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Use of chemical analysis and assays of semipermeable membrane devices extracts to assess the response of bioavailable organic pollutants in streams to urbanization in six metropolitan areas of the United States

Studies to assess the effects of urbanization on stream ecosystems are being conducted as part of the U.S. Geological Survey’s National Water-Quality Assessment (NAWQA) Program. The overall objectives of these studies are to (1) determine how hydrologic, geomorphic, water quality, habitat, and biological characteristics respond to land-use changes associated with urbanization in specific environmental settings, and (2) compare these responses across environmental settings. As part of an integrated assessment, semipermeable membrane devices (SPMDs) were deployed in streams along a gradient of urban land-use intensity in and around Atlanta, Georgia; Raleigh-Durham, North Carolina; and Denver-Fort Collins, Colorado, in 2003; and Dallas-Fort Worth, Texas; Milwaukee-Green Bay, Wisconsin; and Portland, Oregon, in 2004. Sites were selected to avoid point-source discharge and to minimize natural variability within each of the six metropolitan areas. In addition to standard chemical analysis for hydrophobic organic contaminants, three assays were used to address mixtures and potential toxicity: (1) Fluoroscan provides an estimate of the total concentration of polycyclic aromatic hydrocarbons (PAHs); (2) the P450RGS assay indicates the presence and levels of aryl hydrocarbon receptor agonists; and (3) Microtox® measures toxicological effects on photo-luminescent bacteria. Of the 140 compounds targeted or identified by gas chromatography/mass spectrometry analysis in this study, 67 were not detected. In terms of numbers and types of compounds, the following were detected: 2 wood preservatives, 6 insecticides (parent compounds), 5 herbicides, 22 polycyclic aromatic hydrocarbons, 2 dibenzofurans, 4 polychlorinated biphenyls, 7 compounds associated with fragrances or personal care products, 4 steroids associated with wastewater, 5 polydibromated diphenyl ethers (flame retardants), 3 plasticizers, 3 antimicrobials/disinfectants, and 3 detergent metabolites. Of the 73 compounds detected and three assays utilized, 29 were detected in 25 percent or more of the streams and were strongly related to increases in urban intensity (defined as having a Spearman’s rho > 0.5 with percent urban land cover) in at least one of the six metropolitan areas investigated. These 29 endpoints included 16 PAHs, a wood preservative (pentachloroanisole), 2 insecticides (chlorpyrifos and chlordane), 3 herbicides (benfluralin, trifluralin, and dacthal), a synthetic musk (hexahydrohexamethylcyclopentabenzopyran, HHCB), 2 furans (methyldibenzofuran and benzo[b]naphtho[2,3-d]furan), and a flame retardant (BDE 47). In addition, the number of compounds detected and results of the Fluoroscan and P450RGS assays were strongly related to urban intensity. Average water concentrations estimated from SPMDs were compared to screening benchmarks for the protection of human health and aquatic life; of the 14 compounds with available benchmarks, 3 compounds (anthracene, dieldrin, and diazinon) exceeded those levels in one or more streams. Both dieldrin and anthracene exceeded their respective benchmarks in seven streams, and diazinon in only one stream. There were more exceedances in Milwaukee-Green Bay and Raleigh-Durham than in the other metropolitan areas, and there were no exceedances in Dallas-Fort Worth. The six metropolitan areas studied differed in the number and types of endpoints related to urban intensity, probably from a combination of factors governing source strength, transport, and fate of hydrophobic compounds. The number of endpoints strongly related to urban intensity ranged from 3 in Dallas-Fort Worth and Portland to 21 in Raleigh-Durham. High frequencies of detection and strong correlations with urban land cover for pyrogenic PAHs (such as unsubstituted 4-ringed PAHs) in all six metropolitan areas indicate that these compounds are an important component of urbanization, regardless of location. Pentachloroanisole, dibenzofurans, and petrogenic PAHs (alkylated PAHs and heterocyclic dibenzothiophenes) were frequently detected and strongly related to urban intensity in Atlanta, Raleigh-Durham, Milwaukee-Green Bay, and Denver-Fort Collins. Two insecticides were related to urban intensity: chlorpyrifos in Atlanta, Raleigh-Durham, and Dallas-Fort Worth; and chlordane in Raleigh-Durham. Three herbicides were strongly related to urban intensity: trifluralin in Atlanta and Raleigh-Durham; benfluralin in Atlanta, and dacthal in Denver-Fort Collins. The detection frequencies for most wastewater indicator compounds were too low to establish relations with urban intensity. Of the wastewater compounds analyzed, HHCB in Raleigh-Durham and Denver-Fort Collins, and BDE 47 in Denver-Fort Collins and Dallas-Forth Worth, had the strongest relations with urban intensity. In addition to pyrogenic PAHs, levels of aryl hydrocarbon receptor agonists (as measured by the P450RGS assay) were strongly related to increasing urban intensity in all six metropolitan areas. PAHs were the only group of aryl hydrocarbon agonists consistently detected and related with urban intensity in all six metropolitan areas. It is unknown which compounds in the SPMDs caused the increased response in the P450RGS assay because the SPMDs likely contained many aryl hydrocarbon receptor agonists not quantified by chemical analysis. It is clear that bioavailable, aryl hydrocarbon receptor agonists increase in streams with increasing urban intensity in the basin. Potential toxicity mediated by this metabolic pathway should be considered in integrated assessments of the response of aquatic biota to urbanization.

Scientific Investigations Report↗

Gasoline-Related Compounds in Lakes Mead and Mohave, Nevada, 2004-06

The distribution of man-made organic compounds, specifically gasoline-derived compounds, was investigated from 2004 to 2006 in Lakes Mead and Mohave and one of its tributary streams, Las Vegas Wash. Compounds contained in raw gasoline (benzene, toluene, ethylbenzene, xylenes; also known as BTEX compounds) and those produced during combustion of gasoline (polycyclic aromatic hydrocarbon compounds; also known as PAH compounds) were detected at every site sampled in Lakes Mead and Mohave. Water-quality analyses of samples collected during 2004-06 indicate that motorized watercraft are the major source of these organic compounds to the lakes. Concentrations of BTEX increase as the boating season progresses and decrease to less than detectable levels during the winter when few boats are on the water. Volatilization and microbial degradation most likely are the primary removal mechanisms for BTEX compounds in the lakes. Concentrations of BTEX compounds were highest at sampling points near marinas or popular launching areas. Methyl tert-butyl ether (MTBE) was detected during 2004 but concentrations decreased to less than the detection level during the latter part of the study; most likely due to the removal of MTBE from gasoline purchased in California. Distribution of PAH compounds was similar to that of BTEX compounds, in that, concentrations were highest at popular boating areas and lowest in areas where fewer boats traveled. PAH concentrations were highest at Katherine Landing and North Telephone Cove in Lake Mohave where many personal watercraft with carbureted two-stroke engines ply the waters. Lake-bottom sediment is not a sink for PAH as indicated by the low concentrations detected in sediment samples from both lakes. PAH compounds most likely are removed from the lakes by photochemical degradation. PAH compounds in Las Vegas Wash, which drains the greater Las Vegas metropolitan area, were present in relatively high concentrations in sediment from the upstream reaches. Concentrations of PAH compounds were low in water and sediment samples collected farther downstream, thus the bottom sediment in the upstream part of the wash may be an effective trap for these compounds. Bioavailable PAH compounds were present in all samples as determined using the Fluoroscan method. Microtox acute toxicity profiles indicated that Callville Bay in Lake Mead and the two Lake Mohave sites had only minor evidence that toxic compounds are present.

