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Summary of significant results from studies of triazine herbicides and their degradation products in surface water, ground water, and precipitation in the midwestern United States during the 1990s

Nonpoint-source contamination of water resources from triazine herbicides has been a major water-quality issue during the 1990s in the United States. To address this issue, studies of surface water, ground water, and precipitation have been carried out by the U.S. Geological Survey in the Midwestern United States. Reconnaissance studies of 147 streams were conducted to determine the geographic and seasonal distribution of atrazine, cyanazine, propazine, and simazine. These studies showed that high concentrations of herbicides were flushed from cropland and transported through the stream system as pulses in response to spring and summer rainfall. The studies also revealed the persistence of herbicides and their degradation products in streams. An investigation of 76 reservoirs showed that the occurrence and temporal distribution of herbicides and their degradation products in reservoir outflow could be related to reservoir and drainage-basin characteristics, water and land use, herbicide use, and climate. Significant findings showed that concentrations of atrazine and its degradation products remained elevated all summer and into the fall and that recently applied atrazine mixed with atrazine applied the previous year as water moved through a reservoir. Reconnaissance studies of 303 ground-water wells were completed to determine hydrogeological and seasonal occurrence, concentration, and distribution of herbicides and their degradation products. Samples collected from across the Midwestern United States consistently revealed that triazine herbicide degradation products commonly were found more frequently than their parent herbicide and that ground-water age could be an important factor in explaining variations in herbicide contamination. A final study investigated precipitation in the Midwestern United States, northeast to the Atlantic Ocean, and northward to the Canadian border. It found that the highest herbicide concentrations in precipitation occurred following herbicide application to cropland. Atrazine was detected most often, followed by deethylatrazine, cyanazine, and deisoproplyatrazine. Mass deposition of herbicides by precipitation was greatest in areas where herbicide use was intense and decreased with distance from the Midwest. Findings of the 1990s studies include an improved understanding of the occurrence, persistence, chemistry, and transport of triazine herbicides and their degradation products in the hydrologic environment. A significant increase in knowledge of triazine herbicides and development and improvement of analytical methods were accomplished in the past decade. The results produced are not only significant for the present (2005) but provide an important data set for future use.

Midwest region

Surface water-ground water interactions along the lower Dungeness River and vertical hydraulic conductivity of streambed sediments, Clallam County, Washington, September 1999-July 2001

The Dungeness River emerges from the Olympic Mountains and flows generally north toward the Strait of Juan De Fuca, crossing the broad, fertile alluvial fan of the Sequim-Dungeness peninsula in northeastern Clallam County, Washington. Increasing competition for the peninsula's ground-water resources, changing water-use patterns, and recent requirements to maintain minimum in-stream flows to enhance endangered salmon and trout populations have severely strained the peninsula's water resources and necessitated a better understanding of the interaction between surface water and groundwater. Three methods were used to characterize the interchange between surface water and groundwater along the lower 11.8 miles of the Dungeness River corridor between September 1999 and July 2001. In-stream mini-piezometers were used to measure vertical hydraulic gradients between the river and the water-table aquifer at 27 points along the river and helped to define the distribution of gaining and losing stream reaches. Seepage runs were used to quantify the net volume of water exchanged between the river and ground water within each of five river reaches, termed 'seepage reaches.' Continuous water-level and water-temperature monitoring at two off-stream well transects provided data on near-river horizontal hydraulic gradients and temporal patterns of water exchange for a representative gaining stream reach and a representative losing stream reach. Vertical hydraulic gradients in the mini-piezometers generally were negative between river miles 11.8 and 3.6, indicating loss of water from the river to ground water. Gradients decreased in the downstream direction from an average of -0.86 at river mile 10.3 to -0.23 at river mile 3.7. Small positive gradients (+0.01 to +0.02) indicating ground-water discharge occurred in three localized reaches below river mile 3.7. Data from the seepage runs and off-stream transect wells supported and were generally consistent with the mini-piezometer findings. An exception occurred between river miles 8.1 and 5.5 where seepage results showed a small gain and the mini-piezometers showed negative gradients. Vertical hydraulic conductivity of riverbed sediments was estimated using hydraulic gradients measured with the mini-piezometers and estimated seepage fluxes. The resulting conductivity values ranged from an average of 1 to 29 feet per day and are similar to values reported for similar river environments elsewhere. The results of this study will be used to calibrate a transient, three-dimensional ground-water flow model of the Sequim-Dungeness peninsula. The model will be used to assess the potential effects on ground-water levels and river flows that result from future water use and land-use changes on the peninsula.

