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Patrick J. Phillips

Publications and source records attributed to Patrick J. Phillips.

At least 37 records · Page 2Linked to original sources

Spatiotemporal variations in estrogenicity, hormones, and endocrine-disrupting compounds in influents and effluents of selected wastewater-treatment plants and receiving streams in New York, 2008-09

Endocrine-disrupting compounds (EDCs) in wastewater effluents have been linked to changes in sex ratios, intersex (in males), behavioral modifications, and developmental abnormalities in aquatic organisms. Yet efforts to identify and regulate specific EDCs in complex mixtures are problematic because little is known about the estrogen activity (estrogenicity) levels of many common and emerging contaminants. The potential effects of EDCs on the water quality and health of biota in streams of the New York City water supply is especially worrisome because more than 150 wastewater-treatment plants (WWTPs) are permitted to discharge effluents into surface waters and groundwaters of watersheds that provide potable water to more than 9 million people. In 2008, the U.S. Geological Survey (USGS), the New York State Department of Environmental Conservation (NYSDEC), New York State Department of Health (NYSDOH), and New York City Department of Environmental Protection (NYCDEP) began a pilot study to increase the understanding of estrogenicity and EDCs in effluents and receiving streams mainly in southeastern New York. The primary goals of this study were to document and assess the spatial and temporal variability of estrogenicity levels; the effectiveness of various treatment-plant types to remove estrogenicity; the concentrations of hormones, EDCs, and pharmaceuticals, personal care products (PPCPs); and the relations between estrogenicity and concentrations of hormones, EDCs, and PPCPs. The levels of estrogenicity and selected hormones, non-hormone EDCs, and PPCPs were characterized in samples collected seasonally in effluents from 7 WWTPs, once or twice in effluents from 34 WWTPs, and once in influents to 6 WWTPs. Estrogenicity was quantified, as estradiol equivalents, using both the biological e-screen assay and a chemical model. Results generally show that (1) estrogenicity levels in effluents varied spatially and seasonally, (2) a wide range of known and unknown EDCs were present in both WWTP effluents and receiving streams, (3) some effluents may be important sources of estrogenicity in weakly diluted streams, (4) measured levels of biological estrogenicity were often higher than estimated levels of chemical estrogenicity, and (5) the type of treatment had a large effect on the removal efficacy, and consequently, the estrogenicity levels observed in treated effluents.

New York

Contaminants in stream sediments from seven United States metropolitan areas: part I: distribution in relation to urbanization

Organic contaminants and trace elements were measured in bed sediments collected from streams in seven metropolitan study areas across the United States to assess concentrations in relation to urbanization. Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorine pesticides, the pyrethroid insecticide bifenthrin, and several trace elements were significantly related to urbanization across study areas. Most contaminants (except bifenthrin, chromium, nickel) were significantly related to the total organic carbon (TOC) content of the sediments. Regression models explained 45–80 % of the variability in individual contaminant concentrations using degree of urbanization, sediment-TOC, and study-area indicator variables (which represent the combined influence of unknown factors, such as chemical use or release, that are not captured by available explanatory variables). The significance of one or more study-area indicator variables in all models indicates marked differences in contaminant levels among some study areas, even after accounting for the nationally modeled effects of urbanization and sediment-TOC. Mean probable effect concentration quotients (PECQs) were significantly related to urbanization. Trace elements were the major contributors to mean PECQs at undeveloped sites, whereas organic contaminants, especially bifenthrin, were the major contributors at highly urban sites. Pyrethroids, where detected, accounted for the largest share of the mean PECQ. Part 2 of this series (Kemble et al. 2012) evaluates sediment toxicity to amphipods and midge in relation to sediment chemistry.

Archives of Environmental Contamination and Toxico

Pharmaceuticals, hormones, anthropogenic waste indicators, and total estrogenicity in liquid and solid samples from municipal sludge stabilization and dewatering

The ubiquitous presence of pharmaceuticals and other emerging contaminants, or trace organic compounds, in surface water has resulted in research and monitoring efforts to identify contaminant sources to surface waters and to better understand loadings from these sources. Wastewater treatment plant discharges have been identified as an important point source of trace organic compounds to surface water and understanding the transport and transformation of these contaminants through wastewater treatment process is essential to controlling their introduction to receiving waters.

