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Total dissolved gas and water temperature in the lower Columbia River, Oregon and Washington, 2003: Quality-assurance data and comparison to water-quality standards

Significant Findings When water is released through the spillways of dams, air is entrained in the water, increasing the concentration of total dissolved gas. Excess dissolved-gas concentrations can have adverse effects on freshwater aquatic life. The U.S. Geological Survey (USGS), in cooperation with the U.S. Army Corps of Engineers, collected total- dissolved-gas and water-temperature data at seven sites on the lower Columbia River in 2003. Significant findings from the data include: For the seven monitoring sites in water year 2003, an average of 98.9% of the total-dissolved-gas data were received in real time by the USGS satellite downlink and were within 1% saturation of the expected value, based on calibration data, replicate quality-control measurements in the river, and comparison to ambient river conditions at adjacent sites. Most field checks of total-dissolved-gas sensors with a secondary standard were within plus or minus 1% saturation. Field checks of barometric pressure and water temperature were usually within plus or minus 1 millimeter of mercury and plus or minus 0.1 degree Celsius, respectively. The variances to the States of Oregon and Washington water-quality standards for total dissolved gas were exceeded at six of the seven monitoring sites. The sites at Camas and Bonneville forebay had the most days exceeding the variance of 115% saturation. The forebay exceedances may have been the result of the cumulative effects of supersaturated water moving downstream through the lower Columbia River. Apparently, the levels of total dissolved gas did not decrease rapidly enough downstream from the dams before reaching the next site. From mid-July to mid-September, water temperatures were usually above 20 degrees Celsius at each of the seven lower Columbia River sites. According to the Oregon water-quality standard, when the temperature of the lower Columbia River exceeds 20 degrees Celsius, no measurable temperature increase resulting from anthropogenic activities is allowed. Transient increases of about 1 degree Celsius were noted at the John Day forebay site, due to localized solar heating.

Oregon, Washington↗

Hydrogeologic characteristics of four public drinking-water supply springs in northern Arkansas

In October 2000, a study was undertaken by the U.S. Geological Survey (USGS) in cooperation with the Arkansas Department of Health to determine the hydrogeologic characteristics, including the extent of the recharge areas, for Hughes Spring, Stark Spring, Evening Shade Spring, and Roaring Spring, which are used for public-water supply in northern Arkansas. Information pertaining to each spring can be used to enable development of effective management plans to protect these water resources and public health. An integrated approach to determine the ground-water characteristics and the extent of the local recharge areas of the four springs incorporated tools and methods of hydrology, structural geology, geomorphology, geophysics, and geochemistry. Analyses of discharge, temperature, and water quality were completed to describe ground-water flow characteristics, source-water characteristics, and connectivity of the ground-water system with surface runoff. Water-level contour maps were constructed to determine ground-water flow directions and ground-water tracer tests were conducted to determine the extent of the recharge areas and ground-water flow velocities. Hughes Spring supplies water for the city of Marshall, Arkansas, and the surrounding area. The mean annual discharge for Hughes Spring was 2.9 and 5.2 cubic feet per second for water years 2001 and 2002, respectively. Recharge to the spring occurs mainly from the Boone Formation (Springfield Plateau aquifer). Ground-water tracer tests indicate the recharge area for Hughes Spring generally coincides with the surface drainage area (15.8 square miles) and that Hughes Spring is connected directly to the surface flow in Brush Creek. The geochemistry of Hughes Spring demonstrated variations with flow conditions and the influence of surface-runoff in the recharge area. Calcite saturation indices, total dissolved solids concentrations, and hardness demonstrate noticeable differences with flow conditions reflecting the reduced residence time and interaction of water with the source rock within the ground-water system at higher discharges for Hughes Spring. Concentrations of fecal indicator bacteria also demonstrated a substantial increase during high-flow conditions, suggesting that a non-point source of bacteria possibly from livestock may enter the system. Conversely, nutrient concentrations did not vary with flow and were similar to concentrations reported for undeveloped sites in the Springfield Plateau and Ozark aquifers in northern Arkansas and southern Missouri. Deuterium and oxygen-18 data show that the Hughes Spring discharge is representative of direct precipitation and not influenced by water enriched in oxygen-18 through evaporation. Discharge data show that Hughes Spring is dominated by conduit type ground-water flow, but a considerable component of diffuse flow also exists in the ground-water system. Carbon-13 data indicate a substantial component of the recharge water interacts with the surface material (soil and regolith) in the recharge area before entering the ground-water system for Hughes Spring. Tritium data for Hughes Spring indicate that the discharge water is a mixture of recent recharge and sub-modern water (recharged prior to 1952). Stark Spring supplies water for the city of Cushman, Arkansas, and the surrounding area. 2 Hydrogeologic Characteristics of Four Public Drinking-Water Supply Springs in Northern Arkansas The mean annual discharge for Stark Spring was 0.5 and 1.5 cubic feet per second for water years 2001 and 2002, respectively. The discharge and water-quality data show the ground-water system for Stark Spring is dominated by rapid recharge from surface runoff and mainly consists of a conduit- type flow system with little diffuse-type flow. Analyses of discharge data show that the estimated recharge area (0.79 square mile) is larger than the surface drainage area (0.34 square mile). Ground-water tracer tests and the outcrop of the

Water-Resources Investigations Report↗

Methods for estimating flood frequency in Montana based on data through water year 1998