Water-Resources Investigations Report

Effects of the eruptions of Mount St. Helens on physical, chemical, and biological characteristics of surface water, ground water, and precipitation in the Western United States

Over 120 publications that describe the 1980 eruption effects of Mount St. Helens on rivers, lakes, and the Columbia River estuary are reviewed. Water-quality changes ranged from minor, short-lived effects, to totally altered drainage basins and newly created lakes. Turbidity increased; concentrations of cations, anions, and dissolved organic carbon increased. Migrating fish were adversely affected; benthic-invertebrate populations changed. Ground-water levels rose near the Cowlitz River. Precipitation effects included transient, but increased specific conductance and decreased pH.

Water Supply Paper

The Phosphoria Formation at the Hot Springs Mine in Southeast Idaho: A source of selenium and other trace elements to surface water, ground water, vegetation, and biota

Major-element oxides and trace elements in the Phosphoria Formation at the Hot Springs Mine, Idaho were determined by a series of techniques. In this report, we examine the distribution of trace elements between the different solid components aluminosilicates, apatite, organic matter, opal, calcite, and dolomite that largely make up the rocks. High concentrations of several trace elements throughout the deposit, for example, As, Cd, Se, Tl, and U, at this and previously examined sites have raised concern about their introduction into the environment via weathering and the degree to which mining and the disposal of mined waste rock from this deposit might be accelerating that process. The question addressed here is how might the partitioning of trace elements between these solid host components influence the introduction of trace elements into ground water, surface water, and eventually biota, via weathering? In the case of Se, it is partitioned into components that are quite labile under the oxidizing conditions of subaerial weathering. As a result, it is widely distributed throughout the environment. Its concentration exceeds the level of concern for protection of wildlife at virtually every trophic level.

Idaho

Water resources data for Florida, water year 1976; Volume 4. Northwest Florida--surface water, ground water, and quality of water

Water resources data for the 1976 water year for northwest Florida consist of records of stage, discharge, and water quality of streams; elevation and water quality of lakes and reservoirs; water-levels and water quality of wells; and discharge and water quality of springs. Additional water data were collected at various sites, not part of the systematic data collection program, and are published as miscellaneous measurements. These data represent that part of the National Water Data System operated by the U.S. Geological Survey and cooperating state and federal agencies in Florida.

Florida

Water resources data for Florida, water year 1975; Volume 1. Northern Florida--surface water, ground water, and quality of water

Water resources data for the 1975 water year for northern Florida consist of records of stage, discharge, and water quality of streams; elevation and water quality of lakes and reservoirs; water-levels and water quality of wells; and discharge and water quality of springs. Additional water data were collected at various sites, not part of the systematic data collection program, and are published as miscellaneous measurements. These data represent that part of the National Water Data System operated by the U. S. Geological Survey and cooperating state and federal agencies in Florida.

Florida

Water resources data for Florida, water year 1976; Volume 2. South Florida--surface water, ground water, and quality of water

Water resources data for the 1976 water year for south Florida consist of records of stage, discharge, and water quality of streams; elevation and water quality of lakes and reservoirs; water-levels and water quality of wells; and discharge and water quality of springs. Additional water data were collected at various sites, not part of the systematic data collection program, and are published as miscellaneous measurements. These data represent that part of the National Water Data System operated by the U. S. Geological Survey and cooperating state and federal agencies in Florida.