Open-File Report

The use of simulation and multiple environmental tracers to quantify groundwater flow in a shallow aquifer

Measurements of the concentrations of chlorofluorocarbons (CFCs), tritium, and other environmental tracers can be used to calculate recharge ages of shallow groundwater and estimate rates of groundwater movement. Numerical simulation also provides quantitative estimates of flow rates, flow paths, and mixing properties of the groundwater system. The environmental tracer techniques and the hydraulic analyses each contribute to the understanding and quantification of the flow of shallow groundwater. However, when combined, the two methods provide feedback that improves the quantification of the flow system and provides insight into the processes that are the most uncertain. A case study near Locust Grove, Maryland, is used to investigate the utility of combining groundwater age dating, based on CFCs and tritium, and hydraulic analyses using numerical simulation techniques. The results of the feedback between an advective transport model and the estimates of groundwater ages determined by the CFCs improve a quantitative description of the system by refining the system conceptualization and estimating system parameters. The plausible system developed with this feedback between the advective flow model and the CFC ages is further tested using a solute transport simulation to reproduce the observed tritium distribution in the groundwater. The solute transport simulation corroborates the plausible system developed and also indicates that, for the system under investigation with the data obtained from 0.9-m-long (3-foot-long) well screens, the hydrodynamic dispersion is negligible. Together the two methods enable a coherent explanation of the flow paths and rates of movement while indicating weaknesses in the understanding of the system that will require future data collection and conceptual refinement of the groundwater system.

Water Resources Research

Pharmaceutical formulation facilities as sources of opioids and other pharmaceuticals to wastewater treatment plant effluents

Facilities involved in the manufacture of pharmaceutical products are an under-investigated source of pharmaceuticals to the environment. Between 2004 and 2009, 35 to 38 effluent samples were collected from each of three wastewater treatment plants (WWTPs) in New York and analyzed for seven pharmaceuticals including opioids and muscle relaxants. Two WWTPs (NY2 and NY3) receive substantial flows (>20% of plant flow) from pharmaceutical formulation facilities (PFF) and one (NY1) receives no PFF flow. Samples of effluents from 23 WWTPs across the United States were analyzed once for these pharmaceuticals as part of a national survey. Maximum pharmaceutical effluent concentrations for the national survey and NY1 effluent samples were generally <1 microg/L. Four pharmaceuticals (methadone, oxycodone, butalbital, and metaxalone) in samples of NY3 effluent had median concentrations ranging from 3.4 to >400 microg/L. Maximum concentrations of oxycodone (1700 microg/L) and metaxalone (3800 microg/L) in samples from NY3 effluent exceeded 1000 microg/L. Three pharmaceuticals (butalbital, carisoprodol, and oxycodone) in samples of NY2 effluent had median concentrations ranging from 2 to 11 microg/L. These findings suggest that current manufacturing practices at these PFFs can result in pharmaceuticals concentrations from 10 to 1000 times higher than those typically found in WWTP effluents.

Environmental Science & Technology

Composition, distribution, and potential toxicity of organochlorine mixtures in bed sediments of streams