Annual peak discharges having recurrence intervals of 2, 5, 10, 25, 50, 100, 200, and 500 years (T-year floods) were determined for 660 gaged sites in Montana and in adjacent areas of Idaho, Wyoming, and Canada, based on data through water year 1998. The updated flood-frequency information was subsequently used in regression analyses, either ordinary or generalized least squares, to develop equations relating T-year floods to various basin and climatic characteristics, equations relating T-year floods to active-channel width, and equations relating T-year floods to bankfull width. The equations can be used to estimate flood frequency at ungaged sites. Montana was divided into eight regions, within which flood characteristics were considered to be reasonably homogeneous, and the three sets of regression equations were developed for each region. A measure of the overall reliability of the regression equations is the average standard error of prediction. The average standard errors of prediction for the equations based on basin and climatic characteristics ranged from 37.4 percent to 134.1 percent. Average standard errors of prediction for the equations based on active-channel width ranged from 57.2 percent to 141.3 percent. Average standard errors of prediction for the equations based on bankfull width ranged from 63.1 percent to 155.5 percent. In most regions, the equations based on basin and climatic characteristics generally had smaller average standard errors of prediction than equations based on active-channel or bankfull width. An exception was the Southeast Plains Region, where all equations based on active-channel width had smaller average standard errors of prediction than equations based on basin and climatic characteristics or bankfull width. Methods for weighting estimates derived from the basin- and climatic-characteristic equations and the channel-width equations also were developed. The weights were based on the cross correlation of residuals from the different methods and the average standard errors of prediction. When all three methods were combined, the average standard errors of prediction ranged from 37.4 percent to 120.2 percent. Weighting of estimates reduced the standard errors of prediction for all T-year flood estimates in four regions, reduced the standard errors of prediction for some T-year flood estimates in two regions, and provided no reduction in average standard error of prediction in two regions. A computer program for solving the regression equations, weighting estimates, and determining reliability of individual estimates was developed and placed on the USGS Montana District World Wide Web page. A new regression method, termed Region of Influence regression, also was tested. Test results indicated that the Region of Influence method was not as reliable as the regional equations based on generalized least squares regression. Two additional methods for estimating flood frequency at ungaged sites located on the same streams as gaged sites also are described. The first method, based on a drainage-area-ratio adjustment, is intended for use on streams where the ungaged site of interest is located near a gaged site. The second method, based on interpolation between gaged sites, is intended for use on streams that have two or more streamflow-gaging stations.

Montana↗

Changes in ground-water quality near two granular-iron permeable reactive barriers in a sand and gravel aquifer, Cape Cod, Massachusetts, 1997-2000

Two experimental permeable reactive barriers (PRBs) of granular zero-valent iron were emplaced in the path of a tetrachloroethene plume (the Chemical Spill-10 plume) at the Massachusetts Military Reservation, Cape Cod, Massachusetts, in June 1998. The goal of the field experiment was to achieve emplacement of a granular-iron PRB deeper than attempted before. The PRBs were expected to create a reducing environment and degrade the tetrachloroethene by reductive dechlorination. The goal of the work presented in this report was to observe temporary and sustained changes to the ground-water chemistry downgradient from the PRBs. A hydraulic-fracturing method involving injection of the granular iron with a guar-biopolymer and enzyme slurry was used to install the parallel 30- to 33-foot-wide wall-shaped barriers at a depth of 82 to 113 feet below land surface. An acetic acid and enzyme mixture was subsequently injected in wells near the barriers to degrade the guar biopolymer. Prior to the emplacement, tetrachloroethene concentrations in the Chemical Spill-10 plume at the study area were as high as 250 micrograms per liter. Other water properties in the plume generally were similar to the properties of uncontaminated ground water in the area, which typically has dissolved oxygen concentrations of 250 to 375 micromoles per liter, pH of 5.5 to 6.0, and specific conductance of 60 to 90 microsiemens per centimeter. Water-quality samples were collected periodically from monitoring wells near the PRBs to determine how the emplacement of the granular-iron walls altered the ground-water quality. In addition, an automated well-sampling device measured temperature, specific conductance, pH, and dissolved oxygen every 1–4 days for 16 months in a well downgradient from the two parallel PRBs. Temporary increases (lasting about 5 to 6 months) in specific conductance were observed downgradient from the PRBs as a result of the sodium chloride, potassium carbonate, and other salts included in the slurry and the acetic acid and enzyme mixture that was subsequently injected to degrade the guar biopolymer. Temporary increases in the concentrations of major cations (sodium, potassium, magnesium, and calcium) were observed downgradient from the PRBs, as were temporary but substantial increases in the dissolved and total organic carbon concentrations. Methane was detected, sulfate concentrations decreased temporarily, and concentrations of dissolved inorganic carbon increased in samples from wells downgradient from the PRBs. A sustained (longer than 12 months) reducing environment, in which dissolved oxygen concentrations decreased to zero, the pH increased to about 6.8, and dissolved iron concentrations increased substantially, developed as a result of the oxidation (corrosion) of the granular iron; this zone persisted at least 65 feet downgradient from the PRBs. The pH and dissolved iron concentrations increased with distance from the granular-iron walls. Concentrations of arsenic, cobalt, manganese, and phosphorus increased, and nitrate concentrations were reduced to below the detection limit downgradient from the walls. A sustained decrease of tetrachloroethene concentrations was not observed; however, reductive dechlorination products were observed at wells downgradient from the PRBs during several rounds of sampling. The emplacement of zero-valent iron in the aquifer to remove tetrachloroethene from the ground water caused changes in the water chemistry that persisted farther downgradient from the PRBs than has been observed at other sites because of the low chemical reactivity of the quartz-dominated aquifer sediments and the low ambient dissolved chemical concentrations in the ground water. The small transverse dispersion in the aquifer and the probable long-term persistence of the iron indicate that the chemically altered zone probably will extend a substantial distance downgradient from the PRBs for a substantial period of time (years); further investigation would be needed to determine this distance.

