Mark W. Sandstrom

Persistence and potential effects of complex organic contaminant mixtures in wastewater-impacted streams

Natural and synthetic organic contaminants in municipal wastewater treatment plant (WWTP) effluents can cause ecosystem impacts, raising concerns about their persistence in receiving streams. In this study, Lagrangian sampling, in which the same approximate parcel of water is tracked as it moves downstream, was conducted at Boulder Creek, Colorado and Fourmile Creek, Iowa to determine in-stream transport and attenuation of organic contaminants discharged from two secondary WWTPs. Similar stream reaches were evaluated, and samples were collected at multiple sites during summer and spring hydrologic conditions. Travel times to the most downstream (7.4 km) site in Boulder Creek were 6.2 h during the summer and 9.3 h during the spring, and to the Fourmile Creek 8.4 km downstream site times were 18 and 8.8 h, respectively. Discharge was measured at each site, and integrated composite samples were collected and analyzed for >200 organic contaminants including metal complexing agents, nonionic surfactant degradates, personal care products, pharmaceuticals, steroidal hormones, and pesticides. The highest concentration (>100 μg L(-1)) compounds detected in both WWTP effluents were ethylenediaminetetraacetic acid and 4-nonylphenolethoxycarboxylate oligomers, both of which persisted for at least 7 km downstream from the WWTPs. Concentrations of pharmaceuticals were lower (<1 μg L(-1)), and several compounds, including carbamazepine and sulfamethoxazole, were detected throughout the study reaches. After accounting for in-stream dilution, a complex mixture of contaminants showed little attenuation and was persistent in the receiving streams at concentrations with potential ecosystem implications.

Comparative Study of Transport Processes of Nitrogen, Phosphorus, and Herbicides to Streams in Five Agricultural Basins, USA

Agricultural chemical transport to surface water and the linkage to other hydrological compartments, principally ground water, was investigated at five watersheds in semiarid to humid climatic settings. Chemical transport was affected by storm water runoff, soil drainage, irrigation, and how streams were linked to shallow ground water systems. Irrigation practices and timing of chemical use greatly affected nutrient and pesticide transport in the semiarid basins. Irrigation with imported water tended to increase ground water and chemical transport, whereas the use of locally pumped irrigation water may eliminate connections between streams and ground water, resulting in lower annual loads. Drainage pathways in humid environments are important because the loads may be transported in tile drains, or through varying combinations of ground water discharge, and overland flow. In most cases, overland flow contributed the greatest loads, but a significant portion of the annual load of nitrate and some pesticide degradates can be transported under base-flow conditions. The highest basin yields for nitrate were measured in a semiarid irrigated system that used imported water and in a stream dominated by tile drainage in a humid environment. Pesticide loads, as a percent of actual use (LAPU), showed the effects of climate and geohydrologic conditions. The LAPU values in the semiarid study basin in Washington were generally low because most of the load was transported in ground water discharge to the stream. When herbicides are applied during the rainy season in a semiarid setting, such as simazine in the California basin, LAPU values are similar to those in the Midwest basins.

Pesticide fate and transport throughout unsaturated zones in five agricultural settings, USA

Pesticide transport through the unsaturated zone is a function of chemical and soil characteristics, application, and water recharge rate. The fate and transport of 82 pesticides and degradates were investigated at five different agricultural sites. Atrazine and metolachlor, as well as several of the degradates of atrazine, metolachlor, acetochlor, and alachlor, were frequently detected in soil water during the 2004 growing season, and degradates were generally more abundant than parent compounds. Metolachlor and atrazine were applied at a Nebraska site the same year as sampling, and focused recharge coupled with the short time since application resulted in their movement in the unsaturated zone 9 m below the surface. At other sites where the herbicides were applied 1 to 2 yr before sampling, only degradates were found in soil water. Transformations of herbicides were evident with depth and during the 4-mo sampling time and reflected the faster degradation of metolachlor oxanilic acid and persistence of metolachor ethanesulfonic acid. The fraction of metolachlor ethanesulfonic acid relative to metolachlor and metolachlor oxanilic acid increased from 0.3 to >0.9 at a site in Maryland where the unsaturated zone was 5 m deep and from 0.3 to 0.5 at the shallowest depth. The flux of pesticide degradates from the deepest sites to the shallow ground water was greatest (3.0-4.9 micromol m(-2) yr(-1)) where upland recharge or focused flow moved the most water through the unsaturated zone. Flux estimates based on estimated recharge rates and measured concentrations were in agreement with fluxes estimated using an unsaturated-zone computer model (LEACHM).

