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USGS2014

Effects of wastewater effluent discharge and treatment facility upgrades on environmental and biological conditions of Indian Creek, Johnson County, Kansas, June 2004 through June 2013

Indian Creek is one of the most urban drainage basins in Johnson County, Kansas, and environmental and biological conditions of the creek are affected by contaminants from point and other urban sources. The Johnson County Douglas L. Smith Middle Basin (hereafter referred to as the “Middle Basin”) and Tomahawk Creek Wastewater Treatment Facilities (WWTFs) discharge to Indian Creek. In summer 2010, upgrades were completed to increase capacity and include biological nutrient removal at the Middle Basin facility. There have been no recent infrastructure changes at the Tomahawk Creek facility; however, during 2009, chemically enhanced primary treatment was added to the treatment process for better process settling before disinfection and discharge with the added effect of enhanced phosphorus removal. The U.S. Geological Survey, in cooperation with Johnson County Wastewater, assessed the effects of wastewater effluent on environmental and biological conditions of Indian Creek by comparing two upstream sites to four sites located downstream from the WWTFs using data collected during June 2004 through June 2013. Environmental conditions were evaluated using previously and newly collected discrete and continuous data and were compared with an assessment of biological community composition and ecosystem function along the upstream-downstream gradient. This study improves the understanding of the effects of wastewater effluent on stream-water and streambed sediment quality, biological community composition, and ecosystem function in urban areas. After the addition of biological nutrient removal to the Middle Basin WWTF in 2010, annual mean total nitrogen concentrations in effluent decreased by 46 percent, but still exceeded the National Pollutant Discharge Elimination System (NPDES) wastewater effluent permit concentration goal of 8.0 milligrams per liter (mg/L); however, the NPDES wastewater effluent permit total phosphorus concentration goal of 1.5 mg/L or less was achieved at the Middle Basin WWTF. At the Tomahawk Creek WWTF, after the addition of chemically enhanced primary treatment in 2009, effluent discharges also had total phosphorus concentrations below 1.5 mg/L. After the addition of biological nutrient removal, annual total nitrogen and phosphorus loads from the Middle Basin WWTF decreased by 42 and 54 percent, respectively, even though effluent volume increased by 11 percent. Annual total phosphorus loads from the Tomahawk Creek WWTF after the addition of chemically enhanced primary treatment decreased by 54 percent despite a 33-percent increase in effluent volume. Total nitrogen and phosphorus from the WWTFs contributed between 30 and nearly 100 percent to annual nutrient loads in Indian Creek depending on streamflow conditions. In-stream total nitrogen primarily came from wastewater effluent except during years with the highest streamflows. Most of the in-stream total phosphorus typically came from effluent during dry years and from other urban sources during wet years. During 2010 through 2013, annual mean discharge from the Middle Basin WWTF was about 75 percent of permitted design capacity. Annual nutrient loads likely will increase when the facility is operated at permitted design capacity; however, estimated maximum annual nutrient loads from the Middle Basin WWTF were 27 to 38 percent lower than before capacity upgrades and the addition of biological nutrient removal to treatment processes. Thus, the addition of biological nutrient removal to the Middle Basin wastewater treatment process should reduce overall nutrient loads from the facility even when the facility is operated at permitted design capacity. The effects of wastewater effluent on the water quality of Indian Creek were most evident during below-normal and normal streamflows (about 75 percent of the time) when wastewater effluent represented about 24 percent or more of total streamflow. Wastewater effluent had the most substantial effect on nutrient concentrations in Indian Creek. Total and inorganic nutrient concentrations at the downstream sites during below-normal and normal streamflows were 10 to 100 times higher than at the upstream sites, even after changes in treatment practices at the WWTFs. Median total phosphorus concentrations during below-normal and normal streamflows at a downstream site were 43 percent lower following improvements in wastewater treatment processes. Similar decreases in total nitrogen were not observed, likely because total nitrogen concentrations only decreased in Middle Basin effluent and wastewater contributed a higher percentage to streamflows when nutrient samples were collected during the after-upgrade period. The wastewater effluent discharges to Indian Creek caused changes in stream-water quality that may affect biological community structure and ecosystem processes, including higher concentrations of bioavailable nutrients (nitrate and orthophosphorus) and warmer water temperatures during winter months. Other urban sources of contaminants also caused changes in stream-water quality that may affect biological community structure and ecosystem processes, including higher turbidities downstream from construction areas and higher specific conductance and chloride concentrations during winter months. Chloride concentrations exceeded acute and chronic exposure criteria at all Indian Creek study sites, regardless of wastewater influence, for weeks or months during winter. Streambed sediment chemistry was affected by wastewater (elevated nutrient and organic wastewater-indicator compound concentrations) and other contaminants from urban sources (elevated polyaromatic hydrocarbon concentrations). Overall habitat conditions were suboptimal or marginal at all sites; general decline in habitat conditions along the upstream-downstream gradient likely was caused by the cumulative effects of urbanization with increasing drainage basin size. Wastewater effluent likely affected algal periphyton biomass and community composition, primary production, and community respiration in Indian Creek. Functional stream health, evaluated using a preliminary framework based on primary production and community respiration, was mildly or severely impaired at most downstream sites relative to an urban upstream Indian Creek site. The mechanistic cause of the changes in these biological variables are unclear, though elevated nutrient concentrations were positively correlated with algal biomass, primary production, and community respiration. Macroinvertebrate communities indicated impairment at all sites, and Kansas Department of Health and Environment aquatic life support scores indicated conditions nonsupporting of aquatic life, regardless of wastewater influences. Urban influences, other than wastewater effluent discharge, likely control macroinvertebrate community structure in Indian Creek. Changes in treatment processes at the Middle Basin and Tomahawk Creek WWTFs improved wastewater effluent quality and decreased nutrient loads, but wastewater effluent discharges still had negative effects on the environmental and biological conditions at downstream Indian Creek sites. Wastewater effluent discharge into Indian Creek likely contributed to changes in measures of ecosystem structure (streamflow, water and streambed-sediment chemistry, algal biomass, and algal periphyton community composition) and function (primary production and community respiration) along the upstream-downstream gradient. Wastewater effluent discharges maintained streamflows and increased nutrient concentrations, algal biomass, primary production, and community respiration at the downstream sites. Functional stream health was severely impaired downstream from the Middle Basin WWTF and mildly impaired downstream from the Tomahawk WWTF relative to the urban upstream site. As distance from the Middle Basin WWTF increased, nutrient concentrations, algal biomass, primary production, and community respiration decreased, and functional stream health was no longer impaired 9.5 kilometers downstream from the discharge relative to the urban upstream site. Therefore, although wastewater effluent caused persistent changes in environmental and biological conditions and functional stream health at sites located immediately downstream from WWTF effluent discharges, some recovery to conditions more similar to the urban upstream site occurred within a relatively short distance.

