Trends in pesticide concentrations and use for major rivers of the United States.

Trends in pesticide concentrations in 38 major rivers of the United States were evaluated in relation to use trends for 11 commonly occurring pesticide compounds. Pesticides monitored in water were analyzed for trends in concentration in three overlapping periods, 1992-2001, 1997-2006, and 2001-2010 to facilitate comparisons among sites with variable sample distributions over time and among pesticides with changes in use during different periods and durations. Concentration trends were analyzed using the SEAWAVE-Q model, which incorporates intra-annual variability in concentration and measures of long-term, mid-term, and short-term streamflow variability. Trends in agricultural use within each of the river basins were determined using interval-censored regression with high and low estimates of use. Pesticides strongly dominated by agricultural use (cyanazine, alachlor, atrazine and its degradate deethylatrazine, metolachlor, and carbofuran) had widespread agreement between concentration trends and use trends. Pesticides with substantial use in both agricultural and nonagricultural applications (simazine, chlorpyrifos, malathion, diazinon, and carbaryl) had concentration trends that were mostly explained by a combination of agricultural-use trends, regulatory changes, and urban use changes inferred from concentration trends in urban streams. When there were differences, concentration trends usually were greater than use trends (increased more or decreased less). These differences may occur because of such factors as unaccounted pesticide uses, delayed transport to the river through groundwater, greater uncertainty in the use data, or unquantified land use and management practice changes.

Mississippi River nitrate loads from high frequency sensor measurements and regression-based load estimation.

Accurately quantifying nitrate (NO3-) loading from the Mississippi River is important for predicting summer hypoxia in the Gulf of Mexico and targeting nutrient reduction within the basin. Loads have historically been modeled with regression-based techniques, but recent advances with high frequency NO3- sensors allowed us to evaluate model performance relative to measured loads in the lower Mississippi River. Patterns in NO3- concentrations and loads were observed at daily to annual time steps, with considerable variability in concentration-discharge relationships over the two year study. Differences were particularly accentuated during the 2012 drought and 2013 flood, which resulted in anomalously high NO3- concentrations consistent with a large flush of stored NO3- from soil. The comparison between measured loads and modeled loads (LOADEST, Composite Method, WRTDS) showed underestimates of only 3.5% across the entire study period, but much larger differences at shorter time steps. Absolute differences in loads were typically greatest in the spring and early summer critical to Gulf hypoxia formation, with the largest differences (underestimates) for all models during the flood period of 2013. In additional to improving the accuracy and precision of monthly loads, high frequency NO3- measurements offer additional benefits not available with regression-based or other load estimation techniques.

Pesticides in U.S. streams and rivers: occurrence and trends during 1992-2011.

During the 20 years from 1992 to 2011, pesticides were found at concentrations that exceeded aquatic-life benchmarks in many rivers and streams that drain agricultural, urban, and mixed-land use watersheds. Overall, the proportions of assessed streams with one or more pesticides that exceeded an aquatic-life benchmark were very similar between the two decades for agricultural (69% during 1992-2001 compared to 61% during 2002-2011) and mixed-land-use streams (45% compared to 46%). Urban streams, in contrast, increased from 53% during 1992-2011 to 90% during 2002-2011, largely because of fipronil and dichlorvos. The potential for adverse effects on aquatic life is likely greater than these results indicate because potentially important pesticide compounds were not included in the assessment. Human-health benchmarks were much less frequently exceeded, and during 2002-2011, only one agricultural stream and no urban or mixed-land-use streams exceeded human-health benchmarks for any of the measured pesticides. Widespread trends in pesticide concentrations, some downward and some upward, occurred in response to shifts in use patterns primarily driven by regulatory changes and introductions of new pesticides.

Pesticides in groundwater of the United States: decadal-scale changes, 1993-2011.

