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Environmental presence and persistence of pharmaceuticals: An overview

Emerging contaminants (ECs) in the environment – that is, chemicals with domestic, municipal, industrial, or agricultural sources that are not commonly monitored but may have the potential for adverse environmental effects – is a rapidly growing field of research. The use of “emerging” is not intended to infer that the presence of these compounds in the environment is new. These chemicals have been released into the environment as long as they have been in production or, in the case of hormones and other endogenous compounds, since the rise of animal life. What is emerging is the interest by the scientific and lay communities in the presence of these chemicals in the environment, the analytical capabilities required for detection, and the subtle effects that very small concentrations of these chemicals appear to have on aquatic biota. In December 2006, Environmental Science & Technology devoted an entire special issue (volume 40, number 23) to the topic of ECs, illustrating the increased interest in the subject. Within the EGs, one particular class that has seen a substantial increase in research over the past 10 years is pharmaceuticals and personal-care products (PPCPs). This increased research interest can be demonstrated by several means, including requests for proposals from funding agencies, but the clearest indication of a focused effort to understand the introduction, transformation, and potential health and environmental effects of PPCPs and ECs, in general, is the number of published reports. This increase can be shown by examining six environmental journals that regularly publish PPCP-related papers – Chemosphere , Environmental Science & Technology , Environmental Toxicology and Chemistry , Science of the Total Environment , Water Research , and Water Science and Technology . In 1998 there were 22 papers published on pharmaceuticals, antibiotics, or drugs in these 6 journals; by 2006, this number increased sixfold to 132 papers (Figure 1.1). This growth can be attributed to a number of factors. The presence of pharmaceuticals in surface-water samples from Europe and the United States was documented in several sentinel papers. These ground-breaking works encouraged other scientists to examine the rivers, streams, lakes, and reservoirs in their regions for such chemicals. In addition, the intense public attention paid to news reports on the environmental detections of these chemicals and possible effects of aquatic life has made this issue visible to the wastewater-treatment, drinking-water treatment, and regulatory communities. This has driven the funding bodies associated with these communities to fund studies or request proposals that address the presence, fate, and effects of PPCPs in aquatic systems. The release of the first comprehensive reconnaissance of pharmaceuticals and other wastewater contaminants in the United States provides an example of the intense media interest in this topic. Within 6 days on online publication of this study, 72 newspapers across the United States had published articles describing the results, either locally written or based on international media syndicate reports. There also was substantial concurrent coverage by local and national radio and television outlets, including the Cable News Network, ABC World News Tonight , and National Public Radio. A substantial fraction of these news stories may be attributable to press releases and media briefings prior to publication. However, the interest by television and print journalists in reporting the results of a peer-reviewed journal article to the general public was motivated by the recognition that describing the presence of PPCPs in water supplies would be of interest to the public. To better convey the results of the study published by Koplin et al. to the public, a separate general-interest fact sheet was published to summarize the important points of the study. Because PPCPs are commonly and widely used by individuals, there is likely a preexisting, personal identification with these compounds that does not occur for the wide range of other organic and inorganic contaminants whose presence in the environment has previously been described. This greater public “name recognition” makes itself known through the media to the regulatory and technical community and has prompted interest in sponsoring research that defines the composition and concentrations of PPCPs in potential sources and their fate and effects following relase into the environment. Independent of the drivers that potentially fuel the interest in studies of PPCPs, it is clear that PPCP research has grown beyond surface-water studies to examine issues such as: • Presence in other matrices, such as groundwater, landfill leachates, sediments, and biosolids. • Environmental transport and fate in surface water, groundwater, and soils amended with reclaimed water or biosolids. • PPCP source elucidation, such as wastewater treatment plant (WWTP) effluents, confined animal feeding operations (CAFOs), and aquaculture. • Removal during wastewater and drinking-water treatment. • Effects on aquatic ecosystems, terrestrial ecosystems, and human health. The chapters in this book provide an extensive examination of current environmental pharmaceutical research and are divided into three sections: “Occurrence and Analysis of Pharmaceuticals in the Environment,” “Environment Fate and Transformations of Veterinary Pharmaceuticals,” and “treatment of Pharmaceuticals in Drinking Water and Wastewater.” The purpose of this introductory overview chapter is to outline current (2004-2006) knowledge about the presence and concentration of PPCPs as described in the published literature. Previous reviews should be consulted for discussions on pre-2004 publications. Those reviews will provide the reader with a comprehensive introduction to the topic of PPCPs in the environment. This chapter describes the sources of PPCPs and other organic contaminants often associated with human wastewater into the environment, the range of concentrations present in various environmental compartments, and the potential routes of removal/sequestration. An overview of the sources and fate of veterinary pharmaceuticals will be discussed in Chapter 5, “Fate and Transport of Veterinary Medicines in the Soil Environment.”

