Joel M. Galloway

Pharmaceuticals and other organic chemicals in selected north-central and northwestern Arkansas streams

Recently, our attention has focused on the low level detection of many antibiotics, pharmaceuticals, and other organic chemicals in water resources. The limited studies available suggest that urban or rural streams receiving wastewater effluent are more susceptible to contamination. The purpose of this study was to evaluate the occurrence of antibiotics, pharmaceuticals, and other organic chemicals at 18 sites on seven selected streams in Arkansas, USA, during March, April, and August 2004. Water samples were collected upstream and downstream from the influence of effluent discharges in northwestern Arkansas and at one site on a relatively undeveloped stream in north-central Arkansas. At least one antibiotic, pharmaceutical, or other organic chemical was detected at all sites, except at Spavinaw Creek near Mayesville, Arkansas. The greatest number of detections was observed at Mud Creek downstream from an effluent discharge, including 31 pharmaceuticals and other organic chemicals. The detection of these chemicals occurred in higher frequency at sites downstream from effluent discharges compared to those sites upstream from effluent discharges; total chemical concentration was also greater downstream. Wastewater effluent discharge increased the concentrations of detergent metabolites, fire retardants, fragrances and flavors, and steroids in these streams. Antibiotics and associated degradation products were only found at two streams downstream from effluent discharges. Overall, 42 of the 108 chemicals targeted in this study were found in water samples from at least one site, and the most frequently detected organic chemicals included caffeine, phenol, para-cresol, and acetyl hexamethyl tetrahydro naphthalene (AHTN).

Environmental signatures and effects of an oil and gas wastewater spill in the Williston Basin, North Dakota.

Wastewaters from oil and gas development pose largely unknown risks to environmental resources. In January 2015, 11.4ML (million liters) of wastewater (300g/L TDS) from oil production in the Williston Basin was reported to have leaked from a pipeline, spilling into Blacktail Creek, North Dakota. Geochemical and biological samples were collected in February and June 2015 to identify geochemical signatures of spilled wastewaters as well as biological responses along a 44-km river reach. February water samples had elevated chloride (1030mg/L) and bromide (7.8mg/L) downstream from the spill, compared to upstream levels (11mg/L and <0.4mg/L, respectively). Lithium (0.25mg/L), boron (1.75mg/L) and strontium (7.1mg/L) were present downstream at 5-10 times upstream concentrations. Light hydrocarbon measurements indicated a persistent thermogenic source of methane in the stream. Semi-volatile hydrocarbons indicative of oil were not detected in filtered samples but low levels, including tetramethylbenzenes and di-methylnaphthalenes, were detected in unfiltered water samples downstream from the spill. Labile sediment-bound barium and strontium concentrations (June 2015) were higher downstream from the Spill Site. Radium activities in sediment downstream from the Spill Site were up to 15 times the upstream activities and, combined with Sr isotope ratios, suggest contributions from the pipeline fluid and support the conclusion that elevated concentrations in Blacktail Creek water are from the leaking pipeline. Results from June 2015 demonstrate the persistence of wastewater effects in Blacktail Creek several months after remediation efforts started. Aquatic health effects were observed in June 2015; fish bioassays showed only 2.5% survival at 7.1km downstream from the spill compared to 89% at the upstream reference site. Additional potential biological impacts were indicated by estrogenic inhibition in downstream waters. Our findings demonstrate that environmental signatures from wastewater spills are persistent and create the potential for long-term environmental health effects.

