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Cherie V. Miller

Publications and source records attributed to Cherie V. Miller.

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Guidelines for the use of automatic samplers in collecting surface-water quality and sediment data

The importance of fluvial systems in the transport of sediment, dissolved and suspended contaminants, nutrients, and bacteria through the environment is well established. The U.S. Environmental Protection Agency (EPA) identifies sediment as the single most widespread water contaminant affecting the beneficial uses of the Nation’s rivers and streams. The evaluation of water-quality as it relates to agriculture, urbanization, highway and residential construction, mining, industrial and human wastes, and other activities requires an extensive data and sample-collection effort. This is especially the case when studying urbanized river basins, where during hydrologic events, concentration of suspended sediment and contaminants can vary rapidly and over large ranges. Where synoptic studies of watersheds are called for, sampling may be needed at many sites throughout the basin; a complicated and difficult task in some settings. Automatic pumping samplers (autosamplers) are one method for conducting intensive time-varying sampling throughout watersheds. This report presents guidelines for the use of autosamplers for collecting surface-water samples by the U.S. Geological Survey. An autosampler is an automatic, pump-based sampler that collects a prescribed volume of water from streams, lakes, reservoirs, storm drains, or other bodies of water after receiving a command from an internal or external control unit. It deposits this sample into a specified container for later analysis of physical, chemical, or biological constituents. This report provides a general background on types of autosamplers and how they work; guidance for designing, selecting, installing, servicing, and calibrating autosamplers; guidance on standardized operating procedures, and guidance on quality-assurance and quality-control efforts when using an autosampler.

Techniques and Methods

Water quality in the Anacostia River, Maryland and Rock Creek, Washington, D.C.: Continuous and discrete monitoring with simulations to estimate concentrations and yields of nutrients, suspended sediment, and bacteria

Concentrations and loading estimates for nutrients, suspended sediment, and E. coli bacteria were summarized for three water-quality monitoring stations on the Anacostia River in Maryland and one station on Rock Creek in Washington, D.C. Both streams are tributaries to the Potomac River in the Washington, D.C. metropolitan area and contribute to the Chesapeake Bay estuary. Two stations on the Anacostia River, Northeast Branch at Riverdale, Maryland and Northwest Branch near Hyattsville, Maryland, have been monitored for water quality during the study period from 2003 to 2011 and are located near the shift from nontidal to tidal conditions near Bladensburg, Maryland. A station on Paint Branch is nested above the station on the Northeast Branch Anacostia River, and has slightly less developed land cover than the Northeast and Northwest Branch stations. The Rock Creek station is located in Rock Creek Park, but the land cover in the watershed surrounding the park is urbanized. Stepwise log-linear regression models were developed to estimate the concentrations of suspended sediment, total nitrogen, total phosphorus, and E. coli bacteria from continuous field monitors. Turbidity was the strongest predictor variable for all water-quality parameters. For bacteria, water temperature improved the models enough to be included as a second predictor variable due to the strong dependence of stream metabolism on temperature. Coefficients of determination (R 2 ) for the models were highest for log concentrations of suspended sediment (0.9) and total phosphorus (0.8 to 0.9), followed by E. coli bacteria (0.75 to 0.8), and total nitrogen (0.6). Water-quality data provided baselines for conditions prior to accelerated implementation of multiple stormwater controls in the watersheds. Counties are currently in the process of enhancing stormwater controls in both watersheds. Annual yields were estimated for suspended sediment, total nitrogen, total phosphorus, and E. coli bacteria using the U.S. Geological Survey model LOADEST with hourly time steps of turbidity, flow, and time. Yields of all four parameters were within ranges found in other urbanized watersheds in Chesapeake Bay. Annual yields for all four watersheds over the period of study were estimated for suspended sediment (65,500 – 166,000 kilograms per year per square kilometer; kg/yr/km 2 ), total nitrogen (465 - 911 kg/yr/km 2 ), total phosphorus (36 - 113 kg/yr/km 2 ), and E. coli bacteria (6.0 – 38 x 10 12 colony forming units/yr/km 2 ). The length of record was not sufficient to determine trends for any of the water-quality parameters; within confidence intervals of the models, results were similar to loads determined by previous studies for the Northeast and Northwest Branch stations of the Anacostia River.