The national occurrence of 83 pesticide compounds in groundwater of the United States and decadal-scale changes in concentrations for 35 compounds were assessed for the 20-year period from 1993-2011. Samples were collected from 1271 wells in 58 nationally distributed well networks. Networks consisted of shallow (mostly monitoring) wells in agricultural and urban land-use areas and deeper (mostly domestic and public supply) wells in major aquifers in mixed land-use areas. Wells were sampled once during 1993-2001 and once during 2002-2011. Pesticides were frequently detected (53% of all samples), but concentrations seldom exceeded human-health benchmarks (1.8% of all samples). The five most frequently detected pesticide compounds-atrazine, deethylatrazine, simazine, metolachlor, and prometon-each had statistically significant (p < 0.1) changes in concentrations between decades in one or more categories of well networks nationally aggregated by land use. For agricultural networks, concentrations of atrazine, metolachlor, and prometon decreased from the first decade to the second decade. For urban networks, deethylatrazine concentrations increased and prometon concentrations decreased. For major aquifers, concentrations of deethylatrazine and simazine increased. The directions of concentration changes for individual well networks generally were consistent with changes determined from nationally aggregated data. Altogether, 36 of the 58 individual well networks had statistically significant changes in concentrations of one or more pesticides between decades, with the majority of changes attributed to the five most frequently detected pesticide compounds. The magnitudes of median decadal-scale concentration changes were small-ranging from -0.09 to 0.03 µg/L-and were 35- to 230,000-fold less than human-health benchmarks.

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.

Contaminants in stream sediments from seven United States metropolitan areas: part II--sediment toxicity to the amphipod Hyalella azteca and the midge Chironomus dilutus.

Relationships between sediment toxicity and sediment chemistry were evaluated for 98 samples collected from seven metropolitan study areas across the United States. Sediment-toxicity tests were conducted with the amphipod Hyalella azteca (28 day exposures) and with the midge Chironomus dilutus (10 day exposures). Overall, 33 % of the samples were toxic to amphipods and 12 % of the samples were toxic to midge based on comparisons with reference conditions within each study area. Significant correlations were observed between toxicity end points and sediment concentrations of trace elements, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), or organochlorine (OC) pesticides; however, these correlations were typically weak, and contaminant concentrations were usually below sediment-toxicity thresholds. Concentrations of the pyrethroid bifenthrin exceeded an estimated threshold of 0.49 ng/g (at 1 % total organic carbon) in 14 % of the samples. Of the samples that exceeded this bifenthrin toxicity threshold, 79 % were toxic to amphipods compared with 25 % toxicity for the samples below this threshold. Application of mean probable effect concentration quotients (PECQs) based on measures of groups of contaminants (trace elements, total PAHs, total PCBs, OC pesticides, and pyrethroid pesticides [bifenthrin in particular]) improved the correct classification of samples as toxic or not toxic to amphipods compared with measures of individual groups of contaminants.

Watershed Regressions for Pesticides (WARP) Models for Predicting Stream Concentrations of Multiple Pesticides.

Watershed Regressions for Pesticides for multiple pesticides (WARP-MP) are statistical models developed to predict concentration statistics for a wide range of pesticides in unmonitored streams. The WARP-MP models use the national atrazine WARP models in conjunction with an adjustment factor for each additional pesticide. The WARP-MP models perform best for pesticides with application timing and methods similar to those used with atrazine. For other pesticides, WARP-MP models tend to overpredict concentration statistics for the model development sites. For WARP and WARP-MP, the less-than-ideal sampling frequency for the model development sites leads to underestimation of the shorter-duration concentration; hence, the WARP models tend to underpredict 4- and 21-d maximum moving-average concentrations, with median errors ranging from 9 to 38% As a result of this sampling bias, pesticides that performed well with the model development sites are expected to have predictions that are biased low for these shorter-duration concentration statistics. The overprediction by WARP-MP apparent for some of the pesticides is variably offset by underestimation of the model development concentration statistics. Of the 112 pesticides used in the WARP-MP application to stream segments nationwide, 25 were predicted to have concentration statistics with a 50% or greater probability of exceeding one or more aquatic life benchmarks in one or more stream segments. Geographically, many of the modeled streams in the Corn Belt Region were predicted to have one or more pesticides that exceeded an aquatic life benchmark during 2009, indicating the potential vulnerability of streams in this region.

Occurrence and potential sources of pyrethroid insecticides in stream sediments from seven U.S. metropolitan areas.

