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Modeling vegetation heights from high resolution stereo aerial photography: an application for broad-scale rangeland monitoring

Vertical vegetation structure in rangeland ecosystems can be a valuable indicator for assessing rangeland health and monitoring riparian areas, post-fire recovery, available forage for livestock, and wildlife habitat. Federal land management agencies are directed to monitor and manage rangelands at landscapes scales, but traditional field methods for measuring vegetation heights are often too costly and time consuming to apply at these broad scales. Most emerging remote sensing techniques capable of measuring surface and vegetation height (e.g., LiDAR or synthetic aperture radar) are often too expensive, and require specialized sensors. An alternative remote sensing approach that is potentially more practical for managers is to measure vegetation heights from digital stereo aerial photographs. As aerial photography is already commonly used for rangeland monitoring, acquiring it in stereo enables three-dimensional modeling and estimation of vegetation height. The purpose of this study was to test the feasibility and accuracy of estimating shrub heights from high-resolution (HR, 3-cm ground sampling distance) digital stereo-pair aerial images. Overlapping HR imagery was taken in March 2009 near Lake Mead, Nevada and 5-cm resolution digital surface models (DSMs) were created by photogrammetric methods (aerial triangulation, digital image matching) for twenty-six test plots. We compared the heights of individual shrubs and plot averages derived from the DSMs to field measurements. We found strong positive correlations between field and image measurements for several metrics. Individual shrub heights tended to be underestimated in the imagery, however, accuracy was higher for dense, compact shrubs compared with shrubs with thin branches. Plot averages of shrub height from DSMs were also strongly correlated to field measurements but consistently underestimated. Grasses and forbs were generally too small to be detected with the resolution of the DSMs. Estimates of vertical structure will be more accurate in plots having low herbaceous cover and high amounts of dense shrubs. Through the use of statistically derived correction factors or choosing field methods that better correlate with the imagery, vegetation heights from HR DSMs could be a valuable technique for broad-scale rangeland monitoring needs.

California;Nevada↗

Environmental factors and chemical and microbiological water-quality constituents related to the presence of enteric viruses in ground water from small public water supplies in southeastern Michigan

A study of small public ground-water-supply wells that produce water from discontinuous sand and gravel aquifers was done from July 1999 through July 2001 in southeastern Michigan. Samples were collected to determine the occurrence of viral pathogens and microbiological indicators of fecal contamination (“indicators”), determine whether indicators are adequate predictors of the presence of enteric viruses, and determine the factors that affect the presence of enteric viruses. Small systems are those that serve less than 3,300 people. Samples were analyzed for specific enteric viruses by reverse transcriptase-polymerase chain reaction (RT-PCR), for culturable viruses by cell culture, and for the indicators total coliforms, Escherichia coli (E. coli) , enterococci, and F-specific and somatic coliphage. Ancillary environmental and water-quality data were collected or compiled. A total of 169 regular samples and 32 replicate pairs were collected from 38 wells. Replicate pairs were samples collected at the same well on the same date. One well was sampled 6 times, 30 wells were sampled five times, 6 wells were sampled twice, and 1 well was sampled once. By use of RT-PCR, enterovirus was found in four wells (10.5 percent) and hepatitis A virus (HAV) in five wells (13.2 percent). In two of these wells, investigators found both enterovirus and HAV, but on different sampling dates. Culturable viruses were found one time in two wells (5.9 percent), and neither of these wells was positive for viruses by use of RT-PCR on any sampling date. If results for all viruses are combined, 9 of the 38 small public-supply wells were positive for enteric viruses (23.7 percent) by either cell culture or RT-PCR. One or more indicators were found in 18 of 38 wells. Total coliforms, E. coli , enterococci, and F-specific and somatic coliphage were found in 34.2, 10.5, 15.8, 5.9, and 5.9 percent, respectively, of the wells tested. In only 3 out of 18 wells were samples positive for an indicator on more than one date at the same well. The co-occurrence of enteric viruses and any indicator was 55.6 percent; five out of the nine virus-positive wells were also found to be positive for an indicator. Two wells with detections of viruses had a detection of total coliforms, one well had a detection of E. coli , one of enterococci, and one of F-specific coliphage. On a per sample basis, of 11 samples that were positive for enteric viruses, indicator bacteria co-occurred in only 2 samples, and coliphage were not present in any. More virus-positive samples were found at sites served by septic systems than those served by sewerlines. Sampling condition (ground water or a mixture of tank and ground water), distance to septic system, type of and distance to nearest surface-water body, well characteristics, or land use were not related to the presence of viruses or indicators. Among continuous water-quality variables, statistically significant relations were found between total coliforms and dissolved organic carbon and between total coliforms and iron. There was a statistically significant relation between chloride concentrations >20 mg/L and detections of total coliforms. Presence of nitrate and nitrite was related to the presence of other indicators ( E. coli , enterococci, and F-specific and somatic coliphage) or enteric viruses, but not to total coliforms. The data indicated that chloride-to-bromide (C1:Br) ratios may be useful as a screening tool for total coliforms and enteric viruses but not for E. coli , enterococci, and F-specific and somatic coliphage. This study provides evidence for fecal contamination of ground water from small public-supply wells, at least on an intermittent basis. Collecting data on multiple lines of evidence would be needed to reliably predict the presence of enteric viruses and protect public health. Future data collection toward this end could include repeat sampling several times a year for different indicators, measuring dissolved-organic carbon, nitrate plus nitrite, and (or) chloride concentrations, or determining C1:Br ratios. The presence of a site served by a septic system is an indication that the well may be more vulnerable to contamination than a site served by a sewerline.