Scientific Investigations Report↗

Biomonitoring of Environmental Status and Trends (BEST) Program: Environmental contaminants, health indicators, and reproductive biomarkers in fish from the Mobile, Apalachicola-Chattahoochee-Flint, Savannah, and Pee Dee River Basins

Largemouth bass ( Micropterus salmoides ) and common carp ( Cyprinus carpio ) were collected from 13 sites in 4 river basins in the southeastern United States to document spatial trends in accumulative contaminants, health indicators, and reproductive biomarkers. Organochlorine residues, 2,3,7,8- tetrachlorodibenzo-p-dioxin-like activity (TCDD-EQ), and elemental contaminants were measured in composite samples of whole fish, grouped by species and gender, from each site. Fish were field-examined for external and internal anomalies, selected organs were weighed to compute somatic indices, and tissue and fluid samples were preserved for fish health and reproductive biomarker analyses. Mercury concentrations in bass samples from all sites exceeded toxicity thresholds for mammals [>0.1 micrograms per gram wet weight (ug/g ww)], fish (>0.2 ug/g ww), and birds (>0.3 ug/g ww) and were greatest (>0.5 ug/g ww) in samples from the Alabama River at Eureka Landing, Alabama; the Mobile River at Bucks, Alabama; the Apalachicola River at Blountstown, Florida; the Savannah River at Sylvania, Georgia; and the Pee Dee River at Bucksport, South Carolina. Selenium concentrations were relatively high (>0.75 ug/g ww) in fish from the Tombigbee River at Lavaca, Alabama; the Mobile River at Bucks; and the Chattahoochee River at Omaha, Georgia compared to those from other sites. Concentrations of 2,2-bis (p-chlorophenyl)- 1,1-dichloroethylene (p,p'-DDE) were high in fish from the Chattahoochee River at Omaha and the Mobile River near Bucks, which was near a 2,2-bis (p-chlorophenyl)-1,1- dichloroethylene (DDT) formulating facility that historically discharged into the lower Mobile River. Toxaphene concentrations in fish from the Flint River near Albany, Georgia (60-100 nanograms per gram (ng/g) ww) may pose a risk to fish. Concentrations of other formerly used (total chlordanes, dieldrin, endrin, aldrin, mirex, and hexachlorobenzene) and currently used (pentachlorobenzene, pentachloroanisole, dacthal, endosulfan, y-HCH, and methoxychlor) organochlorine residues generally were low or did not exceed toxicity thresholds. Total polychlorinated biphenyls concentrations in samples from the Coosa River at Childersburg, Alabama; the Apalachicola River at Omaha; the Apalachicola River at Blountstown; and the Pee Dee River at Bucksport were >480 ng/g ww and may be a risk to piscivorous wildlife. Dioxin-like activity as measured by TCDD-EQ was greatest [>10 picograms per gram (pg/g)] in male fish from the Coosa River at Childersburg and the Mobile River at Bucks. Hepatic ethoxyresorufin O-deethylase activity generally was greatest in carp from the Mobile River Basin [means >10 picomols per minute per milligram of protein (pmol/min/mg)] and in bass from the Tombigbee River at Lavaca and Pee Dee River at Pee Dee, South Carolina (means >65 pmol/min/mg). Altered biomarkers were noted in fish from all basins. The field necropsy and histopathological examination determined that fish from the Mobile River Basin generally were in poorer health than those from the other basins. In bass, health assessment index scores were correlated with mercury and p,p'-DDE concentrations. High health assessment index scores in Mobile River Basin fish were widespread and caused primarily by parasitic infestations, which were most severe in fish from the Tombigbee River at Lavaca and the Alabama River at Eureka Landing. Tumors were present in few fish (n = 5; 0.01%). Ovarian tumors of the same origin (smooth muscle) were present in two older carp from the Chattahoochee River near Omaha, Georgia and may be contaminant related. Reproductive biomarkers including gonadosomatic index, vitellogenin concentrations, and steroid hormone concentrations were anomalous in fish from various sites but were not consistently related to any particular chemical contaminant. Intersex gonads were identified in 47 male bass (42%) representing 12 sites and may indicate exposure to endocrine disrupting comp

Mobile, Apalachicola-Chattahoochee-Flint, Savannah↗

Sedimentation and occurrence and trends of selected nutrients, other chemical constituents, and diatoms in bottom sediment, Fall River Lake, southeast Kansas, 1948-2006

A combination of available bathymetric-survey information and bottom-sediment coring was used to investigate sedimentation and the occurrence of selected nutrients (total nitrogen and total phosphorus), organic and total carbon, 25 trace elements, diatoms, and the radionuclide cesium-137 in the bottom sediment of Fall River Lake, southeast Kansas. The total estimated volume and mass of bottom sediment deposited from 1948 through 2006 in the original conservation pool of the reservoir was 470 million cubic feet and 18.8 billion pounds, respectively. The estimated sediment volume occupied about 36 percent of the original conservation-pool, water-storage capacity of the reservoir. Mean annual net sediment deposition since 1948 in the original conservation pool of the reservoir was estimated to be 324 million pounds per year. Mean annual net sediment yield from the Fall River Lake Basin was estimated to be 585,000 pounds per square mile per year. The mean annual net loads of total nitrogen and total phosphorus deposited in the bottom sediment of Fall River Lake were estimated to be 648,000 pounds per year and 267,000 pounds per year, respectively. The estimated mean annual net yields of total nitrogen and total phosphorus from the Fall River Lake Basin were 1,170 pounds per square mile per year and 480 pounds per square mile per year, respectively. Throughout the history of Fall River Lake, total nitrogen and total phosphorus concentrations in the deposited sediment were relatively uniform. Trace element concentrations in the bottom sediment of Fall River Lake generally were uniform over time. Arsenic, chromium, nickel, and zinc concentrations typically exceeded the threshold-effects guidelines, which represent the concentrations above which toxic biological effects occasionally occur. Trace element concentrations did not exceed the probable-effects guidelines (available for eight trace elements), which represent the concentrations above which toxic biological effects usually or frequently occur. Diatom occurrence in the bottom sediment of Fall River Lake was dominated by the species Aulacoseira granulata , which is an indicator of eutrophic (nutrient-rich) conditions. The abundance of the diatom Aulacoseira granulata , combined with cyanobacteria evidence and historical water-quality data, indicated that Fall River Lake likely has been eutrophic throughout much of its history.

Kansas↗

Sedimentation, sediment quality, and upstream channel stability, John Redmond Reservoir, east-central Kansas, 1964-2009

