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Kevin J. Breen

Publications and source records attributed to Kevin J. Breen.

7 recordsLinked to original sources
USGS2012

Evaluating changes in matrix based, recovery-adjusted concentrations in paired data for pesticides in groundwater

Pesticide concentration data for waters from selected carbonate-rock aquifers in agricultural areas of Pennsylvania were collected in 1993–2009 for occurrence and distribution assessments. A set of 30 wells was visited once in 1993–1995 and again in 2008–2009 to assess concentration changes. The data include censored matched pairs (nondetections of a compound in one or both samples of a pair). A potentially improved approach for assessing concentration changes is presented where (i) concentrations are adjusted with models of matrix-spike recovery and (ii) area-wide temporal change is tested by use of the paired Prentice-Wilcoxon (PPW) statistical test. The PPW results for atrazine, simazine, metolachlor, prometon, and an atrazine degradate, deethylatrazine (DEA), are compared using recovery-adjusted and unadjusted concentrations. Results for adjusted compared with unadjusted concentrations in 2008–2009 compared with 1993–1995 were similar for atrazine and simazine (significant decrease; 95% confidence level) and metolachlor (no change) but differed for DEA (adjusted, decrease; unadjusted, increase) and prometon (adjusted, decrease; unadjusted, no change). The PPW results were different on recovery-adjusted compared with unadjusted concentrations. Not accounting for variability in recovery can mask a true change, misidentify a change when no true change exists, or assign a direction opposite of the true change in concentration that resulted from matrix influences on extraction and laboratory method performance. However, matrix-based models of recovery derived from a laboratory performance dataset from multiple studies for national assessment, as used herein, rather than time- and study-specific recoveries may introduce uncertainty in recovery adjustments for individual samples that should be considered in assessing change.

Pennsylvania↗
USGS2012

Groundwater quality and simulation of sources of water to wells in the Marsh Creek valley at the U.S. Geological Survey Northern Appalachian Research Laboratory, Tioga County, Pennsylvania

This report provides a November 2010 snapshot of groundwater quality and an analysis of the sources of water to wells at the U.S. Geological Survey (USGS) Northern Appalachian Research Laboratory (NARL) near Wellsboro, Pennsylvania. The laboratory, which conducts fisheries research, currently (2011) withdraws 1,000 gallons per minute of high-quality groundwater from three wells completed in the glacial sand and gravel aquifer beneath the Marsh Creek valley; a fourth well that taps the same aquifer provides the potable supply for the facility. The study was conducted to document the source areas and quality of the water supply for this Department of Interior facility, which is surrounded by the ongoing development of natural gas from the Marcellus Shale. Groundwater samples were collected from the four wells used by the NARL and from two nearby domestic-supply wells. The domestic-supply wells withdraw groundwater from bedrock of the Catskill Formation. Samples were analyzed for major ions, nutrients, trace metals, radiochemicals, dissolved gases, and stable isotopes of oxygen and hydrogen in water and carbon in dissolved carbonate to document groundwater quality. Organic constituents (other than hydrocarbon gases) associated with hydraulic fracturing and other human activities were not analyzed as part of this assessment. Results show low concentrations of all constituents. Only radon, which ranged from 980 to 1,310 picocuries per liter, was somewhat elevated. These findings are consistent with the pristine nature of the aquifer in the Marsh Creek valley, which is the reason the laboratory was sited at this location. The sources of water and areas contributing recharge to wells were identified by the use of a previously documented MODFLOW groundwater-flow model for the following conditions: (1) withdrawals of 1,000 to 3,000 gallons per minute from the NARL wells, (2) average or dry hydrologic conditions, and (3) withdrawals of 1,000 gallons per minute from a new well 3,500 feet to the southwest that was drilled to provide water for Marcellus gas-well operations. Results of simulations indicate that during average hydrologic conditions, infiltration from Straight Run, a tributary to Marsh Creek, provides nearly all the water to the NARL wells. During dry conditions, the areas contributing recharge expand such that Asaph Run contributes about half of the water to the NARL wells when withdrawals are 1,000 or 2,000 gallons per minute. The addition of a simulated withdrawal of 1,000 gallons per minute from the nearby new well does not substantially affect the sources of water captured by the NARL wells. These results are subject to some limitations. The water-quality samples represent a snapshot of groundwater chemistry for only one hydrologic condition; the concentrations of some constituents may change temporally. In addition, samples were collected and analyzed for hydrocarbon gases, but not organic constituents associated with hydraulic fracturing; additional sampling for these constituents would provide a more complete water-quality baseline. The sources contributing water to the NARL wells and the new well were simulated by use of a simplified one-layer model of the glacial sand and gravel aquifer for steady-state conditions that in reality are never achieved. Steady-state simulations of dry hydrologic conditions show that it is possible for the NARL wells to capture water from Asaph Run; however, maps of simulated groundwater time-of-travel indicate that a dry period of unusually long duration would be required. A better analysis could be done by recalibrating the groundwater-flow model with a finite-difference grid having multiple layers, cells smaller than the 200-foot by 200-foot cells used in this study, and transient stress periods.