A nationally consistent approach was used to assess the occurrence and potential sources of pyrethroid insecticides in stream bed sediments from seven metropolitan areas across the United States. One or more pyrethroids were detected in almost half of the samples, with bifenthrin detected the most frequently (41%) and in each metropolitan area. Cyhalothrin, cypermethrin, permethrin, and resmethrin were detected much less frequently. Pyrethroid concentrations and Hyalella azteca mortality in 28-d tests were lower than in most urban stream studies. Log-transformed total pyrethroid toxic units (TUs) were significantly correlated with survival and bifenthrin was likely responsible for the majority of the observed toxicity. Sampling sites spanned a wide range of urbanization and log-transformed total pyrethroid concentrations were significantly correlated with urban land use. Dallas/Fort Worth had the highest pyrethroid detection frequency (89%), the greatest number of pyrethroids (4), and some of the highest concentrations. Salt Lake City had a similar percentage of detections but only bifenthrin was detected and at lower concentrations. The variation in pyrethroid concentrations among metropolitan areas suggests regional differences in pyrethroid use and transport processes. This study shows that pyrethroids commonly occur in urban stream sediments and may be contributing to sediment toxicity across the country.

Regression models for estimating concentrations of atrazine plus deethylatrazine in shallow groundwater in agricultural areas of the United States.

Tobit regression models were developed to predict the summed concentration of atrazine [6-chloro--ethyl--(1-methylethyl)-1,3,5-triazine-2,4-diamine] and its degradate deethylatrazine [6-chloro--(1-methylethyl)-1,3,5,-triazine-2,4-diamine] (DEA) in shallow groundwater underlying agricultural settings across the conterminous United States. The models were developed from atrazine and DEA concentrations in samples from 1298 wells and explanatory variables that represent the source of atrazine and various aspects of the transport and fate of atrazine and DEA in the subsurface. One advantage of these newly developed models over previous national regression models is that they predict concentrations (rather than detection frequency), which can be compared with water quality benchmarks. Model results indicate that variability in the concentration of atrazine residues (atrazine plus DEA) in groundwater underlying agricultural areas is more strongly controlled by the history of atrazine use in relation to the timing of recharge (groundwater age) than by processes that control the dispersion, adsorption, or degradation of these compounds in the saturated zone. Current (1990s) atrazine use was found to be a weak explanatory variable, perhaps because it does not represent the use of atrazine at the time of recharge of the sampled groundwater and because the likelihood that these compounds will reach the water table is affected by other factors operating within the unsaturated zone, such as soil characteristics, artificial drainage, and water movement. Results show that only about 5% of agricultural areas have greater than a 10% probability of exceeding the USEPA maximum contaminant level of 3.0 µg L. These models are not developed for regulatory purposes but rather can be used to (i) identify areas of potential concern, (ii) provide conservative estimates of the concentrations of atrazine residues in deeper potential drinking water supplies, and (iii) set priorities among areas for future groundwater monitoring.

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.

Trends in concentrations and use of agricultural herbicides for Corn Belt rivers, 1996-2006.

Trends in the concentrations and agricultural use of four herbicides (atrazine, acetochlor, metolachlor, and alachlor) were evaluated for major rivers of the Corn Belt for two partially overlapping time periods: 1996-2002 and 2000-2006. Trends were analyzed for 11 sites on the mainstems and selected tributaries in the Ohio, Upper Mississippi, and Missouri River Basins. Concentration trends were determined using a parametric regression model designed for analyzing seasonal variability, flow-related variability, and trends in pesticide concentrations (SEAWAVE-Q). The SEAWAVE-Q model accounts for the effect of changing flow conditions in order to separate changes caused by hydrologic conditions from changes caused by other factors, such as pesticide use. Most of the trends in atrazine and acetochlor concentrations for both time periods were relatively small and nonsignificant, but metolachlor and alachlor were dominated by varying magnitudes of concentration downtrends. Overall, with trends expressed as a percent change per year, trends in herbicide concentrations were consistent with trends in agricultural use; 84 of 88 comparisons for different sites, herbicides, and time periods showed no significant difference between concentration trends and agricultural use trends. Results indicate that decreasing use appears to have been the primary cause for the concentration downtrends during 1996-2006 and that, while there is some evidence that nonuse management factors may have reduced concentrations in some rivers, reliably evaluating the influence of these factors on pesticides in large streams and rivers will require improved, basin-specific information on both management practices and use over time.

Regression models for explaining and predicting concentrations of organochlorine pesticides in fish from streams in the United States.