Quality and Age of Shallow Groundwater in the Bakken Formation Production Area, Williston Basin, Montana and North Dakota

The quality and age of shallow groundwater in the Bakken Formation production area were characterized using data from 30 randomly distributed domestic wells screened in the upper Fort Union Formation. Comparison of inorganic and organic chemical concentrations to health based drinking-water standards, correlation analysis of concentrations with oil and gas well locations, and isotopic data give no indication that energy-development activities affected groundwater quality. It is important, however, to consider these results in the context of groundwater age. Most samples were recharged before the early 1950s and had 14C ages ranging from <1000 to >30,000 years. Thus, domestic wells may not be as well suited for detecting contamination associated with recent surface spills as shallower wells screened near the water table. Old groundwater could be contaminated directly by recent subsurface leaks from imperfectly cemented oil and gas wells, but horizontal groundwater velocities calculated from 14C ages imply that the contaminants would still be less than 0.5 km from their source. For the wells sampled in this study, the median distance to the nearest oil and gas well was 4.6 km. Because of the slow velocities, a long-term commitment to groundwater monitoring in the upper Fort Union Formation is needed to assess the effects of energy development on groundwater quality. In conjunction with that effort, monitoring could be done closer to energy-development activities to increase the likelihood of early detection of groundwater contamination if it did occur.

Large wood distribution, mobility, and recruitment in an inter-dam river reach: A comparison with geomorphic process on the Garrison Reach of the Missouri River pre and post the historical 2011 flood: Large wood distribution in an inter-dam river reach

This study assessed the effect of the largest flood since dam regulation on geomorphic and large wood (LW) trends using LW distributions at three time periods on the 150 km long Garrison Reach of the Missouri River. In 2011, a flood exceeded 4390m/s for a two-week period (705% above mean flow; 500 year flood). LW was measured using high resolution satellite imagery in summer 2010 and 2012. Ancillary data including forest character, vegetation cover, lateral bank retreat, and channel capacity. Lateral bank erosion removed approximately 7400 standing trees during the flood. Other mechanisms, that could account for the other two-thirds of the measured in-channel LW, include overland flow through floodplains and islands. LW transport was commonly near or over 100 km as indicated by longitudinal forest and bank loss and post-flood LW distribution. LW concentrations shift at several locations along the river, both preand post-flood, and correspond to geomorphic river regions created by the interaction of the Garrison Dam upstream and the Oahe Dam downstream. Areas near the upstream dam experienced proportionally higher rates of bank erosion and forest loss but in-channel LW decreased, likely due to scouring. A large amount of LW moved during this flood, the chief anchoring mechanism was not bridges or narrow channel reaches but the channel complexity of the river delta created by the downstream reservoir. Areas near the downstream dam experienced bank accretion and large amounts of LW deposition. This study confirms the results of similar work in the Reach: despite a historic flood longitudinal LWand channel trends remain the same. Dam regulation has created a geomorphic and LW pattern that is largely uninterrupted by an unprecedented dam regulation era flood. River managers may require other tools than infrequent high intensity floods to restore geomorphic and LW patterns. Copyright

Modeled sulfate concentrations in North Dakota streams, 1993-2008, based on spatial basin characteristics

