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Groundwater-quality data in the Monterey–Salinas shallow aquifer study unit, 2013: Results from the California GAMA Program

Groundwater quality in the 3,016-square-mile Monterey–Salinas Shallow Aquifer study unit was investigated by the U.S. Geological Survey (USGS) from October 2012 to May 2013 as part of the California State Water Resources Control Board Groundwater Ambient Monitoring and Assessment (GAMA) Program’s Priority Basin Project. The GAMA Monterey–Salinas Shallow Aquifer study was designed to provide a spatially unbiased assessment of untreated-groundwater quality in the shallow-aquifer systems in parts of Monterey and San Luis Obispo Counties and to facilitate statistically consistent comparisons of untreated-groundwater quality throughout California. The shallow-aquifer system in the Monterey–Salinas Shallow Aquifer study unit was defined as those parts of the aquifer system shallower than the perforated depth intervals of public-supply wells, which generally corresponds to the part of the aquifer system used by domestic wells. Groundwater quality in the shallow aquifers can differ from the quality in the deeper water-bearing zones; shallow groundwater can be more vulnerable to surficial contamination. Samples were collected from 170 sites that were selected by using a spatially distributed, randomized grid-based method. The study unit was divided into 4 study areas, each study area was divided into grid cells, and 1 well was sampled in each of the 100 grid cells (grid wells). The grid wells were domestic wells or wells with screen depths similar to those in nearby domestic wells. A greater spatial density of data was achieved in 2 of the study areas by dividing grid cells in those study areas into subcells, and in 70 subcells, samples were collected from exterior faucets at sites where there were domestic wells or wells with screen depths similar to those in nearby domestic wells (shallow-well tap sites). Field water-quality indicators (dissolved oxygen, water temperature, pH, and specific conductance) were measured, and samples for analysis of inorganic constituents (trace elements, nutrients, major and minor ions, silica, total dissolved solids, and alkalinity) were collected at all 170 sites. In addition to these constituents, the samples from grid wells were analyzed for organic constituents (volatile organic compounds, pesticides and pesticide degradates), constituents of special interest (perchlorate and N -nitrosodimethylamine, or NDMA), radioactive constituents (radon-222 and gross-alpha and gross-beta radioactivity), and geochemical and age-dating tracers (stable isotopes of carbon in dissolved inorganic carbon, carbon-14 abundances, stable isotopes of hydrogen and oxygen in water, and tritium activities). Three types of quality-control samples (blanks, replicates, and matrix spikes) were collected at up to 11 percent of the wells in the Monterey–Salinas Shallow Aquifer study unit, and the results for these samples were used to evaluate the quality of the data from the groundwater samples. With the exception of trace elements, blanks rarely contained detectable concentrations of any constituent, indicating that contamination from sample-collection procedures was not a significant source of bias in the data for the groundwater samples. Low concentrations of some trace elements were detected in blanks; therefore, the data were re-censored at higher reporting levels. Replicate samples generally were within the limits of acceptable analytical reproducibility. The median values of matrix-spike recoveries were within the acceptable range (70 to 130 percent) for the volatile organic compounds (VOCs) and N -nitrosodimethylamine (NDMA), but were only approximately 64 percent for pesticides and pesticide degradates. The sample-collection protocols used in this study were designed to obtain representative samples of groundwater. The quality of groundwater can differ from the quality of drinking water because water chemistry can change as a result of contact with plumbing systems or the atmosphere; because of treatment, disinfection, or blending with water from other sources; or some combination of these. Water quality in domestic wells is not regulated in California, however, to provide context for the water-quality data presented in this report, results were compared to benchmarks established for drinking-water quality. The primary comparison benchmarks were maximum contaminant levels established by the U.S. Environmental Protection Agency and the State of California (MCL-US and MCL-CA, respectively). Non-regulatory benchmarks were used for constituents without maximum contaminant levels (MCLs), including Health Based Screening Levels (HBSLs) developed by the USGS and State of California secondary maximum contaminant levels (SMCL-CA) and notification levels. Most constituents detected in samples from the Monterey–Salinas Shallow Aquifer study unit had concentrations less than their respective benchmarks. Of the 148 organic constituents analyzed in the 100 grid-well samples, 38 were detected, and all concentrations were less than the benchmarks. Volatile organic compounds were detected in 26 of the grid wells, and pesticides and pesticide degradates were detected in 28 grid wells. The special-interest constituent NDMA was detected above the HBSL in three samples, one of which also had a perchlorate concentration greater than the MCL-CA. Of the inorganic constituents, 6 were detected at concentrations above their respective MCL benchmarks in grid-well samples: arsenic (5 grid wells above the MCL of 10 micrograms per liter, μg/L), selenium (3 grid wells, MCL of 50 μg/L), uranium (4 grid wells, MCL of 30 μg/L), nitrate (16 grid wells, MCL of 10 milligrams per liter, mg/L), adjusted gross alpha particle activity (10 grid wells, MCL of 15 picocuries per liter, pCi/L), and gross beta particle activity (1 grid well, MCL of 50 pCi/L). An additional 4 inorganic constituents were detected at concentrations above their respective HBSL benchmarks in grid-well samples: boron (1 grid well above the HBSL of 6,000 μg/L), manganese (8 grid wells, HBSL of 300 μg/L), molybdenum (6 grid wells, HBSL of 40 μg/L), and strontium (6 grid wells, HBSL of 4,000 μg/L). Of the inorganic constituents, 4 were detected at concentrations above their non-health based SMCL benchmarks in grid-well samples: iron (9 grid wells above the SMCL of 300 μg/L), chloride (7 grid wells, SMCL of 500 mg/L), sulfate (14 grid wells, SMCL of 500 mg/L), and total dissolved solids (27 grid wells, SMCL of 1,000 mg/L). Of the inorganic constituents analyzed in the 70 shallow-well tap sites, 10 were detected at concentrations above the benchmarks. Of the inorganic constituents, 3 were detected at concentrations above their respective MCL benchmarks in shallow-well tap sites: arsenic (2 shallow-well tap sites above the MCL of 10 μg/L), uranium (2 shallow-well tap sites, MCL of 30 μg/L), and nitrate (24 shallow-well tap sites, MCL of 10 mg/L). An additional 3 inorganic constituents were detected above their respective HBSL benchmarks in shallow-well tap sites: manganese (4 shallow-well tap sites above the HBSL of 300 μg/L), molybdenum (4 shallow-well tap sites, HBSL of 40 μg/L), and zinc (2 shallow-well tap sites, HBSL of 2,000 μg/L). Of the inorganic constituents, 4 were detected at concentrations above their non-health based SMCL benchmarks in shallow-well tap sites: iron (6 shallow-well tap sites above the SMCL of 300 μg/L), chloride (1 shallow-well tap site, SMCL of 500 mg/L), sulfate (9 shallow-well tap sites, SMCL of 500 mg/L), and total dissolved solids (15 shallow-well tap sites, SMCL of 1,000 mg/L).