A combination of available bathymetric-survey information, bottom-sediment coring, and historical streamgage information was used to investigate sedimentation, sediment quality, and upstream channel stability for John Redmond Reservoir, east-central Kansas. Ongoing sedimentation is reducing the ability of the reservoir to serve several purposes including flood control, water supply, and recreation. The total estimated volume and mass of bottom sediment deposited between 1964 and 2009 in the conservation pool of the reservoir was 1.46 billion cubic feet and 55.8 billion pounds, respectively. The estimated sediment volume occupied about 41 percent of the conservation-pool, water-storage capacity of the reservoir. Water-storage capacity in the conservation pool has been lost to sedimentation at a rate of about 1 percent annually. Mean annual net sediment deposition since 1964 in the conservation pool of the reservoir was estimated to be 1.24 billion pounds per year. Mean annual net sediment yield from the reservoir basin was estimated to be 411,000 pounds per square mile per year Information from sediment cores shows that throughout the history of John Redmond Reservoir, total nitrogen concentrations in the deposited sediment generally were uniform indicating consistent nitrogen inputs to the reservoir. Total phosphorus concentrations in the deposited sediment were more variable than total nitrogen indicating the possibility of changing phosphorus inputs to the reservoir. As the principal limiting factor for primary production in most freshwater environments, phosphorus is of particular importance because increased inputs can contribute to accelerated reservoir eutrophication and the production of algal toxins and taste-and-odor compounds. The mean annual net loads of total nitrogen and total phosphorus deposited in the bottom sediment of the reservoir were estimated to be 2,350,000 pounds per year and 1,030,000 pounds per year, respectively. The estimated mean annual net yields of total nitrogen and total phosphorus from the reservoir basin were 779 pounds per square mile per year and 342 pounds per square mile per year, respectively. Trace element concentrations in the bottom sediment of John Redmond Reservoir generally were uniform over time. As is typical for eastern Kansas reservoirs, arsenic, chromium, and nickel concentrations typically exceeded the threshold-effects guidelines, which represent the concentrations above which toxic biological effects occasionally occur. Trace element concentrations did not exceed the probable-effects guidelines (available for eight trace elements), which represent the concentrations above which toxic biological effects usually or frequently occur. Organochlorine compounds either were not detected or were detected at concentrations that were less than the threshold-effects guidelines. Stream channel banks, compared to channel beds, likely are a more important source of sediment to John Redmond Reservoir from the upstream basin. Other sediment sources include surface-soil erosion in the basin and shoreline erosion in the reservoir.

Scientific Investigations Report↗

Sedimentation and occurrence and trends of selected nutrients, other chemical constituents, and cyanobacteria in bottom sediment, Clinton Lake, northeast Kansas, 1977-2009

A combination of available bathymetric-survey information and bottom-sediment coring was used to investigate sedimentation and the occurrence of selected nutrients (total nitrogen and total phosphorus), organic and total carbon, 25 trace elements, cyanobacterial akinetes, and the radionuclide cesium-137 in the bottom sediment of Clinton Lake, northeast Kansas. The total estimated volume and mass of bottom sediment deposited from 1977 through 2009 in the conservation (multi-purpose) pool of the reservoir was 438 million cubic feet and 18 billion pounds, respectively. The estimated sediment volume occupied about 8 percent of the conservation-pool, water-storage capacity of the reservoir. Sedimentation in the conservation pool has occurred about 70 percent faster than originally projected at the time the reservoir was completed. Water-storage capacity in the conservation pool has been lost to sedimentation at a rate of about 0.25 percent annually. Mean annual net sediment deposition since 1977 in the conservation pool of the reservoir was estimated to be 563 million pounds per year. Mean annual net sediment yield from the Clinton Lake Basin was estimated to be 1.5 million pounds per square mile per year. Typically, the bottom sediment sampled in Clinton Lake was at least 99 percent silt and clay. The mean annual net loads of total nitrogen and total phosphorus deposited in the bottom sediment of Clinton Lake were estimated to be 1.29 million pounds per year and 556,000 pounds per year, respectively. The estimated mean annual net yields of total nitrogen and total phosphorus from the Clinton Lake Basin were 3,510 pounds per square mile per year and 1,510 pounds per square mile per year, respectively. Throughout the history of Clinton Lake, total nitrogen concentrations in the deposited sediment generally were uniform and indicated consistent inputs to the reservoir over time. Likewise, total phosphorus concentrations in the deposited sediment generally were uniform. Although, for two of three coring sites, a possible positive trend in phosphorus deposition was indicated. The Wakarusa River possibly was a larger contributor of nitrogen and phosphorus to Clinton Lake than was Rock Creek. As a principal limiting factor for primary production in most freshwater environments, phosphorus is of particular importance because increased inputs can contribute to accelerated reservoir eutrophication and the production of algal toxins and taste-and-odor compounds. Trace-element concentrations in the bottom sediment of Clinton Lake generally were uniform over time. As is typical for eastern Kansas reservoirs, arsenic, chromium, and nickel concentrations typically exceeded the threshold-effects guidelines, which represent the concentrations above which toxic biological effects occasionally occur. Zinc concentrations frequently exceeded the threshold-effects guideline. Trace-element concentrations did not exceed the probable-effects guidelines (available for eight trace elements), which represent the concentrations above which toxic biological effects usually or frequently occur. Cyanobacterial akinetes (cyanobacteria resting stage) in the bottom sediment of Clinton Lake, combined with historical water-quality data on chlorophyll-a and total phosphorus concentrations, indicated that the reservoir likely has been eutrophic throughout most of its history. A statistically significant increase in cyanobacterial akinetes in the bottom sediment indicated that Clinton Lake may have become more eutrophic over the life of the reservoir. The increase in cyanobacterial akinetes may, in part, be related to a possible increase in total phosphorus concentrations.

Scientific Investigations Report↗

Organic contaminants, trace and major elements, and nutrients in water and sediment sampled in response to the Deepwater Horizon oil spill

Beach water and sediment samples were collected along the Gulf of Mexico coast to assess differences in contaminant concentrations before and after landfall of Macondo-1 well oil released into the Gulf of Mexico from the sinking of the British Petroleum Corporation's Deepwater Horizon drilling platform. Samples were collected at 70 coastal sites between May 7 and July 7, 2010, to document baseline, or "pre-landfall" conditions. A subset of 48 sites was resampled during October 4 to 14, 2010, after oil had made landfall on the Gulf of Mexico coast, called the "post-landfall" sampling period, to determine if actionable concentrations of oil were present along shorelines. Few organic contaminants were detected in water; their detection frequencies generally were low and similar in pre-landfall and post-landfall samples. Only one organic contaminant--toluene--had significantly higher concentrations in post-landfall than pre-landfall water samples. No water samples exceeded any human-health benchmarks, and only one post-landfall water sample exceeded an aquatic-life benchmark--the toxic-unit benchmark for polycyclic aromatic hydrocarbons (PAH) mixtures. In sediment, concentrations of 3 parent PAHs and 17 alkylated PAH groups were significantly higher in post-landfall samples than pre-landfall samples. One pre-landfall sample from Texas exceeded the sediment toxic-unit benchmark for PAH mixtures; this site was not sampled during the post-landfall period. Empirical upper screening-value benchmarks for PAHs in sediment were exceeded at 37 percent of post-landfall samples and 22 percent of pre-landfall samples, but there was no significant difference in the proportion of samples exceeding benchmarks between paired pre-landfall and post-landfall samples. Seven sites had the largest concentration differences between post-landfall and pre-landfall samples for 15 alkylated PAHs. Five of these seven sites, located in Louisiana, Mississippi, and Alabama, had diagnostic geochemical evidence of Macondo-1 oil in post-landfall sediments and tarballs. For trace and major elements in water, analytical reporting levels for several elements were high and variable. No human-health benchmarks were exceeded, although these were available for only two elements. Aquatic-life benchmarks for trace elements were exceeded in 47 percent of water samples overall. The elements responsible for the most exceedances in post-landfall samples were boron, copper, and manganese. Benchmark exceedances in water could be substantially underestimated because some samples had reporting levels higher than the applicable benchmarks (such as cobalt, copper, lead and zinc) and some elements (such as boron and vanadium) were analyzed in samples from only one sampling period. For trace elements in whole sediment, empirical upper screening-value benchmarks were exceeded in 57 percent of post-landfall samples and 40 percent of pre-landfall samples, but there was no significant difference in the proportion of samples exceeding benchmarks between paired pre-landfall and post-landfall samples. Benchmark exceedance frequencies could be conservatively high because they are based on measurements of total trace-element concentrations in sediment. In the less than 63-micrometer sediment fraction, one or more trace or major elements were anthropogenically enriched relative to national baseline values for U.S. streams for all sediment samples except one. Sixteen percent of sediment samples exceeded upper screening-value benchmarks for, and were enriched in, one or more of the following elements: barium, vanadium, aluminum, manganese, arsenic, chromium, and cobalt. These samples were evenly divided between the sampling periods. Aquatic-life benchmarks were frequently exceeded along the Gulf of Mexico coast by trace elements in both water and sediment and by PAHs in sediment. For the most part, however, significant differences between pre-landfall and post-landfall samples were limited to concentrations of PAHs in sediment. At five sites along the coast, the higher post-landfall concentrations of PAHs were associated with diagnostic geochemical evidence of Deepwater Horizon Macondo-1 oil.