Mixtures of organochlorine compounds have the potential for additive or interactive toxicity to organisms exposed in the stream. This study uses a variety of methods to identify mixtures and a modified concentration-addition approach to estimate their potential toxicity at 845 stream sites across the United States sampled between 1992 and 2001 for organochlorine pesticides and polychlorinated biphenyls (PCBs) in bed sediment. Principal-component (PC) analysis identified five PCs that account for 77% of the total variance in 14 organochlorine compounds in the original dataset. The five PCs represent: (1) chlordane-related compounds and dieldrin; (2) p,p′ -DDT and its degradates; (3) o,p′ -DDT and its degradates; (4) the pesticide degradates oxychlordane and heptachlor epoxide; and (5) PCBs. The PC analysis grouped compounds that have similar chemical structure (such as parent compound and degradate), common origin (in the same technical pesticide mixture), and(or) similar relation of concentrations to land use. For example, the highest concentrations of chlordane compounds and dieldrin occurred at urban sites, reflecting past use of parent pesticides for termite control. Two approaches to characterizing mixtures—PC-based mixtures and unique mixtures—were applied to all 299 samples with a detection of two or more organochlorine compounds. PC-based mixtures are defined by the presence (in the sample) of one or more compounds associated with that PC. Unique mixtures are defined as a specific combination of two or more compounds detected in a sample, regardless of how many other compounds were also detected in that sample. The simplest PC-based mixtures (containing compounds from 1 or 2 PCs) commonly occurred in a variety of land use settings. Complex mixtures (containing compounds from 3 or more PCs) were most common in samples from urban and mixed/urban sites, especially in the Northeast, reflecting high concentrations of multiple chlordane, dieldrin, DDT-related compounds, and(or) PCBs. The most commonly occurring unique mixture ( p,p′ -DDE, p,p′ -DDD) occurred in both simple and complex PC-based mixtures, and at both urban and agricultural sites. Mean Probable Effect Concentration Quotients (PEC-Q) values, which estimate the potential toxicity of organochlorine contaminant mixtures, were highest for complex mixtures. Mean PEC-Q values were highest for urban sites in the Northeast, followed by mixed/urban sites in the Northeast and agricultural sites in cotton growing areas. These results demonstrate that the PEC-Q approach can be used in combination with PC-based and unique mixture analyses to relate potential aquatic toxicity of contaminant mixtures to mixture complexity, land use, and other surrogates for contaminant sources.

Science of the Total Environment

Evaluating the behavior of gadolinium and other rare earth elements through large metropolitan sewage treatment plants

A primary pathway for emerging contaminants (pharmaceuticals, personal care products, steroids, and hormones) to enter aquatic ecosystems is effluent from sewage treatment plants (STP), and identifying technologies to minimize the amount of these contaminants released is important. Quantifying the flux of these contaminants through STPs is difficult. This study evaluates the behavior of gadolinium, a rare earth element (REE) utilized as a contrasting agent in magnetic resonance imaging (MRI), through four full-scale metropolitan STPs that utilize several biosolids thickening, conditioning, stabilization, and dewatering processing technologies. The organically complexed Gd from MRIs has been shown to be stable in aquatic systems and has the potential to be utilized as a conservative tracer in STP operations to compare to an emerging contaminant of interest. Influent and effluent waters display large enrichments in Gd compared to other REEs. In contrast, most sludge samples from the STPs do not display Gd enrichments, including primary sludges and end-product sludges. The excess Gd appears to remain in the liquid phase throughout the STP operations, but detailed quantification of the input Gd load and residence times of various STP operations is needed to utilize Gd as a conservative tracer.

Environmental Science & Technology

Method description, quality assurance, environmental data, and other Information for analysis of pharmaceuticals in wastewater-treatment-plant effluents, streamwater, and reservoirs, 2004-2009

Abstract Wastewater-treatment-plant (WWTP) effluents are a demonstrated source of pharmaceuticals to the environment. During 2004-09, a study was conducted to identify pharmaceutical compounds in effluents from WWTPs (including two that receive substantial discharges from pharmaceutical formulation facilities), streamwater, and reservoirs. The methods used to determine and quantify concentrations of seven pharmaceuticals are described. In addition, the report includes information on pharmaceuticals formulated or potentially formulated at the two pharmaceutical formulation facilities that provide substantial discharge to two of the WWTPs, and potential limitations to these data are discussed. The analytical methods used to provide data on the seven pharmaceuticals (including opioids, muscle relaxants, and other pharmaceuticals) in filtered water samples also are described. Data are provided on method performance, including spike data, method detection limit results, and an estimation of precision. Quality-assurance data for sample collection and handling are included. Quantitative data are presented for the seven pharmaceuticals in water samples collected at WWTP discharge points, from streams, and at reservoirs. Occurrence data also are provided for 19 pharmaceuticals that were qualitatively identified. Flow data at selected WWTP and streams are presented. Between 2004-09, 35-38 effluent samples were collected from each of three WWTPs in New York and analyzed for seven pharmaceuticals. Two WWTPs (NY2 and NY3) receive substantial inflows (greater than 20 percent of plant flow) from pharmaceutical formulation facilities (PFF) and one (NY1) receives no PFF flow. Samples of effluents from 23 WWTPs across the United States were analyzed once for these pharmaceuticals as part of a national survey. Maximum pharmaceutical effluent concentrations for the national survey and NY1 effluent samples were generally less than 1 ug/L. Four pharmaceuticals (methadone, oxycodone, butalbital and metaxalone) in samples of NY3 effluent had median concentrations ranging from 3.4 to greater than 400 ug/L. Maximum concentrations of oxycodone (1,700 ug/L) and metaxalone (3,800 ug/L) in samples from NY3 effluent exceeded 1,000 ug/L. Three pharmaceuticals (butalbital, carisoprodol, and oxycodone) in samples of NY2 effluent had median concentrations ranging from 2 to 11 ug/L. These findings suggest that current 2 manufacturing practices at these PFFs can result in pharmaceutical concentrations from 10 to 1,000 times higher than those typically found in WWTP effluents.