Florida

Variations in surface water-ground water interactions along a headwater mountain stream : comparisons between transient storage and water balance analyses

The accumulation of discharge along a stream valley is frequently assumed to be the primary control on solute transport processes. Relationships of both increasing and decreasing transient storage, and decreased gross losses of stream water have been reported with increasing discharge; however, we have yet to validate these relationships with extensive field study. We conducted transient storage and mass recovery analyses of artificial tracer studies completed for 28 contiguous 100 m reaches along a stream valley, repeated under four base-flow conditions. We calculated net and gross gains and losses, temporal moments of tracer breakthrough curves, and best fit transient storage model parameters (with uncertainty estimates) for 106 individual tracer injections. Results supported predictions that gross loss of channel water would decrease with increased discharge. However, results showed no clear relationship between discharge and transient storage, and further analysis of solute tracer methods demonstrated that the lack of this relation may be explained by uncertainty and equifinality in the transient storage model framework. Furthermore, comparison of water balance and transient storage approaches reveals complications in clear interpretation of either method due to changes in advective transport time, which sets a the temporal boundary separating transient storage and channel water balance. We have little ability to parse this limitation of solute tracer methods from the physical processes we seek to study. We suggest the combined analysis of both transient storage and channel water balance more completely characterizes transport of solutes in stream networks than can be inferred from either method alone.

Montana

Precipitation; ground-water age; ground-water nitrate concentrations, 1995-2002; and ground-water levels, 2002-03 in Eastern Bernalillo County, New Mexico

The eastern Bernalillo County study area consists of about 150 square miles and includes all of Bernalillo County east of the crests of the Sandia and Manzanita Mountains. Soil and unconsolidated alluvial deposits overlie fractured and solution-channeled limestone in most of the study area. North of Interstate Highway 40 and east of New Mexico Highway 14, the uppermost consolidated geologic units are fractured sandstones and shales. Average annual precipitation at three long-term National Oceanic and Atmospheric Administration precipitation and snowfall data-collection sites was 14.94 inches at approximately 6,300 feet (Sandia Ranger Station), 19.06 inches at about 7,020 feet (Sandia Park), and 23.07 inches at approximately 10,680 feet (Sandia Crest). The periods of record at these sites are 1933-74, 1939-2001, and 1953-79, respectively. Average annual snowfall during these same periods of record was 27.7 inches at Sandia Ranger Station, 60.8 inches at Sandia Park, and 115.5 inches at Sandia Crest. Seven precipitation data-collection sites were established during December 2000-March 2001. Precipitation during 2001-03 at three U.S. Geological Survey sites ranged from 66 to 94 percent of period-of-record average annual precipitation at corresponding National Oceanic and Atmospheric Administration long-term sites in 2001, from 51 to 75 percent in 2002, and from 34 to 81 percent during January through September 2003. Missing precipitation records for one site resulted in the 34-percent value in 2003. Analyses of concentrations of chlorofluorocarbons CFC-11, CFC-12, and CFC-113 in ground-water samples from nine wells and one spring were used to estimate when the sampled water entered the ground-water system. Apparent ages of ground water ranged from as young as about 10 to 16 years to as old as about 20 to 26 years. Concentrations of dissolved nitrates in samples collected from 24 wells during 2001-02 were similar to concentrations in samples collected from the same wells during 1995, 1997, and (or) 1998. Nitrate concentrations in two wells were larger than the U.S. Environmental Protection Agency primary drinking-water regulation of 10 milligrams per liter in 1998 and in 2001. Ground-water levels were measured during June and July 2002 and during June, July, and August 2003 in 18 monitoring wells. The median change in water level for all 18 wells was a decline of 2.03 feet.