Alabama, Arkansas, Florida, Georgia, Louisiana, Te↗

Quality of streams in Johnson County, Kansas, 2002--10

Stream quality in Johnson County, northeastern Kansas, was assessed on the basis of land use, hydrology, stream-water and streambed-sediment chemistry, riparian and in-stream habitat, and periphyton and macroinvertebrate community data collected from 22 sites during 2002 through 2010. Stream conditions at the end of the study period are evaluated and compared to previous years, stream biological communities and physical and chemical conditions are characterized, streams are described relative to Kansas Department of Health and Environment impairment categories and water-quality standards, and environmental factors that most strongly correlate with biological stream quality are evaluated. The information is useful for improving water-quality management programs, documenting changing conditions with time, and evaluating compliance with water-quality standards, total maximum daily loads (TMDLs), National Pollutant Discharge Elimination System (NPDES) permit conditions, and other established guidelines and goals. Constituent concentrations in water during base flow varied across the study area and 2010 conditions were not markedly different from those measured in 2003, 2004, and 2007. Generally the highest specific conductance and concentrations of dissolved solids and major ions in water occurred at urban sites except the upstream Cedar Creek site, which is rural and has a large area of commercial and industrial land less than 1 mile upstream on both sides of the creek. The highest base-flow nutrient concentrations in water occurred downstream from wastewater treatment facilities. Water chemistry data represent base-flow conditions only, and do not show the variability in concentrations that occurs during stormwater runoff. Constituent concentrations in streambed sediment also varied across the study area and some notable changes occurred from previously collected data. High organic carbon and nutrient concentrations at the rural Big Bull Creek site in 2003 decreased to at least one-fourth of those concentrations in 2007 and 2010 likely because of the reduction in upstream wastewater discharge contributions. The highest concentrations of trace metals in 2010 occurred at urban sites on Mill and Indian Creeks. Zinc was the only metal to exceed the probable effects concentration in 2010, which occurred at a site on Indian Creek. In 2007, chromium and nickel at the upstream urban Cedar Creek site exceeded the probable effects concentrations, and in 2003, no metals exceeded the probable effects concentrations. Of 72 organic compounds analyzed in streambed sediment, 26 were detected including pesticides, polycyclic aromatic hydrocarbons (PAHs), fuel products, fragrances, preservatives, plasticizers, manufacturing byproducts, flame retardants, and disinfectants. All 6 PAH compounds analyzed were detected, and the probable effects concentrations for 4 of the 6 PAH compounds analyzed were exceeded in 2010. Only five pesticide compounds were detected in streambed sediment, including carbazole and four pyrethroid compounds. Chronic toxicity guidelines for pyrethroid compounds were exceeded at five sites. Biological conditions reflected a gradient in urban land use, with the less disturbed streams located in rural areas of Johnson County. About 19 percent of sites in 2010 (four sites) were fully supporting of aquatic life on the basis of the four metrics used by Kansas Department of Health and Environment to categorize sites. This is a notable difference compared to previous years when no sites (in 2003 and 2004) or just one site (in 2007) was fully supporting of aquatic life. Multimetric macroinvertebrate scores improved at the Big Bull Creek site where wastewater discharges were reduced in 2007. Environmental variables that consistently were highly negatively correlated with biological conditions were percent impervious surface and percent urban land use. In addition, density of stormwater outfall points adjacent to streams was significantly negatively correlated with biological conditions. Specific conductance of water and sum of PAH concentrations in streambed sediment also were significantly negatively correlated with biological conditions. Total nitrogen in water and total phosphorus in streambed sediment were correlated with most of the invertebrate variables, which is a notable difference from previous analyses using smaller datasets, in which nutrient relations were weak or not detected. The most important habitat variables were sinuosity, length and continuity of natural buffers, riffle substrate embeddedness, and substrate cover diversity, each of which was correlated with all invertebrate metrics including a 10-metric combined score. Correlation analysis indicated that if riparian and in-stream habitat conditions improve then so might invertebrate communities and stream biological quality. Sixty-two percent of the variance in macroinvertebrate community metrics was explained by the single environmental factor, percent impervious surface. Invertebrate responses to urbanization in Johnson County indicated linearity rather than identifiable thresholds. Multiple linear regression models developed for each of the four macroinvertebrate metrics used to determine aquatic-life-support status indicated that percent impervious surface, as a measure of urban land use, explained 34 to 67 percent of the variability in biological communities. Results indicate that although multiple factors are correlated with stream quality degradation, general urbanization, as indicated by impervious surface area or urban land use, consistently is determined to be the fundamental factor causing change in stream quality. Effects of urbanization on Johnson County streams are similar to effects described in national studies that assess effects of urbanization on stream health. Individually important environmental factors such as specific conductance of water, PAHs in streambed sediment, and stream buffer conditions, are affected by urbanization and, collectively, all contribute to stream impairments. Policies and management practices that may be most important in protecting the health of streams in Johnson County are those minimizing the effects of impervious surface, protecting stream corridors, and decreasing the loads of sediment, nutrients, and toxic chemicals that directly enter streams through stormwater runoff and discharges.

Kansas↗

Water quality of streams draining abandoned and reclaimed mined lands in the Kantishna Hills area, Denali National Park and Preserve, Alaska, 2008–11

The Kantishna Hills are an area of low elevation mountains in the northwest part of Denali National Park and Preserve, Alaska. Streams draining the Kantishna Hills are clearwater streams that support several species of fish and are derived from rain, snowmelt, and subsurface aquifers. However, the water quality of many of these streams has been degraded by mining. Past mining practices generated acid mine drainage and excessive sediment loads that affected water quality and aquatic habitat. Because recovery through natural processes is limited owing to a short growing season, several reclamation projects have been implemented on several streams in the Kantishna Hills region. To assess the current water quality of streams in the Kantishna Hills area and to determine if reclamation efforts have improved water quality, a cooperative study between the U.S. Geological Survey and the National Park Service was undertaken during 2008-11. High levels of turbidity, an indicator of high concentrations of suspended sediment, were documented in water-quality data collected in the mid-1980s when mining was active. Mining ceased in 1985 and water-quality data collected during this study indicate that levels of turbidity have declined significantly. Turbidity levels generally were less than 2 Formazin Nephelometric Units and suspended sediment concentrations generally were less than 1 milligram per liter during the current study. Daily turbidity data at Rock Creek, an unmined stream, and at Caribou Creek, a mined stream, documented nearly identical patterns of turbidity in 2009, indicating that reclamation as well as natural revegetation in mined streams has improved water quality. Specific conductance and concentrations of dissolved solids and major ions were highest from streams that had been mined. Most of these streams flow into Moose Creek, which functions as an integrator stream, and dilutes the specific conductance and ion concentrations. Calcium and magnesium are the dominant cations, and bicarbonate and sulfate are the dominant anions. Water samples indicate that the water from Rock Creek, Moose Creek, Slate Creek, and Eldorado Creek is a calcium bicarbonate-type water. The remaining sites are a calcium sulfate type water. U.S. Environmental Protection Agency guidelines for arsenic and antimony in drinking water were exceeded in water at Slate Creek and Eureka Creek. Concentrations of arsenic, cadmium, chromium, copper, lead, nickel, and zinc in streambed sediments at many sites exceed sediment quality guideline thresholds that could be toxic to aquatic life. However, assessment of these concentrations, along with the level of organic carbon detected in the sediment, indicate that only concentrations of arsenic and chromium may be toxic to aquatic life at many sites. In 2008 and 2009, 104 macroinvertebrate taxa and 164 algae taxa were identified from samples collected from seven sites. Of the macroinvertebrates, 86 percent were insects and most of the algae consisted of diatoms. Based on the National Community Index, Rock Creek, a reference site, and Caribou Creek, and a mined stream that had undergone some reclamation, exhibited the best overall stream conditions; whereas Slate Creek and Friday Creek, two small streams that were mined extensively, exhibited the worst stream conditions. A non-metric multi-dimensional scaling analysis of the macroinvertebrate and algae data showed a distinct grouping between the 2008 and 2009 samples, likely because of differences between a wet, cool summer in 2008 and a dry, warm summer in 2009.