Open-File Report

Fate of estrogenic compounds during municipal sludge stabilization and dewatering

This project brought together a team of experts in the fields of environmental engineering, analytical chemistry and hydrogeology, and biological assay analysis to evaluate the occurrence and fate of estrogenic compounds and the estrogenicity of biosolids derived from wastewater treatment. The primary objective of the study was to provide key baseline information concerning the estrogenicity (measured with in vitro bioassays) and concentrations of individual estrogenic compounds and other trace organic chemicals through common wastewater treatment processes. This research is important for developing information critical to the assessment of the potential risks associated with biosolids land application. Published by WERF. 178 pages. Soft cover and online PDF. (2010)

Report

Hydrogeology and Water Quality of the Pepacton Reservoir Watershed in Southeastern New York. Part 3. Responses of Stream Base-Flow Chemistry to Hydrogeologic Factors and Nonpoint-Sources of Contamination

Base-flow samples were collected seasonally from 20 small streams in the 372-square-mile Pepacton Reservoir watershed to evaluate the effects of hydrogeologic factors and nonpoint sources of contamination on the chemical composition of ground-water discharge. The reservoir provides part of New York City?s water supply. The subbasins represented one of three general types of land use, each with at least 45 percent forested area (mostly on the hillsides): farmed (dairy) land, formerly farmed land with low-density residential development, or forested land with little or no development. The subbasin areas ranged from 0.38 to 10.23 square miles. All streams were sampled in December 2000 and in May, July, and October 2001. Three of the sites were designated as landuse- index sites and were sampled as many as five additional times during the study. No samples exceeded state or federal drinking-water standards for chloride, sodium, nitrate, orthophosphate, herbicides, or herbicide degradates. The chemical composition of base-flow samples was classified into major-ion water types, which were broadly defined as naturally occurring and road-salt-affected water types. About one-third of the base-flow samples were roadsalt- affected types. Natural water types were differentiated as dilute or evolved. Dilute waters have bicarbonate and sulfate as dominant anions and evolved waters have only bicarbonate as a dominant anion. Dilute water types indicate relatively short ground-water residence times or contact with unreactive aquifer material. Evolved waters have either longer ground-water residence time or contact with more reactive aquifer material than dilute ground waters. The larger subbasins with wider valley-bottom areas were more likely to have evolved water types than small subbasins with little floodplain development. Positive correlations between selected constituents and the intensity of nonpoint sources emphasize the connection between land use, shallow ground-water quality, and stream base-flow water quality. Chloride and sodium, which are relatively conservative constituents, showed strong linear relations with annual estimates of road-salt application during all four sampling periods. Nonconservative constituents, such as the nutrients nitrate and orthophosphate, showed linear relations with manure production rate among farmed basins, but only at specific times of the year because of losses through biologic activity. Nitrate showed the strongest relation in winter because losses to biological activity were at a minimum. Orthophosphate showed the strongest relation in early summer, when hydrologic and chemical conditions appear to favor release from sediments. Atmospheric nitrogen deposition is an additional source of nitrogen that can be released from mature or stressed forested basins. Detections of herbicides (atrazine, metolachlor, simazine) and herbicide degradates ( Metolachlor ESA, alachlor ESA, deethylatrazine) in base flow were closely correlated with subbasins in which corn was grown during the study. Atrazine was detected at the farmed index site only in early summer, after application and two rain storms. This detection corresponded to the peak orthophosphate concentration. In contrast, metolachlor ESA was detected in nearly all farmedindex- subbasin samples and peaked in late summer, when percent base-flow contributions from farmed valley-bottom areas were likely highest. The implications of this study are that seasonal and more frequent base-flow surveys of water chemistry from small stream basins can help refine the understanding of local hydrogeologic systems and define the effects of nonpointsource contamination on base-flow water quality. The concentration of most nonpoint sources in valley-bottom or lower-hillside areas helped indicate the relative contributions of water from hillside and valley-bottom areas at different times of year. The positive correlations between the intensity of nonpoint-source activities and nonpoint-source constituents in base flow underscores the link between land use (nonpoint sources), ground-water quality, and surface-water quality.