California↗

Survival of spotted salamander eggs in temporary woodland ponds of coastal Maryland

Temporary ponds on the Atlantic Coastal Plain in maryland were characterized according to water chemistry, rain input, phytoplankton, zooplankton and use by the spotted salamander Ambystoma maculatum during March-October 1983-1984. Neither the number of egg masses per unit of pond surface (abundance) nor the survival of spotted salamander embryos was significantly correlated (P>0.05) with pond pH. Rainfall during May-July significantly increased the hydrogen ion concentration of 5 of 11 ponds evaluated for the impact of rainfall during the previous 48h and the previous week. Survival of egg masses transferred among eight ponds with pH3.66-4.45 and one pond with pH5.18 was significantly reduced (P<or=0.05) only at pH 3.66. Embryonic survival was negatively correlated (P<or=0.05) with the concentration of aluminium in the pond water. The abundance of egg masses was positively correlated (P<or=0.05) with water temperature and magnesium concentration, and total chlorophyll during the larval period. Yearly variability of pond characteristics (e.g. water chemistry, pond longevity) and amphibian reproduction make it difficult to determine the effects of acidic deposition on the spotted salamander. At the present time, pond longevity, water temperature and possibly, oxygen content, seem more important to spotted salamander reproduction than chemical changes caused by annual acidic deposition.

Environmental Pollution↗

Quality of water and chemistry of bottom sediment in the Rillito Creek basin, Tucson, Arizona, 1992-93

Physical and chemical data were collected from four surface-water sites, six ground-water sites, and two bottom-sediment sites during 1992-93. Specific conductance, hardness, alkalinity, and dissolved- solids concentrations generally were higher in ground water than in surface water. The median concentrations of dissolved major ions, with the exception of potassium, were higher in ground water than in surface water. In surface water and ground water, calcium was the dominant cation, and bicarbonate was the dominant anion. Concentrations of dissolved nitrite and nitrite plus nitrate in surface water and ground water did not exceed the U.S. Environmental Protection Agency maximum contaminant levels of 1 and 10 milligrams per liter for drinking water, respectively. Ammonium plus organic nitrogen in bottom sediment was detected at the highest concentration of any nitrogen species. Median values for most of the dissolved trace elements in surface water and ground water were below the detection levels. Dissolved trace elements in surface water and ground water did not exceed the U.S. Environmental Protection Agency maximum contaminant levels for drinking water. Trace-element concentrations in bottom sediment were similar to trace-element concentrations reported for soils of the western conterminous United States. Several organochlorine pesticides and priority pollutants were detected in surface-water and bottom-sediment samples; however, they did not exceed water-quality standards. Pesticides or priority pollutants were not detected in ground-water samples.