Chemical contaminants in water and sediment near fish nesting sites in the Potomac River basin: determining potential exposures to smallmouth bass (Micropterus dolomieu).

The Potomac River basin is an area where a high prevalence of abnormalities such as testicular oocytes (TO), skin lesions, and mortality has been observed in smallmouth bass (SMB, Micropterus dolomieu). Previous research documented a variety of chemicals in regional streams, implicating chemical exposure as one plausible explanation for these biological effects. Six stream sites in the Potomac basin (and one out-of-basin reference site) were sampled to provide an assessment of chemicals in these streams. Potential early life-stage exposure to chemicals detected was assessed by collecting samples in and around SMB nesting areas. Target chemicals included those known to be associated with important agricultural and municipal wastewater sources in the Potomac basin. The prevalence and severity of TO in SMB were also measured to determine potential relations between chemistry and biological effects. A total of 39 chemicals were detected at least once in the discrete-water samples, with atrazine, caffeine, deethylatrazine, simazine, and iso-chlorotetracycline being most frequently detected. Of the most frequently detected chemicals, only caffeine was detected in water from the reference site. No biogenic hormones/sterols were detected in the discrete-water samples. In contrast, 100 chemicals (including six biogenic hormones/sterols) were found in a least one passive-water sample, with 25 being detected at all such samples. In addition, 46 chemicals (including seven biogenic hormones/sterols) were found in the bed-sediment samples, with caffeine, cholesterol, indole, para-cresol, and sitosterol detected in all such samples. The number of herbicides detected in discrete-water samples per site had a significant positive relation to TO(rank) (a nonparametric indicator of TO), with significant positive relations between TO(rank) and atrazine concentrations in discrete-water samples and to total hormone/sterol concentration in bed-sediment samples. Such significant correlations do not necessarily imply causation, as these chemical compositions and concentrations likely do not adequately reflect total SMB exposure history, particularly during critical life stages.

Widespread detection of N,N-diethyl-m-toluamide in U.S. streams: comparison with concentrations of pesticides, personal care products, and other organic wastewater compounds.

One of the most frequently detected organic chemicals in a nationwide study concerning the effects of wastewater on stream water quality conducted in the year 2000 was the widely used insect repellant N,N-diethyl-m-toluamide (DEET). It was detected at levels of 0.02 microg/L or greater in 73% of the stream sites sampled, with the selection of sampling sites being biased toward streams thought to be subject to wastewater contamination (i.e., downstream from intense urbanization and livestock production). Although DEET frequently was detected at all sites, the median concentration was low (0.05 microg/L). The highest concentrations of DEET were found in streams from the urban areas (maximum concentration, 1.1 microg/L). The results of the present study suggest that the movement of DEET to streams through wastewater-treatment systems is an important mechanism that might lead to the exposure of aquatic organisms to this chemical.

Variations in Pesticide Leaching Related to Land Use, Pesticide Properties, and Unsaturated Zone Thickness

Pesticide leaching through variably thick soils beneath agricultural fields in Morgan Creek, Maryland was simulated for water years 1995 to 2004 using LEACHM (Leaching Estimation and Chemistry Model). Fifteen individual models were constructed to simulate five depths and three crop rotations with associated pesticide applications. Unsaturated zone thickness averaged 4.7 m but reached a maximum of 18.7 m. Average annual recharge to ground water decreased from 15.9 to 11.1 cm as the unsaturated zone increased in thickness from 1 to 10 m. These point estimates of recharge are at the lower end of previously published values, which used methods that integrate over larger areas capturing focused recharge in the numerous detention ponds in the watershed. The total amount of applied and leached masses for five parent pesticide compounds and seven metabolites were estimated for the 32-km2 Morgan Creek watershed by associating each hectare to the closest one-dimensional model analog of model depth and crop rotation scenario as determined from land-use surveys. LEACHM parameters were set such that branched, serial, first-order decay of pesticides and metabolites was realistically simulated. Leaching is predicted to be greatest for shallow soils and for persistent compounds with low sorptivity. Based on simulation results, percent parent compounds leached within the watershed can be described by a regression model of the form e(-depth) (a ln t1/2-b ln K OC) where t1/2 is the degradation half-life in aerobic soils, K OC is the organic carbon normalized sorption coefficient, and a and b are fitted coefficients (R2 = 0.86, p value = 7 x 10(-9)).