Michigan↗

Ground-truthing electrical resistivity methods in support of submarine groundwater discharge studies: Examples from Hawaii, Washington, and California

Submarine groundwater discharge (SGD) is an important conduit that links terrestrial and marine environments. SGD conveys both water and water-borne constituents into coastal waters, where these inflows may impact near-shore ecosystem health and sustainability. Multichannel electrical resistivity techniques have proven to be a powerful tool to examine scales and dynamics of SGD and SGD forcings. However, there are uncertainties both in data aquisition and data processing that must be addressed to maximize the effectiveness of this tool in estuarine or marine environments. These issues most often relate to discerning subtle nuances in the flow of electricity through variably saturated media that can also be highly conductive ( i.e., seawater). Three contrasting field sites were examined for this study to assess the effectiveness of electrical resistivity techniques in varying coastal settings by comparing resistivity data to direct salinity and resistivity observations, quantifying changes in lithology and beach geomorphology, and fine-tuning inversion protocols. The three study sites all have substantial (up to 85 cm day −1 ) submarine groundwater discharge rates, but the hydrologic, oceanographic, and geologic characteristics of the sites are all very different. At a site in Pelekane Bay on the Big Island of Hawaii, seasonal flooding introduces very high concentrations of fine to coarse sediment into the bay. Near-shore circulation is limited in Pelekane Bay, so this newly introduced sediment can become deposited in the bay where it accumulates over time. At a site in Hood Canal, a fjord within Puget Sound, Washington, SGD rates can be high because of the large tidal range, abundant recharge, and steep hydrologic gradients. At Younger Lagoon in northern California, the flow of groundwater towards the coast is much more parsimonious, but here marine processes, including recirculated seawater, are important in controlling the flow of material towards the coast. Rigorous ground-truthing at each field site showed that multi-channel electrcial resistivity techniques can reproduce the scales and dynamics of a seepage field when such data are correctly collected, and when the model inversions are tuned to field site characteristics. Such information can provide a unique perspective on the scales and dynamics of exchange processes within a coastal aquifer—information essential to scientists and resource managers alike.

California, Hawaii, Washington↗

Assessment of the potential for in-plume sulphur dioxide gas-ash interactions to influence the respiratory toxicity of volcanic ash

Background Volcanic plumes are complex environments composed of gases and ash particles, where chemical and physical processes occur at different temperature and compositional regimes. Commonly, soluble sulphate- and chloride-bearing salts are formed on ash as gases interact with ash surfaces. Exposure to respirable volcanic ash following an eruption is potentially a significant health concern. The impact of such gas-ash interactions on ash toxicity is wholly un-investigated. Here, we study, for the first time, whether the interaction of volcanic particles with sulphur dioxide (SO 2 ) gas, and the resulting presence of sulphate salt deposits on particle surfaces, influences toxicity to the respiratory system, using an advanced in vitro approach. Methods To emplace surface sulphate salts on particles, via replication of the physicochemical reactions that occur between pristine ash surfaces and volcanic gas, analogue substrates (powdered synthetic volcanic glass and natural pumice) were exposed to SO 2 at 500 °C, in a novel Advanced Gas-Ash Reactor, resulting in salt-laden particles. The solubility of surface salt deposits was then assessed by leaching in water and geochemical modelling. A human multicellular lung model was exposed to aerosolised salt-laden and pristine (salt-free) particles, and incubated for 24 h. Cell cultures were subsequently assessed for biological endpoints, including cytotoxicity (lactate dehydrogenase release), oxidative stress (oxidative stress-related gene expression; heme oxygenase 1 and NAD(P)H dehydrogenase [quinone] 1) and its (pro-)inflammatory response (tumour necrosis factor α, interleukin 8 and interleukin 1β at gene and protein levels). Results In the lung cell model no significant effects were observed between the pristine and SO 2 -exposed particles, indicating that the surface salt deposits, and the underlying alterations to the substrate, do not cause acute adverse effects in vitro . Based on the leachate data, the majority of the sulphate salts from the ash surfaces are likely to dissolve in the lungs prior to cellular uptake. Conclusions The findings of this study indicate that interaction of volcanic ash with SO 2 during ash generation and transport does not significantly affect the respiratory toxicity of volcanic ash in vitro . Therefore, sulphate salts are unlikely a dominant factor controlling variability in in vitro toxicity assessments observed during previous eruption response efforts.

Environmental Research↗

Predicting redox conditions in groundwater at a national scale using random forest classification

Redox conditions in groundwater may markedly affect the fate and transport of nutrients, volatile organic compounds, and trace metals, with significant implications for human health. While many local assessments of redox conditions have been made, the spatial variability of redox reaction rates makes the determination of redox conditions at regional or national scales problematic. In this study, redox conditions in groundwater were predicted for the contiguous United States using random forest classification by relating measured water quality data from over 30,000 wells to natural and anthropogenic factors. The model correctly predicted the oxic/suboxic classification for 78 and 79% of the samples in the out-of-bag and hold-out data sets, respectively. Variables describing geology, hydrology, soil properties, and hydrologic position were among the most important factors affecting the likelihood of oxic conditions in groundwater. Important model variables tended to relate to aquifer recharge, groundwater travel time, or prevalence of electron donors, which are key drivers of redox conditions in groundwater. Partial dependence plots suggested that the likelihood of oxic conditions in groundwater decreased sharply as streams were approached and gradually as the depth below the water table increased. The probability of oxic groundwater increased as base flow index values increased, likely due to the prevalence of well-drained soils and geologic materials in high base flow index areas. The likelihood of oxic conditions increased as topographic wetness index (TWI) values decreased. High topographic wetness index values occur in areas with a propensity for standing water and overland flow, conditions that limit the delivery of dissolved oxygen to groundwater by recharge; higher TWI values also tend to occur in discharge areas, which may contain groundwater with long travel times. A second model was developed to predict the probability of elevated manganese (Mn) concentrations in groundwater (i.e., ≥50 μg/L). The Mn model relied on many of the same variables as the oxic/suboxic model and may be used to identify areas where Mn-reducing conditions occur and where there is an increased risk to domestic water supplies due to high Mn concentrations. Model predictions of redox conditions in groundwater produced in this study may help identify regions of the country with elevated groundwater vulnerability and stream vulnerability to groundwater-derived contaminants.

contiguous United States↗

Determination of human-health pharmaceuticals in filtered water by chemically modified styrene-divinylbenzene resin-based solid-phase extraction and high-performance liquid chromatography/Mass Spectrometry