Book chapter

Effects of wastewater disinfection on waterborne bacteria and viruses

Wastewater disinfection is practiced with the goal of reducing risks of human exposure to pathogenic microorganisms. In most circumstances, the efficacy of a wastewater disinfection process is regulated and monitored based on measurements of the responses of indicator bacteria. However, inactivation of indicator bacteria does not guarantee an acceptable degree of inactivation among other waterborne microorganisms (e.g., microbial pathogens). Undisinfected effluent samples from several municipal wastewater treatment facilities were collected for analysis. Facilities were selected to provide a broad spectrum of effluent quality, particularly as related to nitrogenous compounds. Samples were subjected to bench-scale chlorination and dechlorination and UV irradiation under conditions that allowed compliance with relevant discharge regulations and such that disinfectant exposures could be accurately quantified. Disinfected samples were subjected to a battery of assays to assess the immediate and long-term effects of wastewater disinfection on waterborne bacteria and viruses. In general, (viable) bacterial populations showed an immediate decline as a result of disinfectant exposure; however, incubation of disinfected samples under conditions that were designed to mimic the conditions in a receiving stream resulted in substantial recovery of the total bacterial community. The bacterial groups that are commonly used as indicators do not provide an accurate representation of the response of the bacterial community to disinfectant exposure and subsequent recovery in the environment. UV irradiation and chlorination/dechlorination both accomplished measurable inactivation of indigenous phage; however, the extent of inactivation was fairly modest under the conditions of disinfection used in this study. UV irradiation was consistently more effective as a virucide than chlorination/dechlorination under the conditions of application, based on measurements of virus (phage) diversity and concentration. Taken together, and when considered in conjunction with previously published research, the results of these experiments illustrate several important limitations of common disinfection processes as applied in the treatment of municipal wastewaters. In general, it is not clear that conventional disinfection processes, as commonly implemented, are effective for control of the risks of disease transmission, particularly those associated with viral pathogens. Microbial quality in receiving streams may not be substantially improved by the application of these disinfection processes; under some circumstances, an argument can be made that disinfection may actually yield a decrease in effluent and receiving water quality. Decisions regarding the need for effluent disinfection must account for site-specific characteristics, but it is not clear that disinfection of municipal wastewater effluents is necessary or beneficial for all facilities. When direct human contact or ingestion of municipal wastewater effluents is likely, disinfection may be necessary. Under these circumstances, UV irradiation appears to be superior to chlorination in terms of microbial quality and chemistry and toxicology. This advantage is particularly evident in effluents that contain appreciable quantities of ammonia-nitrogen or organic nitrogen.