Water-Resources Investigations Report↗

Quality of water in the Trinity and Edwards aquifers, south-central Texas, 1996-98

During 1996–98, the U.S. Geological Survey studied surface- and ground-water quality in south-central Texas. The ground-water components included the upper and middle zones (undifferentiated) of the Trinity aquifer in the Hill Country and the unconfined part (recharge zone) and confined part (artesian zone) of the Edwards aquifer in the Balcones fault zone of the San Antonio region. The study was supplemented by information compiled from four ground-water-quality studies done during 1996–98. Trinity aquifer waters are more mineralized and contain larger dissolved solids, sulfate, and chloride concentrations compared to Edwards aquifer waters. Greater variability in water chemistry in the Trinity aquifer likely reflects the more variable lithology of the host rock. Trace elements were widely detected, mostly at small concentrations. Median total nitrogen was larger in the Edwards aquifer than in the Trinity aquifer. Ammonia nitrogen was detected more frequently and at larger concentrations in the Trinity aquifer than in the Edwards aquifer. Although some nitrate nitrogen concentrations in the Edwards aquifer exceeded a U.S. Geological Survey national background threshold concentration, no concentrations exceeded the U.S. Environmental Protection Agency public drinking-water standard. Synthetic organic compounds, such as pesticides and volatile organic compounds, were detected in the Edwards aquifer and less frequently in the Trinity aquifer, mostly at very small concentrations (less than 1 microgram per liter). These compounds were detected most frequently in urban unconfined Edwards aquifer samples. Atrazine and its breakdown product deethylatrazine were the most frequently detected pesticides, and trihalomethanes were the most frequently detected volatile organic compounds. Widespread detections of these compounds, although at small concentrations, indicate that anthropogenic activities affect ground-water quality. Radon gas was detected throughout the Trinity aquifer but not throughout the Edwards aquifer. Fourteen samples from the Trinity aquifer and 10 samples from the Edwards aquifer exceeded a proposed U.S. Environmental Protection Agency public drinking-water standard. Sources of radon in the study area might be granitic sediments underlying the Trinity aquifer and igneous intrusions in and below the Edwards aquifer. The presence of tritium in nearly all Edwards aquifer samples indicates that some component of sampled water is young (less than about 50 years), even for long flow paths in the confined zone. About one-half of the Trinity aquifer samples contained tritium, indicating that only part of the aquifer contains young water. Hydrogen and oxygen isotopes of water provide indicators of recharge sources to the Trinity and Edwards aquifers. Most ground-water samples have a meteorological isotopic signature indicating recharge as direct infiltration of water with little residence time on the land surface. Isotopic data from some samples collected from the unconfined Edwards aquifer indicate the water has undergone evaporation. At the time that ground-water samples were collected (during a drought), nearby streams were the likely sources of recharge to these wells.

Texas↗

Developing analytical approaches to explore the connection between endocrine-active pharmaceuticals in water to effects in fish

The emphasis of this research project was to develop and optimize a solid-phase extraction method and highperformance liquid chromatography-electrospray ionizationmass spectrometry method, such that a linkage between the detection of endocrine-active pharmaceuticals (EAPs) in the aquatic environment and subsequent effects on fish populations could eventually be studied. Four EAPs were studied: tamoxifen (TAM), exemestane (EXE), letrozole (LET), anastrozole (ANA); and three TAM metabolites: 4- hydroxytamoxifen, e/z endoxifen, and n-desmethyl tamoxifen. In aqueous matrices, the use of isotopically labeled standards for the EAPs allowed for the generation of good recoveries, greater than 80 %, and low relative standard deviations (% RSDs) (3 to 27 %). TAM metabolites had lower recoveries in the spiked water matrices: 35 to 93 % in waste/source water compared to 58 to 110 % in DI water. The precision in DI water was acceptable ranging from 8 to 38 % RSD. However, the precision in real environmental wastewaters could be poor, ranging from 15 to 120 % RSD, dependent upon unique matrix effects. In plasma, the overall recoveries of the EAPs were acceptable: 88 to 110 %, with %RSDs of 6 to 18 % (Table 3). The spiked recoveries of the TAM metabolites from plasma were good, ranging from 77 to 120 %, with %RSDs ranging from 27 to 32 %. Two of the TAM metabolites, 4- hydroxytamoxifen and n-desmethyl tamoxifen, were confirmed in most of the environmental aqueous samples. The discovery of TAM metabolites demonstrates that the source of the TAM metabolites, TAM, is constant, introducing a pseudo-persistence of this chemical into the environment.