Kansas↗

USGS2006

Biomarkers of exposure and effects of environmental contaminants on swallows nesting along the Rio Grande, Texas, USA

We collected adult cave swallows (Petrochelidon fulva) and cliff swallows (P. pyrrhonota) during the breeding seasons in 1999 and 2000 from eight locations along the Rio Grande from Brownsville to El Paso (unless otherwise specified, all locations are Texas, USA) and an out-of-basin reference location. Body mass, spleen mass, hepatosomatic index (HSI), gonadosomatic index (GSI), thyroxine (T4) in plasma, DNA damage measured as the half-peak coefficient of variation of DNA content (HPCV) in blood cells, as well as acetylcholinesterase and butyrylcholinesterase in brain were compared with concentrations of organochlorines, metals, and metalloids in carcasses to determine potential effects of contaminants on swallows during the breeding season. Concentrations of 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p,p???-DDE) were significantly greater in swallows from El Paso than in those from most locations, except for Pharr and Llano Grande. All swallows from these three locations had p,p???-DDE concentrations of 3 ??g/g wet weight or greater. Swallows from El Paso either had or shared the highest concentrations of p,p???-DDE, polychlorinated biphenyls, and 13 inorganic elements. Swallows from El Paso exhibited greater spleen mass and HPCV values as well as lower T4 values compared with those from other locations. Thyroxine was a potential biomarker of contaminant exposure in swallows of the Rio Grande, because it was negatively correlated with p,p???-DDE and Se. Spleen mass was positively correlated with selenium and HSI and negatively correlated with body mass, GSI, Mn, and Ni. Overall, the present study suggests that insectivorous birds living in areas of high agricultural and industrial activity along the Rio Grande bioaccumulate environmental contaminants. These contaminants, particularly p,p???-DDE, may be among multiple factors that impact endocrine and hematopoietic function in Rio Grande swallows. ?? 2006 SETAC.

Environmental Toxicology and Chemistry↗

USGS2004

Reach-scale cation exchange controls on major ion chemistry of an Antarctic glacial meltwater stream

McMurdo dry valleys of Antarctica represent the largest of the ice-free areas on the Antarctic continent, containing glaciers, meltwater streams, and closed basin lakes. Previous geochemical studies of dry valley streams and lakes have addressed chemical weathering reactions of hyporheic substrate and geochemical evolution of dry valley surface waters. We examine cation transport and exchange reactions during a stream tracer experiment in a dry valley glacial meltwater stream. The injection solution was composed of dissolved Li + , Na + , K + , and Cl - . Chloride behaved conservatively in this stream, but Li + , Na + , and K + were reactive to varying degrees. Mass balance analysis indicates that relative to Cl - , Li + and K + were taken up in downstream transport and Na + was released. Simulations of conservative and reactive (first-order uptake or generation) solute transport were made with the OTIS (one-dimensional solute transport with inflow and storage) model. Among the four experimental reaches of Green Creek, solute transport simulations reveal that Li + was removed from stream water in all four reaches, K + was released in two reaches, taken up in one reach, and Na + was released in all four reaches. Hyporheic sediments appear to be variable with uptake of Li + in two reaches, uptake of K + in one reach, release of K + in two reaches, and uptake of Na + in one reach. Mass balances of the conservative and reactive simulations show that from 1.05 to 2.19 moles of Li + was adsorbed per reach, but less than 0.3 moles of K + and less than 0.9 moles of Na + were released per reach. This suggests that either (1) exchange of another ion which was not analyzed in this experiment or (2) that both ion exchange and sorption control inorganic solute transport. The elevated cation concentrations introduced during the experiment are typical of initial flows in each flow season, which flush accumulated dry salts from the streambed. We propose that the bed sediments (which compose the hyporheic zone) modulate the flushing of these salts during initial flows each season, due to ion exchange and sorption reactions.