Water Environment Research

A pilot study to assess the influence of infiltrated stormwater on groundwater: Hydrology and trace organic contaminants

Underground infiltration basins (UIBs) mimic the natural hydrologic cycle by allowing stormwater to recharge local groundwater aquifers. However, little is known about the potential transport of organic contaminants to receiving groundwater. We conducted a pilot study in which we collected paired grab samples of stormwater runoff flowing into two UIBs (inflow) and shallow groundwater adjacent to the UIBs. Samples were collected coincident with three rain events and analyzed for volatile organic compounds, semi-volatile organic compounds, pharmaceuticals, and pesticides. Few contaminants were detected in groundwater, compared with inflow, and groundwater concentrations were typically an order of magnitude less. With one exception (trichloroethene), all groundwater concentrations were at least two orders of magnitude below available guidance or screening values. This short communication highlights information gaps in understanding the hydrologic connectivity between UIBs and receiving groundwater and potential consequent contaminant transport to the subsurface from varying climatic conditions.

Minnesota

Spatial and temporal variability of perfluoroalkyl and polyfluoroalkyl substances in major rivers of New Mexico, USA

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are ubiquitous in the environment, but sources that contribute to temporal and spatial variability in surface waters are not well defined. Many states are assessing PFAS in water resources, and insight from these statewide assessments can help guide future sampling efforts. A statewide assessment of 28 PFAS was conducted in New Mexico starting in 2020, and subsequent follow-up sampling has improved understanding of PFAS occurrence and sources throughout the state. PFAS were present in all major rivers of New Mexico (Rio Grande, Pecos River, San Juan River, Animas River, Canadian River, Gila River, Rio Chama, and Rio Puerco) with 13 of 28 analyzed PFAS (PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFBs, PFPeS, PFHxS, PFOS, PFOSA, 6:2 FTS) detected from at least one sample for samples collected between 2020 and 2024. This study found high temporal and spatial variability—PFAS concentrations ranged from below the laboratory detection level to 156 ng/L, with concentrations generally increasing downstream on the major rivers. PFBS was the most frequently detected and highest concentration PFAS in this study, ranging from 1 to 93 ng/L, followed by PFBA and PFPeA, ranging from 0.9 to 32 ng/L. The average of the sum of PFAS detected increased by an order of magnitude from 4 to 46 ng/L in the Rio Grande as it flows through Albuquerque, the largest urban area in New Mexico. PFAS concentration increased by 58% after a stormflow pulse flushed over Albuquerque and contributed water to the Rio Grande. The contribution of wastewater to surface water resources varied diurnally as well as seasonally. Sampling multiple locations on major rivers across multiple seasons, taking into account known anthropogenic inputs, would enhance characterization of temporal and spatial variability of PFAS concentrations. Increased sampling frequency at sites with wastewater contribution and focused investigations in areas with higher than expected PFAS could increase understanding of potential sources and variability of source contributions.

New Mexico

Interpretation of surface flux measurements in heterogeneous terrain during the Monsoon '90 experiment

A network of 9-m-tall surface flux measurement stations were deployed at eight sparsely vegetated sites during the Monsoon '90 experiment to measure net radiation, Q , soil heat flux, G , sensible heat flux, H (using eddy correlation), and latent heat flux, λ E (using the energy balance equation). At four of these sites, 2-m-tall eddy correlation systems were used to measure all four fluxes directly. Also a 2-m-tall Bowen ratio system was deployed at one site. Magnitudes of the energy balance closure ( Q + G + H + λ E ) increased as the complexity of terrain increased. The daytime Bowen ratio decreased from about 10 before the monsoon season to about 0.3 during the monsoons. Source areas of the measurements are developed and compared to scales of heterogeneity arising from the sparse vegetation and the topography. There was very good agreement among simultaneous measurements of Q with the same model sensor at different heights (representing different source areas), but poor agreement among different brands of sensors. Comparisons of simultaneous measurements of G suggest that because of the extremely small source area, extreme care in sensor deployment is necessary for accurate measurement in sparse canopies. A recently published model to estimate fetch is used to interpret measurements of H at the 2 m and 9 m heights. Three sites were characterized by undulating topography, with ridgetops separated by about 200–600 m. At these sites, sensors were located on ridgetops, and the 9-m fetch included the adjacent valley, whereas the 2-m fetch was limited to the immediate ridgetop and hillside. Before the monsoons began, vegetation was mostly dormant, the watershed was uniformly hot and dry, and the two measurements of H were in close agreement. After the monsoons began and vegetation fully matured, the 2-m measurements of H were significantly greater than the 9-m measurements, presumably because the vegetation in the valleys was denser and cooler than on the ridgetops and hillsides. At one lowland site with little topographic relief, the vegetation was more uniform, and the two measurements of H were in close agreement during peak vegetation. Values of λ E could only be compared at two sites, but the 9-m values were greater than the 2-m values, suggesting λ E from the dense vegetation in the valleys was greater than elsewhere.