Maryl

Summary and interpretation of discrete and continuous water-quality monitoring data, Mattawoman Creek, Charles County, Maryland, 2000-11

Discrete samples and continuous (15-minute interval) water-quality data were collected at Mattawoman Creek (U.S. Geological Survey station number 01658000) from October 2000 through January 2011, in cooperation with the Charles County (Maryland) Department of Planning and Growth Management, the Maryland Department of the Environment, and the Maryland Geological Survey. Mattawoman Creek is a fourth-order Maryland tributary to the tidal freshwater Potomac River; the creek’s watershed is experiencing development pressure due to its proximity to Washington, D.C. Data were analyzed for the purpose of describing ambient water quality, identifying potential contaminant sources, and quantifying nutrient and sediment loads to the tidal freshwater Mattawoman estuary. Continuous data, collected at 15-minute intervals, included discharge, derived from stage measurements made using a pressure transducer, as well as water temperature, pH, specific conductance, dissolved oxygen, and turbidity, all measured using a water-quality sonde. In addition to the continuous data, a total of 360 discrete water-quality samples, representative of monthly low-flow and targeted storm conditions, were analyzed for suspended sediment and nutrients. Continuous observations gathered by a second water-quality sonde, which was temporarily deployed in 2011 for quality-control purposes, indicated substantial lateral water-quality gradients due to inflow from a nearby tributary, representing about 10 percent of the total gaged area upstream of the sampling location. These lateral gradients introduced a time-varying bias into both the continuous and discrete data, resulting in observations that were at some times representative of water-quality conditions in the main channel and at other times biased towards conditions in the tributary. Despite this limitation, both the continuous and discrete data provided insight into the watershed-scale factors that influence water quality in Mattawoman Creek. Annual precipitation over the study period was representative of the long-term record for southern Maryland. The median value of continuously measured discharge was 25 cubic feet per second (ft 3 /s), and the maximum observed value was 3,210 ft 3 /s; there were 498 days, or about 15 percent of the study period, when flow was zero or too low to measure. Continuously measured water temperature followed a seasonal trend characteristic of the geographic setting; the trend in dissolved oxygen was inverted relative to temperature, and reflected nearly saturated conditions year round. Relations between discharge and both pH and specific conductance indicate that stream water can be conceptualized as a mixture of acidic, dilute precipitation with pH-neutral groundwater of higher conductance. Specific conductance data showed a pronounced winter peak in both median and extreme measurements, indicating the influence of road salt. However, this influence is minor relative to that observed in the Northeast Branch Anacostia River (U.S. Geological Survey station number 01649500), a nearby, more heavily urbanized comparison basin. The median suspended-sediment concentration in discrete samples was 24 milligrams per liter (mg/L), with minimum and maximum concentrations of 1 mg/L and 2,890 mg/L, respectively. Total nitrogen ranged from 0.21 mg/L to 4.09 mg/L, with a median of 0.69 mg/L; total phosphorus ranged from less than 0.01 mg/L to 0.98 mg/L, with a median of 0.07 mg/L. Total nitrogen was dominated by the dissolved organic fraction (49 percent based on median species concentrations); total phosphorus was predominantly particulate (70 percent). Seasonal trends in suspended-sediment concentration indicate a supply subsidy in late winter and spring; this could be linked to flood-plain interaction, mobilization of sediment from the channel or banks, or anthropogenic input. Seasonal trends for both total phosphorus and total nitrogen generally corresponded to seasonal trends for suspended sediment, indicating a common underlying physical control, likely acting in synchrony with seasonal biological controls on total nutrient concentrations. Speciation of phosphorus, including proportional concentration of the biologically available dissolved inorganic fraction, did not vary seasonally. The speciation of nitrogen reflected demand for inorganic nitrogen and associated transformation into organic nitrogen during the growing season. Stepwise regression models were developed, using continuous data corresponding to collection times for discrete samples as candidate surrogates for suspended sediment, total phosphorus, and total nitrogen. Turbidity and discharge were both included in the model for suspended sediment (R 2 = 0.76, n = 185); only turbidity was selected as a robust predictor of total phosphorus and nitrogen (R 2 = 0.68 and 0.61, respectively, n = 186 for both). Loads of sediment and nutrients to the downstream Mattawoman estuary were computed using the U.S. Geological Survey computer program LOADEST. Load estimation included comparison of a routinely applied seven-parameter regression model based on time, season, and discharge, with an eight-parameter model that also includes turbidity. Adding turbidity decreased total load estimates, based on hourly data for a fixed 2-month period, by 21, 8, and 3 percent for suspended sediment, total phosphorus, and total nitrogen, respectively, in addition to decreasing the standard error of prediction for all three constituents. The seasonal pattern in specific conductance, reflecting road salt application, is the strongest evidence of the effect of upstream development on water quality at Mattawoman Creek. Accordingly, ongoing continuous monitoring for trends in specific conductance would be the most reliable means of detecting further degradation associated with increased development.