Scientific Investigations Report

Hydrogeology and water quality of the Pepacton Reservoir Watershed in southeastern New York. Part 1. Concentrations of pesticides and their degradates in stream baseflow, 2000-2001

Baseflow samples were collected from 20 small streams in the Pepacton Reservoir watershed in Delaware County, N.Y., from December 2000 through November 2001 as part of an investigation to define the occurrence of pesticides in shallow ground water in watersheds containing either a recent (2001) corn crop, a previous (1993-94) corn crop, or no history of row-crop cultivation. Baseflow water quality was assumed to represent the chemical quality of shallow ground water within the drainage area above each sampling site. Baseflow samples were analyzed for 57 pesticides and pesticide degradates. Three herbicides (atrazine, metolachlor and simazine) and three herbicide degradates (alachlor ESA [ethanesulfonic acid], deethylatrazine, and metolachlor ESA) were detected, but no concentrations exceeded any Federal or State water-quality criteria, and the maximum concentrations of all compounds except metolachlor ESA were less than 0.10 microgram per liter. The most frequently detected compounds (atrazine, metolachlor, deethylatrazine and metolachlor ESA) are either those typically used on corn crops, or those whose parent compounds are commonly used on corn crops and have been detected in streams that drain row-crop settings elsewhere in New York State. The pesticide and pesticide-degradate concentrations in baseflow samples collected in December 2000 and July 2001 samples generally corresponded to the amount of cornfield acreage in each watershed in 2001. The types of pesticides detected, and their median concentrations, were similar to those noted in two previous ground-water studies in row-crop areas elsewhere in upstate New York. Also the SAM ratios (ratio of metolachlor ESA concentration to metolachlor concentration) for the Pepacton samples were similar to those for ground-water samples from other agricultural settings in upstate New York, but were significantly higher than that for stormflow and baseflow samples collected in 1997-98 from Canajoharie Creek, an upstate stream that drains row-crop farmland. These comparisons confirm that the baseflow samples were derived from, and were representative of, ground water in their respective watersheds. Late-summer decreases in atrazine and deethylatrazine concentrations at a site where corn was grown in 2001 may have resulted from the seasonally dry conditions and the accompanying decrease in ground-water discharge from the upper-most part of the surficial aquifer system to streams. The lack of a similar decrease in metolachlor ESA concentrations during this period may reflect the transport of metolachlor ESA to deeper parts of the surficial aquifer that continued to discharge to streams during the dry period.

New York

Seasonal Variability and Effects of Stormflow on Concentrations of Pesticides and their Degradates in Kisco River and Middle Branch Croton River Surface Water, Croton Reservoir System, New York, May 2000-February 2001