Water Environment Research

Occurrence and distribution of microbiological indicators in groundwater and stream water

A total of 136 stream water and 143 groundwater samples collected in five important hydrologic systems of the United States were analyzed for microbiological indicators to test monitoring concepts in a nationally consistent program. Total coliforms were found in 99%, Escherichia coli in 97%, and Clostridium perfringens in 73% of stream water samples analyzed for each bacterium. Total coliforms were found in 20%, E. coli in less than 1%, and C. perfringens in none of the groundwater samples analyzed for each bacterium. Although coliphage analyses were performed on many of the samples, contamination in the laboratory and problems discerning discrete plaques precluded quantification. Land use was found to have the most significant effect on concentrations of bacterial indicators in stream water. Presence of septic systems on the property near the sampling site and well depth were found to be related to detection of coliforms in groundwater, although these relationships were not statistically significant. A greater diversity of sites, more detailed information about some factors, and a larger dataset may provide further insight to factors that affect microbiological indicators.

Water Environment Research

Evaluation of the persistence of micropollutants through pure-oxygen activated sludge nitrification and denitrification

The persistence of pharmaceuticals, hormones, and household and industrial chemicals through a pure-oxygen activated sludge, nitrification, denitrification wastewater treatment facility was evaluated. Of the 125 micropollutants that were tested in this study, 55 compounds were detected in the untreated wastewater, and 27 compounds were detected in the disinfected effluent. The persistent compounds included surfactants, fire-retardant chemicals, pesticides, fragrance compounds, hormones, and one pharmaceutical. Physical-chemical properties of micropollutants that affected partitioning onto wastewater solids included vapor pressure and octanol-water partition coefficients.

Water Environment Research

Development of a depth-integrated sample arm to reduce solids stratification bias in stormwater sampling

A new depth-integrated sample arm (DISA) was developed to improve the representation of solids in stormwater, both organic and inorganic, by collecting a water quality sample from multiple points in the water column. Data from this study demonstrate the idea of vertical stratification of solids in storm sewer runoff. Concentrations of suspended sediment in runoff were statistically greater using a fixed rather than multi-point collection system. Median suspended sediment concentrations measured at the fixed location (near the pipe invert) were approximately double those collected using the DISA. In general, concentrations and size distributions of suspended sediment decreased with increasing vertical distance from the storm sewer invert. Coarser particles tended to dominate the distribution of solids near the storm sewer invert as discharge increased. In contrast to concentration and particle size, organic material, to some extent, was distributed homogenously throughout the water column, likely the result of its low specific density, which allows for thorough mixing in less turbulent water.

Water Environment Research

Multi-year microbial source tracking study characterizing fecal contamination in an urban watershed

Microbiological and hydrological data were used to rank tributary stream contributions of bacteria to the Little Blue River in Independence, Missouri. Concentrations, loadings and yields of E. coli and microbial source tracking (MST) markers, were characterized during base flow and storm events in five subbasins within Independence, as well as sources entering and leaving the city through the river. The E. coli water quality threshold was exceeded in 29% of base-flow and 89% of storm-event samples. The total contribution of E. coli and MST markers from tributaries within Independence to the Little Blue River, regardless of streamflow, did not significantly increase the median concentrations leaving the city. Daily loads and yields of E. coli and MST markers were used to rank the subbasins according to their contribution of each constituent to the river. The ranking methodology used in this study may prove useful in prioritizing remediation in the different subbasins.