Alaska↗

Occurrence and trends of selected nutrients, other chemical constituents, diatoms, and cyanobacteria in bottom sediment, Lake Maxinkuckee, northern Indiana

Bottom-sediment cores collected in 2013 were used to investigate the recent and predevelopment (pre-1863) occurrence of selected nutrients (total nitrogen and total phosphorus), carbon, 39 trace elements, diatoms, cyanobacterial akinetes, and 3 radionuclides in the bottom sediment of Lake Maxinkuckee, a kettle lake in northern Indiana. Total nitrogen concentrations in the recent sediment (since about 1970) were variable with no consistent trend indicated. Total phosphorus concentrations in the recent sediment generally were uniform from about 1970 to about 2000 and indicated consistent inputs to the lake during that time. Subsequently, the history of total phosphorus deposition apparently was obscured by postdepositional upward diffusion. Trace-element concentrations in the bottom sediment of Lake Maxinkuckee generally were not cause for concern. Elevated concentrations of cadmium, copper, lead, mercury, and zinc in the recent sediment, compared to the predevelopment sediment, indicated likely human-related contamination; however, the trace-element concentrations were less than probable-effects guidelines (available for nine trace elements), which represent the concentrations above which toxic aquatic biological effects usually or frequently occur. Arsenic concentrations typically exceeded the threshold-effects guideline, which represents the concentration above which toxic aquatic biological effects occasionally occur, in the recent and predevelopment sediment. The arsenic likely originated from natural sources. Lead concentrations historically exceeded the threshold-effects guideline, but since had decreased below it in the recent sediment at most coring sites. The decreasing trend likely was indicative of the effect of the phase out of leaded gasoline. Biological indicators in the bottom sediment provided evidence for an improving, or at least not worsening, lake trophic condition. The occurrence of multiple diatom species, none of which were overwhelmingly dominant, was indicative of a minimally contaminated lake ecosystem. The combined evidence of several diatom species in the recent sediment indicated that the lake had not become more productive in recent decades. The combined evidence provided by akinetes for three cyanobacterial genera in the recent and predevelopment sediment indicated similar nutrient conditions in the lake during the past 40 years and possibly back to at least the mid-1800s.

Indiana↗

Chemical and biological quality of water in Grand Lake St. Marys, Ohio, 2011-12, with emphasis on cyanobacteria

Grand Lake St. Marys (GLSM) is a shallow lake in northwest Ohio, which is about 9 miles long and 3 miles wide with depths averaging less than 8 feet. Cyanobacteria blooms are common in GLSM, and high concentrations of microcystins—toxins produced by cyanobacteria—have been documented therein. During 2011–12, the U.S. Geological Survey collected 11 sets of water samples at 6 locations in the lake. The water samples were analyzed for concentrations of nutrients, chlorophyll, and microcystin and to determine plankton community structure and abundance. Analysis by quantitative polymerase chain reaction (qPCR) and quantitative reverse-transcription polymerase chain reaction (qRT-PCR) was used to identify the relations between microcystin concentrations and Planktothrix and Microcystis genotypes (toxic versus non-toxic). The qPCR analysis targets deoxyribonucleic acid (DNA) genes and quantifies the potential for toxin production, whereas the qRT-PCR analysis targets ribonucleic acid (RNA) transcripts and quantifies the expression of the toxin gene. Water samples were collected six times at one site for analyses of major ions and trace elements. In addition, field measurements were made to determine transparency, temperature, dissolved oxygen, pH, and specific conductance of the water. GLSM is shallow with a long fetch, which contributes to the warm and turbid water conditions. Secchi-disk measurements generally ranged from 0.2 to 0.3 meters, and summer water temperatures in GLSM frequently exceed 25 degrees Celsius (°C), with peak temperatures greater than 30 °C. Dissolved oxygen readings below 0.5 milligrams per liter (mg/L) occurred at the lake bottom, which can lead to the internal recycling of phosphorus in the lake. Phytoplankton analyses indicated that GLSM is dominated by cyanobacteria with Planktothrix , the dominant genera during 2011–12. Nitrate ranged from 0.19 to 3.23 mg/L, although concentrations in most samples were less than 1 mg/L. Total nitrogen concentrations ranged from 1.86 to 5.42 mg/L. Orthophosphate (as P) concentrations ranged from less than 0.004 to 0.067 mg/L, although concentrations of most samples were less than 0.004 mg/L. Total phosphorus (as P) concentrations ranged from 0.12 to 0.43 mg/L. Microcystin concentrations ranged from 7.3 to 83 micrograms per liter. Microcystin concentrations were correlated to cyanobacteria biovolumes, and to concentrations of one ion (sodium) and three trace elements (molybdenum, antimony, and lithium). Concentrations of toxin genes ( mcyE ) determined by qPCR were consistently low for Microcystis and consistently high for Planktothrix throughout both sampling years. Concentrations of cyanobacteria found by qPCR were correlated to microcystin concentrations, cyanobacteria biovolumes, selected nutrient concentrations, and other parameters. Results from qRT-PCR assays showed that toxin gene expression was predominantly from the genus Planktothrix , and concentrations of the RNA transcript varied throughout the two sampling years. A number of conditions that may play a role in the dominance of Planktothrix and the production of microcystin were identified including water temperature; low-light transmission; low concentrations of silica and manganese; and relatively high concentrations of sodium, sulfate, and the trace elements of strontium, vanadium, and boron.