Pennsylvania↗
USGS2009

Pesticides in ground water in selected agricultural land-use areas and hydrogeologic settings in Pennsylvania, 2003-07

This report was prepared by the U.S. Geological Survey (USGS) in cooperation with the Pennsylvania Department of Agriculture (PDA) as part of the Pennsylvania Pesticides and Ground Water Strategy (PPGWS). Monitoring data and extensive quality-assurance data on the occurrence of pesticides in ground water during 2003–07 are presented and evaluated; decreases in the land area used for agriculture and corresponding changes in the use of pesticides also are documented. In the Pennsylvania ground waters assessed since 2003, concentrations of pesticides did not exceed any maximum contaminant or health advisory levels established by the U.S. Environmental Protection Agency; PPGWS actions are invoked by the PDA at fractions of these levels and were needed only in areas designated by the PDA for special ground-water protection. Previous investigations through 1998 of pesticides in Pennsylvania ground water identified land use, as a surrogate for pesticide use, and rock type of the aquifer combined with physiography as key hydrogeologic setting variables for understanding aquifer vulnerability to contamination and the common occurrence of atrazine and metolachlor in ground water. Of 20 major hydrogeologic settings in a framework established in 1999 for pesticide monitoring in Pennsylvania, 9 were identified as priorities for data collection in order to change the monitoring status from "inadequate" to "adequate" for the PPGWS. Agricultural and forested land-use areas are decreasing because of urban and suburban growth. In the nine hydrogeologic settings evaluated using 1992 and 2001 data, decreases of up to 12 percent for agricultural land and 10 percent for forested land corresponded to increases of up to 11 percent for urban land. Changes in agricultural pesticide use were computed from crop data. For example, from 1996 to 2004–05, atrazine use declined by about 15 percent to 1,314,000 lb/yr (pounds per year) and metolachlor use increased by about 20 percent to 895,000 lb/yr; these compounds are the two most-used agricultural pesticides statewide. In 2003–07, a baseline assessment of pesticides was conducted in five of nine hydrogeologic settings with inadequate monitoring data—the Blue Ridge crystalline and Triassic Lowland siliciclastic, Eastern Lake surficial, Devonian-Silurian carbonate, Great Valley siliciclastic, and Northeastern Glaciated surficial settings. Between 20 and 30 wells in each setting were monitored. Of the 126 wells sampled, 96 well-water samples were analyzed for at least 52 pesticide compounds at the USGS National Water Quality Laboratory (NWQL) using a method with a minimum reporting level (MRL) at or above 0.002 µg/L (micrograms per liter). Of the 96 well waters analyzed by NWQL, 43 had measureable concentrations of one or more pesticides. Atrazine and (or) deethylatrazine (CIAT), a degradation product of atrazine, were reported at or above the MRL in 39 of the 43 well waters. Neither atrazine nor CIAT were reported at concentrations exceeding 0.10 µg/L; all measured concentrations in these five settings were below PPGWS action levels. Metolachlor was present in 7 of the 43 well waters with measureable concentrations of 1 or more pesticides; however, concentrations were below the MRL. The other 30 samples (10 of 20 wells in the Blue Ridge crystalline and Triassic Lowland siliciclastic setting and all 20 wells in the Eastern Lake surficial setting) were analyzed for at least 19 pesticide compounds at