Missouri

Evaluation of estimation methods for organic carbon normalized sorption coefficients

A critically evaluated set of 94 soil water partition coefficients normalized to soil organic carbon content ( K oc ) is presented for 11 classes of organic chemicals. This data set is used to develop and evaluate K oc estimation methods using three different descriptors. The three types of descriptors used in predicting K oc were octanol/water partition coefficient ( K ow ), molecular connectivity ( m X t ) and linear solvation energy relationships (LSERs). The best results were obtained estimating K oc from K ow , though a slight improvement in the correlation coefficient was obtained by using a two-parameter regression with K ow and the third order difference term from m X t . Molecular connectivity correlations seemed to be best suited for use with specific chemical classes. The LSER provided a better fit than m X t but not as good as the correlation with K oc . The correlation to predict K oc from K ow was developed for 72 chemicals; log K oc = 0.903* log K ow + 0.094. This correlation accounts for 91% of the variability in the data for chemicals with log K ow ranging from 1.7 to 7.0. The expression to determine the 95% confidence interval on the estimated K oc is provided along with an example for two chemicals of different hydrophobicity showing the confidence interval of the retardation factor determined from the estimated K oc . The data showed that K oc is not likely to be applicable for chemicals with log K ow < 1.7. Finally, the K oc correlation developed using K ow as a descriptor was compared with three nonclass-specific correlations and two 'commonly used' class-specific correlations to determine which method(s) are most suitable.

Water Environment Research

A comparison of surface-grab and cross sectionally integrated stream-water-quality sampling methods

Stream sampling for water quality data has commonly employed simple surface-grab procedures as opposed to more involved, cross sectionally integrated techniques. Paired samples for analysis of selected constituents were collected over various flow conditions at four sites to evaluate differences between the two sampling methods. Concentrations of dissolved constituents were not consistently different. However, concentrations of suspended sediment and the total forms of some sediment-associated constituents, such as phosphorus, iron, and manganese, were significantly lower in the surface-grab samples than in the cross sectionally integrated samples. The largest median percent difference in concentration for a site was 60% (total recoverable manganese). Median percent differences in concentration for sediment-associated constituents considering all sites grouped were in the range of 20-25%. The surface-grab samples underrepresented concentrations of suspended sediment and some sediment-associated constituents, thus limiting the applicability of such data for certain purposes. An association was also demonstrated between site streamflow characteristics and the observed differences.

Water Environment Research

USGS advances in integrated, high-resolution sea-floor mapping: inner continental shelf to estuaries

The U.S. Geological Survey (USGS) has been involved in geological mapping of the sea floor for the past thirty years. Early geophysical and acoustic mapping efforts using GLORIA (Geologic LOng Range Inclined ASDIC) a long-range sidescan-sonar system, provided broad-scale imagery of deep waters within the U.S. Exclusive Economic Zone (EEZ). In the early 1990's, research emphasis shifted from deep- to shallow-water environments to address pertinent coastal research and resource management issues. Use of shallow-water, high-resolution geophysical systems has enhanced our understanding of the processes shaping shallow marine environments. However, research within these shallow-water environments continues to present technological challenges.

Conference Paper

USGS microbiome research

Microbiomes are the communities of microorganisms (for example, bacteria, viruses, and fungi) that live on, in, and around people, plants, animals, soil, water, and the atmosphere. Microbiomes are active in the functioning of diverse ecosystems, for instance, by influencing water quality, nutrient acquisition and stress tolerance in plants, and stability of soil and aquatic environments. Microbiome research conducted by the U.S. Geological Survey spans many of our mission areas. Key research areas include water quality, understanding climate effects on soil and permafrost, ecosystem and wildlife health, invasive species, contaminated environments to improve bioremediation, and enhancing energy production. Microbiome research will fundamentally strengthen the ability to address the global challenges of maintaining clean water, ensuring adequate food supply, meeting energy needs, and preserving human and ecosystem health.