Ohio↗

Chloride concentrations, loads, and yields in four watersheds along Interstate 95, southeastern Connecticut, 2008-11: factors that affect peak chloride concentrations during winter storms

Chloride (Cl - ) concentrations and loads and other water chemistry characteristics were assessed to evaluate potential effects of road-deicer applications on streamwater quality in four watersheds along Interstate 95 (I–95) in southeastern Connecticut from November 1, 2008, through September 30, 2011. Streamflow and water quality were studied in the Four Mile River, Oil Mill Brook, Stony Brook, and Jordan Brook watersheds, where developed land ranged from 9 to 32 percent. Water-quality samples were collected and specific conductance was measured continuously at paired water-quality monitoring sites, upstream and downstream from I–95. Specific conductance values were related to Cl - concentrations to assist in determining the effects of road-deicing operations on the levels of Cl - in the streams. Streamflow and water-quality data were compared with weather data and with the timing, amount, and composition of deicers applied to State highways. Grab samples were collected during winter stormwater-runoff events, such as winter storms or periods of rain or warm temperatures in which melting takes place. Grab samples were also collected periodically during the spring and summer and during base-flow conditions. The estimated Cl - concentrations at the eight water-quality monitoring sites during winter storms peaked as high as 270 milligrams per liter (mg/L) and were well below the U.S. Environmental Protection Agency (EPA) recommended acute chloride toxicity criterion of 860 mg/L and the chronic 4-day average toxicity criterion of 230 mg/L. Cl - concentrations in streams, particularly at sites downstream from I–95, peaked during increased streamflow in the winter and early spring as a result of deicers applied to roads and washed off by stormwater or meltwater. Cl - concentrations during most of the nonwinter seasons decreased during increases in streamflow because storm runoff was more dilute than base flow. However, peaks in specific conductance and estimated chloride concentrations at streams in more urbanized watersheds corresponded to peaks in streamflow well after winter snow or ice events; these delayed peaks in Cl - concentration likely resulted from deicer residue that remained in melting snow piles and on roadsides and (or) that were flushed from soils and shallow groundwater, then discharged downstream. Estimated peak Cl - concentrations varied with the type of winter storm event and were highest during or after winter storms of frozen precipitation and rain, in which the rain or meltwater effectively washed off the deicers. Estimated peak Cl - concentrations correlated positively with the duration of deicer application but generally not with streamflow. Estimated peak Cl - concentrations during the winter season were highest during low streamflow at most sites. Chloride concentrations varied considerably in shallow groundwater as a result of land-use differences. Cl - concentrations were very high (as high as 800 mg/L) in shallow groundwater downstream from I–95 at the Four Mile River site. Chloride/bromide mass concentration ratios and the proximity of a former landfill and sewage lagoon upstream indicate a likely source of Cl - is landfill leachate and possibly sewage leachate. Cl - loads in streams generally were highest in the winter and early spring. The estimated daily Cl - yield for the four monitoring sites downstream from I–95 ranged from 0.0004 ton per day per square mile for one of the least developed watersheds to 0.052 ton per day per square mile for the watershed with the highest percentage of urban development and impervious area. The estimated median contribution of Cl - load from atmospheric deposition was small and ranged from 0.07 percent of Cl - load at the Jordan Brook watershed to 0.57 percent at the Oil Mill Brook watershed. The Cl - loads in streams (outputs) were compared with Cl - load inputs, which include atmospheric deposition and deicer applications; Cl - load inputs were slightly larger than the Cl - load outputs at most of the sites during most years but do not account for the Cl - load in groundwater leaving the watersheds. A multiple linear regression model was developed to describe the variability of the natural log of peak specific conductance, as well as estimated Cl - concentrations. Five significant variables best explained the variability in the natural log of the peak specific conductance after deicing events: (1) snow on ground before deicing event; (2) winter precipitation with rain; (3) specific conductance in base flow; (4) State-operated road lane miles divided by watershed area; and (5) amount of Cl - from deicers applied to State-operated roads per lane mile. In this report, winter precipitation is defined as any type of precipitation, including frozen precipitation and rain, that occurs during the active deicing season, typically November through March. Frozen precipitation is defined here as snow, sleet, freezing rain, or any winter precipitation except rain. The addition of a lane mile in both directions on I–95 would result in an estimate of approximately 2 to 11 percent increase in Cl - input from deicers applied to I–95 and other roads maintained by Connecticut Department of Transportation. The largest estimated increase in Cl - load was in the watersheds with the greatest number miles of I–95 corridor relative to the total lane miles maintained by Connecticut Department of Transportation. On the basis of these estimates and the estimated peak Cl - concentrations during the study period, it is unlikely that the increased use of deicers on the additional lanes would lead to Cl - concentrations that exceed the aquatic habitat criteria.

Connecticut↗

Surface-water quality and suspended-sediment quantity and quality within the Big River Basin, southeastern Missouri, 2011-13

Missouri was the leading producer of lead in the United States—as well as the world—for more than a century. One of the lead sources is known as the Old Lead Belt, located in southeast Missouri. The primary ore mineral in the region is galena, which can be found both in surface deposits and underground as deep as 200 feet. More than 8.5 million tons of lead were produced from the Old Lead Belt before operations ceased in 1972. Although active lead mining has ended, the effects of mining activities still remain in the form of large mine waste piles on the landscape typically near tributaries and the main stem of the Big River, which drains the Old Lead Belt. Six large mine waste piles encompassing more than 2,800 acres, exist within the Big River Basin. These six mine waste piles have been an available source of trace element-rich suspended sediments transported by natural erosional processes downstream into the Big River. A study was performed by the U.S. Geological Survey in cooperation with U.S. Environmental Protection Agency, Region 7, to calculate and characterize suspended-sediment quantity and quality within the Big River basin after reclamation of the mine waste piles ended in 2012. Streamflow and suspended sediments were quantified and sampled at two locations along a 68-mile reach of the Big River between Bonne Terre and Byrnes Mill, Missouri. The results will help regulatory agencies, such as the U.S. Environmental Protection Agency and U.S. Fish and Wildlife Service, determine impaired reaches and ecosystems for remedial and restoration efforts. Continuous stream stage, water temperature, and turbidity, and discrete suspended-sediment concentration data were collected at the two sites between October 2011 and September 2013. Suspended-sediment samples were collected during various hydrologic conditions to develop a regression model between discrete suspended-sediment concentration and continuous turbidity. Suspended sediments collected during stormflow events were analyzed for concentrations of trace elements such as barium, cadmium, lead, and zinc within two sediment size fractions. Event loads and annual loads of suspended sediment and select trace elements in suspended sediments also were calculated. Suspended-sediment loads computed by the regression model increased downstream from about 201,000 tons at the upstream site to about 355,000 tons at the downstream site during the study period. Stormflow-event-based (hereinafter referred to as “event-based”) suspended-sediment loads ranged from 180 to 32,000 tons at the upstream sampling site and 390 to 53,000 tons at the downstream site along the Big River. Although only seven stormflow events at the upstream site and six at the downstream site were sampled, the event-based suspended-sediment loads accounted for nearly 30 percent of the total suspended-sediment loads computed at both sites, indicating most of the suspended sediment transported through the Big River occurs during higher streamflows. Sediment quality guidelines, known as the threshold effect concentration and the probable effect concentration, used to assess toxicity of trace-element concentrations in sediments were compared to the cadmium, lead, and zinc concentrations in suspended sediment samples collected during stormflow events. All concentrations of cadmium, lead, and zinc in event-based suspended sediment samples exceeded the threshold and probable effect concentrations. Lead and zinc concentrations in the sediment size fraction less than 0.063 millimeters also exceeded the toxic effect threshold, above which sediment is considered to be heavily polluted causing adverse effects on sediment-dwelling organisms. Concentrations of cadmium and zinc in event-based suspended sediment samples were notably higher in samples from the upstream site than samples from the downstream site, indicating the sources of sediments enriched in these trace elements decrease in the downstream area of the watershed. The reduction in concentration of cadmium and zinc could be from dissolution of the constituents during transport or possibly a decrease in downstream source material. The lead concentration exceedance of the probable effects concentration as well as the threshold effects concentration indicates that lead-rich suspended sediments in the fraction less than 0.063 millimeters are readily available within the Big River Basin for transport. These sediments remain in the system from historical mining, and as the reclamation of mine waste piles in the upstream area of the watershed reduce additional sediment loadings, these fine sediments may be continually released as the river scours the streambed and erodes stream banks causing the lead-rich suspended sediment to remain in a state of equilibrium. Barium concentrations in suspended-sediments were nearly twice as high in stormflow event samples collected at the downstream site as compared to samples from the upstream site. The source of barium in the Big River could be from Mineral Fork and Mill Creek, which flow through the historical barite (barium sulfate, also known as tiff) mining district in Washington County, and discharge into the Big River between the two study sites. Total trace-element loads and yields in suspended sediments were computed from the sampled events for each year in the study. The total barium loads in suspended sediments were higher for sampled events collected at the downstream site than the upstream site during both study years. Cadmium and zinc loads in suspended sediments were lower at the downstream site than the upstream site, although the decrease in total load was not substantial during the study period. Lead loads in suspended sediments were lower at the downstream site during the first study year, with a slightly higher load downstream in the second year though the increase from upstream to downstream was small. Event-based yields were higher at the upstream site, indicating that readily available sediment sources are closer to the upstream site where more mining affected areas are located. The estimates determined during large precipitation events indicate that large sources of suspended sediments with large concentrations of trace elements are still available for transport within the Big River.