the Pennsylvania Department of Environmental Protection Laboratory (PADEPL); the PADEPL reported no concentrations of pesticides at or above an MRL of 0.10 µg/L. Statistical tests using the NWQL analytical results showed correlations between pesticide occurrence and two indicators of water-quality degradation—the occurrence of total coliform bacteria and nitrate concentration. A 2 × 2 contingency-table test indicated a relation between presence or absence of atrazine or metolachlor and presence or absence of bacteria only for the 10 wells representing the Blue Ridge crystalline and Triassic Lowland siliciclastic setting. Results of Spearman’s rank test showed strong positive correlations in the Devonian-Silurian carbonate setting between 1) the number of pesticides above the MRLs and nitrate concentration, and 2) concentrations of atrazine and nitrate. Atrazine concentration and nitrate concentration also showed a statistically significant positive correlation in the Great Valley siliciclastic setting. An additional component of baseline monitoring was to evaluate changes in pesticide concentration in water from wells representing hydrogeologic settings most vulnerable to contamination from pesticides. In 2003, 16 wells originally sampled in the 1990s were resampled—4 each in the Appalachian Mountain carbonate, Triassic Lowland siliciclastic, Great Valley carbonate, and Piedmont carbonate settings. Nine of these wells, where pesticide concentrations from 1993 and 2003 were analyzed at the NWQL, were chosen for a paired-sample analysis using concentrations of atrazine and metolachlor. A statistically significant decrease in atrazine concentration was identified using the Wilcoxon signed-rank test (p = 0.004); significant temporal changes in metolachlor concentrations were not observed (p = 0.625). Monitoring in three areas of special ground-water protection, where selected pesticide concentrations in well water were at or above the PPGWS action levels, was done at wells BE 1370 (Berks County, Oley Township), BA 437 (Blair County, North Woodbury Township), and LN 1842 (Lancaster County, Earl Township). Co-occurrence of pesticide-degradation products with parent compounds was documented for the first time in ground-water samples collected from these three wells. Degradation products of atrazine, cyanazine, acetochlor, alachlor, and metolachlor were commonly at larger concentrations than the parent compound in the same water sample. Pesticide occurrence in water from wells neighboring the hot-spot wells was highly variable; however, the same sets of pesticide compounds that were present in wells BA 437, BE 1370, and LN 1842 were present to some degree in water from neighboring wells. To evaluate temporal changes in concentration, nonparametric statistical tests were used to determine overall and seasonal monotonic trends. Concentrations of alachlor, atrazine, metolachlor, and nitrate were examined using the 5-year (2003–07) and the long-term data from wells BA 437 and LN 1842 (1996–2007 and 1995–2007, respectively), and the long-term data for well BE 1370 (1998–2007); results showed either downward trends or no trends. Trends in acetochlor concentrations were tested only at well LN 1842 using the 5-year data; no trends were observed. Homogeneity of trend tests indicated statistically significant downward concentration trends in the long-term data were due to seasonal trends as follows: BA 437—alachlor and atrazine (summer); BE 1370—atrazine and metolachlor (winter) and alachlor (winter and spring); LN 1842—alachlor (summer and fall) and atrazine (spring and fall).