Analytical and Bioanalytical Chemistry↗

Fluid geochemistry of Yucca Mountain and vicinity

Yucca Mountain, a site in southwest Nevada, has been proposed for a deep underground radioactive waste repository. An extensive database of geochemical and isotopic characteristics has been established for pore waters and gases from the unsaturated zone, perched water, and saturated zone waters in the Yucca Mountain area. The development of this database has been driven by diverse needs of the Yucca Mountain Project, especially those aspects of the project involving process modeling and performance assessment. Water and gas chemistries influence the sorption behavior of radionuclides and the solubility of the radionuclide compounds that form. The chemistry of waters that may infiltrate the proposed repository will be determined in part by that of water present in the unsaturated zone above the proposed repository horizon, whereas pore-water compositions beneath the repository horizon will influence the sorption behavior of the radionuclides transported toward the water table. However, more relevant to the discussion in this chapter, development and testing of conceptual flow and transport models for the Yucca Mountain hydrologic system are strengthened through the incorporation of natural environmental tracer data into the process. Chemical and isotopic data are used to establish bounds on key hydrologic parameters and to provide corroborative evidence for model assumptions and predictions. Examples of specific issues addressed by these data include spatial and temporal variability in net fluxes, the role of faults in controlling flow paths, fracture-matrix interactions, the age and origin of perched water, and the distribution of water traveltimes.

Nevada↗

Groundwater quality and occurrence and distribution of selected constituents in the Aquia and Upper Patapsco aquifers, Naval Air Station Patuxent River, St. Mary's County, Maryland, July 2008

The Naval Air Station Patuxent River in southern Maryland has continued to expand in the first decade of the 21st century, contributing to rapid population growth in the surrounding area. The increase in population has caused State and County water managers and others to be concerned about the impact of population growth on the quantity and quality of groundwater supplies. The U.S. Geological Survey has been investigating the groundwater resources of the air station since 1998. As part of that ongoing investigation, groundwater was sampled in 2008 in six wells in the Aquia aquifer and two wells in the Upper Patapsco aquifer in the vicinity of Naval Air Station Patuxent River and Webster Outlying Field. Groundwater samples were analyzed for basic chemistry (field parameters, major ions, and nutrients) as well as several water-quality issues of concern including the occurrence of arsenic and tungsten, and saltwater intrusion. The results of the 2008 groundwater-quality sampling indicate that the overall quality of groundwater in the Aquia aquifer has not changed since 1943; data are too limited to determine if groundwater quality has changed in the Upper Patapsco aquifer. At one well in the Aquia aquifer, the arsenic concentration exceeded the U.S. Environmental Protection Agency standard for drinking water. Arsenic was not detected in samples from the Upper Patapsco aquifer. Tungsten concentrations were detected at low concentrations near the laboratory reporting level in all eight samples. There was no evidence of saltwater intrusion in any of the wells.

Maryl↗

Chemical and physical controls on mercury source signatures in stream fish from the northeastern United States

Streams in the northeastern U.S. receive mercury (Hg) in varying proportions from atmospheric deposition and legacy point sources, making it difficult to attribute shifts in fish concentrations directly back to changes in Hg source management. Mercury stable isotope tracers were utilized to relate sources of Hg to co-located fish and bed sediments from 23 streams across a forested to urban-industrial land-use gradient within this region. Mass-dependent isotopes (δ202Hg) in prey and game fish at forested sites were depleted (medians -0.95 and -0.83 ‰, respectively) in comparison to fish from urban-industrial settings (medians -0.26 and -0.38 ‰, respectively); the forested site group also had higher prey fish Hg concentrations. The separation of Hg isotope signatures in fish was strongly related to in-stream and watershed land-use indicator variables. Fish isotopes were strongly correlated with bed sediment isotopes, but the comparison of isotopic composition between fish and sediment was variable due to differing ecosystem-specific drivers controlling the extent of MeHg formation. The multivariable approach of analyzing watershed characteristics and stream chemistry reveals that the Hg isotope composition in fish is linked to current and historic Hg sources in the northeastern U.S. and can be used to trace bioaccumulated Hg.

Environmental Science & Technology↗

Development of high surface area organosilicate nanoparticulate thin films for use in sensing hydrophobic compounds in sediment and water

The scope of this study was to apply advances in materials science, specifically the use of organosilicate nanoparticles as a high surface area platform for passive sampling of chemicals or pre-concentration for active sensing in multiple-phase complex environmental media. We have developed a novel nanoporous organosilicate (NPO) film as an extraction phase and proof of concept for application in adsorbing hydrophobic compounds in water and sediment. We characterized the NPO film properties and provided optimization for synthesis and coatings in order to apply the technology in environmental media. NPO films in this study had a very high surface area, up to 1325 m 2 /g due to the high level of mesoporosity in the film. The potential application of the NPO film as a sorbent phase for sensors or passive samplers was evaluated using a model hydrophobic chemical, polychlorinated biphenyls (PCB), in water and sediment. Sorption of PCB to this porous high surface area nanoparticle platform was highly correlated with the bioavailable fraction of PCB measured using whole sediment chemistry, porewater chemistry determined by solid-phase microextraction fiber methods, and the Lumbriculus variegatus bioaccumulation bioassay. The surface-modified NPO films in this study were found to highly sorb chemicals with a log octanol-water partition coefficient (K ow ) greater than four; however, surface modification of these particles would be required for application to other chemicals.