Massachusetts↗

Drought conditions in Maine, 1999-2002: A historical perspective

Hydrologic drought can be defined as reduced streamflow, declining ground-water levels, and (or) reductions in lake or reservoir levels. Monthly precipitation totals, annual 7-day low-flow surface-water recurrence intervals, and month-end ground-water levels from drought years 1999-2002 show that 1999-2002 was the driest period of hydrologic drought in more than 50 years of record in Maine. Record lows were set in all three data sets at select locations in central Maine in April 1999, and in September 2001 and 2002. Although streamflows recovered to normal levels during 2000, ground-water levels in central Maine indicate that the drought carried over through 2000 into 2001 and 2002 in some locations. In 2001, annual 7-day low flows with greater than 100-year recurrence intervals were recorded in central Maine and low flows with up to 75-year recurrence intervals were recorded in coastal areas. In 2002, annual 7-day low flows with greater than 100-year recurrence intervals were recorded at 4 of 14 stations analyzed statewide, placing it as the driest single year of hydrologic drought on record. Month-end ground-water levels at one location in central Maine indicate that the recent hydrologic drought years were the most severe in more than 50 years in that region. The period from 1947 to 1950 may have been the only comparable period of drought to the 1999-2002 period, in Maine. The 1960s drought, although extreme in the far northern and far southern regions of the State, was most exceptional for its duration from 1963 to 1969.

Maine↗

Effects of abandoned coal-mine drainage on streamflow and water quality in the Shamokin Creek Basin, Northumberland and Columbia Counties, Pennsylvania, 1999-2001

This report assesses the contaminant loading, effects to receiving streams, and possible remedial alternatives for abandoned mine drainage (AMD) within the upper Shamokin Creek Basin in east-central Pennsylvania. The upper Shamokin Creek Basin encompasses an area of 54 square miles (140 square kilometers) within the Western Middle Anthracite Field, including and upstream of the city of Shamokin. Elevated concentrations of acidity, metals, and sulfate in the AMD from flooded underground anthracite coal mines and (or) unreclaimed culm (waste rock) piles degrade the aquatic ecosystem and water quality of Shamokin Creek to its mouth and along many of its tributaries within the upper basin. Despite dilution by unpolluted streams that more than doubles the streamflow of Shamokin Creek in the lower basin, AMD contamination and ecological impairment persist to its mouth on the Susquehanna River at Sunbury, 20 miles (32 kilometers) downstream from the mined area. Aquatic ecological surveys were conducted by the U.S. Geological Survey (USGS) in cooperation with Bucknell University (BU) and the Northumberland County Conservation District (NCCD) at six stream sites in October 1999 and repeated in 2000 and 2001 on Shamokin Creek below Shamokin and at Sunbury. In 1999, fish were absent from Quaker Run and Shamokin Creek upstream of its confluence with Carbon Run; however, creek chub ( Semotilus atromaculatus ) were present within three sampled reaches of Carbon Run. During 1999, 2000, and 2001, six or more species of fish were identified in Shamokin Creek below Shamokin and at Sunbury despite ph as low as 4.2 at Sunbury and elevated concentrations of dissolved iron and iron-encrusted streambeds at these sites. Data on the flow rate and chemistry for 46 AMD sources and 22 stream sites throughout the upper basin plus 1 stream site at Sunbury were collected by the USGS with assistance from BU and the Shamokin Creek Restoration Alliance (SCRA) during low base-flow conditions in August 1999 and high baseflow conditions in March 2000. The water-quality data were used to determine priority ranks of the AMD sources on the basis of loadings of iron, manganese, and aluminum and to identify possible remedial alternatives, including passive-treatment options, for consideration by water-resource managers. The ranking sequence for the top AMD sources based on the high base-flow data generally matched that based on the low base-flow data. The contaminant loadings generally increased with flow, and 10 previously identified intermittent AMD sources were not discharging during the low base-flow sampling period. The top 3 AMD sources (SR19, SR12, and SR49) on the basis of dissolved metals loading in March 2000 accounted for more than 50 percent of the metals loading to Shamokin Creek, whereas the top 15 AMD sources accounted for more than 98 percent of the metals loading. When sampled in March 2000, these AMD sources had flow rates ranging from 0.7 to 19 cubic feet per second (1,138 to 32,285 liters per minute) and pH from 3.5 to 6.4 standard units. Only 1 of the top 15 AMD sources (SR21) was net alkaline (alkalinity > acidity); the others were net acidic and will require additional alkalinity to facilitate metals removal and maintain near-neutral pH. For the top 15 AMD sources, dissolved iron was the principal source of acidity and metals loading; concentrations of iron ranged from 3.7 to 57 milligrams per liter. Dissolved manganese ranged from 1.8 to 7.1 milligrams per liter. Dissolved aluminum exceeded 3.8 milligrams per liter at six of the sites but was less than 0.2 milligram per liter at six others. Alkalinity can be acquired by the dissolution of limestone and (or) bacterial sulfate reduction within various passive-treatment systems including anoxic or oxic limestone drains, limestone- lined channels, or compost wetlands. Subsequently, the gradual oxidation and consequent precipitation of iron and manganese can be accommodated within settling ponds or aerobic wetlands. Assuming an iron removal rate of 180 pounds per acre per day (20 grams per square meter per day), constructed treatment wetlands at the top 15 AMD sites would require a minimum area ranging from 0.1 to 17.8 acres (405 to 71,670 square meters). Implementation of passive treatment would not be feasible at most of the top 15 and many lower priority AMD sites considering the proximity of many discharges to streams, roads, or railroads, and the limited availability or access to land at the discharge location. The reduction of infiltration and removal of culm waste and (or) the relocation of the discharge to nearby areas could decrease the AMD quantities and facilitate treatment at some of the priority AMD sites.