In 1999, the Methods Research and Development Program of the U.S. Geological Survey National Water Quality Laboratory began the process of developing a method designed to identify and quantify human-health pharmaceuticals in four filtered water-sample types: reagent water, ground water, surface water minimally affected by human contributions, and surface water that contains a substantial fraction of treated wastewater. Compounds derived from human pharmaceutical and personal-care product use, which enter the environment through wastewater discharge, are a newly emerging area of concern; this method was intended to fulfill the need for a highly sensitive and highly selective means to identify and quantify 14 commonly used human pharmaceuticals in filtered-water samples. The concentrations of 12 pharmaceuticals are reported without qualification; the concentrations of two pharmaceuticals are reported as estimates because long-term reagent-spike sample recoveries fall below acceptance criteria for reporting concentrations without qualification. The method uses a chemically modified styrene-divinylbenzene resin-based solid-phase extraction (SPE) cartridge for analyte isolation and concentration. For analyte detection and quantitation, an instrumental method was developed that used a high-performance liquid chromatography/mass spectrometry (HPLC/MS) system to separate the pharmaceuticals of interest from each other and coextracted material. Immediately following separation, the pharmaceuticals are ionized by electrospray ionization operated in the positive mode, and the positive ions produced are detected, identified, and quantified using a quadrupole mass spectrometer. In this method, 1-liter water samples are first filtered, either in the field or in the laboratory, using a 0.7-micrometer (μm) nominal pore size glass-fiber filter to remove suspended solids. The filtered samples then are passed through cleaned and conditioned SPE cartridges at a rate of about 15 milliliters per minute. Excess water is eliminated from the cartridge sorbent bed by passing air through the cartridges, and the analytes retained on the SPE bed are eluted from the cartridge sequentially, first with methanol, followed by acidified methanol, and combined in collection tubes. This sample extract then is reduced from about 10 milliliters (mL) to about 0.1 mL (or 100 microliters) under a stream of purified nitrogen gas with the collection tubes in a heated (40°C) water bath. The reduced extracts then are fortified with an internal standard solution (when using internal standard quantitation), brought to a final volume of 1 mL with an aqueous ammonium formate buffer solution, and filtered through a 0.2-μm Teflon syringe filter as they are transferred into vials for instrumental analysis. Instrumental analysis by the HPLC/MS procedure permits determination of individual pharmaceutical concentrations from 0.005 to 1.0 microgram per liter, based on the lowest and the highest calibration standards routinely used. The reporting levels for this method are compound dependent, and have been experimentally determined based on the precision of quantitation of compounds from eight fortified organic-free water samples in single-operator experiments. The method detection limits and interim reporting levels for the compounds determined by this method were calculated from recoveries of the pharmaceuticals from reagent-water samples amended at 0.05 microgram per liter, and ranged between 0.0069 and 0.0142 microgram per liter, and 0.015 and 0.10 microgram per liter, respectively. Concentrations for 12 compounds are reported without qualification, and for two compounds are reported as qualified estimates. After initial development, the method was applied to more than 1,800 surface-, ground-, and wastewater samples from 2002 to 2005 and documented in a number of published studies. This research application of the method provided the opportunity to collect a large data set of ambient environmental concentrations and also permitted the collection of an extensive set of reagent blanks and spike quality-control (QC) samples. This multiple-year set of QC samples enabled further evaluation of method performance under multiple operator and multiple instrument conditions typical of routine laboratory operation. These results are an important part of the entire data set contained in this report because they document method performance over an extended time. Because sample matrix can substantially affect method performance, inclusion of environmental matrix-spike samples is required as a routine component of study plan quality control. Method performance has been measured by long-term tracking of observed recoveries from fortified organic-free water samples processed with environmental samples (laboratory reagent spikes), as well as by observed recoveries from multiple fortified environmental water samples. The fortified environmental samples included surface water, wastewater effluent-dominated surface water, and ground water, fortified at two environmentally relevant concentrations and corrected for ambient environmental concentrations. Because the responses of individual pharmaceuticals vary as a function of proton affinity, the ionization efficiency, and thus relative response, of each pharmaceutical, the quality-control surrogate compounds, and the quantitation internal standard can be suppressed or enhanced by the presence of the sample matrix. As a result, several quality-control sample types are required to properly interpret the ambient environmental concentrations of pharmaceuticals in aqueous samples. The quality-control sample types and results include laboratory reagent spikes and laboratory reagent blanks to provide insight into the performance of the method in the absence of a sample matrix, and matrix-spike recovery samples and replicate environmental samples, collected from representative sample matrix types within the aquatic system under study.