Biosensors↗

The role of hydrates, competing chemical constituents, and surface composition on CLNO2 formation

Atomic chlorine (Cl • ) affects air quality and atmospheric oxidizing capacity. Nitryl chloride (ClNO 2 ) – a common Cl • source–forms when chloride-containing aerosols react with dinitrogen pentoxide (N 2 O 5 ). A recent study showed that saline lakebed (playa) dust is an inland source of particulate chloride (Cl – ) that generates high ClNO 2 . However, the underlying physiochemical factors responsible for observed yields are poorly understood. To elucidate these controlling factors, we utilized single particle and bulk techniques to determine the chemical composition and mineralogy of playa sediment and dust samples from the southwest United States. Single particle analysis shows trace highly hygroscopic magnesium and calcium Cl-containing minerals are present and likely facilitate ClNO 2 formation at low humidity. Single particle and mineralogical analysis detected playa sediment organic matter that hinders N 2 O 5 uptake as well as 10 Å-clay minerals (e.g., Illite) that compete with water and chloride for N 2 O 5 . Finally, we show that the composition of the aerosol surface, rather than the bulk, is critical in ClNO 2 formation. These findings underscore the importance of mixing state, competing reactions, and surface chemistry on N 2 O 5 uptake and ClNO 2 yield for playa dusts and, likely, other aerosol systems. Therefore, consideration of particle surface composition is necessary to improve ClNO 2 and air quality modeling.

Environmental Science Technology↗

Sources and sinks of nitrogen and phosphorus to a deep, oligotrophic lake, Lake Crescent, Olympic National Park, Washington

Lake Crescent, in Olympic National Park in the northwest corner of Washington State is a deep-water lake renowned for its pristine water quality and oligotrophic nature. To examine the major sources and sinks of nutrients (as total nitrogen, total phosphorus, and dissolved nitrate), a study was conducted in the Lake Crescent watershed. The study involved measuring five major inflow streams, the Lyre River as the major outflow, recording weather and climatic data, coring lake bed sediment, and analyzing nutrient chemistry in several relevant media over 14 months. Water samples for total nitrogen, total phosphorous, and dissolved nitrate from the five inflow streams, the outlet Lyre River, and two stations in the lake were collected monthly from May 2006 through May 2007. Periodic samples of shallow water from temporary sampling wells were collected at numerous locations around the lake. Concentrations of nutrients detected in Lake Crescent and tributaries were then applied to the water budget estimates to arrive at monthly and annual loads from various environmental components within the watershed. Other sources, such as leaf litter, pollen, or automobile exhaust were estimated from annual values obtained from various literature sources. This information then was used to construct a nutrient budget for total nitrogen and total phosphorus. The nitrogen budget generally highlights vehicle traffic-diesel trucks in particular-along U.S. Highway 101 as a potential major anthropogenic source of nitrogen compounds in the lake. In contrast, contribution of nitrogen compounds from onsite septic systems appears to be relatively minor related to the other sources identified.

Washington↗

A ground electromagnetic survey used to map sulfides and acid sulfate ground waters at the abandoned Cabin Branch Mine, Prince William Forest Park, northern Virginia gold-pyrite belt