Water-Resources Investigations Report↗

Source and Movement of Ground Water in the Western Part of the Mojave Desert, Southern California, USA

Delta oxygen-18 and delta deuterium composition of precipitation and water from wells in the Mojave River and the Morongo ground-water basins in the western part of the Mojave Desert show that ground-water recharge occurs primarily from winter precipitation near low-altitude passes in the San Bernardino and the San Gabriel Mountains?as opposed to runoff from higher altitudes in the mountains. The resulting deuterium composition of the ground water, about -64 per mil, contrasts sharply with the isotopic composition of water from wells recharged by runoff from higher altitudes of the San Gabriel and the San Bernardino Mountains, about -84 per mil. These differences define the 3-dimensional movement of ground water between aquifers especially downgradient from faults that act as barriers to ground-water flow. Water recharged from runoff in the mountains farther to the east in the Mojave Desert plots to the right of the meteoric water line and after accounting for evaporative effects had an isotopic composition lighter than present-day precipitation.

Water-Resources Investigations Report↗

Movement and Age of Ground Water in the Western Part of the Mojave Desert, Southern California, USA

Tritium and carbon-14 data in water from wells in the Mojave River and the Morongo ground-water basins in the western part of the Mojave Desert show recent recharge focused in the floodplain aquifer along the Mojave River. Older ground water was present in parts of the regional aquifer that surround and underlie the floodplain aquifer. Movement of water between the floodplain and the regional aquifers occurs near on the upgradient side of faults as water from the regional aquifer discharges to the floodplain aquifer and on the downgradient side of the faults where water from the floodplain aquifer recharges the regional aquifer. On the basis of carbon-14 ages, corrected for mineralogic reactions with aquifer materials, water from some wells was recharged more than 20,000 years ago. Geochemical data show ground-water recharge has gradually decreased as the climate changed since that time.

Water-Resources Investigations Report↗

Occurrence of arsenic in ground water of Suffolk County, New York, 1997-2002

Water-quality data from public and private drinking-water supply wells that were sampled from October 1997 through March 2001 in Suffolk County, New York were evaluated to define the occurrence and concentrations of arsenic throughout the county. The data bases of the Suffolk County Water Authority (SCWA) and the Suffolk County Department of Health Services (SCDHS) included 14 wells at which arsenic concentrations approached or exceeded the 2002 U.S. Environmental Protection Agency (USEPA) drinking-water guideline of 10 micrograms per liter (µg/L). As a followup, 19 wells were sampled from June through August 2002; 7 were wells previously reported to have had high arsenic concentrations; 7 were near other wells reported to have high concentrations, and the remaining 5 were in areas where detectable concentrations of arsenic were suspected. Arsenic concentrations near 10 µg/L were detected at only 2 of the 19 wells sampled; arsenic concentrations in samples from the remaining 17 wells were reported as less than the USGS Central Laboratory reporting limits of 2 µg/L or 4 µg/L. The elevated concentrations previously reported (1997 through 2001) for at least three of the wells were due to incompletely flushed carbon filters in the supply-well system or were typographical errors. A decrease in arsenic concentration was indicated at six of the seven resampled wells; no reasons are apparent. Arsenic concentrations in ground water that exceed drinking-water guidelines were found only at one site. On the basis of limited sampling data available for this study, the concentrations of arsenic above drinking-water standards (10 µg/L) do not appear to indicate a countywide problem with regards to arsenic concentrations in ground water.

New York↗

Summary of available state ambient stream-water-quality data, 1990-98, and limitations for national assessment

The investigation described in this report summarized data from State ambient stream-water-quality monitoring sites for 10 water-quality constituents or measurements (suspended solids, fecal coliform bacteria, ammonia as nitrogen, nitrite plus nitrate as nitrogen, total phosphorus, total arsenic, dissolved solids, chloride, sulfate, and pH). These 10 water-quality constituents or measurements commonly are listed nationally as major contributors to degradation of surface water. Water-quality data were limited to that electronically accessible from the U.S. Environmental Protection Agency Storage and Retrieval System (STORET), the U.S. Geological Survey National Water Information System (NWIS), or individual State databases. Forty-two States had ambient stream-water-quality data electronically accessible for some or all of the constituents or measurements summarized during this investigation. Ambient in this report refers to data collected for the purpose of evaluating stream ecosystems in relation to human health, environmental and ecological conditions, and designated uses. Generally, data were from monitoring sites assessed for State 305(b) reports. Comparisons of monitoring data among States are problematic for several reasons, including differences in the basic spatial design of monitoring networks; water-quality constituents for which samples are analyzed; water-quality criteria to which constituent concentrations are compared; quantity and comprehensiveness of water-quality data; sample collection, processing, and handling; analytical methods; temporal variability in sample collection; and quality-assurance practices. Large differences among the States in number of monitoring sites precluded a general assumption that statewide water-quality conditions were represented by data from these sites. Furthermore, data from individual monitoring sites may not represent water-quality conditions at the sites because sampling conditions and protocols are unknown. Because of these factors, a high level of uncertainty exists in a national assessment of water quality. The purpose of this report is to present a summary of electronically available State ambient stream-water-quality data for 10 selected constituents and measurements from monitoring sites with nine or more analyses for 199098 and to discuss limitations for use of the data for national assessment. These analyses were statistiscally summarized by monitoring site and State, and the results presented in tabular format. Most of the selected constituents or measurements have U.S. Environmental Protection Agency criteria or guidelines for aquatic-life or drinking-water purposes. A significant finding of this investigation is that for a large percentage of monitoring sites in the Nation, there are insufficient data to meet U.S. Environmental Protection Agency recommendations for determining if water-quality conditions are degraded and for making informed decisions regarding total maximum daily loads.