Missouri↗

Hydrology-driven chemical loads transported by the Green River to the Lower Duwamish Waterway near Seattle, Washington, 2013–17

The sediments in the Lower Duwamish Waterway Superfund site in Seattle, Washington, are contaminated with chemicals including metals such as arsenic, polychlorinated biphenyls (PCBs), carcinogenic polycyclic aromatic hydrocarbons (cPAHs), and dioxins/furans from decades of intense anthropogenic activities. The U.S. Geological Survey, in cooperation with the Washington State Department of Ecology, collected new data from 2013 to 2017 to estimate sediment and chemical loads transported by the Green/Duwamish River to the Lower Duwamish Waterway Superfund site (the final 8-kilometer reach of the river) in support of sediment remediation within the site. Chemical loads were calculated as the product of river suspended-sediment loads and suspended sediment-bound chemical concentrations measured at river kilometer 16.7. Using four different approaches, annual suspended sediment-bound chemical load estimates transported by the river to the Lower Duwamish Waterway were in the range of 1,120–1,470 kilograms arsenic, 2,810–8,200 grams (g) toxic equivalent cPAHs, 205–407 milligrams toxic equivalent dioxins/furans, and 340–1,180 g PCBs. Storm events contributed a disproportionately large amount of the load of anthropogenic organic compounds such as cPAHs (54 percent), dioxins/furans (44 percent), and PCBs (52 percent) as compared to overall time (17 percent). Chemical concentrations and load estimates often were underestimated using results from unfiltered water analysis only, especially in samples with high suspended-sediment concentrations and for hydrophobic organic chemicals such as cPAHs that prefer to sorb to particulates and are at low concentrations near or below the analytical limits of water methods. For metals and PCBs, the dissolved concentration was relatively low and consistent between sampling events, whereas the suspended sediment-bound chemical concentrations contributed most of the chemical concentration in the water column during periods of high river suspended-sediment concentrations. However, the dissolved fraction, on average, contributed more than one-third of the estimated total chemical load in the river system for arsenic and PCBs, even given the hydrophobic nature of the chemicals. These results suggest that the sum of the chemical concentrations measured on two separate fractions—the particulate fraction and the dissolved fraction—more fully represents the total chemical concentration as compared to analysis of an unfiltered water sample, especially in samples with high suspended-sediment concentrations. Most of the suspended-sediment load (97 percent) and sediment-bound chemical load (92–94 percent) occurred during the wet winter half of the year from October 15 to April 14. However, the highest sediment-bound chemical concentrations often occurred during short intense storms or “first flush” autumn runoff events during the dry summer half of the year from April 15 to October 14. Because of the highly variable and dynamic river system characteristics (including precipitation, discharge, sediment concentration, and tidal fluctuations), it is critical to characterize the occurrence, frequency, concentrations, and loads during extreme conditions (for example, when the river is affected by storm-derived runoff) rather than time-averaged conditions. These short extreme events have a high potential for acute effects on ecological and human health, and may have a great influence on the effectiveness of the sediment remediation activities that are underway in the Lower Duwamish Waterway.

Washington↗

Geochemical and mineralogical study of the Red Mountain porphyry copper-molybdenum deposit and vicinity, Santa Cruz County, Arizona

The Red Mountain porphyry copper-molybdenum deposit (Cu-Mo deposit or PCD) is located in the northern part of the Patagonia Mountains, Santa Cruz County, Arizona. Extensive core drilling has delineated a large, deep-seated, structurally intact mineral system that extends from the present surface to depths of more than 1,765 meters. This system is hosted in a thick complex of predominantly felsic to andesitic volcanic rocks of the Cretaceous Period. This complex was intruded by scattered bodies of the Tertiary Period that are predominantly quartz monzonite porphyry; no major associated source intrusion has yet been found at depth. A total of 818 samples of core were analyzed for as many as 44 elements. The abundances and distributions at depth of at least 17 of these elements (silver [Ag], arsenic [As], gold [Au], boron [B], bismuth [Bi], copper [Cu], mercury [Hg], potassium [K], molybdenum [Mo], lead [Pb], sulfur [S], antimony [Sb], tin [Sn], tellurium [Te], thallium [Tl], tungsten [W], and zinc [Zn]) are related mostly to events that generated the Red Mountain system. Many of these same samples were also analyzed by X-ray diffraction for a suite of minerals. The multielement and mineralogical analyses of the core samples provide important information about the concentrations, associations, and distributions of select elements and minerals, including zoning patterns that may not be apparent from visual examination of core samples. The distributions of selected elements and minerals in these samples reveal an unusually complete mineral system that extends from a typical PCD with potassic alteration at depth to peripheral zones of phyllic and advanced argillic alteration as well as a copper-rich supergene enriched zone and the remnants of a leached cap. R-mode factor analysis was run with 34 elements for a set of samples from the deep part of the hypogene Cu-Mo deposit and another set from the part of the supergene zone with the highest copper enrichment. For the hypogene zone dataset, five factors are related to the PCD: (1) Ag, Cu, Mo, S, and Te; (2) As, B, Hg, and Sb; (3) Au and sodium (Na); (4) manganese (Mn), Pb, and Zn; and (5) K and Tl. For the supergene dataset, the deposit-related factors include (1) Cu, Mo, S, and Te; (2) Ag, As, Hg, Pb, Sb, and Tl; (3) Au and Na; and (4) K and rubidium (Rb). The changes in element associations between the two datasets indicate that some of these new associations are a result of formation of several suites of hypogene minerals in the deep part of the deposit and different hypogene mineral suites in the peripheral part of the deposit. Some changes may be because of the effects of supergene processes. Zones containing deposit-related elements and minerals common to many PCDs are present at Red Mountain. These zones include a crude, inverted cup-shaped shell containing anomalous copper accompanied by high concentrations of Ag, Au, K, Mo, total S, sulfate S, Sb, Te, and Tl, as well as local concentrations of As, B, Hg, Pb, and Zn. Hydrothermal minerals spatially associated with the deep hypogene Cu-Mo deposit include chalcopyrite, molybdenite, pyrite, plagioclase, orthoclase, biotite, magnetite, calcite, quartz, and anhydrite. Many of the hydrothermally deposited elements that are spatially related to the deposit are also concentrated in zones above the deep part of the deposit, including Ag, As, K, Pb, Sb, Te, Tl, and Zn. These elements are concentrated either (1) in generally wide, flat zones present in the upper part of the system or (2) in crudely arcuate peripheral zones found mainly in the middle part of the system and surrounding the deep part of the deposit. Near-surface, restricted hypogene anomalies are present for bismuth, mercury, tin, and tungsten. The upper part of the deposit has been subjected to supergene enrichment and weathering. Deposit-related elements that remain anomalous in this area include Ag, As, Au, B, Bi, cobalt (Co), Cu, Hg, Mo, Pb, S, Sb, Sn, Te, Tl, uranium (U), and W. These positive concentrations indicate that, with the exception of copper and possibly mercury and uranium, these elements had relatively low chemical mobilities in the supergene enrichment and later weathering environments at Red Mountain. Most may have been deposited during one or more hypogene events and then redistributed locally during later events. Zinc is the only deposit-related element that has clearly been depleted as a result of supergene and (or) weathering events. Minerals that are common in the unweathered upper part of the system include chalcocite, pyrite, quartz, sericite, alunite, and pyrophyllite, as well as less common covellite, enargite, tennantite, tourmaline, barite, anglesite, and other sulfide or sulfate minerals. Subsequent to formation of the Red Mountain Cu-Mo deposit and supergene enrichment, chemical weathering produced an area of pervasive hematite and other iron oxides in the near-surface part of the deposit to form a leached cap. These iron-rich minerals formed primarily as a result of the oxidation of pyrite. This event was accompanied by losses of cobalt, mercury, magnesium, and zinc, as well as destruction of sericite, plagioclase, pyrite, clay minerals, and pyrophyllite. A total of 122 rock samples, 119 soil samples, and samples of three plant species (57 mesquite, 108 oak, and 68 juniper) were collected over and around Red Mountain. For the rock and soil samples, the distributions of anomalous Ag, As, Bi, Cu, Fe, Mo, Pb, Sb, Te, and Tl best delineated the exposed part of the deposit. The highest concentrations of many of these elements are centered on one or both of two main areas with exposures of quartz monzonite porphyry. The high concentrations of arsenic in the deposit area (as much as 390 parts per million (ppm) in rock and 1,500 ppm in soil) and of lead (as much as 2,370 ppm in rock and 1,490 ppm in soil) are particularly noteworthy. The concentrations of various elements in the plant ash vary widely among the three species and are species dependent. Many of the deposit-related elements are either nonessential for plant growth or are considered toxic at certain concentration ranges. In spite of this, the distributions of potentially toxic Ag, As, Bi, Cd, Cu, Mo, Pb, Sb, selenium (Se), and Zn produce deposit-related anomalies for one or more of the three species. Vegetation sampling offered no advantage over rock or soil sampling as an exploration tool. From an environmental standpoint, however, the plant analyses provide baseline data for both essential and nonessential elements that might be useful, for example, for selecting native plant species for revegetating mine waste areas. The exposed part of the Red Mountain deposit has not been greatly disturbed as a result of mining and other activities. However, some of the rock, soil, and plant samples that were collected near the Harshaw Creek and Alum Gulch drainages, which are peripheral to Red Mountain, are also anomalous for various deposit-related elements. These anomalies are probably the result of dispersion of stream sediments contaminated with material from past mining.