INTRODUCTION AND BACKGROUND: Prince William Forest Park is situated at the northeastern end of the Virginia Gold-Pyrite belt northwest of the town of Dumfries, VA. The U. S. Marine Corps Reservation at Quantico borders the park on the west and south, and occupies part of the same watershed. Two abandoned mines are found within the park: the Cabin Branch pyrite mine, a historic source of acid mine drainage, and the Greenwood gold mine, a source of mercury contamination. Both are within the watershed of Quantico Creek (Fig.1). The Cabin Branch mine (also known as the Dumfries mine) lies about 2.4 km northwest of the town of Dumfries. It exploited a 300 meter-long, lens-shaped body of massive sulfide ore hosted by metamorphosed volcanic rocks; during its history over 200,000 tons of ore were extracted and processed locally. The site became part of the National Capitol Region of the National Park Service in 1940 and is currently managed by the National Park Service. In 1995 the National Park Service, in cooperation with the Virginia Department of Mines, Minerals, and Energy reclaimed the Cabin Branch site. The Virginia Gold-Pyrite belt, also known as the central Virginia volcanic-plutonic belt, is host to numerous abandoned metal mines (Pavlides and others, 1982), including the Cabin Branch deposit. The belt itself extends from its northern terminus near Cabin Branch, about 50 km south of Washington, D.C., approximately 175 km to the southwest into central Virginia. It is underlain by metamorphosed volcanic and clastic (non-carbonate) sedimentary rocks, originally deposited approximately 460 million years ago during the Ordovician Period (Horton and others, 1998). Three kinds of deposits are found in the belt: volcanic-associated massive sulfide deposits, low-sulfide quartz-gold vein deposits, and gold placer deposits. The massive sulfide deposits such as Cabin Branch were historically mined for their sulfur, copper, zinc, and lead contents, but also yielded byproduct gold and silver. The environmental impact of massive sulfide deposits can be substantial. These deposits are characterized by high concentrations of heavy-metal sulfide minerals, hosted by silicate rocks. Thus, weathering of these deposits and their mine wastes has the potential to generate heavy-metal laden sulfuric acid that can have negative impacts on aquatic ecosystems. In addition, lead associated with solid mine wastes has the potential for human health impacts through ingestion. The heavy metals that are encountered in these deposits and are most likely to cause environmental impacts include copper, zinc, lead, cadmium, and arsenic. In addition, the weathering of pyrite releases large amounts of iron, and the acid generated attacks the country rocks and causes the release of large amounts of aluminum, which also can severely impact aquatic ecosystems. A reclamation attempt was made at the site in 1995, including construction of storm-water diversion trenches around the abandoned mine area, grading tailings away from the stream bank, addition of pulverized limestone and topsoil, and revegetation. The post-reclamation chemistry of shallow groundwaters (<3 meters deep) shows a neutral pH on the southwestern bank of the stream but pH of 4.1 to 4.5 on the northeastern bank. The dominant ions are Fe2+ and SO42- (Seal, Haffner, Meier, and Pollio, 1999) A ground electromagnetic survey was conducted over the site in 1999 as part of a wider study ( Seal, Haffner, and Meier, 1998a,b, 1999). It was hoped that a 3-D map of the soil conductivity derived from the survey could provide insight into the distribution of the mobilized sulfides present under the ground.

Virginia↗

Geochemical characterization and modeling of regional groundwater contributing to the Verde River, Arizona between Mormon Pocket and the USGS Clarkdale gage

We use synoptic surveys of stream discharge, stable isotopes, and dissolved noble gases to identify the source of groundwater discharge to the Verde River in central Arizona. The Verde River more than doubles in discharge in Mormon Pocket over a 1.4 km distance that includes three discrete locations of visible spring input to the river and other diffuse groundwater inputs. A detailed study of the Verde River between Mormon Pocket and the USGS Clarkdale Gage was conducted to better constrain the location of groundwater inputs, the geochemical signature and constrain the source of groundwater input. Discharge, water quality parameters (temperature, pH, specific conductance, and dissolved oxygen), stable isotopes (δ18O and δ2H), noble gases (He, Ne, Ar, Kr and Xe), and radon (222Rn) from river water were collected. Groundwater samples from springs and wells in the area were collected and analyzed for tracers measured in the stream along with some additional analytes (major ions, strontium isotopes (87Sr/86Sr), carbon-14, δ13C, and tritium). Groundwater isotopic signature is consistent with a regional groundwater source. Groundwater springs discharging to the river have a depleted stable isotopic signature indicating recharge source up to 1000 m higher than the discharge location in the Verde River and are significantly fresher than stream water. Spring water has a radiocarbon age of several thousand years and some areas have tritium less than the laboratory reporting level or low concentrations of tritium (1.5 TU). The strontium isotopes indicate groundwater interaction with tertiary volcanic rock and Paleozoic sedimentary rocks. Along the study reach with distance downstream, Verde stream water chemistry shows increased 222Rn, freshening, increased 4He, and isotopic depletion with distance downstream. We estimated total groundwater discharge by inverting a stream transport model against 222Rn and discharge measured in the stream. The salinity, 4He, and stable isotope composition of discharging groundwater was then estimated by fitting modeled values to observed in-stream values. Estimated groundwater inflow to the stream was well within the ranges observed in springs, indicating that the main source of streamflow is deep, regional groundwater. These results show that synoptic surveys of environmental tracers in streams can be used to estimate the isotopic composition and constrain the source of groundwater discharging to streams. Our data provide direct field evidence that deep, regional groundwater discharge can be a significant source of streamflow generation in arid, topographically complex watersheds.