Aquatic Geochemistry↗

USGS2014

USGS Field Activities 12BHM01, 12BHM02, 12BHM03, 12BHM04, and 12BHM05 on the West Florida Shelf, in February, April, May, June, and August 2012

Atmospheric carbon dioxide (CO 2 ) is absorbed by the ocean’s surface where it combines with seawater to form a weak, naturally occurring acid called carbonic acid (H 2 CO 3 ). Increasing carbon dioxide in the atmosphere results in the absorption of more CO 2 by the ocean and, therefore, increases in the acidity of seawater. This process, known as ocean acidification, has the potential to elicit change in ecosystems and organisms by disrupting biological processes. For example, ocean acidification is a problem for marine organisms such as corals, foraminifera, and algae that precipitate calcium carbonate to form their skeletons and shells (Kleypas and others, 2006). The effects are related to corresponding changes in the carbonate saturation state (Ω), where Ω is the ratio of the ion concentration product (Ca 2+ x CO 3 2- ) to the stoichiometric aragonite solubility product (K*sp) (Langdon and Atkinson, 2005). Because pH and CO 3 2- are strongly interdependent through the inorganic carbon system, the decrease in pH will cause a proportionally greater decrease in CO 3 2- . Globally, ocean acidification is occurring faster than at any time in the last 300 million years (Broeker and others, 1979). Recent evidence indicates that individual oceans are responding at different rates, depending on physical and biological processes. For example in the Arctic Ocean, the rate of saturation state decrease was 2.1 percent per year between 1997 and 2010 (Robbins and others., 2013) in an area as large as Montana, largely because of increases in melt of ice, versus the average rate observed for the Pacific Ocean (0.36 percent per year) (Feely and others, 2012). Unfortunately, comparative data sets over multiyear time frames are often not available because time series baseline carbon information has not been collected in many oceans. Data are needed in subtropical latitudes where carbonate saturation states are already naturally low and fluctuate seasonally. These data will help construct a baseline for the assessment of future changes. As part of the U.S. Geological Survey (USGS) Coastal and Marine Geology Program project "R esponse of Florida Shelf Ecosystems to Climate Change " and in partnership with Kendra Daly, University of South Florida ( USF ), data on surface ocean carbonate chemistry were collected on five cruises along transects on the shallow inner west Florida shelf and northern Gulf of Mexico in 2012. Data from the 2011 cruises were also published (Robbins and others., 2013). The data collected allows the USGS, National Oceanic and Atmospheric Administration ( NOAA ), and USF scientists to map variations in ocean chemistry including carbonate saturation states along designated tracks. The USGS also partners with NOAA and the National Aeronautics and Space Administration ( NASA ) to model air-sea flux as part of a Gulf of Mexico Carbon Synthesis project led by NASA.

Florida↗

USGS2002

Presence of organoarsenicals used in cotton production in agricultural water and soil of the Southern United States

Arsenicals have been used extensively in agriculture in the United States as insecticides and herbicides. Mono- and disodium methylarsonate and dimethylarsinic acid are organoarsenicals used to control weeds in cotton fields and as defoliation agents applied prior to cotton harvesting. Because the toxicity of most organoarsenicals is less than that of inorganic arsenic species, the introduction of these compounds into the environment might seem benign. However, biotic and abiotic degradation reactions can produce more problematic inorganic forms of arsenic, such as arsenite [As(III)] and arsenate [As(V)]. This study investigates the occurrences of these compounds in samples of soil and associated surface and groundwaters. Preliminary results show that surface water samples from cotton-producing areas have elevated concentrations of methylarsenic species (>10 ??g of As/L) compared to background areas (<1 ??g of As/L). Species transformations also occur between surface waters and adjacent soils and groundwaters, which also contain elevated arsenic. The data indicate that point sources of arsenic related to agriculture might be responsible for increased arsenic concentrations in local irrigation wells, although the elevated concentrations did not exceed the new (2002) arsenic maximum contaminant level of 10 ??g/L in any of the wells sampled thus far.

Journal of Agricultural and Food Chemistry↗

USGS1989

The geology, botany and chemistry of selected peat-forming environments from temperate and tropical latitudes

Peat has been studied in several geologic settings: (1) glaciated terrain in cold temperate Maine and Minnesota, U.S.A.; (2) an island in the Atlantic Ocean off the coast of Maine, where sea level is rising; (3) the warm temperate U.S. Atlantic and Gulf Coastal Plains, where sea level has changed often; and (4) the tropical coast of Sarawak, Malaysia, and the tropical delta of the Batang Hari River, Sumatra, Indonesia. Most of these deposits are domed (ombrotrophic or partly ombrotrophic) bogs in which peat accumulation continued above the surface of the surrounding soil. However, the bogs of the U.S. Atlantic and Gulf Coastal Plains are comparatively not as domed, and many have almost level surfaces. In some bogs, aquatic or semi-aquatic plant materials accumulated, replaced water in the depressions, and formed a surface on which marsh or swamp vegetation could subsequently live, die, and accumulate. In others, the plant materials accumulated initially on level silt or sand surfaces supporting marshes or swamps. As the peat dome formed, plants growing on it changed from luxuriant ones near the base of the dome, where nutrients were brought into the bog by surface and ground water, to stunted ones at the top of the dome, where the raised bogs are fed by nutrient-poor precipitation. The physical and chemical changes that take place in the sequence of environments from the pond stage of deposit development, through the grassy marsh stage, through the forested swamp stage, and finally through the heath dome stage can be measured in terms of acidity and ash, volatile matter, carbon, hydrogen, nitrogen, sulfur and oxygen contents, as well as in the kind and distribution of trace elements. The organic and inorganic contents of the deposits relate to geomorphology, and geomorphology relates to their settings. As models of coal formation, some domed peat deposits may help in solving problems of distribution and character of ancient coal beds. But clearly not all peat deposits are precursors of coal. Most Holocene peat deposits are subject to destruction by erosion, fire and decomposition through microbial and chemical oxidation before burial. The best environments for coal precursors have biomass accumulation, a continuously rising water table within the mass, and minimum influx of clay and silt until preservation by burial. The most suitable settings for future economic coal deposits are domed bogs that accumulate thick, widespread peat having low ash and low sulfur contents. The ombrotrophic peat deposits of tropical Sarawak and Sumatra are thick and extensive, contain low-ash and low-sulfur peat, and have high heating values. They are considered to be the best tropical coal analogs because of their extent and chances of preservation; the base of the peat is below adjacent river levels, and chemical and structural conditions are favorable for accumulation.