Techniques and Methods↗

Aquatic assessment of the Ely Copper Mine Superfund site, Vershire, Vermont

The Ely Mine, which operated from 1821 to 1905, and its area of downstream impact constitute the Ely Copper Mine Superfund site. The site was placed on the National Priorities List in 2001. The mine comprises underground workings, foundations from historical structures, several waste-rock piles, roast beds associated with the smelting operation, and slag piles resulting from the smelting. The mine site is drained by Ely Brook, which includes several tributaries, one of which drains a series of six ponds. Ely Brook empties into Schoolhouse Brook, which flows 3.3 kilometers and joins the Ompompanoosuc River. The aquatic ecosystem at the site was assessed using a variety of approaches that investigated surface-water quality, sediment quality, and various ecological indicators of stream-ecosystem health. The degradation of surface-water quality is dominated by copper with localized effects caused by iron, aluminum, cadmium, and zinc. Chronic water-quality criteria for copper are exceeded in the surface water of four of the six ponds on the Ely Brook tributary, and all of Ely Brook and Schoolhouse Brook, and of the Ompompanoosuc River downstream of the confluence with Schoolhouse Brook. Comparison of hardness-based and Biotic Ligand Model-based water-quality criteria for copper yields similar results with respect to extent of impairment. However, the Biotic Ligand Model criteria are mostly lower than the hardness-based criteria and thus suggest a greater degree of impairment, particularly in the Ely Brook watershed, where dissolved organic carbon concentrations and pH values are lower. Surface-water toxicity testing correlates strongly with the extent of impact. Likewise, riffle-habitat benthic invertebrate richness and abundance data support these results through the stream environment. Similarly, the index of biotic integrity for the fish community in Schoolhouse Brook and the Ompompanoosuc River document degraded habitats throughout Schoolhouse Brook from Ely Brook down to the Ompompanoosuc River. The sediment environment shows similar extents of impairment also dominated by copper, although localized degradation due to chromium, nickel, lead, and zinc was documented on the basis of probable effects concentrations. In contrast, equilibrium-partitioning sediment benchmarks indicate no toxic effects would be expected in sediments at the reference sites, and uncertain toxic effects throughout Ely Brook and Schoolhouse Brook, except for the reference sites and site EB-600M. The results for site EB-600M indicate predicted toxic effects. Acute toxicity testing of in situ pore waters using Hyalella azteca indicates severe impacts in Ely Brook reaching 100 percent lethality at site EB-90M. Acute toxicity testing of in situ pore waters using Chironomus dilutus shows similar, but not as severe, toxicity. Neither set of in situ pore-water toxicity tests showed significant impairment in Schoolhouse Brook or the Ompompanoosuc River. Chronic sediment toxicity testing using Hyalella azteca indicated significant toxicity in Ely Brook, except at site EB-90M, and in Schoolhouse Brook. The low toxicity of EB-90M may be a reflection of the low lability of copper in that sediment as indicated by a low proportion of extractable copper (1.1 percent). Depositional-targeted habitat invertebrate richness and abundance data support these conclusions for the entire watershed, as do the index of biotic integrity data from the fish community. The information was used to develop an overall assessment of the impact on the aquatic system that appears to be a result of the acid rock drainage at the Ely Mine. More than 700 meters of Ely Brook, including two of the six ponds, were found to be severely impacted, on the basis of water-quality data and biological assessments. The reference location was of good quality based on the water quality and biological assessment. More than 3,125 meters of Schoolhouse Brook are also severely impacted, on the basis of water-quality data and biological assessments. The biological community begins to recover near the confluence with the Ompompanoosuc River. The evidence is less conclusive regarding the Ompompanoosuc River. The sediment data suggest that the sediments could be a source of toxicity in Ely Brook and Schoolhouse Brook. The surface-water assessment is consistent with the outcome of a surface-water toxicity testing program performed by the U.S. Environmental Protection Agency for Ely Brook and Schoolhouse Brook and a surface-water toxicity testing program and in situ amphibian testing program for the ponds.

Vermont↗

Retrospective study of the diagnostic criteria in a lead-poisoning survey of waterfowl

Between 1983 and 1986 the National Wildlife Health Center (NWHC) conducted a nationwide study of lead poisoning of waterfowl from federal and state refuges. This survey was done to assist in identifying zones with lead-poisoning problems. One thousand forty one moribund or dead waterfowl were collected and examined. The presence or absence of 13 gross lesions selected as indicators of lead poisoning and 3 lesions indicating body condition was recorded. Lead-poisoning diagnoses were based on the finding of at least 6 8 ppm (wet weight) lead in the liver and either lead shot in the gizzard content or at least one convincing gross lesion indicative of lead poisoning. Four hundred and twenty-one of these waterfowl were diagnosed as lead-poisoned. The NWHC survey provided a comprehensive basis for estimating the sensitivities, specificities, and likelihood ratios of the gross lesions of lead poisoning and the associated hepatic lead concentrations for several species of waterfowl. Some of the 13 defined gross lesions were more common than others; frequencies ranged from 3% to 80% in the 421 lead-poisoned waterfowl. The most reliable indicators of lead poisoning were impactions of the upper alimentary tract, submandibular edema, myocardial necrosis, and biliary discoloration of the liver. Each of the 13 lesions occurred more frequently in the lead-poisoned birds, but each of the lesions also occurred in waterfowl that died of other causes. The number of lead shot present in a bird?s gizzard was only weakly correlated with its hepatic lead concentration; however, this weak correlation may have been adequate to account for differences in hepatic lead concentrations among species, once the weights of the species were taken into account. Although lead-poisoned ducks tended to have higher hepatic mean lead concentrations than did lead-poisoned geese or swans, the differences were probably a result of a greater dose of shot per body weight than to kinetic differences between species. Hepatic lead concentrations were independent of age and sex. Ninety-five percent of waterfowl diagnosed as lead-poisoned had hepatic lead concentrations of at least 38 ppm, dry weight (10 ppm, wet weight). Fewer than 1% of the waterfowl that died of other causes had a concentration that high. This 5th percentile, of 38 ppm dry weight (10 ppm wet weight), is a defensible criterion for identifying lead-poisoned waterfowl when interpreting hepatic lead concentrations in the absence of pathological observations.

Archives of Environmental Contamination and Toxico↗

Discharge, water temperature, and water quality of Warm Mineral Springs, Sarasota County, Florida: A retrospective analysis