Fact Sheet

Quality-Assurance Data for Routine Water Analyses by the U.S. Geological Survey Laboratory in Troy, New York-July 1997 through June 1999

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance/quality-control data for the time period addressed in this report were stored in the laboratory's SAS data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality- control samples analyzed from July 1997 through June 1999. Results for the quality-control samples for 18 analytical procedures were evaluated for bias and precision. Control charts indicate that data for eight of the analytical procedures were occasionally biased for either high-concentration and (or) low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, total monomeric aluminum, total aluminum, ammonium, calcium, chloride, specific conductance, and sulfate. The data from the potassium and sodium analytical procedures are insufficient for evaluation. Results from the filter-blank and analytical-blank analyses indicate that the procedures for 11 of 13 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. Blank analysis results for chloride showed that 22 percent of blanks did not meet data-quality objectives and results for dissolved organic carbon showed that 31 percent of the blanks did not meet data-quality objectives. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 14 of the 18 analytes. At least 90 percent of the samples met data-quality objectives for all analytes except total aluminum (70 percent of samples met objectives) and potassium (83 percent of samples met objectives). Results of the USGS interlaboratory Standard Reference Sample (SRS) Project indicated good data quality for most constituents over the time period. The P-sample (low-ionic-strength constituents) analysis had good ratings in two of these studies and a satisfactory rating in the third. The results of the T-sample (trace constituents) analysis indicated high data quality with good ratings in all three studies. The N-sample (nutrient constituents) studies had one each of excellent, good, and satisfactory ratings. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 80 percent of the samples met data-quality objectives for 9 of the 13 analytes; the exceptions were dissolved organic carbon, ammonium, chloride, and specific conductance. Data-quality objectives were not met for dissolved organic carbon in two NWRI studies, but all of the samples were within control limits for the last study. Data-quality objectives were not met in 41 percent of samples analyzed for ammonium, 25 percent of samples analyzed for chloride, and 30 percent of samples analyzed for specific conductance. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 84 percent of the samples analyzed for calcium, chloride, magnesium, pH, and potassium. Data-quality objectives were met by 73 percent of those analyzed for sulfate. The data-quality objective was not met for sodium. The data are insufficient for evaluation of the specific conductance results.

Open-File Report

Quality-Assurance Data for Routine Water Analyses by the U.S. Geological Survey Laboratory in Troy, New York--July 1999 through June 2001

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's LabMaster data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality-control samples analyzed from July 1999 through June 2001. Results for the quality-control samples for 18 analytical procedures were evaluated for bias and precision. Control charts indicate that data for eight of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, total monomeric aluminum, total aluminum, calcium, chloride and nitrate (ion chromatography and colormetric method) and sulfate. The total aluminum and dissolved organic carbon procedures were biased throughout the analysis period for the high-concentration sample, but were within control limits. The calcium and specific conductance procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The magnesium procedure was biased for the high-concentration and low concentration samples, but was within control limits. Results from the filter-blank and analytical-blank analyses indicate that the procedures for 14 of 15 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for dissolved organic carbon. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 17 of the 18 analytes. At least 90 percent of the samples met data-quality objectives for all analytes except ammonium (81 percent of samples met objectives), chloride (75 percent of samples met objectives), and sodium (86 percent of samples met objectives). Results of the USGS interlaboratory Standard Reference Sample (SRS) Project indicated good data quality over the time period, with most ratings for each sample in the good to excellent range. The P-sample (low-ionic-strength constituents) analysis had one satisfactory rating for the specific conductance procedure in one study. The T-sample (trace constituents) analysis had one satisfactory rating for the aluminum procedure in one study and one unsatisfactory rating for the sodium procedure in another. The remainder of the samples had good or excellent ratings for each study. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 89 percent of the samples met data-quality objectives for 10 of the 14 analytes; the exceptions were ammonium, total aluminum, dissolved organic carbon, and sodium. Results indicate a positive bias for the ammonium procedure in all studies. Data-quality objectives were not met in 50 percent of samples analyzed for total aluminum, 38 percent of samples analyzed for dissolved organic carbon, and 27 percent of samples analyzed for sodium. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 91 percent of the samples analyzed for calcium, chloride, fluoride, magnesium, pH, potassium, and sulfate. Data-quality objectives were met by 75 percent of the samples analyzed for sodium and 58 percent of the samples analyzed for specific conductance.