Pennsylvania↗
USGS2007

Natural gases in ground water near Tioga Junction, Tioga County, north-central Pennsylvania: Occurrence and use of isotopes to determine origins, 2005

In January 2001, State oil and gas inspectors noted bubbles of natural gas in well water during a complaint investigation near Tioga Junction, Tioga County, north-central Pa. By 2004, the gas occurrence in ground water and accumulation in homes was a safety concern; inspectors were taking action to plug abandoned gas wells and collect gas samples. The origins of the natural-gas problems in ground water were investigated by the U.S. Geological Survey, in cooperation with the Pennsylvania Department of Environmental Protection, in wells throughout an area of about 50 mi2, using compositional and isotopic characteristics of methane and ethane in gas and water wells. This report presents the results for gas-well and water-well samples collected from October 2004 to September 2005. Ground water for rural-domestic supply and other uses near Tioga Junction is from two aquifer systems in and adjacent to the Tioga River valley. An unconsolidated aquifer of outwash sand and gravel of Quaternary age underlies the main river valley and extends into the valleys of tributaries. Fine-grained lacustrine sediments separate shallow and deep water-bearing zones of the outwash. Outwash-aquifer wells are seldom deeper than 100 ft. The river-valley sediments and uplands adjacent to the valley are underlain by a fractured-bedrock aquifer in siliciclastic rocks of Paleozoic age. Most bedrock-aquifer wells produce water from the Lock Haven Formation at depths of 250 ft or less. A review of previous geologic investigations was used to establish the structural framework and identify four plausible origins for natural gas. The Sabinsville Anticline, trending southwest to northeast, is the major structural feature in the Devonian bedrock. The anticline, a structural trap for a reservoir of deep native gas in the Oriskany Sandstone (Devonian) (origin 1) at depths of about 3,900 ft, was explored and tapped by numerous wells from 1930-60. The gas reservoir in the vicinity of Tioga Junction, depleted of native gas, was converted to the Tioga gas-storage field for injection and withdrawal of non-native gases (origin 2). Devonian shale gas (shallow native gas) also has been reported in the area (origin 3). Gas might also originate from microbial degradation of buried organic material in the outwash deposits (origin 4). An inventory of combustible-gas concentrations in headspaces of water samples from 91 wells showed 49 wells had water containing combustible gases at volume fractions of 0.1 percent or more. Well depth was a factor in the observed occurrence of combustible gas for the 62 bedrock wells inventoried. As well-depth range increased from less than 50 ft to 51-150 ft to greater than 151 ft, the percentage of bedrock-aquifer wells with combustible gas increased. Wells with high concentrations of combustible gas occurred in clusters; the largest cluster was near the eastern boundary of the gas-storage field. A subsequent detailed gas-sampling effort focused on 39 water wells with the highest concentrations of combustible gas (12 representing the outwash aquifer and 27 from the bedrock aquifer) and 8 selected gas wells. Three wells producing native gas from the Oriskany Sandstone and five wells (two observation wells and three injection/withdrawal wells) with non-native gas from the gas-storage field were sampled twice. Chemical composition, stable carbon and hydrogen isotopes of methane (13CCH4 and DCH4), and stable carbon isotopes of ethane (13CC2H6) were analyzed. No samples could be collected to document the composition of microbial gas originating in the outwash deposits (outwash or 'drift' gas) or of native natural gas originating solely in Devonian shale at depths shallower than the Oriskany Sandstone, although two of the storage-field observation wells sampled reportedly yielded some Devonian shale gas. Literature values for outwash or 'drift' gas and Devonian shale gases were used to supplement the data collection. Non-native gases fr

Pennsylvania↗
USGS2000

Quality-assurance design applied to an assessment of agricultural pesticides in ground water from carbonate bedrock aquifers in the Great Valley of eastern Pennsylvania