Arizona↗

Occurrence of Uranium and 222Radon in Glacial and Bedrock Aquifers in the Northern United States, 1993-2003

Water-quality data collected from 1,426 wells during 1993-2003 as part of the U.S. Geological Survey National Water-Quality Assessment (NAWQA) program were evaluated to characterize the water quality in glacial and bedrock aquifers of the northern United States. One of the goals of the NAWQA program is to synthesize data from individual studies across the United States to gain regional- and national-scale information about the behavior of contaminants. This study focused on the regional occurrence and distribution of uranium and 222radon in ground water in the glacial aquifer system of the United States as well as in the Cambrian-Ordovician and the New York and New England crystalline aquifer systems that underlie the glacial aquifer system. The occurrence of uranium and 222radon in ground water has long been a concern throughout the United States. In the glacial aquifers, as well as the Cambrian-Ordovician and the New York and New England crystalline aquifer systems of the United States, concentrations of uranium and 222radon were highly variable. High concentrations of uranium and 222radon affect ground water used for drinking water and for agriculture. A combination of information or data on (1) national-scale ground-water regions, (2) regional-scale glacial depositional models, (3) regional-scale geology, and (4) national-scale terrestrial gamma-ray emissions were used to confirm and(or) refine the regions used in the analysis of the water-chemistry data. Significant differences in the occurrence of uranium and 222radon, based primarily on geologic information were observed and used in this report. In general, uranium was highest in the Columbia Plateau glacial, West-Central glacial, and the New York and New England crystalline aquifer groups (75th percentile concentrations of 22.3, 7.7, and 2.9 micrograms per liter (ug/L), respectively). In the Columbia Plateau glacial and the West-Central glacial aquifer groups, more than 10 percent of wells sampled had concentrations of uranium that exceeded the U.S. Environmental Protection Agency (USEPA) Maximum Contaminant Level of 30 ug/L; in the New York and New England crystalline aquifer group, 4 percent exceeded 30 ug/L. Ground-water samples with high concentrations of uranium were commonly linked to geologic sources rich in uranium. In eight of nine aquifer groups defined for this study, concentrations of uranium correlated significantly with concentrations of sulfate in ground water (Spearman's rho = 0.20 to 0.56; p < 0.05). In the Columbia Plateau, glacial aquifers were derived in part from basaltic lava flows, some felsic volcanic rocks, and some paleo-lake bed materials that may be rich in uranium. In the Columbia Plateau and West-Central glacial aquifer groups, uranium correlated with total dissolved solids, bicarbonate, boron, lithium, selenium, and strontium. In the West-Central glacial aquifer group, rocks such as Cretaceous marine shales, which are abundant in uranium, probably contribute to the high concentrations in ground water; in the southern part of this group, which extends into Nebraska, the glacial or glacial-related sediment may be interbedded with uranium-rich materials that originated to the north and west and in the Rocky Mountains. In New England, crystalline bedrock that is granitic, such as two-mica granites, as well as other high-grade metamorphic rocks, has abundant uranium that is soluble in the predominantly oxic to sub-oxic geochemical conditions. This appears to contribute to high uranium concentrations in ground water. The highest 222radon concentrations were present in samples from wells completed in the New York and New England crystalline aquifer group; the median value (2,122 picocurries per liter (pCi/L)) was about 10 times the median values of all other aquifer groups. More than 25 percent of the samples from the New York and New England crystalline aquifer group wells had 222radon concentrations that exceeded the USEPA Alternative

Scientific Investigations Report↗

Luquillo Experimental Forest: Catchment science in the montane tropics

Catchments in the Luquillo Experimental Forest (LEF) of Puerto Rico are warm, wet and tropical with steep elevational relief creating gradients in temperature and rainfall. Long-term objectives of research at the site are to understand how changing climate and disturbance regimes alter hydrological and biogeochemical processes in the montane tropics and to provide information critical for managing and conserving tropical forest ecosystems globally. Measurements of hydrology and meteorology span decades, and currently include temperature, humidity, precipitation, cloud base level, throughfall, groundwater table elevation and stream discharge. The chemistry of rain, throughfall, and streams is measured weekly and lysimeters and wells are sampled monthly to quarterly. Multiple data sets document the effects of major hurricanes including Hugo (1989), Georges (1998) and Maria (2017) on vegetation, biota and catchment biogeochemistry and provide some of the longest available records of biogeochemical fluxes in tropical forests. Here we present an overview of the findings and the data sets that have been generated from the LEF, highlighting their importance for understanding montane tropical watersheds in the context of disturbance and global environmental change.

