L as N, respectively. Chemical and isotopic data (&delta; 15 N of ammonium and nitrate, and &delta; 18 O of nitrate) show two processes remove nitrogen discharged from OWTS. Where groundwater was reducing, sorption of ammonium resulted in 30 to 50% nitrogen removal. Where groundwater was initially oxic, nitrification with subsequent denitrification as reducing conditions developed, resulted in up to 60% nitrogen removal. Nitrogen removal through sorption dominated during the cooler April sample period, and denitrification dominated during the warmer July sample period. The combination of mixing and nitrogen removal due to denitrification, sorption, and volatilization produces a &delta; 15 N apparent fractionation factor (&epsilon; app = -5), that can be explained using laboratory-derived fractionation factors (&epsilon;) for the individual processes. Phosphate concentrations ranged from <0.04 to 2 mg/L as phosphorous. Sorption to iron oxides on the surfaces of mineral grains at near-neutral pH's removed some phosphate; however, little removal occurred at more alkaline pH's (>7.3).

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Alpha-emitting isotopes and chromium in a coastal California aquifer

The unadjusted 72-h gross alpha activities in water from two wells completed in marine and alluvial deposits in a coastal southern California aquifer 40 km north of San Diego were 15 and 25 picoCuries per liter (pCi/L). Although activities were below the Maximum Contaminant Level (MCL) of 15 pCi/L, when adjusted for uranium activity; there is concern that new wells in the area may exceed MCLs, or that future regulations may limit water use from the wells. Coupled well-bore flow and depth-dependent water-quality data collected from the wells in 2011 (with analyses for isotopes within the uranium, actinium, and thorium decay-chains) show gross alpha activity in marine deposits is associated with decay of naturally-occurring 238 U and its daughter 234 U. Radon activities in marine deposits were as high as 2230 pCi/L. In contrast, gross alpha activities in overlying alluvium within the Piedra de Lumbre watershed, eroded from the nearby San Onofre Hills, were associated with decay of 232 Th, including its daughter 224 Ra. Radon activities in alluvium from Piedra de Lumbre of 450 pCi/L were lower than in marine deposits. Chromium VI concentrations in marine deposits were less than the California MCL of 10 &mu;g/L (effective July 1, 2014) but &delta; 53 Cr compositions were near zero and within reported ranges for anthropogenic chromium. Alluvial deposits from the nearby Las Flores watershed, which drains a larger area having diverse geology, has low alpha activities and chromium as a result of geologic and geochemical conditions and may be more promising for future water-supply development.

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The effects of artificial recharge on groundwater levels and water quality in the west hydrogeologic unit of the Warren subbasin, San Bernardino County, California