Complex mixtures of Pesticides in Midwest U.S. streams indicated by POCIS time-integrating samplers

The Midwest United States is an intensely agricultural region where pesticides in streams pose risks to aquatic biota, but temporal variability in pesticide concentrations makes characterization of their exposure to organisms challenging. To compensate for the effects of temporal variability, we deployed polar organic chemical integrative samplers (POCIS) in 100 small streams across the Midwest for about 5 weeks during summer 2013 and analyzed the extracts for 227 pesticide compounds. Analysis of water samples collected weekly for pesticides during POCIS deployment allowed for comparison of POCIS results with periodic water-sampling results. The median number of pesticides detected in POCIS extracts was 62, and 141 compounds were detected at least once, indicating a high level of pesticide contamination of streams in the region. Sixty-five of the 141 compounds detected were pesticide degradates. Mean water concentrations estimated using published POCIS sampling rates strongly correlated with means of weekly water samples collected concurrently, however, the POCIS-estimated concentrations generally were lower than the measured water concentrations. Summed herbicide concentrations (units of ng/POCIS) were greater at agricultural sites than at urban sites but summed concentrations of insecticides and fungicides were greater at urban sites. Consistent with these differences, summed concentrations of herbicides correlate to percent cultivated crops in the watersheds and summed concentrations of insecticides and fungicides correlate to percent urban land use. With the exception of malathion concentrations at nine sites, POCIS-estimated water concentrations of pesticides were lower than aquatic-life benchmarks. The POCIS provide an alternative approach to traditional water sampling for characterizing chronic exposure to pesticides in streams across the Midwest region.

Recovery data for surface water, groundwater and lab reagent samples analyzed by the USGS National Water Quality Laboratory schedule 2437, water years 2013-15

Analytical recovery is the concentration of an analyze measured in a water-quality sample expressed as a percentage of the known concentration added to the sample (Mueller and others, 2015). Analytical recovery (hereafter referred to as recovery ) can be used to understand method bias and variability and to assess the temporal changes in a method over time (Martin and others, 2009). This data set includes two tables: one table of field spike recovery data and one table of lab reagent spike recovery data. The table of field spike recovery data includes results from paired environmental and spike samples collected by the National Water Quality Program, National Water-Quality Assessment (NAWQA) Project in surface water and groundwater. These samples were collected as part of the NAWQA Project s National Water Quality Network: Rivers and Streams assessment, Regional Stream Quality Assessment studies and in multiple groundwater networks following standard practices (Mueller and others, 1997). This table includes environmental and spike water-quality sample data stored in the USGS National Water Information System (NWIS) database (https://dx.doi.org/10.5066/F7P55KJN). Concentrations of pesticides in spike samples, while stored in the NWIS database, are not publically available. The calculation of recovery based on these field sample data is outlined in Mueller and others (2015). Lab reagent spikes are pesticide-free reagent water spiked with a known concentration of pesticide. Lab reagent spikes are prepared in the lab and their recovery can be directly measured. The table of lab reagent spike data contains quality control sample information stored in the USGS National Water Quality Laboratory (NWQL) database. Both tables include fields for data-quality indicators that are described in the data processing steps of this metadata file. These tables were developed in order to support a USGS Scientific Investigations Report with the working title Considerations for the Preparation of Pesticide Data Analyzed with National Water Quality Laboratory Schedule 2437 Martin, J.D., Stone, W.W, Wydoski, D.S., and Sandstrom, M.W., 2009, Adjustment of pesticide concentrations for temporal changes in analytical recovery, 1992 2006: U.S. Geological Survey Scientific Investigations Report 2009 5189, 23 p. plus appendixes. Mueller, D.K., Schertz, T.L., Martin, J.D., and Sandstrom, M.W., 2015, Design, analysis, and interpretation of field quality-control data for water-sampling projects: U.S. Geological Survey Techniques and Methods, book 4, chap. C4, 54 p., https://dx.doi.org/10.3133/tm4C4. Mueller, D.K., Martin, J.D. and Lopes, T.J., 1997, Quality-Control Design for Surface-Water Sampling in the National Water-Quality Assessment Program: U.S. Geological Survey Open-File Report 97-223, 8 p. plus appendixes.