Charles County, Maryl

Pesticides in groundwater in the Anacostia River and Rock Creek watersheds in Washington, D.C., 2005 and 2008

The U.S. Geological Survey (USGS), in cooperation with the District Department of the Environment, conducted a groundwater-quality investigation to (a) determine the presence, concentrations, and distribution of selected pesticides in groundwater, and (b) assess the presence of pesticides in groundwater in relation to selected landscape, hydrogeologic, and groundwater-quality characteristics in the shallow groundwater underlying the Anacostia River and Rock Creek watersheds in Washington, D.C. With one exception, well depths were 100 feet or less below land surface. The USGS obtained or compiled ancillary data and information on land use (2001), subsurface sediments, and groundwater samples from 17 wells in the lower Anacostia River watershed from September through December 2005, and from 14 wells in the lower Anacostia River and lower Rock Creek watersheds from August through September 2008. Twenty-seven pesticide compounds, reflecting at least 19 different types of pesticides, were detected in the groundwater samples obtained in 2005 and 2008. No fungicides were detected. In relation to the pesticides detected, degradate compounds were as or more likely to be detected than applied (parent) compounds. The detected pesticides chiefly reflected herbicides commonly used in urban settings for non-specific weed control or insecticides used for nonspecific haustellate insects (insects with specialized mouthparts for sucking liquid) or termite-specific control. Detected pesticides included a combination of pesticides currently (2008) in use, banned or under highly restricted use, and some that had replaced the banned or restricted-use pesticides. The presence of banned and restricted-use pesticides illustrates their continued persistence and resistance to complete degradation in the environment. The presence of the replacement pesticides indicates the susceptibility of the surficial aquifer to contamination irrespective of the changes in the pesticides used. A preliminary review of the data collected in 2005 and 2008 indicated that differences in the surficial geology, land use (as a surrogate for pesticide use), and above-average precipitation for most of 2004 through 2008, as well as differences in the number and performance of USGS laboratory methods used, could have led to more pesticides detected in groundwater samples collected in 2008 than in groundwater samples collected in 2005. Thus, although data from both years of collection were used for interpretive analysis, emphasis was placed on the analysis of the data obtained in 2008. The presence of pesticides in shallow groundwater (less than approximately 100 ft (feet), or 30 m (meters), below land surface) indicated at least the upper surficial aquifer in Washington, D.C. was susceptible to contamination. One or more herbicides or insecticides were detected in groundwater samples collected from 50 percent of the shallow wells sampled in 2005, and from 62 percent of the shallow wells sampled in 2008. Differences among types of pesticides in shallow groundwater were apparent. The most frequently detected class of herbicides was the s-triazine compounds—atrazine, simazine, or prometon, or the atrazine-degradate compounds—2-chloro-4-ethylamino-6-amino-s-triazine (desethylatrazine or CIAT) and 2-chloro-4-isopropylamino-6-amino-s-triazine (hydroxyatrazine or OIET). The next most frequently detected classes of herbicides were the chloroacetanilides, including metolachlor and acetochlor, and the ureic herbicides, including diuron (and degradate, 3,4-dichloroaniline), fluometuron, metsulfuron methyl, sulfameturon, bromacil, and tebuthiuron. Insecticides also were detected, but less frequently than herbicides, with one or more insecticides present in groundwater samples from 38 percent of shallow wells sampled in 2008. Detected insecticides included parent or degradate compounds commonly used for either nonspecific or haustellate (sucking) insects, including chlorpyrifos and dichlorodiphenyldichloroethane (p,p’-DDD; a degradate of dichlorodiphenyltrichloroethane, DDT), and for termite control, including dieldrin, chlordane, heptachlor epoxide, (a degradate of heptachlor), fipronil, and the sulfone and sulfide degradates of fipronil. The concentrations of individual pesticides in shallow groundwater in both years were low. Maximum concentrations were no greater than a few tenths of a microgram per liter (μg/L); typical concentrations often were less than 0.1 μg/L. Multiple pesticides, however, commonly were present in groundwater. For example, in 2008, approximately 88 percent (7 of 8) of the wells that yielded a sample with at least one detectable pesticide contained five or more pesticides. The highest number of detections occurred in a groundwater sample from well WE Ca 32, which is located in a highly developed urban area; this sample contained 15 different pesticide residues. In relation to human and aquatic health, no pesticide concentration in either 2005 or 2008 exceeded Federal drinking-water standards. Groundwater samples from a few sites, however, contained levels of chiefly banned or restricted-use pesticides that exceeded other human-health and (or) aquatic-health guidelines. For example, concentrations of dieldrin in 2008 groundwater samples from three wells—WE Ca 32 (0.028 μg/L), WE Ba 11 (0.016 μg/L), and WW Ac 8 (0.014 μg/L)—fell within the range of concern for 2004 Federally approved non-regulatory USGS Health-Based Assessment benchmarks (0.002 to 0.2 μg/L), and exceeded earlier (1999) Federal criteria for drinking water (0.000052 μg/L). Other individual compounds whose concentrations exceeded 1999 Federal guidelines for samples from one or more of these three sites, or another site, included p,p’-DDD, dichlorodiphenyldichloroethylene (p,p’-DDE; another degradate of DDT), chlordane, and heptachlor epoxide. Pesticide concentrations in groundwater also were compared to three aquatic-health guidelines for freshwater (United States, Great Lakes, or Canada). One or more of these guidelines were exceeded in groundwater samples obtained in 2005 or 2008 for one or more of the compounds chlordane, dieldrin, heptachlor epoxide, p,p’-DDE, p,p’-DDD, and chlorpyrifos. The spatial distribution of pesticides in the shallow groundwater appeared to be related, in part, to land use, a surrogate for pesticide use. Although most of the wells sampled in this study are in parklands or other relatively open and accessible space, multiple pesticides most often were detected in 2008 groundwater samples collected from wells where a considerable percentage (in excess of 60 percent) of the land within a 500-m radius is developed space (residential, commercial, or other urban infrastructure). Insecticides were detected in wells surrounded by at least 50 percent, and most commonly by more than 80 percent, development. Well WE Ca 32, the site associated with the highest number of pesticide residues in groundwater (8 herbicides and 7 insecticides), is in a small residential park, where 99 percent of the surrounding land is well-maintained residential and commercial development. The vertical distribution of detected pesticides in shallow groundwater appeared to be related, in part, to depth below land surface, surficial-bedrock type, and differences in the chemistry of shallow groundwater. Pesticides were detected at relatively shallow depths in wells that may not have fully penetrated the shallow aquifer. For wells in which at least one pesticide was detected, the median depth below land surface to the top of the well screen was 5.8 m, and the maximum depth was 8.5 m. Among the types of surficial materials in which wells were completed—alluvium, terrace deposits, or Potomac Formation sub- or outcrops in the Coastal Plain Province, and saprolite or fractured bedrock (Laurel and Sykesville Formations) underlying saprolite in the Piedmont Province—no pesticides were detected in groundwater associated with wells completed in the alluvium or fractured bedrock. Detections occurred in some but not all wells completed in the other surficial materials. Overall, the pattern in occurrence appeared related to the local permeability of these sediments and groundwater chemistry. Groundwater with multiple pesticide detections tended to occur in permeable sediments (absent any appreciable overlying clay, silt, or clay-silt layers), in conjunction with other common urban contaminants (elevated chloride in excess of tens to hundreds of milligrams per liter (mg/L), and oxic, rather than reduced, groundwater as evidenced by elevated (in excess of 5 mg/L) concentrations of nitrate). The results of this investigation were compared to results from two other similar and recent studies on pesticide occurrence in the shallow aquifer. These included a study in the nearby Maryland and Delaware Coastal Plain Physiographic Province and one in the Maryland and Virginia Piedmont Physiographic Province. Results from these studies were similar to the current study in relation to (a) the types, frequencies, concentrations, and mixtures of pesticides detected; (b) compounds that exceeded human-and aquatic-health criteria; and (c) the occurrence and distribution of pesticides within the surficial aquifer in relation to depths, sediment types, and groundwater chemistries.