New Mexico

A national look at nitrate contamination of ground water

Ground water provides drinking water for more than one-half of the Nation's population (Solley and others, 1993), and is the sole source of drinking water for many rural communities and some large cities. In 1990, ground water accounted for 39 percent of water withdrawn for public supply for cities and towns and 96 percent of water withdrawn by self-supplied systems for domestic use. A variety of chemicals, including nitrate, can pass through the soil and potentially contaminate ground water. Nitrate comes from nitrogen, a plant nutrient supplied by inorganic fertilizer and animal manure. Additionally, airborne nitrogen compounds given off by industry and automobiles are deposited on the land in precipitation and dry particles. Other nonagricultural sources of nitrate include lawn fertilizers, septic systems, and domestic animals in residential areas. Beneath agricultural lands, nitrate is the primary form of nitrogen. It is soluble in water and can easily pass through soil to the ground-water table. Nitrate can persist in ground water for decades and accumulate to high levels as more nitrogen is applied to the land surface every year. Knowing where and what type of risks to ground water exist can alert water-resource managers and private users of the need to protect water supplies. Although nitrate generally is not an adult public-health threat, ingestion in drinking water by infants can cause low oxygen levels in the blood, a potentially fatal condition (Spalding and Exner, 1993). For this reason, the U.S. Environmental Protection Agency (EPA) has established a drinking-water standard of 10 milligrams per liter (mg/L) nitrate as nitrogen (U.S. Environmental Protection Agency, 1995). Nitrate concentrations in natural ground waters are usually less than 2 mg/L (Mueller and others, 1995).

Water Conditioning and Purification

Modeling decadal timescale interactions between surface water and ground water in the central Everglades, Florida, USA

Surface-water and ground-water flow are coupled in the central Everglades, although the remoteness of this system has hindered many previous attempts to quantify interactions between surface water and ground water. We modeled flow through a 43,000 ha basin in the central Everglades called Water Conservation Area 2A. The purpose of the model was to quantify recharge and discharge in the basin's vast interior areas. The presence and distribution of tritium in ground water was the principal constraint on the modeling, based on measurements in 25 research wells ranging in depth from 2 to 37 m. In addition to average characteristics of surface-water flow, the model parameters included depth of the layer of 'interactive' ground water that is actively exchanged with surface water, average residence time of interactive ground water, and the associated recharge and discharge fluxes across the wetland ground surface. Results indicated that only a relatively thin (8 m) layer of the 60 m deep surfical aquifer actively exchanges surface water and ground water on a decadal timescale. The calculated storage depth of interactive ground water was 3.1 m after adjustment for the porosity of peat and sandy limestone. Modeling of the tritium data yielded an average residence time of 90 years in interactive ground water, with associated recharge and discharge fluxes equal to 0.01 cm d -1. 3H/3He isotopic ratio measurements (which correct for effects of vertical mixing in the aquifer with deeper, tritium-dead water) were available from several wells, and these indicated an average residence time of 25 years, suggesting that residence time was overestimated using tritium measurements alone. Indeed, both residence time and storage depth would be expected to be overestimated due to vertical mixing. The estimate of recharge and discharge (0.01 cm d-1) that resulted from tritium modeling therefore is still considered reliable, because the ratio of residence time and storage depth (used to calculated recharge and discharge) is much less sensitive to vertical mixing compared with residence time alone. We conclude that a small but potentially significant component of flow through the Everglades is recharged to the aquifer and stored there for years to decades before discharged back to surface water. Long-term storage of water and solutes in the ground-water system beneath the wetlands has implications for restoration of Everglades water quality.