Arizona↗

Element concentrations and grain size of sediment from the Similkameen River above Enloe Dam (Enloe Reservoir) near Oroville, Washington, 2019

In 2019, the U.S. Geological Survey conducted a reconnaissance survey of concentrations of 41 trace elements present in bed sediment in the reservoir on the Similkameen River upstream from Enloe Dam, near Oroville, Washington. The Similkameen River drains a watershed containing highly mineralized geologic deposits with current (2019) and historical mining activity. Results of this survey indicated that surface and subsurface sediment are substantially enriched in element concentrations of silver (Ag), arsenic (As), gold (Au), bismuth (Bi), cadmium (Cd), copper (Cu), manganese (Mn), antimony (Sb), selenium (Se), tin (Sn), and tellurium (Te) relative to average concentrations found in upper continental-crustal material. Conversely, concentrations of mercury (Hg) and lead (Pb) in sediment above Enloe Dam (Enloe Reservoir) were generally less than average concentrations in upper continental-crustal material (Hg = 0.05 milligrams per kilogram [mg/kg]; Pb =17 mg/kg). Concentrations of most trace elements were higher in the less than 63-micrometer fraction (silt) and tended to be higher in subsurface than in surface sediment. The concentrations of trace elements were compared to consensus-based aquatic toxicity reference concentrations, Washington State Department of Ecology sediment management standards, and average concentrations of upper continental-crustal material. Arsenic concentrations were consistently elevated above these criteria among samples and often exceeded sediment management standards and aquatic toxicity reference values (both threshold effects and probable effects concentrations). High concentrations of As were measured in sediment with proportionally more material in the less than 63-micrometer size fraction; this result may be related to the presence of ore-processing waste material that has entered the aquatic system from approximately 125 years of mining operations in the basin. Elevated concentrations of chromium and copper that exceed the same criteria as arsenic (As) were measured less consistently and predominantly in the fine-grain size fraction.

Washington↗

Hydrologic framework and characterization of the Little Colorado River alluvial aquifer near Leupp, Arizona

The Little Colorado River alluvial aquifer near Leupp, Arizona, was investigated as a possible source of irrigation water for the Leupp and Birdsprings Chapters of the Navajo Nation. The physical, chemical, and hydraulic characteristics of the alluvial aquifer were studied using geophysical surveys, installation of observation wells, water-level measurements, chemical analyses, groundwater pumping simulations, and review of previous investigations. Geophysical surveys and well borings revealed that the aquifer ranges in thickness from near 0 feet around its periphery to about 100 feet in its thickest parts. Water levels were monitored in nine alluvial wells within the study area and compared with earlier measurements collected in 1998 and 1999. Comparison of those earlier water levels with water levels collected as part of this study showed a decline of between about 5 and 12 feet has occurred in the last 23 years. The water chemistry of the aquifer was analyzed for salinity hazard, sodium-adsorption hazard, and specific-ion toxicity. The sodium-adsorption hazard and specific-ion toxicity of alluvial aquifer water were found to be low. However, the salinity hazard was high enough in most areas that it could negatively affect salt-sensitive crops. Well-field pumping scenarios conducted for this study demonstrated that using groundwater from the alluvial aquifer for irrigated agriculture is theoretically possible but may be economically challenging owing to the hydraulic properties of the aquifer.

Arizona↗

Ecological effects on streams from forest fertilization: Literature review and conceptual framework for future study in the western Cascades

Fertilization of forests with urea-nitrogen has been studied numerous times for its effects on water quality. Stream nitrogen concentrations following fertilization are typically elevated during winter, including peaks in the tens-of-thousands of parts per billion range, with summer concentrations often returning to background or near-background levels. Despite these increases, water-quality criteria for nitrogen have rarely been exceeded. However, such criteria are targeted at fish toxicity or human health and are not relevant to concentrations that could cause ecological disturbances. Studies of the responses of stream biota to fertilization have been rare and have targeted either immediate, toxicity-based responses or used methods insensitive to ongoing ecological processes. This report reviews water-quality studies following forest fertilizations, emphasizing Cascade streams in the Pacific Northwest and documented biological responses in those streams. A conceptual model predicting potential ecological response to fertilization, which includes effects on algal growth and primary production, is presented. In this model, applied fertilizer nitrogen reaching streams is mostly exported during winter. However, some nitrogen retained in soils or stream and riparian areas may become available to aquatic biota during spring and summer. Biological responses may be minimal in small streams nearest to application because of light limitation, but may be elevated downstream where light is sufficient to allow algal growth. Ultimately, algal response could be greatest in downstream reaches, although ambient nutrient concentrations remain low due to uptake and benthic nutrient recycling. Ground-water flow paths and hyporheic processing could be critical in determining the fate of applied nitrogen. A framework is provided for testing this response in the Little River watershed, a tributary to the North Umpqua River, Oregon, at basic and intensive levels of investigation.

Oregon↗