Washington D.C.

Occurrence and Distribution of Organic Wastewater Compounds in Rock Creek Park, Washington, D.C., 2007-08

The U.S. Geological Survey, and the National Park Service Police Aviation Group, conducted a high-resolution, low-altitude aerial thermal infrared survey of the Washington, D.C. section of Rock Creek Basin within the Park boundaries to identify specific locations where warm water was discharging from seeps or pipes to the creek. Twenty-three stream sites in Rock Creek Park were selected based on the thermal infrared images. Sites were sampled during the summers of 2007 and 2008 for the analysis of organic wastewater compounds to verify potential sources of sewage and other anthropogenic wastewater. Two sets of stormwater samples were collected, on June 27-28 and September 6, 2008, at the Rock Creek at Joyce Road water-quality station using an automated sampler that began sampling when a specified stage threshold value was exceeded. Passive-sampler devices that accumulate organic chemicals over the duration of deployment were placed in July 2008 at the five locations that had the greatest number of detections of organic wastewater compounds from the June 2007 base-flow sampling. During the 2007 base-flow synoptic sampling, there were ubiquitous low-level detections of dissolved organic wastewater indicator compounds such as DEET, caffeine, HHCB, and organophosphate flame retardants at more than half of the 23 sites sampled in Rock Creek Park. Concentrations of DEET and caffeine in the tributaries to Rock Creek were variable, but in the main stem of Rock Creek, the concentrations were constant throughout the length of the creek, which likely reflects a distributed source. Organophosphate flame retardants in the main stem of Rock Creek were detected at estimated concentrations of 0.2 micrograms per liter or less, and generally did not increase with distance downstream. Overall, concentrations of most wastewater indicators in whole-water samples in the Park were similar to the concentrations found at the upstream sampling station at the Maryland/District of Columbia boundary. Polycyclic aromatic hydrocarbons were the dominant organic compounds found in the stormwater samples at the Joyce Road station. Polycyclic aromatic hydrocarbons were consistently found in higher concentrations either in sediment or in whole-water samples than in the dissolved samples collected during base-flow conditions at the 23 synoptic sites, or in the Joyce Road station stormwater samples.

Scientific Investigations Report

Water quality in the upper Anacostia River, Maryland: Continuous and discrete monitoring with simulations to estimate concentrations and yields, 2003-05

From 2003 through 2005, continuous and discrete waterquality data were collected at two stations on the Anacostia River in Maryland: Northeast Branch at Riverdale, Maryland (U.S. Geological Survey Station 01649500) and Northwest Branch near Hyattsville, Maryland (Station 01651000). Both stations are above the heads of tide for the river, and measurements approximately represent contributions of chemicals from the nontidal watersheds in the Anacostia River. This study was a cooperative effort between the U.S. Geological Survey, the Prince George’s County Department of Environmental Resources, the Maryland Department of the Environment, the U.S. Environmental Protection Agency, and George Mason University. Samples were collected for suspended sediment, nutrients, and trace metals; data were used to calculate loads of selected chemical parameters, and to evaluate the sources and transport processes of contaminants. Enrichment factors were calculated for some trace metals and used to interpret patterns of occurrence over different flow regimes. Some metals, such as cadmium, lead, and zinc, were slightly enriched as compared to global averages for shales; overall, median values of enrichment factors for all metals were approximately 15 to 35. Stepwise linear regression models were developed on log-transformed concentrations to estimate the concentrations of suspended sediment, total nitrogen, and total phosphorus from continuous data of discharge and turbidity. The use of multiple explanatory variables improved the predictions over traditional rating curves that use only streamflow as the explanatory variable, because other variables such as turbidity measure the hysteretic effects of fine-grained suspended sediment over storm hydrographs. Estimates of the concentrations of suspended sediment from continuous discharge and turbidity showed coefficients of determination for the predictions (multiple R2) of 0.95 and biases of less than 4 percent. Models to estimate the concentrations of total phosphorus and total nitrogen had lower values of multiple R2 than suspended sediment, but the estimated bias for all the models was similar. The models for total nitrogen and total phosphorus tended to under-predict high concentrations and to over-predict low concentrations as compared to measured values. Annual yields (loads per square area in kilograms per year per square kilometer) were estimated for suspended sediment, total nitrogen, and total phosphorus using the U.S. Geological Survey models ESTIMATOR and LOADEST. The model LOADEST used hourly time steps and allowed the use of turbidity, which is strongly correlated to concentrations of suspended sediment, as a predictor variable. Annual yields for total nitrogen and total phosphorus were slightly higher but similar to previous estimates for other watersheds of the Chesapeake Bay, but annual yields for suspended sediment were higher by an order of magnitude for the two Anacostia River stations. Annual yields of suspended sediment at the two Anacostia River stations ranged from 131,000 to 248,000 kilograms per year per square kilometer for 2004 and 2005. LOADEST estimates were similar to those determined with ESTIMATOR, but had reduced errors associated with the estimates.