Between the late 1940s and 1994, groundwater levels in the Warren subbasin, California, declined by as much as 300 feet because pumping exceeded sparse natural recharge. In response, the local water district, Hi-Desert Water District, implemented an artificial-recharge program in early 1995 using imported water from the California State Water Project. Subsequently, the water table rose by as much as 250 feet; however, a study done by the U.S. Geological Survey found that the rising water table entrained high-nitrate septic effluent, which caused nitrate (as nitrogen) concentrations in some wells to increase to more than the U.S. Environmental Protection Agency maximum contaminant level of 10 milligrams per liter.. A new artificial-recharge site (site 3) was constructed in 2006 and this study, which started in 2004, was done to address concerns about the possible migration of nitrates in the unsaturated zone. The objectives of this study were to: (1) characterize the hydraulic, chemical, and microbiological properties of the unsaturated zone; (2) monitor changes in water levels and water quality in response to the artificial-recharge program at site 3; (3) determine if nitrates from septic effluent infiltrated through the unsaturated zone to the water table; (4) determine the potential for nitrates within the unsaturated zone to mobilize and contaminate the groundwater as the water table rises in response to artificial recharge; and (5) determine the presence and amount of dissolved organic carbon because of its potential to react with disinfection byproducts during the treatment of water for public use. Two monitoring sites were installed and instrumented with heat-dissipation probes, advanced tensiometers, suction-cup lysimeters, and wells so that the arrival and effects of recharging water from the State Water Project through the 250 to 425 foot-thick unsaturated zone and groundwater system could be closely observed. Monitoring site YVUZ-1 was located between two recharge ponds in the middle of site 3, and YVUZ-2 was located approximately 1,200 feet down-gradient and to the southeast in an area where septic systems have been in use since about 1960. Site YVUZ-3 only went to a depth of 42 feet and was used to sample the upper part of the unsaturated zone near a golf course. Prior to the start of artificial recharge at site 3, nitrate concentrations reported as nitrogen from the soil leachate below YVUZ-1 did not exceed 1.58 milligrams per kilogram. Nitrate-reducing bacteria concentrations of 4,300 most probable number were found at about 220 feet below land surface and at the top of the water table at YVUZ-1. Nitrate concentrations at YVUZ-2 reached a maximum concentration of about 25 milligrams per kilogram between about 100 and 121 feet below land surface; concentrations of nitrate-reducing or denitrifying bacteria were as high as 21,000 most probable number at 36 feet below land surface but did not exceed 40 most probable number below about 150 feet below land surface. Between June 2006 and September 2009, more than 9,800 acre feet of water from the State Water Project was released to site 3 ponds. The infiltration of the recharge water was predominantly vertical with limited lateral spreading to a depth of about 200 feet below land surface at YVUZ-1. Lateral spreading of the recharge water with depth was caused by geologic heterogeneities within the unsaturated zone, and resulted in varied arrival times of the recharge water to the instruments and slower rates of vertical movement with depth. No abrupt changes in soil moisture were observed at YVUZ-2, indicating that the recharge water had not reached that site by September 2009. Water levels from the monitoring wells at both sites and from five production wells nearby showed that the water table rose at a mean rate of about 0.08 feet per day between June 2006 and January 2009. The arrival of the water from the State Water Project caused relatively rapid changes in the stable-isotopic ratios from the lysimeters at YVUZ-1. The estimated average rate of infiltration of the recharge water through the unsaturated zone ranged from 3.7 to 25 feet per day. The recharge water arrived at the monitoring well below the recharge ponds between August 2007 and March 2008; the rate of vertical movement to the monitoring well was between 0.6 and 0.9 feet per day. By September 2008, a production well located 375 feet west of site 3 was producing almost 100 percent infiltrated recharge water. By contrast, the stable-isotope data from the lysimeters at YVUZ-2 showed that the recharge water had not reached this site by September 2009, but that septic effluent in the unsaturated zone likely had mixed with the native pore water to at least 154 feet below land surface. Assuming vertical infiltration, the minimum rate of infiltration of septic effluent since 1960 was about 3 feet per year. The isotopic data from the lysimeters at YVUZ-3 indicated two different sources of water to the upper 43 feet–irrigation-return flow and precipitation. Nitrate concentrations of the water from the State Water Project did not exceed 1 milligram per liter. Prior to artificial recharge, nitrate concentrations of the pore water at YVUZ-1 ranged between 6 to 18.2 milligrams per liter. After the arrival of the recharge water, the nitrate concentrations from the lysimeters and well at YVUZ-1 decreased to less than 1 milligram per liter, with the exception of samples collected at 205.5 feet, which did not exceed 4.12 milligrams per liter. The decrease in nitrate concentrations after artificial recharge indicated that the rising water table did not result in an increase of nitrates below YVUZ-1. At YVUZ-2, nitrate concentrations ranged between 12 to 479 milligrams per liter. The highest nitrate concentrations were at 92 feet below land surface and were almost seven times that of samples collected from a nearby septic tank. Nitrate concentrations from the lysimeter at 273 feet below land surface increased from 6 to almost 58 milligrams per liter after it was saturated by the rising water table in December 2007. These increases could be the result of the mobilization of high-nitrate water from regional sources of septic effluent after saturation, or the result of high-nitrate water present at the top of the water table that may be diluted deeper in the aquifer. Nitrate concentrations in groundwater from five nearby production wells and from both monitoring wells were less than 5 milligrams per liter before artificial recharge started. Nitrate concentrations decreased to less than 3 milligrams per liter in three of the production wells and the monitoring well below the recharge ponds after artificial recharge. Dissolved organic carbon concentrations were measured in the recharge water and groundwater because of the potential for dissolved organic carbon to react with chlorine to form trihalomethanes during the water-treatment process. The dissolved organic carbon concentrations of the recharge water were 3.1 milligrams per liter or less, and dissolved organic carbon concentrations of the groundwater were less than 1 milligram per liter. Even though recharge water was present in some of the wells by September 2008, the concentrations of both dissolved organic carbon and trihalomethane formation potential in the groundwater did not increase. Interpretation of these data suggests that the dissolved organic carbon from the recharge water is altered or metabolized in the unsaturated zone, either by absorption to the grain particles in the soil or by microbiological processes.