Open-File Report

Quality-Assurance Data for Routine Water Analyses by the U.S. Geological Survey Laboratory in Troy, New York - July 2001 Through June 2003

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's Lab Master data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality control samples analyzed from July 2001 through June 2003. Results for the quality-control samples for 19 analytical procedures were evaluated for bias and precision. Control charts indicate that data for six of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, chloride, magnesium, nitrate (ion chromatography), potassium, and sodium. The calcium procedure was biased throughout the analysis period for the high-concentration sample, but was within control limits. The total monomeric aluminum and fluoride procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The total aluminum, pH, specific conductance, and sulfate procedures were biased for the high-concentration and low-concentration samples, but were within control limits. Results from the filter-blank and analytical-blank analyses indicate that the procedures for 16 of 18 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for the dissolved organic carbon or specific conductance procedures. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 18 of the 21 analytes. At least 90 percent of the samples met data-quality objectives for all procedures except total monomeric aluminum (83 percent of samples met objectives), total aluminum (76 percent of samples met objectives), ammonium (73 percent of samples met objectives), dissolved organic carbon (86 percent of samples met objectives), and nitrate (81 percent of samples met objectives). The data-quality objective was not met for the nitrite procedure. Results of the USGS interlaboratory Standard Reference Sample (SRS) Project indicated satisfactory or above data quality over the time period, with most performance ratings for each sample in the good-to-excellent range. The N-sample (nutrient constituents) analysis had one unsatisfactory rating for the ammonium procedure in one study. The T-sample (trace constituents) analysis had one unsatisfactory rating for the magnesium procedure and one marginal rating for the potassium procedure in one study and one unsatisfactory rating for the sodium procedure in another. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 90 percent of the samples met data-quality objectives for 10 of the 14 analytes; the exceptions were acid-neutralizing capacity, ammonium, dissolved organic carbon, and sodium. Data-quality objectives were not met in 37 percent of samples analyzed for acid-neutralizing capacity, 28 percent of samples analyzed for dissolved organic carbon, and 30 percent of samples analyzed for sodium. Results indicate a positive bias for the ammonium procedure in one study and a negative bias in another. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 90 percent of the samples analyzed for calcium, chloride, magnesium, pH, potassium, and sodium. Data-quality objectives were met by 78 percent of

Open-File Report

Quality-assurance data for routine water analyses by the U.S. Geological Survey laboratory in Troy, New York - July 2003 through June 2005