Luquillo Experimental Forest, Puerto Rico↗

The environmental geochemistry of Arsenic – An overview

Arsenic is one of the most prevalent toxic elements in the environment. The toxicity, mobility, and fate of arsenic in the environment are determined by a complex series of controls dependent on mineralogy, chemical speciation, and biological processes. The element was first described by Theophrastus in 300 B.C. and named arsenikon (also arrhenicon; Caley and Richards 1956 ) referring to its “potent” nature, although it was originally considered an alternative form of sulfur ( Boyle and Jonasson 1973 ). Arsenikon is believed to be derived from the earlier Persian, zarnik (online etymology dictionary, http://www.etymonline.com/index.php?term=arsenic ). It was not until the thirteenth century that an alchemist, Albertus Magnus, was able to isolate the element from orpiment, an arsenic sulfide (As 2 S 3 ). The complex chemistry required to do this led to arsenic being considered a “bastard metal” or what we now call a “metalloid,” having properties of both metals and non-metals. As a chemical element, arsenic is widely distributed in nature and can be concentrated in many different ways. In the Earth’s crust, arsenic is concentrated by magmatic and hydrothermal processes and has been used as a “pathfinder” for metallic ore deposits, particularly gold, tin, copper, and tungsten ( Boyle and Jonasson 1973 ; Cohen and Bowell 2014 ). It has for centuries been considered a potent toxin, is a common poison in actual and fictional crimes, and has led to significant impacts on human health in many areas of the world ( Cullen 2008 ; Wharton 2010 ).

Reviews in Mineralogy and Geochemistry↗

The influence of seep habitats on sediment macrofaunal biodiversity and functional traits

Chemosynthetic ecosystems in the Gulf of Mexico (GOM) support dense communities of seep megafaunal invertebrates that rely on endosymbiotic bacteria for nutrition. Distinct infaunal communities are associated with the biogenic habitats created by seep biota, where habitat heterogeneity and sediment geochemistry influence local macrofaunal community structure. Here we examine the community structure and function of seep infaunal communities in the GOM in relation to environmental drivers and estimated proximity to seeps. We modeled seep distribution within 3 major seep fields (AC601, GC852, and AT340), and examined the influence of proximity to seep and associated sediment environment on infaunal community structure and function. To model seep habitat distribution, we used known seep occurrence data from ROV and towed camera images, terrain variables derived from high resolution multibeam bathymetry (gridded to 3 m resolution), and a maximum entropy (Maxent) approach. Model performance was high, with mean area under the curve for each habitat ranging from 0.851 for mussel to 0.908 for tubeworm habitat, with the models highly influenced by terrain rugosity. Replicate sediment cores were collected from the three sites in 2007 and processed for macrofauna and environmental characteristics. A majority of the taxa (86%) occurred within 16 m of modeled seep habitat and increased distance from modeled seeps was generally associated with lower calculated seep index coupled with decreased macrofaunal densities. Distance-based linear regression indicated that patterns in macrofaunal communities were driven by proximity to modeled seep habitat and profile curvature, a metric for the shape of the maximum slope. Similarly, variance in infaunal functional traits was best explained by proximity to seep, but also sediment C:N, reflecting the relative influence of sediment chemistry, including organic content, on infaunal communities. Results suggest that northern GOM seep infaunal community assemblages and their function are structured by factors that influence food availability and habitat heterogeneity. Given the abundance of seeps in the GOM and in the world’s oceans, this study supports the premise that the sphere of influence of seeps is spatially extensive.

Deep-Sea Research Part I: Oceanographic Research P↗

Exploring spatial and temporal symptoms of the freshwater salinization syndrome in a rural to urban watershed

The freshwater salinization syndrome (FSS), a concomitant watershed-scale increase in salinity, alkalinity, and major-cation and trace-metal concentrations, over recent decades, has been described for major rivers draining extensive urban areas, yet few studies have evaluated temporal and spatial FSS variations, or causal factors, at the subwatershed scale in mixed-use landscapes. This study examines the potential influence of land-use practices and wastewater treatment plant (WWTP) effluent on the export of major ions and trace metals from the mixed-use East Branch Brandywine Creek watershed in southeastern Pennsylvania, during the 2019 water year. Separate analysis of baseflow and stormflow subsets revealed similar correlations among land-use characteristics and streamwater chemistry. Positive associations between percent impervious surface cover, which ranged from 1.26 % to 21.9 % for the 13 sites sampled, and concentrations of Ca 2+ , Mg 2+ , Na + , and Cl − are consistent with road-salt driven reverse cation exchange and weathering of the built environment. The relative volume of upstream WWTP was correlated with Cu and Zn, which may be derived in part from corroded water-conveyance infrastructure; chloride to sulfate mass ratios (CSMR) ranged from ~6.3 to ~7.7× the 0.5 threshold indicating serious corrosivity potential. Observed exceedances of U.S. Environmental Protection Agency Na + and Cl − drinking water and aquatic life criteria occurred in winter months. Finally, correlations between percent cultivated cropland and As and Pb concentrations may be explained by the persistence of agricultural pesticides that had been used historically. Study results contribute to the understanding of FSS solute origin, fate, and transport in mixed-use watersheds, particularly those in road salt-affected regions. Study results also emphasize the complexity of trace-metal source attribution and explore the potential for FSS solutes to affect human health, aquatic life, and infrastructure.

Pennsylvania↗