Seven herbicides (2,4-D, 2,4-D methyl ester, bromacil, dicamba, diuron, imazaquin, and sulfometuron), four insecticides (carbaryl, diazinon, imidacloprid, and malathion), two fungicides (metalaxyl and myclobutanil), and caffeine (an indicator of wastewater) were detected in at least one sample from the Kisco River at concentrations above 0.1 ug/L (micrograms per liter). Four of these compounds - 2,4-D, 2,4-D methyl ester, dicamba, and metalaxyl - were detected in at least one sample from the Kisco River at a concentration above 1 ug/L. Only three herbicides (2,4-D, imazethapyr, and prometon) and caffeine were detected at concentrations above 0.1 ug/L in one or more of the Middle Branch Croton River samples, and no compounds were detected above 0.4 ug/L in Middle Branch Croton River samples. No samples contained concentrations of pesticides that exceeded human health-based water-quality standards. However, samples from the Kisco River contained four insecticides (carbaryl, chlorpyrifos, diazinon, and malathion) and one herbicide (2,4-D) in concentrations that exceeded water-quality criteria for the protection of aquatic life. Aquatic-life protection criteria were generally exceeded only in stormflow samples collected in June, September, and December 2000. No samples from the Middle Branch Croton River contained target compounds that exceeded water-quality criteria for the protection of aquatic life. Pesticide concentrations were generally higher, and the numbers of compounds generally larger in samples from the Kisco River than in samples from the Middle Branch Croton River, probably because the Kisco River watershed has a greater population density and is more extensively developed. The highest concentrations of most compounds in both streams were detected in stormflow samples collected in June, September, and December 2000. This indicates that stormflow sampling is essential in assessments of pesticide occurrence in streams that drain developed lands. The lowest concentrations of most compounds at both sites were detected in baseflow samples collected from October 2000 through February 2001, although the concentrations of several compounds increased substantially during stormflows at the Kisco River site in November and December, 2000.

Water-Resources Investigations Report

Concentrations of pesticides and pesticide degradates in the Croton River Watershed in southeastern New York, July-September 2000

Thirty-seven pesticides and (or) pesticide degradates were detected in baseflow samples collected from 47 stream sites in the Croton River Watershed (374 square miles) in southeastern New York in the summer of 2000. The Croton Reservoir provides about 10 percent of New York City's water supply. Maximum concentrations of most pesticides detected did not exceed 0.1 μg/L (micrograms per liter). This study, by the U.S. Geological Survey in cooperation with the New York State Department of Environmental Conservation, was conducted from July through September 2000 and entailed analysis of the samples for more than 150 pesticides and their degradates. Nine compounds were detected at a concentration greater than 0.10 μg/L; three of these were insecticides (diazinon, carbaryl, and imidacloprid), one was a fungicide (mycobutanil), and five were herbicides (simazine, 2,4-D, diuron, hexazinone, and 2,4-D methyl esther). Only two of these compounds (simazine and 2,4-D) were detected at a concentration exceeding 1 μg/L; the simazine concentration exceeded the New York State surface-water standard of 0.5 μg/L. Two insecticides (diazinon and azinphos-methyl) exceeded aquatic-life-protection standard in one sample each. Concentrations of three insecticides (chlorpyrifos, carbaryl, and malathion) were more than 50 percent of the aquatic-life-protection standards in one sample each. Total concentrations of insecticides and herbicides (the sum of the concentrations, whereby all concentrations below the detection limit were set to zero), and the concentrations of the herbicide prometon and the insecticide diazinon, were highest in samples from watersheds with population densities greater than 510 per square mile (21 sites); therefore, the presence of these compounds is attributable to urban, residential, and other developed land uses. The data obtained in this study are useful for making general comparisons among watersheds with differing land uses, but the concentrations represent baseflow conditions and, thus, are probably lower than the annual maximum concentrations in these streams. A July baseflow sample had total insecticide and fungicide concentrations of less than 0.03 μg/L, whereas a stormflow sample collected at the same site 2 weeks later had a corresponding concentration greater than 0.10 μg/L. Total herbicide concentrations for the July baseflow and stormflow samples were around 0.03 μg/L, but that for a stormflow sample collected at the same site 2 months later was greater than 20 μg/L.