International Journal of Coal Geology↗

USGS1997

Ambient quality of ground water in the vicinity of Naval Submarine Base Bangor, Kitsap County, Washington, 1995

A study of the ambient ground-water quality in the vicinity of Naval Submarine Base (SUBASE) Bangor was conducted to provide the U.S. Navy with background levels of selected constituents. The Navy needs this information to plan and manage cleanup activities on the base. During March and April 1995, 136 water-supply wells were sampled for common ions, trace elements, and organic compounds; not all wells were sampled for all constituents. Man-made organic compounds were detected in only two of fifty wells, and the sources of these organic compounds were attributed to activities in the immediate vicinities of these off-base wells. Drinking water standards for trichloroethylene, iron, and manganese were exceeded in one of these wells, which was probably contaminated by an old local (off-base) dump. Ground water from wells open to the following hydrogeologic units (in order from shallow to deep) was investigated: the Vashon till confining unit (Qvt, three wells); the Vashon aquifer (Qva, 54 wells); the Upper confining unit (QC1, 16 wells); the Permeable interbeds within QC1 (QC1pi, 34 wells); and the Sea-level aquifer (QA1, 29 wells).The 50th and 90th percentile ambient background levels of 35 inorganic constituents were determined for each hydrogeologic unit. At least ten measurements were required for a constituent in each hydrogeologic unit for determination of ambient background levels, and data for three wells determined to be affected by localized activities were excluded from these analyses. The only drinking water standards exceeded by ambient background levels were secondary maximum contaminant levels for iron (300 micrograms per liter), in QC1 and QC1pi, and manganese (50 micrograms per liter), in all of the units. The 90th percentile values for arsenic in QC1pi, QA1, and for the entire study area are above 5 micrograms per liter, the Model Toxics Control Act Method A value for protecting drinking water, but well below the maximum contaminant level of 50 micrograms per liter for arsenic. The manganese standard was exceeded in 38 wells and the standard for iron was exceeded in 12 wells. Most of these wells were in QC1 or QC1pi and had dissolved oxygen concentrations of less than 1 milligram per liter and dissolved organic carbon concentrations greater than 1 milligram per liter. The dissolved oxygen concentration is generally lower in the deeper units, while pH increases; the recommended pH range of 6.5-8.5 standard units was exceeded in 9 wells. The common-ion chemistry was similar for all of the units.

Washington↗

USGS2015

Arsenic and antimony geochemistry of mine wastes, associated waters and sediments at the Giant Mine, Yellowknife, Northwest Territories, Canada

Elevated levels of arsenic (As) and antimony (Sb) in water and sediments are legacy residues found downstream from gold-mining activities at the Giant Mine in Yellowknife, Northwest Territories (NWT), Canada. To track the transport and fate of As and Sb, samples of mine-waste from the mill, and surface water, sediment, pore-water, and vegetation downstream of the mine were collected. Mine waste, pore-water, and sediment samples were analyzed for bulk chemistry, and aqueous and solid-state speciation. Sediment and vegetation chemistry were evaluated using scanning electron microscope imaging, synchrotron-based element mapping and electron microprobe analysis. The distributions of As and Sb in sediments were similar, yet their distributions in the corresponding pore-waters were mostly dissimilar, and the mobility of As was greater than that of Sb. Competition for sorption sites is the most likely cause of elevated Sb concentrations in relatively oxidized pore-water and surface water. The aqueous and solid-state speciation of As and Sb also differed. In pore-water, As(V) dominated in oxidizing environments and As(III) in reducing environments. In contrast, the Sb(V) species dominated in all but one pore-water sample, even under reducing conditions. Antimony(III) appears to preferentially precipitate or adsorb onto sulfides as evidenced by the prevalence of an Sb(III)-S secondary solid-phase and the lack of Sb(III)(aq) in the deeper zones. The As(V)–O solid phase became depleted with depth below the sediment–water interface, and the Sb(V)–O phase persisted under relatively reducing conditions. In the surficial zone at a site populated by Equisetum fluviatile (common horsetail), As and Sb were associated with organic material and appeared mobile in the root zone. In the zone below active plant growth, As and Sb were associated primarily with inorganic phases suggesting a release and reprecipitation of these elements upon plant death. The co-existence of reduced and oxidized As and Sb species, instability of some phases under changing redox conditions, and plant uptake and release pose challenges for remediation efforts at the mine.

Northwest Territories↗

USGS1990

Toxicity of inorganic and organic selenium to Daphnia magna (cladocera) and Chironomus riparius (diptera)

Elevated concentrations of selenium (Se) have been previously measured in biota sampled from the Kesterson National Wildlife Refuge (KNWR) in the San Joaquin Valley of central California. We conducted acute and chronic toxicity tests with the cladoceran Daphnia magna and the midge Chironomus riparius to determine the toxicity or bioaccumulation of waterborne Se in a reconstituted water similar to the San Joaquin River. Daphnids were more acutely sensitive than midges to the toxic effects of inorganic Se. An organic form of Se (seleno-[L]-methionine) was extremely toxic to daphnids, but was relatively nontoxic to midges. In long-term exposure to a 6:1 mixture of selenate to selenite (a mixture representative of KNWR), the emergence time of adult midges was delayed at Se concentrations ≥ 837 μg/L. Daphnid reproduction and intrinsic rate of natural increase ( r ) were reduced at Se concentrations ≥ 348 μg/L and growth of adults was reduced at ≥ 156 μg/L. Whole body Mg, K and Na concentrations in daphnids were not affected by chronic Se exposure; however, whole body Ca concentration increased at intermediate Se exposure concentrations. In addition, whole body Cl concentration was reduced at 711 μg Se/L. Daphnids accumulated potentially toxic concentrations of Se from water that may adversely affect fish or waterfowl through the food chain.