Journal of Hydrology

Movement of agricultural chemicals between surface water and ground water, lower Cedar River basin, Iowa

Movement of agricultural chemicals alachlor, atrazine, cyanazine, deethylatrazine, deisopropylatrazine, and metolachlor between surface water and ground water is documented by data collected from May 1989 through July 1991 at an unfarmed study site adjacent to the Cedar River in Iowa. During periods of runoff, these chemicals moved from the Cedar River into the alluvial aquifer with bank-storage water. Results of simulation of ground-water flow conditions during March-April 1990 indicated that bank-storage water moving through the river bottom accounted for 70 percent of the total bank-storage water, whereas the remaining 30 percent moved through the riverbank. The largest concentrations of the chemicals in bank-storage water during 1990 were: alachlor, 2.1 micrograms per liter ( μ g/L); atrazine, 4.7 μ g/L; cyanazine, 3.2 μ g/L; deethylatrazine, 0.54 μ g/L; deisopropylatrazine, 0.33 μ g/L; and metolachlor, 2.2 μ g/L. Larger concentrations of some herbicides and their metabolites were detected in the ground water after the study site was inundated by floodwater between June and August 1990. The concentrations in a water sample from one well after this flooding on February 5, 1991, were: alachlor, 0.06 μ g/L; atrazine, 18 μ g/L; cyanazine, 1.3 μ g/L; deethylatrazine, 1.4 μ g/L; deisopropylatrazine, 0.40 μ g/L; and metolachlor, 7.0 μ g/L. During base-flow conditions, the movement of agricultural chemicals from ground water to surface water was quantified for two periods of time in 1989 and 1990 along a 117-kilometer reach of the Cedar River. The principal source of atrazine, deethylatrazine, deisopropylatrazine, and metolachlor in the Cedar River during base flow was ground water discharged directly from the alluvial aquifer adjacent to the Cedar River. This discharge exceeded the combined tributary inflow of the chemicals along the entire reach. Bank storage is probably an important source of agricultural chemicals discharged from the alluvial aquifer but becomes depleted with time after surface runoff. Herbicides discharged from the alluvial aquifer during periods of extended base flow entered the alluvial aquifer with ground-water recharge at some distance from the river. The movement of nitrate between surface water and ground water is minor, when compared to the herbicides, even though nitrite was detected in the Cedar River during runoff.

Iowa, Minnesota

Field Techniques for Estimating Water Fluxes Between Surface Water and Ground Water

This report focuses on measuring the flow of water across the interface between surface water and ground water, rather than the hydrogeological or geochemical processes that occur at or near this interface. The methods, however, that use hydrogeological and geochemical evidence to quantify water fluxes are described herein. This material is presented as a guide for those who have to examine the interaction of surface water and ground water. The intent here is that both the overview of the many available methods and the in-depth presentation of specific methods will enable the reader to choose those study approaches that will best meet the requirements of the environments and processes they are investigating, as well as to recognize the merits of using more than one approach. This report is designed to make the reader aware of the breadth of approaches available for the study of the exchange between surface and ground water. To accomplish this, the report is divided into four chapters. Chapter 1 describes many well-documented approaches for defining the flow between surface and ground waters. Subsequent chapters provide an in-depth presentation of particular methods. Chapter 2 focuses on three of the most commonly used methods to either calculate or directly measure flow of water between surface-water bodies and the ground-water domain: (1) measurement of water levels in well networks in combination with measurement of water level in nearby surface water to determine water-level gradients and flow; (2) use of portable piezometers (wells) or hydraulic potentiomanometers to measure hydraulic gradients; and (3) use of seepage meters to measure flow directly. Chapter 3 focuses on describing the techniques involved in conducting water-tracer tests using fluorescent dyes, a method commonly used in the hydrogeologic investigation and characterization of karst aquifers, and in the study of water fluxes in karst terranes. Chapter 4 focuses on heat as a tracer in hydrological investigations of the near-surface environment.

Techniques and Methods

Determining temperature and thermal properties for heat-based studies of surface-water ground-water interactions: Appendix A of Heat as a tool for studying the movement of ground water near streams (Cir1260)

Advances in electronics leading to improved sensor technologies, large-scale circuit integration, and attendant miniaturization have created new opportunities to use heat as a tracer of subsurface flow. Because nature provides abundant thermal forcing at the land surface, heat is particularly useful in studying stream-groundwater interactions. This appendix describes methods for obtaining the thermal data needed in heat-based investigations of shallow subsurface flow.