Connecticut, New York

Stream-water chemistry, nutrients, and pesticides in Town Brook, a headwater stream of the Cannonsville Reservoir Watershed, Delaware County, New York, 1999

Stream-water chemistry was monitored from January 1 through December 31, 1999, in the Town Brook watershed (TBW) in Delaware County, N.Y. to provide a basis for future evaluation of the effectiveness of Best Management Practices (BMPs) in decreasing agricultural nutrient and pesticide leaching to receiving waters. Total runoff from the watershed during 1999 was 664 millimeters (mm). Annual nutrient export (in kilograms per hectare) values were: ammonia (NH 3 ), 0.25; nitrate (NO 3 - ), 4.3; total nitrogen (TN), 10.6; orthophosphate (OP), 0.26; total dissolved phosphorus (TDP), 0.30; and total phosphorus (TP), 1.2 during 1999. Streamwater samples were collected during baseflow, elevated baseflow, and stormflow conditions. Stormflow, which produced the greatest flowweighted mean nutrient concentrations, represented only 41 percent of the annual runoff but accounted from 49 to 68 percent of the annual nutrient export. The highest seasonal flow-weighted mean concentrations were measured during the summer; the highest concentrations occurred during a large storm on July 4, 1999 with a recurrence interval greater than 100 years. The greatest seasonal export of dissolved nutrients (NH 3 , NO 3 - , OP, and TDP) occurred during the winter, whereas the greatest export of TN and TP was during the summer. Most of the TN and TP export during the summer occurred during the July 4 storm. That storm, together with a second large storm on September 16, 1999, accounted for the following percentages of annual export: ammonia, 17 percent; NO 3 - , 21 percent; TN, 45 percent; OP, 21 percent; TDP, 21 percent; and TP, 56 percent. Although these results provide information on the quantity and timing of nutrient export, they do not indicate the nutrient source nor the transport mechanisms by which nutrients are delivered to the stream. Baseflow and stormflow samples were collected for pesticide analyses at the Town Brook watershed outlet from January through July 1999. Eight pesticides and pesticide metabolites (degradation products) were detected in the samples. Four compounds (metolachlor, atrazine, metolachlor ESA, and metolachlor OA) were detected in concentrations greater than 1 micrograms per liter (μg/L) in one or more samples. Two of these compounds.the herbicide metabolites metalochlor ESA and metalochlor OA.were detected in concentrations higher than those of the parent compound metolachlor. Only one sample, collected during the July 4 storm, exceeded New York State surface-water-quality standards for any pesticide (simazine); its concentration of 0.53 μg/L was 0.03 μg/L higher than the New York State standard (0.50 μg/L). No concentrations exceeded Federal water-quality standards. Pesticide and metabolite concentrations were as much as 25 times greater during stormflow than during baseflow. Stormflow pesticide concentrations were indicative of a spring 'flushing', in which stream pesticide concentrations are elevated from concentrations typical during the rest of the year during the first few storms after pesticide application. Pesticides and pesticide metabolites were detected in all stormflow samples. These results illustrate the need to include baseflow and stormflow in pesticide sampling routines. The results of this study emphasize the need for (1) baseflow and stormflow sampling to capture the range of nutrient and pesticide concentrations from agricultural watersheds, and (2) research to define the mechanisms of nutrient and pesticide export in agriculutral watersheds.

New York

Pesticides and their metabolites in selected surface-water public supplies in New York State, 1999