Environmental Toxicology and Chemistry↗

USGS2024

Simulated sea level rise in coastal peat oils stimulates mercury methylation

Coastal wetlands are vulnerable to sea level rise with unknown consequences for mercury (Hg) cycling, particularly the potential for exacerbating neurotoxic methylmercury (MeHg) production and bioaccumulation in food webs. Here, the effect of sea level rise on MeHg formation in the Florida Everglades was evaluated by incubating peat cores from a freshwater wetland for 0–20 days in the laboratory at five salinity conditions (0.16–6.0 parts-per-thousand; 0.20–454 mg L –1 sulfate (SO 4 2– )) to simulate the onset of sea level rise within coastal margins. Isotopically enriched inorganic mercury ( 201 Hg(II)) was used to track MeHg formation and peat-porewater partitioning. In all five salinity treatments, porewaters became anoxic within 1 day and became progressively enriched in dissolved organic matter (DOM) of greater aromatic composition over the 20 days compared to ambient conditions. In the four highest salinity treatments, SO 4 2– concentrations decreased and sulfide concentrations increased over time due to microbial dissimilatory SO 4 2– reduction that was concurrent with 201 Hg(II) methylation. Importantly, elevated salinity resulted in a greater proportion of produced Me 201 Hg observed in porewaters as opposed to bound to peat, interpreted to be due to the complexation of MeHg with aromatic DOM released from peat. The findings highlight the potential for enhanced production and mobilization of MeHg in coastal wetlands of the Florida Everglades due to the onset of saltwater intrusion.

Florida↗

USGS2014

Environmental contaminants and chromosomal damage associated with beak deformities in a resident North American passerine

A large cluster of beak abnormalities among black-capped chickadees ( Poecile atricapillus ) in Alaska raised concern about underlying environmental factors in this region. Metals and trace elements, organochlorine pesticides, polychlorinated biphenyls (PCBs), and polychlorinated dibenzo-dioxins and polychlorinated dibenzofurans (PCDD-Fs) were analyzed in adults, nestlings, and eggs of the affected population; local bird seed was also tested for organochlorine pesticides. The results offered no support for the hypothesis that selenium or any other inorganic element was responsible for beak deformities among chickadees, but some evidence that organochlorine compounds may be contributing factors. Adults with beak deformities had an elevated level of chromosomal damage, which was correlated with lipid level and concentrations of several organochlorine compounds. Multivariate analyses of pesticides and PCBs did not distinguish abnormal from normal adults, but subsequent univariate analysis demonstrated higher concentrations of heptachlor epoxide and PCB-123 in abnormal adults. Concentrations of all organochlorine compounds were low, and none is known to cause beak or keratin abnormalities. Patterns of PCB congener concentrations differed between nestlings with normal and abnormal parents. Eggs from clutches with low hatchability had higher concentrations of hexachlorobenzene and PCDD-Fs than those with high hatching success, and hexachlorobenzene was found in seeds. Additional testing for PCDD-Fs, polycyclic aromatic hydrocarbons, and other emerging contaminants, including brominated compounds, is needed to rule out environmental contaminants as a cause of beak deformities in chickadees in Alaska.

Environmental Toxicology and Chemistry↗

USGS2021

Isotope fractionation from In Vivo methylmercury detoxification in waterbirds

The robust application of stable mercury (Hg) isotopes for mercury source apportionment and risk assessment necessitates the understanding of mass-dependent fractionation (MDF) due to internal transformations within organisms. Here, we used high energy-resolution XANES spectroscopy and isotope ratios of total mercury (δ202THg) and methylmercury (δ202MeHg) to elucidate the chemical speciation of Hg and the resultant MDF due to internal MeHg demethylation in waterbirds. In three waterbirds (Clark’s grebe, Forster’s tern, south polar skua), between 17-86% of the MeHg was demethylated to inorganic mercury (iHg) species primarily in the liver and kidneys as Hg-tetraselenolate (Hg(Sec)4) and minor Hg-dithiolate (Hg(SR)2) complexes. Tissular differences between δ202THg and δ202MeHg correlated linearly with %iHg (Hg(Sec)4 + Hg(SR)2), and were interpreted to reflect a kinetic isotope effect during in vivo MeHg demethylation. The product-reactant isotopic enrichment factor (εp/r) for the demethylation of MeHg  Hg(Sec)4 was −2.2 ± 0.1‰. δ202MeHg values were unvarying within each bird regardless of Hg(Sec)4 abundance, indicating fast internal cycling or replenishment of MeHg relative to demethylation. Our findings document a universal selenium-dependent demethylation reaction in birds, provide new insights on the internal transformations and cycling of MeHg and Hg(Sec)4, and allow for mathematical correction of δ202THg values due to the MeHg  Hg(Sec)4 reaction.

ACS Earth and Space Chemistry↗

USGS2024

The role of sediment ingestion in exposing bottom-feeding fish to chemical elements

Digesta were collected from the intestines of seven species of bottom-feeding fish to better understand the role of incidental ingestion of sediment in exposing fish to inorganic contaminants. A composite sediment tracer variable, based on concentrations of Co, Cr, Ni, Ti, V, and Y in digesta and in sediment, was calculated to estimate sediment content of digesta. Concentration factors (mg/kg in digesta divided by mg/kg in sediment) of eight elements of interest were linearly regressed on this tracer variable. The relative importance of sediment ingestion to oral exposure was quantified. Zinc, Cd, and Cu were ingested mainly from sediment-free food. Arsenic, Cr, Ni, Al, and Pb, in contrast, were ingested mainly from sediment. As an example, 93% of the Ni in digesta from a brown bullhead ( Ameiurus nebulosus ) was from sediment and only 7% from food. Regressions of Al and Pb in digesta of suckers (Catostomidae) suggested an additional oral source, possibly from oxides coating biotic or abiotic surfaces. Overall, concentrations of 12 of 21 elements studied were positively correlated with sediment content ( p < 0.005). Including sediment ingestion as a pathway for bottom-feeding fish is essential for accurately estimating exposures in toxicological studies.