Warm Mineral Springs, located in southern Sarasota County, Florida, is a warm, highly mineralized, inland spring. Since 1946, a bathing spa has been in operation at the spring, attracting vacationers and health enthusiasts. During the winter months, the warm water attracts manatees to the adjoining spring run and provides vital habitat for these mammals. Well-preserved late Pleistocene to early Holocene-age human and animal bones, artifacts, and plant remains have been found in and around the spring, and indicate the surrounding sinkhole formed more than 12,000 years ago. The spring is a multiuse resource of hydrologic importance, ecological and archeological significance, and economic value to the community. The pool of Warm Mineral Springs has a circular shape that reflects its origin as a sinkhole. The pool measures about 240 feet in diameter at the surface and has a maximum depth of about 205 feet. The sinkhole developed in the sand, clay, and dolostone of the Arcadia Formation of the Miocene-age to Oligocene-age Hawthorn Group. Underlying the Hawthorn Group are Oligocene-age to Eocene-age limestones and dolostones, including the Suwannee Limestone, Ocala Limestone, and Avon Park Formation. Mineralized groundwater, under artesian pressure in the underlying aquifers, fills the remnant sink, and the overflow discharges into Warm Mineral Springs Creek, to Salt Creek, and subsequently into the Myakka River. Aquifers described in the vicinity of Warm Mineral Springs include the surficial aquifer system, the intermediate aquifer system within the Hawthorn Group, and the Upper Floridan aquifer in the Suwannee Limestone, Ocala Limestone, and Avon Park Formation. The Hawthorn Group acts as an upper confining unit of the Upper Floridan aquifer. Groundwater flow paths are inferred from the configuration of the potentiometric surface of the Upper Floridan aquifer for September 2010. Groundwater flow models indicate the downward flow of water into the Upper Floridan aquifer in inland areas, and upward flow toward the surface in coastal areas, such as at Warm Mineral Springs. Warm Mineral Springs is located in a discharge area. Changes in water use in the region have affected the potentiometric surface of the Upper Floridan aquifer. Historical increase in groundwater withdrawals resulted in a 10- to 20-foot regional decline in the potentiometric surface of the Upper Floridan aquifer by May 1975 relative to predevelopment levels and remained at approximately that level in May 2007 in the area of Warm Mineral Springs. Discharge measurements at Warm Mineral Springs (1942–2014) decreased from about 11–12 cubic feet per second in the 1940s to about 6–9 cubic feet per second in the 1970s and remained at about that level for the remainder of the period of record. Similarity of changes in regional water use and discharge at Warm Mineral Springs indicates that basin-scale changes to the groundwater system have affected discharge at Warm Mineral Springs. Water temperature had no significant trend in temperature over the period of record, 1943–2015, and outliers were identified in the data that might indicate inconsistencies in measurement methods or locations. Within the regional groundwater basin, Warm Mineral Springs is influenced by deep Upper Floridan aquifer flow paths that discharge toward the coast. Associated with these flow paths, the groundwater temperatures increase with depth and toward the coast. Multiple lines of evidence indicate that a source of warm groundwater to Warm Mineral Springs is likely the permeable zone of the Avon Park Formation within the Upper Floridan aquifer at a depth of about 1,400 to 1,600 feet, or deeper sources. The permeable zone contains saline groundwater with water temperatures of at least 95 degrees Fahrenheit. The water quality of Warm Mineral Springs, when compared with other springs in Florida had the highest temperature and the greatest mineralized content. Warm Mineral Springs water is characterized by a slight-green color, with varying water clarity, low dissolved oxygen (indicative of deep groundwater), and a hydrogen sulfide odor. Water-quality samples detected ammonium-nitrogen and nitrates, but at low concentrations. The drinking water standard for nitrate adopted by the U.S. Environmental Protection Agency is 10 milligrams per liter, measured as nitrogen. Water samples collected at spring vents by divers on April 29, 2015, had concentrations of 0.9 milligram per liter nitrate-nitrogen at vent A and 0.04–0.05 milligram per liter at vents B, C, and D. Typically, the water clarity is highest in the morning (about 30 feet Secchi depth) and often decreases throughout the day. Analysis of existing data provided some insight into the hydrologic processes affecting Warm Mineral Springs; however, data have been sparsely and discontinuously collected since the 1940s. Continuous monitoring of hydrologic characteristics such as discharge, water temperature, specific conductance, and water-quality indicators, such as nitrate and turbidity (water clarity), would be valuable for monitoring and development of models of spring discharge and water quality. In addition, water samples could be analyzed for isotopic tracers, such as strontium, and the results used to identify and quantify the sources of groundwater that discharge at Warm Mineral Springs. Groundwater flow/transport models could be used to evaluate the sensitivity of the quality and quantity of water flowing from Warm Mineral Springs to changes in climate, aquifer levels, and water use.

Florida↗

Contaminants in fishes from Great Lakes-influenced sections and above dams of three Michigan rivers. II: Implications for health of mink

Populations of mink ( Mustela vison ) have declined in many areas of the world. Such declines have been linked to exposures to synthetic, halogenated hydrocarbons. In the Great Lakes region, mink are fewer in areas along the shore of the Great Lakes and their tributaries where mink have access to fish from the Great Lakes. Recently, there has been discussion of the relative merits of passage of fishes around hydroelectric dams on rivers in Michigan. A hazard assessment was conducted to determine the potential for adverse effects on mink, which could consume such fishes from above or below dams on the rivers. Concentrations of organochlorine insecticides, polychlorinated biphenyls (PCBs), 2,3,7,8-tetrachloridibenzo- p -dioxin equivalents (TCDD-EQ), and total mercury were measured in composite samples of fishes from above or below hydroelectric dams on the Manistee and Muskegon Rivers, which flow into Lake Michigan, and the Au Sable River, which flows into Lake Huron. Concentrations of organochlorine insecticides, PCBs, and TCDD-EQ were all greater in fishes from below the dams than those from above. Concentrations of neither organochlorine insecticides nor mercury in fishes are currently a risk to mink above or below the dams. All of the species of fishes collected from downstream of the dams contained concentrations of PCBs and TCDD-EQ, which represent a hazard to mink. The hazard index for PCBs was less than one for the average of all species from the upstream reaches of the Manistee and Au Sable Rivers, but not the Muskegon. The hazard index (concentration in fish/NOAEC) was greater than 1 for all of the species collected from below the dams, in all three rivers. The greatest hazard index was observed for carp ( Cyprinus carpio ) downstream on the Muskegon River. Because the concentrations of PCBs used in the hazard assessment were corrected for relative toxic potencies, the hazard ratios based on PCBs should be similar to those based on TCDD-EQ. This was found to be true. Thus, either total PCBs or TCDD-EQ could be used as the critical toxicant in the hazard assessment. However, if uncorrected concentrations of PCBs, expressed as Aroclors ® , were used in the hazard assessment, the toxicity of the weathered mixture would have been underestimated by approximately five-fold, and, in that instance, TCDD-EQ would be the critical contaminant for the hazard assessment. The average maximum allowable percentage of fish from above the dams, which would result in no observable adverse effects of TCDD-EQ, was 70%. Based on the average TCDD-EQ concentrations in the fishes, an average of 8.6% of the diet could be made up of fishes from below dams on the rivers. The most restrictive daily allowable intakes were for carp on the Muskegon and steelhead trout ( Onchorhyncus mykiss ) on the Manistee Rivers. Only 2.7% of the diet could be made up of these two species from influenced portion of the Au Sable River, they would be exposed to 390 μg PCBs and 8.55 ng of TCDD-EQ per day, respectively (Giesy et al. 1994b). Thus, it would take 15.1 or 77 days for mink to receive their total annual dose of PCBs or TCDD-EQ, respectively. At least for chinook salmon, the critical contaminant for the purposes of hazard assessment would be total concentrations of PCBs. Consuming chinook salmon for as little as 2 weeks would deliver the annual allowable dose of PCBs to mink.