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Electromagnetic-induction logging to monitor changing chloride concentrations

Water from the San Joaquin Delta, having chloride concentrations up to 3590 mg/L, has intruded fresh water aquifers underlying Stockton, California. Changes in chloride concentrations at depth within these aquifers were evaluated using sequential electromagnetic (EM) induction logs collected during 2004 through 2007 at seven multiple-well sites as deep as 268 m. Sequential EM logging is useful for identifying changes in groundwater quality through polyvinyl chloride-cased wells in intervals not screened by wells. These unscreened intervals represent more than 90% of the aquifer at the sites studied. Sequential EM logging suggested degrading groundwater quality in numerous thin intervals, typically between 1 and 7 m in thickness, especially in the northern part of the study area. Some of these intervals were unscreened by wells, and would not have been identified by traditional groundwater sample collection. Sequential logging also identified intervals with improving water quality—possibly due to groundwater management practices that have limited pumping and promoted artificial recharge. EM resistivity was correlated with chloride concentrations in sampled wells and in water from core material. Natural gamma log data were used to account for the effect of aquifer lithology on EM resistivity. Results of this study show that a sequential EM logging is useful for identifying and monitoring the movement of high-chloride water, having lower salinities and chloride concentrations than sea water, in aquifer intervals not screened by wells, and that increases in chloride in water from wells in the area are consistent with high-chloride water originating from the San Joaquin Delta rather than from the underlying saline aquifer.

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Delta Chromium-53/52 isotopic composition of native and contaminated groundwater, Mojave Desert, USA

Chromium(VI) concentrations in groundwater sampled from three contaminant plumes in aquifers in the Mojave Desert near Hinkley, Topock and El Mirage, California, USA, were as high as 2600, 5800 and 330 μg/L, respectively. δ 53/52 Cr compositions from more than 50 samples collected within these plumes ranged from near 0‰ to almost 4‰ near the plume margins. Assuming only reductive fractionation of Cr(VI) to Cr(III) within the plume, apparent fractionation factors for δ 53/52 Cr isotopes ranged from ε app = 0.3 to 0.4 within the Hinkley and Topock plumes, respectively, and only the El Mirage plume had a fractionation factor similar to the laboratory derived value of ε = 3.5. One possible explanation for the difference between field and laboratory fractionation factors at the Hinkley and Topock sites is localized reductive fractionation of Cr(VI) to Cr(III), with subsequent advective mixing of native and contaminated water near the plume margin. Chromium(VI) concentrations and δ 53/52 Cr isotopic compositions did not uniquely define the source of Cr near the plume margin, or the extent of reductive fractionation within the plume. However, Cr(VI) and δ 53/52 Cr data contribute to understanding of the interaction between reductive and mixing processes that occur within and near the margins of Cr contamination plumes. Reductive fractionation of Cr(VI) predominates in plumes having higher ε app , these plumes may be suitable for monitored natural attenuation. In contrast, advective mixing predominates in plumes having lower ε app , the highly dispersed margins of these plumes may be difficult to define and manage.

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