Environmental Toxicology and Chemistry↗

USGS2004

Chemistry of ground water in the Silver Springs basin, Florida, with an emphasis on nitrate

The Silver Springs group, in central Marion County, Florida, has a combined average discharge rate of 796 cubic feet per second and forms the headwaters of the Silver River. The springs support a diverse ecosystem and are an important cultural and economic resource. Concentrations of nitrite-plus-nitrate (nitrate-N) in water from the Main Spring increased from less than 0.5 milligrams per liter (mg/L) in the 1960s to about 1.0 mg/L in 2003. The Upper Floridan aquifer supplies the ground water to support spring discharge. This aquifer is at or near land surface in much of the ground-water basin; nutrients leached at land surface can easily percolate downward into the aquifer. Sources of nitrogen in ground water in the Silver Springs basin include atmospheric deposition, fertilizers used by agricultural and urban activities, and human and animal wastes. During 2000-2001, 56 wells in the area contributing recharge to Silver Springs were sampled for major ions, nutrients, and some trace constituents. Selected wells also were sampled for a suite of organic constituents commonly found in domestic and industrial wastewater and for the ratio of nitrogen isotopes (15N/14N) to better understand the sources of nitrate. Wells were selected to be representative of both confined and unconfined conditions of the Upper Floridan aquifer, as well as a variety of land-use types. Data from this study were compared to data collected from 25 wells in 1989-90. Concentrations of nitrate-N in ground water during this study ranged from less than the detection limit of 0.02 to 12 mg/L, with a median of 1.2 mg/L. For data from 1989-90, the range was from less than 0.02 to 3.6 mg/L, with a median of 1.04 mg/L. Water from wells in agricultural land-use areas had the highest median nitrate-N concentration (1.7 mg/L), although it is uncertain if the 12 mg/L maximum concentration was influenced by land-use activities or proximity to a septic tank. The median value for all urban land-use areas was 1.15 mg/L. Because fewer wells were in rangeland or forested areas, those categories were grouped together. The median concentration for that group was 0.09 mg/L. The ratio of 15N/14N in ground-water samples ranged from -0.5 to 11.5 per mil. The median value for ground-water samples from 35 wells, 4.9 per mil, is near the top of the range that indicates inorganic nitrogen sources. In agricultural areas, the median 15N/14N was 4.8 per mil, indicating mostly inorganic (fertilizer) sources. In urban areas, the median 15N/14N was 5.4 per mil, indicating more influence of organic nitrogen (N) sources. Thus, in both agricultural and urban areas, fertilizer is an important inorganic source of N in ground water (and, therefore, in spring water as well). The influence of organic N is more apparent in urban areas than in agricultural areas. Two distinct 15N/14N values were observed in water from the Main Spring, one indicating an inorganic nitrogen source and the other indicating a mixture of sources with a strong influence of organic nitrogen. Thirty-five wells and three springs of the Silver Springs group (the Main Spring, the Abyss, and the Blue Grotto) were sampled for a suite of 63 compounds common in wastewater. A total of 38 compounds was detected, nearly all in very low concentrations. The most frequently detected compound was the insecticide N,N-diethyl-meta-toluamide (DEET), which was detected in water from 27 wells and all three springs. The presence or absence of DEET in ground-water samples did not seem to be related to land use; however, hydrogeologic conditions at the well sites (confined or unconfined) generally did affect the presence or absence of DEET in the ground water. DEET also appears to be a useful tracer for the presence of reused water. Water samples were collected from the Main Spring and two other springs of the Silver Springs group and analyzed for concentrations of dissolved gasses and for chlorofluorocarbons (CFCs), sulfur hexaflu

Scientific Investigations Report↗

USGS2000

Hydrogeology, water quality, and stormwater-sediment chemistry of the Grande Wash area, Fort McDowell Indian Reservation, Maricopa County, Arizona