Water-Resources Investigations Report↗

Surface-Water, Water-Quality, and Ground-Water Assessment of the Municipio of Mayaguez, Puerto Rico, 1999-2002

The surface-water assessment portion of this study focused on analysis of low-flow characteristics in local streams and rivers, because the supply of safe drinking water was a critical issue during recent dry periods. Low-flow characteristics were evaluated at one continuous-record gaging station based on graphical curve-fitting techniques and log-Pearson Type III frequency curves. Estimates of low-flow characteristics for 20 partial-record stations were generated using graphical-correlation techniques. Flow-duration characteristics for the continuous- and partial-record stations were estimated using the relation curves developed for the low-flow study. Stream low-flow statistics document the general hydrology under current land use, water-use, and climatic conditions. A survey of streams and rivers utilized 37 sampling stations to evaluate the sanitary quality of about 165 miles of stream channels. River and stream samples for fecal coliform and fecal streptococcus analyses were collected on two occasions at base-flow conditions. Bacteriological analyses indicate that a significant portion of the stream reaches within the municipio of Mayaguez may have fecal coliform bacteria concentrations above the water-quality goal (standard) established by the Puerto Rico Environmental Quality Board (Junta de Calidad Ambiental de Puerto Rico) for inland surface waters. Sources of fecal contamination may include: illegal discharge of sewage to storm-water drains, malfunctioning sanitary sewer ejectors, clogged and leaking sewage pipes, septic tank leakage, unfenced livestock, and runoff from livestock pens. Long-term fecal coliform data from five sampling stations located within or in the vicinity of the municipio of Mayaguez have been in compliance with the water-quality goal for fecal coliform concentration established in July 1990. Geologic, topographic, soil, hydrogeologic, and streamflow data were compiled into a database and used to divide the municipio of Mayaguez into five hydrogeologic terranes. This integrated database then was used to evaluate the ground-water potential of each hydrogeologic terrane. Lineament-trace analysis was used to help assess the ground-water development potential in the hydrogeologic terranes containing igneous rocks. Analyses suggest that areas with slopes greater than 15 degrees have relatively low ground-water development potential. The presence of fractures, independent of the topographic slope, may locally enhance the water-bearing properties in the hydrogeologic terranes containing igneous rocks. The results of this study indicate that induced streamflow generally is needed to sustain low to moderate ground-water withdrawal rates in the five hydrogeologic terranes. The ground-water flow systems in the hydrogeologic terranes are only able to sustain small withdrawal rates that rarely exceed 50 gallons per minute. Areas with a high density of fractures, as could be the case at the intersection of lineament traces in the upper parts of the Rio Ca?as and Rio Yaguez watersheds, are worthy of exploratory drilling for ground-water development.

Water-Resources Investigations Report↗

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Determination of polycyclic aromatic hydrocarbon compounds in sediment by gas chromatography/mass spectrometry

A method for the determination of 28 polycyclic aromatic hydrocarbons (PAHs) and 25 alkylated PAH homolog groups in sediment samples is described. The compounds are extracted from sediment by solvent extraction, followed by partial isolation using high-performance gel permeation chromatography. The compounds are identified and uantitated using capillary-column gas chromatography/mass spectrometry. The report presents performance data for full-scan ion monitoring. Method detection limits in laboratory reagent matrix samples range from 1.3 to 5.1 micrograms per kilogram for the 28 PAHs. The 25 groups of alkylated PAHs are homologs of five groups of isomeric parent PAHs. Because of the lack of authentic standards, these homologs are reported semiquantitatively using a response factor from a parent PAH or a specific alkylated PAH. Precision data for the alkylated PAH homologs are presented using two different standard reference manuals produced by the National Institute of Standards and Technology: SRM 1941b and SRM 1944. The percent relative standard deviations for identified alkylated PAH homolog groups ranged from 1.55 to 6.98 for SRM 1941b and from 6.11 to 12.0 for SRM 1944. Homolog group concentrations reported under this method include the concentrations of individually identified compounds that are members of the group. Organochlorine (OC) pesticides--including toxaphene, polychlorinated biphenyls (PCBs), and organophosphate (OP) pesticides--can be isolated simultaneously using this method. In brief, sediment samples are centrifuged to remove excess water and extracted overnight with dichloromethan (95 percent) and methanol (5 percent). The extract is concentrated and then filtered through a 0.2-micrometer polytetrafluoroethylene syringe filter. The PAH fraction is isolated by quantitatively injecting an aliquot of sample onto two polystyrene-divinylbenzene gel-permeation chromatographic columns connected in series. The compounds are eluted with dichloromethane, a PAH fraction is collected, and a portion of the coextracted interferences, including elemental sulfur, is separated and discarded. The extract is solvent exchanged, the volume is reduced, and internal standard is added. Sample analysis is completed using a gas chromatograph/mass spectrometer and full-scan acquisition.