Michigan↗

Effects of dissolved carbon dioxide on the physiology and behavior of fish artificial streams

A new technology for treating waters contaminated with acid mine drainage involves the dissolution of limestone particles using carbon dioxide at pressures above ambient. Because of the fish health risks associated with episodes of high carbon dioxide levels in treated waters, we subjected three species of fish, brook trout ( Salvelinus fontinalis ), slimy sculpin ( Cottus cognatus ), and blacknose dace ( Rhinichthys atratulus ), to 24 h exposures of elevated dissolved carbon dioxide (CO 2 ) at three levels, ranging from 1.0 (low) to 6.3 (high)%, under laboratory conditions. We measured blood physiological variables as well as behavior, including feeding responses, before, during, and after exposure. Physiological responses differed by species, but all species had elevated hematocrits after 1 h of exposure. Brook trout hematocrits were higher at medium and high levels of CO 2 than in a control group (0.0% CO 2 ) after 24 h of exposure. Slimy sculpin hematocrits were higher in medium- and high-level exposure groups than in controls after 1 h, but not after 24 h, of exposure. Blacknose dace hematocrits were higher in all three exposure groups than in controls after 1 h but only in medium-level exposure groups after 24 h. Brook trout plasma glucose was significantly higher in medium- and high-level exposure groups after 1 h, and in the high-level group after 24 h, than in controls. Slimy sculpin plasma glucose was not significantly different in elevated CO 2 exposure groups from that of controls throughout exposure. Branchial ventilation was significantly greater in all species at elevated CO 2 during exposure, indicating stress; however, no difference was observed between treatment and control groups of blacknose dace after 24 h, indicating acclimation. Pectoral fin beats and cough rates were not consistently related to CO 2 exposure throughout the study. Brook trout had the longest lasting reaction to stress at lower levels of CO 2 among the three species tested. Many of the 11 observed behavioral variables, related to swimming, feeding, social, and illness factors, were affected by elevations of dissolved CO 2 . Two to seven behavioral variables (18–64% of those measured) were affected by treatment level of dissolved CO 2 with a trend by species for the number of variables affected: brook trout>blacknose dace>slimy sculpin. However, behavioral sensitivity to treatment level was greatest in blacknose dace. Recovery to pre-treatment activity rates for most behavior patterns (including feeding) was observed 24 h after cessation of exposure in all three species. Recovery was independent of treatment level, was most rapid in blacknose dace, and was slowest in brook trout. Overall, slimy sculpin was least affected behaviorally by elevated CO 2 . Although all three species showed stress response and changes in behavior at moderate levels of CO 2 (≥2%), brook trout and blacknose dace showed evidence of ability to avoid harmful CO 2 levels by swimming out of affected waters, whereas the slimy sculpin showed minimal behavioral changes despite remaining in place during exposure. Thus, predation risk and other sources of mortality seem minimal in the event of technological malfunction at a stream treatment site involving the use of CO 2 under pressure.

Environmental Toxicology↗

Quality of water from crystalline rock aquifers in New England, New Jersey, and New York, 1995-2007