Sulfate concentration data collected from North Dakota streams during recent (1993–2008) years indicates generally higher sulfate concentrations across much of the State compared to concentrations during earlier years. The higher sulfate concentrations have been attributed in other studies to wetter climatic conditions, associated increases in contributing drainage areas, and rising water tables. The State’s current (2013) stream classification system, which includes a standard for 30-day average sulfate concentration, is based on earlier data and thus may not reflect natural conditions for more recent years. The U.S. Geological Survey, in cooperation with the North Dakota Department of Health and the North Dakota State Water Commission, completed a study to evaluate the relation of maximum seasonal (30-day moving average) sulfate concentrations during 1993–2008 to characteristics of the contributing basins to model expected naturally-occurring sulfate concentrations in North Dakota streams. Sulfate concentration data for 75 stream sampling sites in North Dakota were analyzed for this study. A spatial analysis was conducted with digital data using a Geographic Information System to obtain selected basin characteristics, which were in turn used as explanatory variables in a regression analysis to model the maximum seasonal (30-day moving average) sulfate concentration. Characteristics used in the regression analysis included mean annual precipitation, mean percent soil clay content, and mean percent saturation overland flow. Modeled sulfate concentrations generally were highest (greater than 750 milligrams per liter) in basins in western North Dakota and lowest (less than 250 milligrams per liter) in basins in the upper Sheyenne River and upper James River. Area-weighted means for the basin characteristics also were computed for 10-digit and 8-digit hydrologic units for streams in North Dakota and modeled sulfate concentrations were computed from the characteristics. The resulting distribution of modeled sulfate concentrations was similar to the distribution of estimates for the 12-digit hydrologic units, but less variable because the basin characteristics were averaged over larger areas. Introduction Soils across North Dakota have naturally high sulfur content that readily oxidizes to highly soluble sulfate ions (Franzen, 2007). Therefore, sulfate concentrations in North Dakota streams tend to be relatively high. North Dakota waterquality standards, specifically for sulfate, are intended for the protection of municipal drinking water supplies and aquatic life (North Dakota Department of Health, 2010). The sulfate standards are 250 milligrams per liter (mg/L) (expressed as a 30-day arithmetic average) for Class I streams and 450 mg/L (expressed as a 30-day arithmetic average) for Class IA and II streams. The sulfate standard for all Class III streams in North Dakota, as well as the Sheyenne River from its headwaters to 0.1 mile downstream from Baldhill Dam (located at site 34 on fig. 1), is 750 mg/L (expressed as a 30-day arithmetic average). The standards for Class I, IA, and II streams are intended for the protection of drinking water use, whereas the 750 mg/L sulfate standard is intended to be protective of aquatic life (North Dakota Department of Health, 2010). Recent analyses of water-quality data collected from streams in North Dakota indicated trends of increasing sulfate concentrations across the State (Galloway and others, 2012; Vecchia, 2003; Vecchia, 2005). Water-quality analysis by the North Dakota Department of Health (NDDH) also indicated that the sulfate standards have been exceeded at a number of stream water-quality monitoring locations across the State, some by an order of magnitude (Michael Ell, North Dakota Department of Health, written commun., 2013). Previous studies (Vecchia, 2005; Schuh and Hove, 2006) have indicated that the increasing sulfate concentrations probably were caused by generally wetter conditions that resulted in increases in contributing drainage areas and water tables beginning about 1993. The increasing sulfate across the State has prompted questions about whether the State’s current stream classification system still appropriately reflects natural conditions. Where natural conditions cause exceedances of the existing sulfate standards, the NDDH may consider changes to the classification status of certain streams to reflect the higher sulfate concentrations. Modeled Sulfate Concentrations in North Dakota Streams, 1993–2008, Based on Spatial Basin Characteristics By Joel M. Galloway and Aldo V. Vecchia 2 Modeled Sulfate Concentrations in North Dakota Streams, 1993–2008, Based on Spatial Basin Characteristics The U.S. Geological Survey (USGS), in cooperation with the North Dakota Department of Health (NDDH) and the North Dakota State Water Commission (NDSWC), conducted a study to evaluate the relation of maximum seasonal (30-day moving average) sulfate concentrations at monitoring sites in North Dakota to characteristics of the contributing basins. Characteristics that can potentially mobilize sulfate from the soil were used to model the expected naturally-occurring sulfate concentrations in streams. These characteristics included runoff from precipitation, the presence of clay in soil (often associated with higher sulfate content; Franzen, 2007), and characteristics that reflect the interaction of the runoff