Water-Resources Investigations Report↗

Delineation of Areas Contributing Water to the Dry Brook Public-Supply Well, South Hadley, Massachusetts

Areas contributing water to the Dry Brook public-supply well in South Hadley, Massachusetts, were delineated with a numerical ground-water-flow model that is based on geologic and hydrologic information for the confined sand and gravel aquifer pumped by the supply well. The study area is along the Connecticut River in central Massachusetts, about 12 miles north of Springfield, Massachusetts. Geologic units in the study area consist of Mesozoic-aged sedimentary and igneous bedrock, late-Pleistocene glaciolacustrine sediments, and recent alluvial deposits of the Connecticut River flood plain. Dry Brook Hill, immediately south of the supply well, is a large subaqueous lacustrine fan and delta formed during the last glacial retreat by sediment deposition into glacial Lake Hitchcock from a meltwater tunnel that was likely near where the Connecticut River cuts through the Holyoke Range. The sediments that compose the aquifer grade from very coarse sand and gravel along the northern flank of the hill, to medium sands in the body of the hill, and to finer-grained sediments along the southern flank of the hill. The interbedded and overlapping fine-grained lacustrine sediments associated with Dry Brook Hill include varved silt and clay deposits. These fine-grained sediments form a confining bed above the coarse-grained aquifer at the supply well and partially extend under the Connecticut River adjacent to the supply well. Ground-water flow in the aquifer supplying water to Dry Brook well was simulated with the U.S. Geological Survey ground-water-flow modeling code MODFLOW. The Dry Brook aquifer model was calibrated to drawdown data collected from 8 observation wells during an aquifer test conducted by pumping the supply well for 10 days at a rate of 122.2 cubic feet per minute (ft3/min; 914 gallons per minute) and to water levels collected from observation wells across the study area. Generally, the largest hydraulic conductivity values used in the model were in the sand and gravel aquifer near the Dry Brook well, which is consistent with the geologic information. Results of aquifer-test simulation indicated that spatially variable aquifer hydraulic properties and boundary conditions affected heads and ground-water flow near the well. A comparison and analysis of water-level fluctuations in study area wells to fluctuations in the Connecticut River indicated a hydraulic connection of the aquifer with the river, which is also consistent with geologic information. Simulated ground-water levels indicated that most ground water in the study area flowed toward and discharged to the Connecticut River and the Dry Brook well. Small amounts of ground water also discharged to smaller streams (Dry Brook and Bachelor Brook) in the study area. Areas contributing water to the well were delineated with the MODPATH particle-tracking routine. Results of the contributing-area analysis indicated that the greatest sources of water to the well were recharge in the Dry Brook Hill area and infiltration of Connecticut River water in an area beyond the extent of the confining bed where the aquifer is in hydraulic connection with the river. The amount of water entering the Dry Brook well from recharge dominated at a lower pumping rate (40.0 ft3/min); about 90 percent of the pumped water originated from recharge and boundary flow, and infiltration from the Connecticut River supplied the remaining 10 percent. At a high pumping rate (122.2 ft3/min), however, about half of the water pumped from the Dry Brook well originated from recharge and boundary flow (49 percent), and half originated from infiltration of water from the Connecticut River (51 percent). Results of a sensitivity analysis of the extent of areas contributing water to the Dry Brook well when pumped at 122.2 ft3/min indicated that the size of these areas did not substantially change when aquifer properties were varied. In contrast, however, the size of these areas changed most when the recharge

Water-Resources Investigations Report↗

Secondary Mineral Deposits and Evidence of Past Seismicity and Heating of the Proposed Repository Horizon at Yucca Mountain, Nevada

The Drift Degradation Analysis (DDA) (BSC, 2003) for the proposed high-level radioactive waste repository at Yucca Mountain, Nevada, describes model simulations of the effects of pre- and post-closure seismicity and waste-induced heating on emplacement drifts. Based on probabilistic seismic hazard analyses of the intensity and frequency of future seismic events in the region (CRWMS M&O, 1998), the DDA concludes that future seismicity will lead to substantial damage to emplacement drifts, particularly those in the lithophysal tuffs, where some simulations predict complete collapse of the drift walls. Secondary mineral studies conducted by the U.S. Geological Survey since 1995 indicate that secondary calcite and silica have been deposited in some fractures and lithophysal cavities in the unsaturated zone (UZ) at Yucca Mountain during at least the past 10 million years (m.y.), and probably since the tuffs cooled to less than 100?C. Tuff fragments, likely generated by past seismic activity, have commonly been incorporated into the secondary mineral depositional sequences. Preliminary observations indicate that seismic activity has generated few, if any, tuff fragments during the last 2 to 4 m.y., which may be inconsistent with the predictions of drift-wall collapse described in the DDA. Whether or not seismicity-induced tuff fragmentation occurring at centimeter to decimeter scales in the fracture and cavity openings relates directly to failure of tuff walls in the 5.5-m-diameter waste emplacement drifts, the deposits do provide a potential record of the spatial and temporal distribution of tuff fragments in the UZ. In addition, the preservation of weakly attached coatings and (or) delicate, upright blades of calcite in the secondary mineral deposits provides an upper limit for ground motion during the late stage of deposition that might be used as input to future DDA simulations. Finally, bleaching and alteration at a few of the secondary mineral sites indicate that they were subjected to heated gases at approximately the temperatures expected from waste emplacement. These deposits provide at least limited textural and mineralogic analogs for waste-induced, high-humidity thermal alteration of emplacement drift wall rocks.