Empirical regression models were developed for estimating concentrations of dieldrin, total chlordane, and total DDT in whole fish from U.S. streams. Models were based on pesticide concentrations measured in whole fish at 648 stream sites nationwide (1992-2001) as part of the U.S. Geological Survey's National Water Quality Assessment Program. Explanatory variables included fish lipid content, estimates (or surrogates) representing historical agricultural and urban sources, watershed characteristics, and geographic location. Models were developed using Tobit regression methods appropriate for data with censoring. Typically, the models explain approximately 50 to 70% of the variability in pesticide concentrations measured in whole fish. The models were used to predict pesticide concentrations in whole fish for streams nationwide using the U.S. Environmental Protection Agency's River Reach File 1 and to estimate the probability that whole-fish concentrations exceed benchmarks for protection of fish-eating wildlife. Predicted concentrations were highest for dieldrin in the Corn Belt, Texas, and scattered urban areas; for total chlordane in the Corn Belt, Texas, the Southeast, and urbanized Northeast; and for total DDT in the Southeast, Texas, California, and urban areas nationwide. The probability of exceeding wildlife benchmarks for dieldrin and chlordane was predicted to be low for most U.S. streams. The probability of exceeding wildlife benchmarks for total DDT is higher but varies depending on the fish taxon and on the benchmark used. Because the models in the present study are based on fish data collected during the 1990s and organochlorine pesticide residues in the environment continue to decline decades after their uses were discontinued, these models may overestimate present-day pesticide concentrations in fish.

How well can we predict the toxicity of pesticide mixtures to aquatic life?

Results of publised pesticide mixure toxicity experiments conducted with aquatic organisms were compiled and evaluated to assess the accuracy of predictive mixture models. Three types of models were evaluated: Concentration addition (CA), independent action (IA), and simple interaction (SI). The CA model was the most often tested (207 experiments), followed by SI (59) and IA (37). The reviewed experiments are listed in the Supplemental material to provide a resource for future investigators. The predictive accuracy of each model was quantified for each experiment by the model deviation ratio (MDR), which was calculated by dividing the predicted toxicity by the observed toxicity. Eighty-eight percent of all experiments that evaluated the CA model had observed effective concentrations within a factor of 2 of predicted values (MDR values from 0.5-2.0). The median MDR was 1, about 5% of MDRs were less than 0.5, and about 5% were greater than 2, indicating unbiased estimates overall. The predictive accuracy of CA and IA models was influenced, however, by the different modes of action (MOA) of the pesticides. For experiments with pesticides with the same MOA, CA more accurately predicted effective concentrations for more experiments compared to IA, which tended to underpredict toxicity. The IA model was somewhat more accurate than the CA model for most mixtures with different MOAs, but in most cases there were relatively small differences between the models. Additionally, 80% of SI experiments had an MDR value below 2.0 despite a bias towards experiments that are likely to have an interaction. Thus, results indicate that the CA model may be used as a slightly conservative, but broadly applicable model with a relatively small likelihood of underestimating effects due to interactions.

Relative toxicity and occurrence patterns of pesticide mixtures in streams draining agricultural watersheds dominated by corn and soybean production.

To evaluate the relative toxicity and the occurrence patterns of pesticide mixtures in streams draining agricultural watersheds, a 3-step approach was used. First, a landscape of interest was identified, defined, and isolated. Second, the relative toxicity of mixtures, on the basis of pesticide toxicity index scores, was compared with the relative toxicity of the highest individual pesticide, on the basis of highest toxicity quotient values. Third, occurrence patterns of pesticide mixtures were identified for use in follow-up mechanistic studies. The landscape of interest was identified as the corn and soybeans crop setting and concentrations of pesticides in streams within this crop setting were determined from US Geological Survey data. Pesticide toxicity index scores for individual samples were highest for the primary producers, Pseudokirchneriella subcapitata and Lemna gibba; with 95th percentile pesticide toxicity index scores of 4.7 and 1.9, respectively. The 95th percentile pesticide toxicity index score for Daphnia magna was 0.40 when a chronic sublethal endpoint was used. Pesticide toxicity index values were above the highest toxicity quotient values, indicating that consideration of mixtures does increase the estimated risk, but pesticide toxicity index scores were generally within a factor of 2 of highest toxicity quotient values, indicating that the increased risk is not large for most samples. Pesticide toxicity index scores tended to be dominated by individual pesticides and simple mixtures. Two different prioritization strategies were used to identify important mixtures for further study on the basis of potential effects on P. subcapitata. Both techniques decreased the complexity of the pesticide mixtures to consider by reducing the number of components within the identified mixtures as well as identifying a few specific combinations that constitute the majority of mixtures within the sample. Nearly all important pesticides for P. subcapitata were herbicides from 2 chemical classes: acetanilide and triazine herbicides.