Sixteen different pesticides or their metabolites (degradations products) where detected in water samples collected in 1999 from three networks of lakes and reservoirs in upstate New York that are sources of public water supply. The networks sampled included the New York City network (10 reservoirs); the Finger Lakes-Great Lakes network (three Finger Lakes and two Great Lakes that supply large and small cities) and the western New York reservoir network (three reservoirs that supply small cities or towns). The concentrations of the compounds detected in the samples generally were low. Only a few of the compounds detected had a concentration exceeding 1 mg/L (microgram per liter), and no compounds detected in the New York City reservoirs network had concentrations exceeding 0.05 mg/L. None of the compounds detected exceeded any Federal or State water-quality standard. Compounds that were most frequently detected, and whose concentrations were highest, were the three herbicides atrazine, metolachlor, and simazine, and two herbicide metabolites (the atrazine metabolite deethylatrazine, and the metolachlor metabolite metolachlor ESA). Most of these compounds, or their parent compounds, are used on corn or other row crops. Median total pesticide and metabolite concentration for each network ranged from less than 0.02 mg/L for the New York City reservoirs network to more than 2 mg/L for the western New York reservoir network; the median for the Finger Lakes.Great Lakes network was about 0.1 mg/L. These differences reflect the amount of agricultural land use within each of the three networks, although other factors can affect pesticide and metabolite concentrations. The watersheds of the New York City reservoirs have the lowest percentage of agricultural land, and those of the western New York reservoirs have the highest. The highest herbicide or herbicide-metabolite concentrations among the New York City reservoirs were in the Cannonsville reservoir, whose watershed has a high percentage of agricultural land. The highest pesticide concentrations of the Lake sites were in Cayuga Lake, and the highest pesticide concentrations of the western New York reservoir sites were at the LeRoy reservoir. The drought conditions in 1999 resulted in a general decrease in median total concentrations, and in the median number of detected compounds, in all networks, from January through September. Pesticide concentrations at the western New York reservoir sites were lower in 1999 than in 1998, as a result of the late-spring and early-summer drought conditions in 1999. Concentrations of pesticides in surface-water supplies are likely to be higher during years with normal or high streamflows than in years of drought, and the small reservoirs are likely to show a greater change in pesticide concentrations from drought year to nondrought years than the larger water bodies.

New York

Pesticides and their metabolites in wells of Suffolk County, New York, 1998

Five insecticide residues and 20 herbicide residues were detected in water samples collected from 50 shallow wells screened in the surficial sand and gravel aquifer in Suffolk County, Long Island in areas with known or suspected residues. Laboratory analytical methods with extremely low detection limits - from 0.001 to 0.2 ?g/L (micrograms per liter) - were used to analyze the samples for 60 pesticide residues. Forty-four of the samples contained at least one pesticide residue, and some samples contained as many as 11 different pesticides or pesticide metabolites. Only four water- quality standards were exceeded in the samples collected in this study. Dieldrin exceeded the New York State Class GA standard (0.004 ?g/L) in samples from eight wells. The Federal and New York State Maximum Contaminant Level for simazine (4 ?g/L) was exceeded in samples from two wells, and the State Class GA standard for simazine (0.5 ?g/L) was exceeded in samples from six wells. Federal water-quality standards have not been established for many of the compounds detected in this study, including herbicide metabolites. Maximum concentrations of four herbicide metabolites -metolachlor ESA (ethanesulfonic acid), metolachlor OA (oxanilic acid), and the alachlor metabolites alachlor ESA and alachlor OA -exceeded 20 ?g/L. The maximum concentration of one herbicide (tebuthiuron) exceeded 10 ?g/L, and the maximum concentration of three herbicides (simazine, metolachlor, and atrazine) and one herbicide metabolite (deisopropylatrazine) ranged from 1 to 10 ?g/L. The herbicide metolachlor, which is used on potato fields in Suffolk County, and its metabolites (metolachlor ESA and metolachlor OA) were most frequently detected in samples from agricultural areas. The herbicides simazine and tebuthiuron, which were used in utility rights-of-way, and the simazine metabolite deisopropylatrazine were detected at concentrations greater than 0.05 ?g/L most frequently in samples from residential and mixed land-use areas. The results of this investigation are not necessarily representative of conditions throughout the remainder of Long Island, because these samples were collected in areas of known or suspected residues.

Water-Resources Investigations Report

Isotopes as indicators of environmental change

In addition to providing an understanding of processes within a catchment system, isotopic techniques have been instrumental in providing reconstructions of catchment climate and other environmental indicators at various time scales. Many recent changes are a direct consequence of anthropogenic activities. Isotopic analysis serves as a valuable tool for distinguishing between natural variations in long-term climatic patterns and anthropogenic effects, yielding improved understanding of natural feedback mechanisms and the development of realistic remediation strategies. This chapter discusses the examples of isotopic techniques that have been applied to understand several types of ongoing and recent environmental changes, and in paleo-environmental studies. It discusses isotope geochemistry, hydrology, and climatology to look at new ways of applying isotopic tracing techniques to provide information on environmental change. It also gives an overview on how isotopic indicators are being applied in investigations of environmental change in continental settings.

Book chapter