Crystalline bedrock aquifers in New England and parts of New Jersey and New York (NECR aquifers) are a major source of drinking water. Because the quality of water in these aquifers is highly variable, the U.S. Geological Survey (USGS) statistically analyzed chemical data on samples of untreated groundwater collected from 117 domestic bedrock wells in New England, New York, and New Jersey, and from 4,775 public-supply bedrock wells in New England to characterize the quality of the groundwater. The domestic-well data were from samples collected by the USGS National Water-Quality Assessment (NAWQA) Program from 1995 through 2007. The public-supply-well data were from samples collected for the U.S. Environmental Protection Agency (USEPA) Safe Drinking Water Act (SDWA) Program from 1997 through 2007. Chemical data compiled from the domestic wells include pH, specific conductance, dissolved oxygen, alkalinity, and turbidity; 6 nitrogen and phosphorus compounds, 14 major ions, 23 trace elements, 222 radon gas (radon), 48 pesticide compounds, and 82 volatile organic compounds (VOCs). Additional samples were collected from the domestic wells for the analysis of gross alpha- and gross beta-particle radioactivity, radium isotopes, chlorofluorocarbon isotopes, and the dissolved gases methane, carbon dioxide, nitrogen, and argon. Chemical data compiled from the public-supply wells include pH, specific conductance, nitrate, iron, manganese, sodium, chloride, fluoride, arsenic, uranium, radon, combined radium ( 226 radium plus 228 radium), gross alpha-particle radioactivity, and methyl tert -butyl ether (M t BE). Patterns in fluoride, arsenic, uranium, and radon distributions were discernable when the data were compared to lithology groupings of the bedrock, indicating that the type of bedrock has an effect on the quality of groundwater from NECR aquifers. Fluoride concentrations were significantly higher in groundwater samples from the alkali granite, peraluminous granite, and metaluminous granite lithology groups than from samples in the other lithology groups. Water samples from 1.4 percent of 2,167 studied wells had fluoride concentrations that were equal to or greater than the maximum contaminant level (MCL) of 4 milligrams per liter (mg/L) and 7.5 percent of the wells had fluoride concentrations that were equal to or greater than the secondary MCL of 2 mg/L. For arsenic, groundwater samples from the calcareous metasedimentary rocks in the New Hampshire-Maine geologic province, peraluminous granite, and pelitic rocks lithology groups had higher concentrations than did samples from the other lithology groups. Water samples from 13.3 percent of 2,054 studied wells had arsenic concentrations that were equal to or greater than the MCL of 10 micrograms per liter (μg/L), about double the national rate of occurrence in community-supply systems and in domestic wells of the United States. Uranium concentrations were significantly higher in groundwater samples from the peraluminous granite, alkali granite, and calcareous metasedimentary rocks in the New Hampshire-Maine geologic province lithology groups than from samples in the other lithology groups. Water samples from 14.2 percent of 556 studied wells had uranium concentrations equal to or greater than the MCL of 30 μg/L. Radon activities were equal to or greater than the proposed MCL of 300 picocuries per liter (pCi/L) in 95 percent of 943 studied wells, and 33 percent of the wells had radon activities were equal to or greater than the proposed alternative maximum contaminant level (AMCL) of 4,000 pCi/L. Radon activities exceeded the proposed AMCL in 20 percent or more of groundwater samples in each of the studied lithology groups with a minimum of 9 samples, but radon activities were significantly higher in groundwater samples from the alkali granite, peraluminous granite, and Narragansett basin metasedimentary rocks lithology groups. Water samples from 3.2 percent of 564 studied wells had combined radium activities equal to or greater than the MCL of 5 pCi/L; however, combined radium activities were not significantly different among the studied lithology groups. Land use and population density also were evaluated to explain patterns in water quality. Concentrations of nitrate, sodium, chloride, and MtBE from the studied wells were significantly greater in areas of high population density (≥50 persons per square kilometer) than in areas of low population density (<50 persons per square kilometer). Concentrations of sodium, chloride, and M t BE from the studied wells were significantly greater in areas classified as developed (urban lands) than in areas classified as undeveloped (forested), agricultural, or mixed (no dominant land use). Nitrate concentrations from the public-supply wells were not significantly different among the four land use categories, but nitrate concentrations from the domestic wells were significantly greater in areas classified as developed than in areas classified as undeveloped, agricultural, or mixed. Chloride to bromide mass ratios in the domestic well samples indicate that the groundwater was probably affected by at least three halogen sources: local precipitation and recharge waters, remnant seawater and connate waters evolved from seawater, and recharge waters affected by road salt. The groundwater in the NECR aquifers generally contained low concentrations of nitrate, VOCs, and pesticides. Less than 1 percent of water samples from 4,781 studied wells had concentrations of nitrate greater than the MCL of 10 mg/L. Less than 1 percent of water samples from 1,299 studied wells exceeded the USEPA advisory level of 20 to 40 μg/L for M t BE. None of the other studied VOCs exceeded a human health benchmark. M t BE (36 percent frequency detection) and chloroform (32.9 percent frequency detection) were the most frequently detected (>0.02 μg/L) VOCs in the domestic wells. M t BE was detected more often in water samples with apparent ages of less than 25 years than in water samples with apparent ages greater than 25 years. This finding is consistent with the time period of high M t BE use in areas in the United States where reformulated gasoline was mandated. The largest pesticide concentration was an estimated concentration of 0.06 μg/L for the herbicide metolachlor. Deethylatrazine, a degradate of atrazine, (18 percent frequency detection) and atrazine (8 percent frequency detection) were the only pesticide compounds detected (>0.001 μg/L) in more than 3 percent of the domestic wells. None of the detected pesticide compounds exceeded human health benchmarks. Concentrations of nitrate and gross alpha-particle activities were significantly greater in the water samples from the domestic wells than in samples from the public-supply wells. Concentrations of sodium, chloride, iron, manganese, and uranium were significantly greater in the water samples from the public-supply wells than in the samples from the domestic wells. One possible explanation may be related to differences in field processing (filtered samples from the domestic wells compared to unfiltered samples from the public-supply wells). The high frequency of detections for a wide variety of manmade and naturally occurring contaminants in both domestic and public-supply wells shows the vulnerability of NECR aquifers to contamination. The highly variable water quality and the association with highly variable lithology of crystalline bedrock underscores the importance of testing individual wells to determine if concentrations for the most commonly detected contaminants exceed human health benchmarks.

Connecticut, Maine, Massachusetts, New Hampshire, ↗

Sources and characteristics of organic matter in the Clackamas River, Oregon, related to the formation of disinfection by-products in treated drinking water