Water-Resources Investigations Report↗

Simulated effects of ground-water augmentation on the hydrology of Round and Halfmoon Lakes in northwestern Hillsborough County, Florida

Pumpage from the Upper Floridan aquifer in northwest Hillsborough County near Tampa, Florida, has induced downward leakage from the overlying surficial aquifer and lowered the water table in many areas. Leakage is highest where the confining layer separating the aquifers is breached, which is common beneath many of the lakes in the study area. Leakage of water to the Upper Floridan aquifer has lowered the water level in many lakes and drained many wetlands. Ground water from the Upper Floridan aquifer has been added (augmented) to some lakes in an effort to maintain lake levels, but the resulting lake-water chemistry and lake leakage patterns are substantially different from those of natural lakes. Changes in lake-water chemistry can cause changes in lake flora, fauna, and lake sediment composition, and large volumes of lake leakage are suspected to enhance the formation of sinkholes near the shoreline of augmented lakes. The leakage rate of lake water through the surficial aquifer to the Upper Floridan aquifer was estimated in this study using ground-water-flow models developed for an augmented lake (Round Lake) and non-augmented lake (Halfmoon Lake). Flow models developed with MODFLOW were calibrated through nonlinear regression with UCODE to measured water levels and monthly net ground-water-flow rates from the lakes estimated from lake-water budgets. Monthly estimates of ground-water recharge were computed using an unsaturated flow model (LEACHM) that simulated daily changes in storage of water in the soil profile, thus estimating recharge as drainage to the water table. Aquifer properties in the Round Lake model were estimated through transient-state simulations using two sets of monthly recharge rates computed during July 1996 to February 1999, which spanned both average conditions (July 1996 through October 1997), and an El Niño event (November 1997 through September 1998) when the recharge rate doubled. Aquifer properties in the Halfmoon Lake model were estimated through steady-state simulations of average conditions in July 1996. Simulated hydrographs computed by the Round and Halfmoon Lake models closely matched measured water-level fluctuations, except during El Niño, when the Halfmoon Lake model was unable to accurately reproduce water levels. Possibly, potential recharge during El Niño was diverted through ground-water-flow outlets that were not represented in the Halfmoon Lake model, or a large part of the rainfall was diverted into runoff before it could become recharge. Solute transport simulations with MT3D indicate that leakage of lake water extended 250 to 400 feet into the surficial aquifer around Round Lake, and from 75 to 150 feet around Halfmoon Lake before flowing to the underlying Upper Floridan aquifer. These results are in agreement with concentrations of stable isotopes of oxygen-18 (d18O) and deuterium (dD) in the surficial aquifer. Schedules of monthly augmentation rates to maintain constant stages in Round and Halfmoon Lakes were computed using an equation that accounted for changes in the Upper Floridan aquifer head and the deviation from the mean recharge rate. Resulting lake stages were nearly constant during the first half of the study, but increased above target lake stages during El Niño; modifying the computation of augmentation rates to account for the higher recharge rate during El Niño resulted in lake stages that were closer to the target lake stage. Substantially more lake leakage flows to the Upper Floridan aquifer from Round Lake than from Halfmoon Lake, because the estimated vertical hydraulic conductivities of lake and confining layer sediments and breaches in the confining layer beneath Round Lake are much greater. Augmentation rates required to maintain the low guidance stages in Round Lake (53 feet) and Halfmoon Lake (42 feet) under average Upper Floridan aquifer heads are estimated as 33,850 cubic feet per day and 1,330 to 10,000 cubic feet per day, respectively. These rates equate to 26 inches per month of water applied to the entire surface of Round Lake and 0.34 to 2.5 inches per month of water applied to Halfmoon Lake.