Maryland

Chemical and Ecological Health of White Sucker (Catostomus Commersoni) in Rock Creek Park, Washington, D.C., 2003-04

Several classes of chemicals that are known or suspected contaminants were found in bed sediment in Rock Creek, including polyaromatic hydrocarbons (PAHs), phthalate esters, organochlorine pesticides, dioxins and furans, trace metals and metalloids (mercury, arsenic, cadmium, chromium, cobalt, copper, lead, nickel, silver, and zinc), and polychlorinated biphenyls (total PCBs and selected aroclors). Concentrations of many of these chemicals consistently exceeded threshold or chronic-effects guidelines for the protection of aquatic life and often exceeded probable effects levels (PELs). Exceedance of PELs was dependent on the amount of total organic carbon in the sediments. Concurrent with the collection of sediment-quality data, white sucker (Catostomus commersoni) were evaluated for gross-external and internal-organ anomalies, whole-body burdens of chemical contaminants, and gut contents to determine prey. The histopathology of internal tissues of white sucker was compared to contaminant levels in fish tissue and bed sediment. Gut contents were examined to determine preferential prey and thus potential pathways for the bioaccumulation of chemicals from bed sediments. Male and female fish were tested separately. Lesions and other necroses were observed in all fish collected during both years of sample collection, indicating that fish in Rock Creek have experienced some form of environmental stress. No direct cause and effect was determined for chemical exposure and compromised fish health, but a substantial weight of evidence indicates that white sucker, which are bottom-feeding fish and low-order consumers in Rock Creek, are experiencing some reduction in vitality, possibly due to immunosuppression. Abnormalities observed in gonads of both sexes of white sucker and observations of abnormal behavior during spawning indicated some interruption in reproductive success.

Scientific Investigations Report

Summary of water- and sediment-quality data for Anacostia River well sites sampled in July-August 2002

This data report is a summary of chemical analyses conducted by the U.S. Geological Survey on ground water and sediment in the tidal Anacostia River watershed, Washington, D.C. during July-August 2002. Cores were drilled and wells were established at three shoreline sites: two wells at the New York Avenue overpass, two wells at the Kenilworth Aquatic Gardens, and one well at Anacostia Park. Additionally, two cores were collected by hoverprobe in mudflats on the river: one by Benning Road and one in the mouth of Beaverdam Creek. Chemical analyses included volatile organic compounds, semi-volatile organic compounds or polyaromatic hydrocarbons, organochlorine pesticides, aroclors and total polychlorinated biphenyls, metals, nutrients, biochemical and chemical oxygen demands, total phenols, total cyanide, oil and grease, and total suspended and dissolved solids in aqueous phases.

Open-File Report

Ground-water contamination from lead shot at Prime Hook National Wildlife Refuge, Sussex County, Delaware