Report

Quality of surface water and ground water in the proposed artificial-recharge project area, Rillito Creek basin, Tucson, Arizona, 1994

Controlled artificial recharge of surface runoff is being considered as a water-management technique to address the problem of ground-water overdraft. The planned use of recharge facilities in urban areas has caused concern about the quality of urban runoff to be recharged and the potential for ground-water contamination. The proposed recharge facility in Rillito Creek will utilize runoff entering a 1-mile reach of the Rillito Creek between Craycroft Road and Swan Road for infiltration and recharge purposes within the channel and excavated overbank areas. Physical and chemical data were collected from two surface-water and two ground-water sites in the study area in 1994. Analyses of surface-water samples were done to determine the occurrence and concentration of potential contaminants and to determine changes in quality since samples were collected during 1987-93. Analyses of ground-water samples were done to determine the variability of ground-water quality at the monitoring wells throughout the year and to determine changes in quality since samples were collected in 1989 and 1993. Surface-water samples were collected from Tanque Verde Creek at Sabino Canyon Road (streamflow-gaging station Tanque Verde Creek at Tucson, 09484500) and from Alamo Wash at Fort Lowell Road in September and May 1994, respectively. Ground-water samples were collected from monitoring wells (D- 13-14)26cbb2 and (D-13-14)26dcb2 in January, May, July, and October 1994. In surface water, calcium was the dominant cation, and bicarbonate was the dominant anion. In ground water, calcium and sodium were the dominant cations and bicarbonate was the dominant anion. Surface water in the area is soft, and ground water is moderately hard to hard. In surface water and ground water, nitrogen was found predominantly as nitrate. Concentrations of manganese in ground-water samples ranged from 60 to 230 micrograms per liter and exceeded the U.S. Environmental Protection Agency secondary maximum contaminant level for drinking water of 50 micrograms per liter. None of the constituents in surface-water and ground-water samples exceeded the U.S. Environmental Protection Agency primary maximum contaminant levels for drinking water or State of Arizona aquifer water-quality standards. Concentrations of major ions, nutrients, and trace elements in water from the monitoring wells did not vary significantly throughout the year and were not significantly different from concentrations in samples collected in March 1989 and January and September 1993. Priority pollutants were not found in surface-water samples or ground-water samples, and organochlorine pesticides were not found in ground-water samples. Dieldrin and biphenyl polychlor were the only pesticides found in surface water and were at the minimum reporting levels in one sample from Alamo Wash.

Water-Resources Investigations Report

Water-quality assessment of south-central Texas: Occurrence and distribution of volatile organic compounds in surface water and ground water, 1983-94, and implications for future monitoring

The study area of the South-Central Texas study unit of the National Water-Quality Assessment Program comprises the Edwards aquifer in the San Antonio region and its catchment area. The first phase of the assessment includes evaluation of existing water-quality data for surface water and ground water, including volatile organic compounds, to determine the scope of planned monitoring. Most analyses of volatile organic compounds in surface water are from the National Pollutant Discharge Elimination System sites in San Antonio, Texas. Nine volatile organic compounds were detected at the six sites. The three compounds with the most detections at National Pollutant Discharge Elimination System sites are 1,2,4-trimethylbenzene, toluene, and xylene. Analysis of volatile organic compounds in ground water was limited to Edwards aquifer wells. Twenty-eight volatile organic compounds were detected in samples from 89 wells. The five most commonly detected compounds in samples from wells, in descending order, are tetrachloroethene, trichloroethene, bromoform, chloroform, and dibromochloromethane. Detections of volatile organic compounds in surface water and ground water within the South-Central Texas study area are limited to site-specific sources associated with development; therefore, planned monitoring for possible detections of volatile organic compounds as part of the National Water-Quality Assessment Program will emphasize areas of expanding population and development. Monitoring of volatile organic compounds is planned at National Pollutant Discharge Elimination System sites, at basic fixed surface-water sites, and in the ground-water study-unit surveys.

Texas