Assessments to determine whether agricultural pesticides are present in ground water are performed by the Commonwealth of Pennsylvania under the aquifer monitoring provisions of the State Pesticides and Ground Water Strategy. Pennsylvania's Department of Agriculture conducts the monitoring and collects samples; the Department of Environmental Protection (PaDEP) Laboratory analyzes the samples to measure pesticide concentration. To evaluate the quality of the measurements of pesticide concentration for a groundwater assessment, a quality-assurance design was developed and applied to a selected assessment area in Pennsylvania. This report describes the quality-assurance design, describes how and where the design was applied, describes procedures used to collect and analyze samples and to evaluate the results, and summarizes the quality assurance results along with the assessment results. The design was applied in an agricultural area of the Delaware River Basin in Berks, Lebanon, Lehigh, and Northampton Counties to evaluate the bias and variability in laboratory results for pesticides. The design—with random spatial and temporal components—included four data-quality objectives for bias and variability. The spatial design was primary and represented an area comprising 30 sampling cells. A quality-assurance sampling frequency of 20 percent of cells was selected to ensure a sample number of five or more for analysis. Quality-control samples included blanks, spikes, and replicates of laboratory water and spikes, replicates, and 2-lab splits of groundwater. Two analytical laboratories, the PaDEP Laboratory and a U.S. Geological Survey Laboratory, were part of the design. Bias and variability were evaluated by use of data collected from October 1997 through January 1998 for alachlor, atrazine, cyanazine, metolachlor, simazine, pendimethalin, metribuzin, and chlorpyrifos. Results of analyses of field blanks indicate that collection, processing, transport, and laboratory analysis procedures did not contaminate the samples; there were no false-positive results. Pesticides were detected in water when pesticides were spiked into (added to) samples. There were no false negatives for the eight pesticides in all spiked samples. Negative bias was characteristic of analytical results for the eight pesticides, and bias was generally in excess of 10 percent from the ‘true’ or expected concentration (34 of 39 analyses, or 87 percent of the ground-water results) for pesticide concentrations ranging from 0.31 to 0.51 mg/L (micrograms per liter). The magnitude of the negative bias for the eight pesticides, with the exception of cyanazine, would result in reported concentrations commonly 75-80 percent of the expected concentration in the water sample. The bias for cyanazine was negative and within 10 percent of the expected concentration. A comparison of spiked pesticide-concentration recoveries in laboratory water and ground water indicated no effect of the ground-water matrix, and matrix interference was not a source of the negative bias. Results for the laboratory-water spikes submitted in triplicate showed large variability for recoveries of atrazine, cyanazine, and pendimethalin. The relative standard deviation (RSD) was used as a measure of method variability over the course of the study for laboratory waters at a concentration of 0.4 mg/L. An RSD of about 11 percent (or about ?0.05 mg/L)characterizes the method results for alachlor, chlorpyrifos, metolachlor, metribuzin, and simazine. Atrazine and pendimethalin have RSD values of about 17 and 23 percent, respectively. Cyanazine showed the largest RSD at nearly 51 percent. The pesticides with low variability in laboratory-water spikes also had low variability in ground water. The assessment results showed that atrazinewas the most commonly detected pesticide in ground water in the assessment area. Atrazine was detected in water from 22 of the 28 wells sampled, and recovery results for atrazine were some of the worst (largest negative bias). Concentrations of the eight pesticides in ground water from wells were generally less than 0.3 µg/L. Only six individual measurements of the concentrations in water from six of the wells were at or above 0.3 µg/L, five for atrazine and one for metolachlor. There were eight additional detections of metolachlor and simazine at concentrations less than 0.1 µg/L. No well water contained more than one pesticide at concentra-tions at or above 0.3 µg/L. Evidence exists, how-ever, for a pattern of co-occurrence of metolachlor and simazine at low concentrations with higher concentrations of atrazine. Large variability in replicate samples and negative bias for pesticide recovery from spiked samples indicate the need to use data for pesticide recovery in the interpretation of measured pesti-cide concentrations in ground water. Data from samples spiked with known amounts of pesticides were a critical component of a quality-assurance design for the monitoring component of the Pesti-cides and Ground Water Strategy. Trigger concentrations, the concentrations that require action under the Pesticides and Ground Water Strategy, should be considered maximums for action. This consideration is needed because of the magnitude of negative bias.

Water-Resources Investigations Report↗
USGS1998

Water quality in the lower Susquehanna River basin, Pennsylvania and Maryland, 1992-95

This report is intended to summarize major findings that emerged between 1992 and 1995 from the water-quality assessment of the lower Susquehanna River basin study unit and to relate these findings to water-quality issues of regional and national concern. The information is primarily intended for those who are involved in water-resource management. Yet, the information contained here may also interest those who simply wish to know more about the quality of water in the rivers and aquifers in the area where they live.

Circular↗