Prime Hook National Wildlife Refuge is located in southeastern Delaware in coastal lowlands along the margin of Delaware Bay. For 37 years, the Broadkiln Sportsman?s Club adjacent to the refuge operated a trap-shooting range, with the clay-target launchers oriented so that the expended lead shot from the range dropped into forested wetland areas on the refuge property. Investigators have estimated that up to 58,000 shotgun pellets per square foot are present in locations on the refuge where the lead shot fell to the ground. As part of the environmental risk assessment for the site, the U.S. Geological Survey (USGS) investigated the potential for lead contamination in ground water. Results from two sampling rounds in 19 shallow wells indicate that elevated levels of dissolved lead are present in ground water at the site. The lead and associated metals, such as antimony and arsenic (common shotgun pellet alloys), are being transported along shallow ground-water flowpaths toward an open-water slough in the forested wetland adjacent to the downrange target area. Water samples from wells located along the bank of the slough contained dissolved lead concentrations higher than 400 micrograms per liter, and as high as 1 milligram per liter. In contrast, a natural background concentration of lead from ground water in a well upgradient from the site is about 1 microgram per liter. Two water samples collected several months apart from the slough directly downgradient of the shooting range contained 24 and 212 micrograms per liter of lead, respectively. The data indicate that lead from a concentrated deposit of shotgun pellets on the refuge has been mobilized through a combination of acidic water conditions and a very sandy, shallow, unconfined aquifer, and is moving along ground-water flowpaths toward the surface-water drainage. Data from this study will be used to help delineate the lead plume, and determine the fate and transport of lead from the source area.

Water-Resources Investigations Report

Water quality, sediment quality, and stream-channel classification of Rock Creek, Washington, D.C., 1999-2000

Rock Creek Park is within the National Capital Region in Washington, D.C., and is maintained by the National Park Service. Part of Montgomery County, Maryland, and part of the District of Columbia drain into Rock Creek, which is a tributary of the Potomac River. Water quality in Rock Creek is important to biotic life in and near the creek, and in the Potomac River Basin and the Chesapeake Bay. The water quality of the Rock Creek Basin has been affected by continued urban and agricultural growth and development. The U.S. Geological Survey, in cooperation with the National Park Service, investigated water quality and sediment quality in Rock Creek over a 2-year period (1998?2000), and performed a stream-channel classification to determine the distribution of bottom sediment in Rock Creek. This report presents and evaluates water quality and bottom sediment in Rock Creek for water years 1999 (October 1, 1998 to September 30, 1999) and 2000 (October 1, 1999 to September 30, 2000). A synoptic surface-water assessment was conducted at five stations from June 23 to June 25, 1999, a temporal surface-water assessment was conducted at one station from February 18, 1999 to September 26, 2000, and bed-sediment samples were collected and assessed from three stations from August 17 to August 19, 1999. The synoptic surface-water assessment included pesticides (parent compounds and selected transformation products), field parameters, nutrients, and major ions. The temporal surface-water assessment included pesticides (parent compounds and selected transformation products) and field parameters. The bed-sediment assessment included trace elements and organic compounds (including low- and high-molecular weight polycyclic aromatic hydrocarbons, poly-chlorinated biphenyls, pesticides, and phthalates). Some, but not all, of the pesticides known to be used in the area were included in the synoptic water-quality assessment, the temporal water-quality assessment, and the bed-sediment assessment. In addition to the water-quality and sediment-quality assessments, a Rosgen stream-channel classification was performed on a 900-foot-long segment of Rock Creek. In the synoptic water-quality assessment, two pesticides were found to be above published criteria for the protection of aquatic life. In the temporal water-quality assessment, four pesticides were found to be above published criteria for the protection of aquatic life. In the bed-sediment assessment, 8 trace elements, 14 polycyclic aromatic hydrocarbons, 6 pesticides, and 1 phthalate compound were found to be above published criteria for the protection of aquatic life. In the Rosgen classification, a comparison to a previous classification for this segment showed an increase in sands and other fine-grained sediments in the creek bed.

Water-Resources Investigations Report

Organic compounds and trace elements in the Pocomoke River and tributaries, Maryland

In response to concern about recent blooms of the dinoflagellate, Pfiesteria piscicida, samples of sediment and water were collected from the lower Pocomoke River Basin and were screened for trace elements, pesticides, and other organic compounds. A large group of steroid and fatty acid methyl-ester compounds was detected in streamwater using gas chromatography/mass spectroscopy in scan mode. Some of these steroid compounds have been identified and further quantified in bed-sediment extracts. Spatial patterns of the concentrations of cholesterol suggest that these compounds are linked to the runoff of animal wastes into the river. Many of the organic compounds found in the Pocomoke River sediments have not yet been identified, but at least several are in the class of hormone compounds related to estradiols and have the potential to promote endocrine-disrupting effects in aquatic life. Particulate forms of arsenic and zinc are slightly elevated above normal levels for streams, but the sources for these elements are still undetermined. Several pesticides were found in low, parts-per-trillion concentrations, but were within the ranges commonly found in streams of this region.

Maryland