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's Lab Master data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality control samples analyzed from July 2003 through June 2005. Results for the quality-control samples for 20 analytical procedures were evaluated for bias and precision. Control charts indicate that data for five of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, total monomeric aluminum, pH, silicon, and sodium. Seven of the analytical procedures were biased throughout the analysis period for the high-concentration sample, but were within control limits; these procedures were: dissolved organic carbon, chloride, nitrate (ion chromatograph), nitrite, silicon, sodium, and sulfate. The calcium and magnesium procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The total aluminum and specific conductance procedures were biased for the high-concentration and low-concentration samples, but were within control limits. Results from the filter-blank and analytical-blank analyses indicate that the procedures for 17 of 18 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for dissolved organic carbon. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 18 of the 22 analytes. At least 85 percent of the samples met data-quality objectives for all analytes except total monomeric aluminum (82 percent of samples met objectives), total aluminum (77 percent of samples met objectives), chloride (80 percent of samples met objectives), fluoride (76 percent of samples met objectives), and nitrate (ion chromatograph) (79 percent of samples met objectives). The ammonium and total dissolved nitrogen did not meet the data-quality objectives. Results of the USGS interlaboratory Standard Reference Sample (SRS) Project indicated good data quality over the time period, with ratings for each sample in the satisfactory, good, and excellent ranges or less than 10 percent error. The P-sample (low-ionic-strength constituents) analysis had one marginal and two unsatisfactory ratings for the chloride procedure. The T-sample (trace constituents)analysis had two unsatisfactory ratings and one high range percent error for the aluminum procedure. The N-sample (nutrient constituents) analysis had one marginal rating for the nitrate procedure. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 84 percent of the samples met data-quality objectives for 11 of the 14 analytes; the exceptions were ammonium, total aluminum, and acid-neutralizing capacity. The ammonium procedure did not meet data quality objectives in all studies. Data-quality objectives were not met in 23 percent of samples analyzed for total aluminum and 45 percent of samples analyzed acid-neutralizing capacity. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 86 percent of the samples analyzed for calcium, chloride, fluoride, magnesium, pH, potassium, sodium, and sulfate. Data-quality objectives were not met by samples analyzed for fluoride.

Open-File Report

Quality-Assurance Data for Routine Water Analyses by the U.S. Geological Survey Laboratory in Troy, New York - July 2005 through June 2007

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's Lab Master data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality control samples analyzed from July 2005 through June 2007. Results for the quality-control samples for 19 analytical procedures were evaluated for bias and precision. Control charts indicate that data for eight of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: total aluminum, calcium, magnesium, nitrate (colorimetric method), potassium, silicon, sodium, and sulfate. Eight of the analytical procedures were biased throughout the analysis period for the high-concentration sample, but were within control limits; these procedures were: total aluminum, calcium, dissolved organic carbon, chloride, nitrate (ion chromatograph), potassium, silicon, and sulfate. The magnesium and pH procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The acid-neutralizing capacity, total monomeric aluminum, nitrite, and specific conductance procedures were biased for the high-concentration and low-concentration samples, but were within control limits. Results from the filter-blank and analytical-blank analyses indicated that the procedures for 16 of 17 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for dissolved organic carbon. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 18 of the 21 analytes. At least 93 percent of the samples met data-quality objectives for all analytes except acid-neutralizing capacity (85 percent of samples met objectives), total monomeric aluminum (83 percent of samples met objectives), total aluminum (85 percent of samples met objectives), and chloride (85 percent of samples met objectives). The ammonium and total dissolved nitrogen did not meet the data-quality objectives. Results of the USGS interlaboratory Standard Reference Sample (SRS) Project met the Troy Laboratory data-quality objectives for 87 percent of the samples analyzed. The P-sample (low-ionic-strength constituents) analysis had two outliers each in two studies. The T-sample (trace constituents) analysis and the N-sample (nutrient constituents) analysis had one outlier each in two studies. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 85 percent of the samples met data-quality objectives for 11 of the 14 analytes; the exceptions were acid-neutralizing capacity, total aluminum and ammonium. Data-quality objectives were not met in 41 percent of samples analyzed for acid-neutralizing capacity, 50 percent of samples analyzed for total aluminum, and 44 percent of samples analyzed for ammonium. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 86 percent of the samples analyzed for calcium, magnesium, pH, potassium, and sodium. Data-quality objectives were met by 76 percent of the samples analyzed for chloride, 80 percent of the samples analyzed for specific conductance, and 77 percent of the samples analyzed for sulfate.

Open-File Report