Grande Wash is a tributary of the Verde River and drains an area of 13 square miles within the McDowell Mountains and the Town of Fountain Hills in Central Arizona. The wash enters the Fort McDowell Indian Reservation at the eastern boundary of Fountain Hills and is incised in coarse-grained alluvium that is contiguous with the alluvial aquifer along the Verde River. The aquifer is used by the Fort McDowell Indian Community and the City of Phoenix for municipal water supplies. Episodic flows in Grande Wash, in response to storms, carry potentially hazardous runoff from Fountain Hills onto the reservation. Additional potential hazards to ground water include contamination from a wastewater-treatment plant located less than 1 mile upstream from the reservation boundary, and from a landfill and a cement-processing plant immediately adjacent to the main channel of the wash. Coarse-grained deposits in Grande Wash also include recent stream-channel deposits, soil backfill, landfill material, and the upper coarse-grained layer of basin-fill sediments. Surface-geophysical surveys and drilling indicated that the coarse-grained deposits are less than 60-feet thick along the wash and in adjacent areas within the reservation, and are underlain by a thick clay and silt unit, the base of which is below the bottom of the deepest monitor well (317 feet below land surface). The coarse-grained deposits form the alluvial aquifer beneath Grande Wash. Ground water in the alluvial aquifer beneath the wash is shallow and mounded above a less permeable clay and silt unit. Depth to water in the aquifer ranges from 1 to 22 feet below land surface. Saturation of the coarse-grained deposits does not extend laterally for more than about 1,000 feet from the main channel of Grande Wash; the extent varies in response to recharge amounts. Flux of ground water through the alluvial aquifer beneath the wash is toward the Verde River and is estimated to be about 8,000 cubic feet per day (about 0.2 acre-feet per day). The flow rate is four orders of magnitude less than the flow rate in the Verde River. Vertical flux of ground water through the underlying clay and silt unit is estimated to be 7,000 cubic feet per day (0.17 acre-feet per day). The volume of ground water in storage in the alluvial aquifer beneath Grande Wash is estimated to be about 5.6 million cubic feet (129 acre-feet). Concentrations of dissolved inorganic constituents in ground water and surface water are high relative to concentrations found in the regional aquifer in surrounding areas and are indicative of salts that can be expected to be mobilized by runoff in the drainage area. Concentrations of nitrate, chloride, and sulfate are near U.S. Environmental Protection Agency Primary or Secondary Drinking-Water Regulations. Concentrations of arsenic, antimony, and strontium are below drinking-water standards but can be attributed to geologic deposits in and near the study area. Low concentrations of anthropogenic compounds, including chloroform and dichlorobromomethane, were detected. These compounds are disinfection by-products of chlorinated water. Eight pesticide compounds were detected in the surface water, and two pesticide compounds were detected in the ground water. Pesticide concentrations were below U.S. Environmental Protection Agency Maximum Contaminant Levels. Several other organic anthropogenic compounds that probably originated from commercial activities in the area were detected but at concentrations below laboratory calibration standards. Concentrations of trace metals in the stormwater sediment collected from the sediment retention basin in the lowest part of the wash were low and several were below the laboratory’s detection limits. Concentrations of most organic compounds in the stormwater sediment were below detection limits. Organic compounds present at concentrations above detection limits were p-cresol and two phthalate esters—bis (2-ethylhexyl) phthalate and dibutyl phthalate. P-cresol is used in pesticides or in disinfectants and deodorizers, and phthalate esters are commonly used in plastics, hydraulic fluid, and electric capacitors.

Arizona↗

USGS2015

Status and understanding of groundwater quality in the Northern Coast Ranges study unit, 2009: California GAMA Priority Basin Project

Groundwater quality in the 633-square-mile (1,639-square-kilometer) Northern Coast Ranges (NOCO) study unit was investigated as part of the Priority Basin Project (PBP) of the Groundwater Ambient Monitoring and Assessment (GAMA) Program and the U.S. Geological Survey (USGS) National Water-Quality Assessment Program. The study unit is composed of two study areas (Interior Basins and Coastal Basins) and is located in northern California in Napa, Sonoma, Lake, Colusa, Mendocino, Glenn, Humboldt, and Del Norte Counties. The GAMA-PBP is being conducted by the California State Water Resources Control Board in collaboration with the USGS and the Lawrence Livermore National Laboratory. The GAMA NOCO study was designed to provide a spatially unbiased assessment of the quality of untreated (ambient) groundwater in the primary aquifer system within the study unit. The assessment is based on water-quality and ancillary data collected in 2009 by the USGS from 58 sites and on water-quality data from the California Department of Public Health (CDPH) database. The primary aquifer system is defined by the perforation intervals of sites listed in the CDPH water-quality database for the NOCO study unit. Groundwater quality in the primary aquifer system may differ from the quality in the shallow or deep water-bearing zones. The first component of this study, the status assessment of the current quality of the groundwater resource, was performed by using data from samples analyzed for inorganic constituents (such as trace elements and major and minor ions), organic constituents (volatile organic compounds and pesticides and pesticide degradates), the special-interest constituent perchlorate, and microbial indicators. This status assessment is intended to characterize the quality of groundwater resources in the primary aquifer system of the NOCO study unit, not the quality of treated drinking water delivered to consumers by water purveyors. Relative-concentrations (sample concentration divided by the health- or aesthetic-based benchmark concentration) were used for evaluating groundwater quality for those constituents that have Federal or California regulatory or nonregulatory benchmarks for drinking-water quality. A relative-concentration greater than (>) 1.0 indicates a concentration greater than a benchmark, and a relative-concentration less than or equal to (≤) 1.0 indicates a concentration less than or equal to a benchmark. Relative-concentrations of organic constituents and perchlorate were classified as “high” (relative-concentration >1.0), “moderate” (0.1 < relative-concentration ≤1.0), or “low” (relative-concentration ≤0.1). Relative-concentrations of inorganic constituents were classified as “high” (relative-concentration >1.0), “moderate” (0.5 < relative-concentration ≤1.0), or “low” (relative-concentration ≤0.5). Aquifer-scale proportion was used as the primary metric in the status assessment for evaluating regional-scale groundwater quality. High aquifer-scale proportion was defined as the percentage of the area of the primary aquifer system with a relative-concentration >1.0 for a particular constituent or class of constituents; the percentage is based on an aerial rather than a volumetric basis. Moderate and low aquifer-scale proportions were defined as the percentage of the primary aquifer system with moderate and low relative-concentrations, respectively. Two statistical approaches—grid-based and spatially weighted—were used to evaluate aquifer-scale proportions for individual constituents and classes of constituents. Grid-based and spatially weighted estimates were comparable in the NOCO study unit (within 90 percent confidence intervals). Inorganic constituents (one or more) with health-based benchmarks were detected at high relative-concentrations in 10.3 percent and at moderate relative-concentrations in 13.8 percent of the primary aquifer system. The high aquifer-scale proportion of inorganic constituents primarily reflected high aquifer-scale proportions of boron (in 8.6 percent of the primary aquifer system), arsenic (in 3.4 percent), and barium (in 1.7 percent). Inorganic constituents with aesthetic-based benchmarks were detected at high relative-concentrations in 39.7 percent and at moderate relative-concentrations in 10.3 percent of the primary aquifer system. The constituents present at high relative-concentrations were iron (25.9 percent) and manganese (39.7 percent). Relative-concentrations of organic constituents with health-based benchmarks (one or more) were high in 0.2 percent, moderate in 1.7 percent, and low in 39.7 percent of the primary aquifer system. Organic constituents were not detected in 58.4 percent of the primary aquifer system. Of the 168 organic constituents analyzed, 11 constituents were detected. Two organic constituents had detection frequencies >10 percent: the trihalomethane chloroform and the herbicide simazine. For the 10 detected organic constituents that had health-based benchmarks, nearly all detections had low relative-concentrations. The special-interest constituent perchlorate was detected at moderate relative-concentrations in 1.7 percent and at low relative-concentrations in 22.4 percent of the primary aquifer system. Perchlorate was not detected in 75.9 percent of the primary aquifer system. The second component of this study, the understanding assessment , evaluated relations between constituent concentrations and values of selected potential explanatory factors to identify the factors potentially affecting the concentrations and occurrences of constituents found at high relative-concentrations or, for organic constituents, with detection frequencies >10 percent. The potential explanatory factors evaluated were land use (including density of septic tanks and leaking or formerly leaking underground fuel tanks), well construction (well depth and depth to the top of the perforated interval in the well), hydrologic conditions (aridity index, field water temperature, and distance to nearest hot spring and geothermal well), pH, dissolved oxygen concentration, study area, groundwater age distribution, and geochemical conditions. High and moderate relative-concentrations of boron primarily occurred in the Interior Basins study area and may be attributed to groundwater interacting with hydrothermal systems. High and moderate relative-concentrations of boron were associated with elevated groundwater temperatures, groundwater chemistry characteristics similar to those of geothermal waters, and distance to known geothermal areas. Boron concentrations generally were higher where low dissolved oxygen concentrations or anoxic conditions exist. High and moderate relative-concentrations of arsenic predominantly occur in the Interior Basins study area under reducing conditions. Arsenic concentrations also may be influenced by hydrothermal systems (when present). Chloroform, simazine, and perchlorate were observed in the Interior Basins and Coastal Basins study areas, predominantly at shallow sites with top-of-perforation depths ≤70 feet below land surface, with modern water (post-1950s), and with oxic groundwater conditions.