water with soils in the contributing basins. Purpose and Scope The purpose of this report is to describe a regression analysis to provide modeled maximum seasonal (30-day moving average) sulfate concentrations for 1993–2008 in streams in North Dakota based on basin characteristics derived using spatial data on soil properties, runoff characteristics, and precipitation. Modeled sulfate concentrations will be used by the NDDH to determine if the existing classifications of streams in North Dakota are appropriate in light of the higher sulfate concentrations. Estimates of the maximum seasonal sulfate concentrations at selected sites used in the regression analyses were obtained using measured sulfate concentration data from Galloway and others (2012). Methods A regression model was developed from regression analysis to model maximum seasonal sulfate concentrations in basins across North Dakota from selected characteristics of the basins. Sites and associated sulfate concentration data are a subset of the sites and data presented in Galloway and others (2012). The period selected for analysis of sulfate concentrations was from 1993 through 2008. This period was selected to maximize the number of sites with a common period of record and to make the results representative of current conditions. Compared to earlier years, climatic conditions in North Dakota generally became wetter and more variable after 1993 (Hoerling and others, 2010; Vecchia, 2008), and thus streamflow and sulfate concentration data collected in the recent period are expected to better represent future conditions than streamflow and concentration data collected before 1993. Sites from Galloway and others (2012) that had at least 10 samples between 1993 and 2008 were used in the initial dataset for the regression analysis in this report. From the initial dataset, sites were further eliminated that had most of their basin located in Canada and that were located below major dams and may not reflect seasonal sulfate concentrations associated with characteristics of the upstream watersheds. Sites that may redundantly represent a large basin such as multiple sites on the Red River of the North that did not have much variation in basin size were also removed (fig. 1). The final dataset used for the regression analysis included 75 sites (table 1; figs. 1 and 2). The site identification numbers in table 1 and figs. 1 and 2 are the same as the site numbers from Galloway and others (2012). The concentration data used for this analysis are based on samples collected by the North Dakota Department of Health, North Dakota State Water Commission, and U.S. Geological Survey and are described in more detail in Galloway and others (2012). This section describes the methods used for obtaining selected basin characteristics and the statistical methods used for developing relations between basin characteristics and sulfate concentrations at the selected sites. Spatial Data Computation A spatial analysis was conducted with digital data using a Geographic Information System (GIS) to obtain selected basin characteristics. Characteristics from several datasets were extracted for each 12-digit Hydrologic Unit (HU) (U.S Geological Survey and others, 2012) that encompassed streams in North Dakota (fig. 2). Characteristics extracted for each HU included the mean annual precipitation (MAP), mean percent soil clay content (SCC), and mean percent saturation overland flow (SOF). A much larger set of potential basin characteristics was considered for inclusion in the regression analysis, but exploratory analysis of the larger set using the stepwise procedure from the statistical package S-Plus (TIBCO Software Inc., 2010) with the “exhaustive” option to evaluate all possible subsets of explanatory variables and determine the subsets with the smallest mean-squared errors, indicated the three selected characteristics described in this section provided the best combination of explanatory variables. Precipitation is an important variable for evaluating sulfate concentrations because basins with higher precipitation (especially snow that produces spring snowmelt runoff) can result in more dilution of shallow groundwater runoff and hence lower sulfate concentration compared to basins with less precipitation. The mean annual precipitation (MAP) from 1981 to 2010 was obtained from Parameter-Elevation Regressions on Independent Slopes Model (PRISM) data (PRISM Climate Group, 2012). The PRISM model is an analytical model that uses point data and an

Water quality of Lake Pontchartrain and outlets to the Gulf of Mexico following Hurricanes Katrina and Rita: Chapter 7E in Science and the storms-the USGS response to the hurricanes of 2005

Water-quality samples collected from drainage canals, from Lake Pontchartrain, La., and from flood waters contained contaminants typically found in waters influenced by urban runoff. Pesticides and wastewater compounds were detected in all water samples, but none exceeded U.S. Environmental Protection Agency (EPA) drinking water or aquatic life criteria. Although metals were detected in all samples, copper, nickel, and silver occurred in concentrations greater than water-quality criteria for salt water. Salinity levels in the freshwater marshes south of New Orleans were typical of Gulf of Mexico waters for an extended period of time, and levels did not return to prehurricane levels until February 2006.