Florida↗

Hydrologic Effects of the 1988 Galena Fire, Black Hills Area, South Dakota

The Galena Fire burned about 16,788 acres of primarily ponderosa pine forest during July 5-8, 1988, in the Black Hills area of South Dakota. The fire burned primarily within the Grace Coolidge Creek drainage basin and almost entirely within the boundaries of Custer State Park. A U.S. Geological Survey gaging station with streamflow records dating back to 1977 was located along Grace Coolidge Creek within the burned area. About one-half of the gaging station's 26.8-square-mile drainage area was burned. The drainage basin for Bear Gulch, which is tributary to Grace Coolidge Creek, was burned particularly severely, with complete deforestation occurring in nearly the entirety of the area upstream from a gaging station that was installed in 1989. A study to evaluate effects of the Galena Fire on streamflow, geomorphology, and water quality was initiated in 1988. The geomorphologic and water-quality components of the study were completed by 1990 and are summarized in this report. A data-collection network consisting of streamflow- and precipitation-gaging stations was operated through water year 1998 for evaluation of effects on streamflow characteristics, including both annual-yield and peak-flow characteristics, which are the main focus of this report. Moderately burned areas did not experience a substantial increase in the rate of surface erosion; however, severely burned areas underwent surficial erosion nearly twice that of the unburned areas. The sediment production rate of Bear Gulch estimated 8 to 14 months after the fire was 870 ft3/acre (44 tons/acre). Substantial degradation of stream channels within the severely burned headwater areas of Bear Gulch was documented. Farther downstream, channel aggradation resulted from deposition of sediments transported from the headwater areas. The most notable water-quality effect was on concentrations of suspended sediment, which were orders of magnitude higher for Bear Gulch than for the unburned control area. Effects on several other water-quality constituents, such as organic carbon and nitrogen and phosphorus nutrient constituents, probably were influenced by the large concentrations of suspended matter that were documented in initial post-fire, storm-flow events. The first post-fire stormflow produced the highest measured concentrations of specific conductance, nitrogen, phosphorus, organic carbon, calcium, magnesium, potassium, manganese, and sulfate in the burned areas. For most constituents sampled, differences in concentrations between burned and unburned areas were no longer discernible within about 1 year following the Galena Fire. The effects of the Galena Fire on annual-yield characteristics of Grace Coolidge Creek were evaluated primarily from comparisons with long-term streamflow records for Battle Creek, which is hydrogeologically similar and is located immediately to the north. Annual yield for Grace Coolidge Creek increased by about 20 percent as a result of the fire. This estimate was based on relations between annual yield for Grace Coolidge Creek and Battle Creek for pre- and post-burn periods. Many of the post-burn data points are well beyond the range of the pre-burn data, which is a source of uncertainty for this estimate. Substantial increases in peak-flow characteristics for severely burned drainages were visually apparent from numerous post-fire field observations. Various analyses of streamflow data indicated substantial increases in peak-flow response for burned drainage areas; however, quantification of effects was particularly difficult because peak-flow response diminished quickly and returned to a generally pre-burn condition by about 1991. Field observations of vegetation and analysis of remotely sensed data indicated that establishment of grasses and forbs occurred within a similar timeframe. Comparison of pre-fire peak flows to post-1991 peak flows indicates that these grasses and forbs were equally effective in suppressing peak flows

Water-Resources Investigations Report↗

Characterization of channel substrate, and changes in suspended-sediment transport and channel geometry in white sturgeon spawning habitat in the Kootenai River near Bonners Ferry, Idaho, following the closure of Libby Dam

Many local, State, and Federal agencies have concerns over the declining population of white sturgeon (Acipenser transmontanus) in the Kootenai River and the possible effects of the closure and subsequent operation of Libby Dam in 1972. In 1994, the Kootenai River white sturgeon was listed as an Endangered Species. A year-long field study was conducted in cooperation with the Kootenai Tribe of Idaho along a 21.7-kilometer reach of the Kootenai River including the white sturgeon spawning reach near Bonners Ferry, Idaho, approximately 111 to 129 kilometers below Libby Dam. During the field study, data were collected in order to map the channel substrate in the white sturgeon spawning reach. These data include seismic subbottom profiles at 18 cross sections of the river and sediment cores taken at or near the seismic cross sections. The effect that Libby Dam has on the Kootenai River white sturgeon spawning substrate was analyzed in terms of changes in suspended-sediment transport, aggradation and degradation of channel bed, and changes in the particle size of bed material with depth below the riverbed. The annual suspended-sediment load leaving the Kootenai River white sturgeon spawning reach decreased dramatically after the closure of Libby Dam in 1972: mean annual pre-Libby Dam load during 1966–71 was 1,743,900 metric tons, and the dam-era load during 1973–83 was 287,500 metric tons. The amount of sand-size particles in three suspended-sediment samples collected at Copeland, Idaho, 159 kilometers below Libby Dam, during spring and early summer high flows after the closure of Libby Dam is less than in four samples collected during the pre-Libby Dam era. The supply of sand to the spawning reach is currently less due to the reduction of high flows and a loss of 70 percent of the basin after the closure of Libby Dam. The river's reduced capacity to transport sand out of the spawning reach is compensated to an unknown extent by a reduced load of sand entering the spawning reach. Since the closure of Libby Dam, the most notable change in channel geometry at the Copeland streamflow gaging station was the initiation of cyclical aggradation and degradation of the riverbed in the center of the channel. The aggradation and degradation of the riverbed are reflected in a twofold increase, from 1.3 to 2.5 meters, in the fluctuation of the minimum riverbed elevation, which suggests that during the Libby Dam era, parts of the riverbed in the spawning reach may have aggraded or degraded by as much as 2.5 meters. Before the closure of Libby Dam, there was a greater propensity for aggradation and degradation of sand over the discontinuous gravel and cobble layers in the buried gravelcobble reach at Bonners Ferry. The gravel and cobble in this reach, 111.3 to 115.9 kilometers below Libby Dam, are buried by sand. Unregulated spring snowmelt-runoff flows flushed part of the sand layer and exposed some of the buried gravel-cobble layer because streamflow velocities were higher at that time. Unregulated autumn-winter base flows gradually deposited silt and sand and reestablished a sand layer, burying the gravel-cobble layer. This cyclical process of aggradation and degradation of the riverbed sediment is reflected in the alternating gravel-cobble layers and sand layers found in sediment core K18-TH taken as part of this project. White sturgeon spawning substrate in the Kootenai River meander reach is currently composed of alluvial sand that forms sand dunes and of minor amounts of lacustrine clay and silt that generally are found in the river's thalweg. The present substrate composition in the meander reach is considered similar to that which existed prior to closure of Libby Dam, with one possible exception. Prior to closure of Libby Dam, minor amounts of gravel and cobble may have been exposed on the riverbed in the spawning reach just below the mouth of Myrtle Creek 230 kilometers below Libby Dam. The substrate composition near Shorty Island, 234 kilometers below Libby Dam, a notable white sturgeon spawning reach, is predominantly sand and is similar to that which existed prior to closure of Libby Dam.

Idaho;Montana↗