California↗

USGS1991

Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 2. Modeling carbon sources, sinks, and δ13C evolution

Stable isotope data for dissolved inorganic carbon (DIC), carbonate shell material and cements, and microbial CO 2 were combined with organic and inorganic chemical data from aquifer and confining-bed pore waters to construct geochemical reaction models along a flowpath in the Black Creek aquifer of South Carolina. Carbon-isotope fractionation between DIC and precipitating cements was treated as a Rayleigh distillation process. Organic matter oxidation was coupled to microbial fermentation and sulfate reduction. All reaction models reproduced the observed chemical and isotopic compositions of final waters. However, model 1, in which all sources of carbon and electron-acceptors were assumed to be internal to the aquifer, was invalidated owing to the large ratio of fermentation CO 2 to respiration CO 2 predicted by the model (5–49) compared with measured ratios (two or less). In model 2, this ratio was reduced by assuming that confining beds adjacent to the aquifer act as sources of dissolved organic carbon and sulfate. This assumption was based on measured high concentrations of dissolved organic acids and sulfate in confining-bed pore waters (60–100 μM and 100–380 μM, respectively) relative to aquifer pore waters (from less than 30 μM and 2–80 μM, respectively). Sodium was chosen as the companion ion to organic-acid and sulfate transport from confining beds because it is the predominant cation in confining-bed pore waters. As a result, excessive amounts of Na-for-Ca ion exchange and calcite precipitation (three to four times more cement than observed in the aquifer) were required by model 2 to achieve mass and isotope balance of final water. For this reason, model 2 was invalidated. Agreement between model-predicted and measured amounts of carbonate cement and ratios of fermentation CO 2 to respiration CO 2 were obtained in a reaction model that assumed confining beds act as sources of DIC, as well as organic acids and sulfate. This assumption was supported by measured high concentrations of DIC in confining beds (2.6–2.7 mM). Results from this study show that geochemical models of confined aquifer systems must incorporate the effects of adjacent confining beds to reproduce observed groundwater chemistry accurately.

South Carolina↗

USGS2019

Isolation of methylmercury using distillation and anion-exchange chromatography for isotopic analyses in natural matrices

The development of mercury (Hg) stable isotope measurements has enhanced the study of Hg sources and transformations in the environment. As a result of the mixing of inorganic Hg (iHg) and methylmercury (MeHg) species within organisms of the aquatic food web, understanding species-specific Hg stable isotopic compositions is of significant importance. The lack of MeHg isotope measurements is due to the analytical difficulty in the separation of the MeHg from the total Hg pool, with only a few methods having been tested over the past decade with varying degrees of success, and only a handful of environmentally relevant measurements. Here, we present a novel anion-exchange resin separation method using AG 1-X4 that further isolates MeHg from the sample matrix, following a distillation pretreatment, in order to obtain ambient MeHg stable isotopic compositions. This method avoids the use of organic reagents, does not require complex instrumentation, and is applicable across matrices. Separation tests across sediment, water, and biotic matrices showed acceptable recoveries (98 ± 5%, n = 54) and reproducible δ 202 Hg isotope results (2 SDs ≤ 0.15‰) down to 5 ng of MeHg. The measured MeHg pools in natural matrices, such as plankton and sediments, showed large deviations from the non-speciated total Hg measurement, indicating that there is an important isotopic shift during methylation that is not recorded by typical measurements, but is vital in order to assess sources of Hg during bioaccumulation.

Analytical and Bioanalytical Chemistry↗