This study characterized the amount and quality of organic matter in the Clackamas River, Oregon, to gain an understanding of sources that contribute to the formation of chlorinated and brominated disinfection by-products (DBPs), focusing on regulated DBPs in treated drinking water from two direct-filtration treatment plants that together serve approximately 100,000 customers. The central hypothesis guiding this study was that natural organic matter leaching out of the forested watershed, in-stream growth of benthic algae, and phytoplankton blooms in the reservoirs contribute different and varying proportions of organic carbon to the river. Differences in the amount and composition of carbon derived from each source affects the types and concentrations of DBP precursors entering the treatment plants and, as a result, yield varying DBP concentrations and species in finished water. The two classes of DBPs analyzed in this study-trihalomethanes (THMs) and haloacetic acids (HAAs)-form from precursors within the dissolved and particulate pools of organic matter present in source water. The five principal objectives of the study were to (1) describe the seasonal quantity and character of organic matter in the Clackamas River; (2) relate the amount and composition of organic matter to the formation of DBPs; (3) evaluate sources of DBP precursors in the watershed; (4) assess the use of optical measurements, including in-situ fluorescence, for estimating dissolved organic carbon (DOC) concentrations and DBP formation; and (5) assess the removal of DBP precursors during treatment by conducting treatability "jar-test" experiments at one of the treatment plants. Data collection consisted of (1) monthly sampling of source and finished water at two drinking-water treatment plants; (2) event-based sampling in the mainstem, tributaries, and North Fork Reservoir; and (3) in-situ continuous monitoring of fluorescent dissolved organic matter (FDOM), turbidity, chlorophyll- a , and other constituents to continuously track source-water conditions in near real-time. Treatability tests were conducted during the four event-based surveys to determine the effectiveness of coagulant and powdered activated carbon (PAC) on the removal of DBP precursors. Sample analyses included DOC, total particulate carbon (TPC), total and dissolved nutrients, absorbance and fluorescence spectroscopy, and, for regulated DBPs, concentrations of THMs and HAAs in finished water and laboratory-based THM and HAA formation potentials (THMFP and HAAFP, respectively) for source water and selected locations throughout the watershed. The results of this study may not be typical given the record and near record amounts of precipitation that occurred during spring that produced streamflow much higher than average in 2010-11. Although there were algal blooms, lower concentrations of chlorophyll- a were observed in the water column during the study period compared to historical data. Concentrations of DBPs in finished (treated) water averaged 0.024 milligrams per liter (mg/L) for THMs and 0.022 mg/L for HAAs; maximum values were about 0.040 mg/L for both classes of DBPs. Although DBP concentrations were somewhat higher within the distribution system, none of the samples collected for this study or for the quarterly compliance monitoring by the water utilities exceeded levels permissible under existing U.S. Environmental Protection Agency (USEPA) regulations: 0.080 mg/L for THMs and 0.060 mg/L for HAAs. DOC concentrations were generally low in the Clackamas River, typically about 1.0-1.5 mg/L. Concentrations in the mainstem occasionally increased to nearly 2.5 mg/L during storms; DOC concentrations in tributaries were sometimes much higher (up to 7.8 mg/L). The continuous in-situ FDOM measurements indicated sharp rises in DOC concentrations in the mainstem following rainfall events; concentrations were relatively stable during summer base flow. Even though the first autumn storm mobilized appreciable quantities of carbon, higher concentrations of DBPs in finished water were observed 3-weeks later, after the ground was saturated from additional rainfall. The majority of the DOC in the lower Clackamas River appears to originate from the upper basin, suggesting terrestrial carbon was commonly the dominant source. Lower-basin tributaries typically contained the highest concentrations of DOC and DBP precursors and contributed substantially to the overall loads in the mainstem during storms. During low-flow periods, tributaries were not major sources of DOC or DBP precursors to the Clackamas River. Although the dissolved fraction of organic carbon contributed the majority of DBP precursors, at times the particulate fraction (inorganic sediment and organic particles including detritus and algal material) contributed a substantial fraction of DBP precursors. Considering just the main-stem sites, on average, 10 percent of THMFP and 32 percent of HAAFP were attributed to particulate carbon. This finding suggests water-treatment methods that remove particles prior to chlorination would reduce finished-water DBP concentrations to some degree. Overall, concentrations of THM and HAA precursors were closely linked to DOC concentrations; laboratory DBP formation potentials (DBPFPs) clearly showed that THMFP and HAAFP were greatest in the downstream tributaries that contained elevated carbon concentrations. However, carbon-normalized "specific" formation potentials for THMs and HAAs (STHMFP and SHAAFP, respectively) revealed changes in carbon character over time that affected the two types of DBP classes differently. HAA precursors were elevated in waters containing aromatic-rich soil-derived material arising from forested areas. In contrast, THM precursors were associated with carbon having a lower aromatic content; highest STHMFP occurred in autumn 2011 in the mainstem from North Fork Reservoir downstream to LO DWTP. This pattern suggests the potential for a link between THM precursors and algal-derived carbon. The highest STHMFP value was measured within North Fork Reservoir, indicating reservoir derived carbon may be important for this class of DBPs. Weak correlations between STHMFP and SHAAFP emphasize that precursor sources for these types of DBPs may be different. This highlights not only that different locations within the watershed produce carbon with different reactivity (specific DBPFP), but also that different management approaches for each class of DBP precursors could be required for control. Treatability tests conducted on source water during four basin-wide surveys demonstrated that an average of about 40 percent of DOC can be removed by coagulation. While the decrease in THMFP following coagulation was similar to DOC, the decrease in HAAFP was much greater (approximately 70 percent), indicating coagulation is particularly effective at removing HAA precursors'likely because of the aromatic nature of the carbon associated with HAA precursors. Several findings from this study have direct implications for managing drinking-water resources and for providing useful information that may help improve treatment-plant operations. For example, the use of in-situ fluorometers that measure FDOM provided an excellent proxy for DOC concentration in this system and revealed short-term, rapid changes in DOC concentration during storm events. In addition, the strong correlation between FDOM values measured in-situ and HAA5 concentrations in finished water may permit estimation of continuous HAA concentrations, as was done here. As part of this study, multiple in-situ FDOM sensors were deployed continuously and in real-time to characterize the composition of dissolved organic matter. Although the initial results were promising, additional research and engineering developments will be needed to demonstrate the full utility of these sensors for this purpose. In conclusion, although DBPFPs were strongly correlated to DOC concentration, some DBPs formed from particulate carbon, including terrestrial leaf material and algal material such as planktonic species of blue-green algae and sloughed filaments, stalks, and cells of benthic algae. Different precursor sources in the watershed were evident from the data, suggesting specific actions may be available to address some of these sources. In-situ measurements of FDOM proved to be an excellent proxy for DOC concentration as well as HAA formation during treatment, which suggests further development and refinement of these sensors have the potential to provide real-time information about complex watershed processes to operators at the drinking-water treatment plants. Follow-up studies could examine the relative roles that terrestrial and algal sources have on the DBP precursor pool to better understand how watershed-management activities may be affecting the transport of these compounds to Clackamas River drinking-water intakes. Given the low concentrations of algae in the water column during this study, additional surveys during more typical river conditions could provide a more complete understanding of how algae contribute DBP precursors. Further development of FDOM-sensor technology can improve our understanding of carbon dynamics in the river and how concentrations may be trending over time. This study was conducted in collaboration with Clackamas River Water and the City of Lake Oswego water utilities. Other research partners included Oregon Health and Science University in Hillsboro, Oregon, Alexin Laboratory in Tigard, Oregon, U.S. Geological Survey National Research Program Laboratory in Denver, Colorado, and the U.S. Geological Survey Water Science Centers in Portland, Oregon, and Sacramento, California. This project was supported with funding from Clackamas River Water, City of Lake Oswego, the U.S. Geological Survey, and the Water Research Foundation.

Oregon↗