Pesticide and Transformation Product Detections and Age‐Dating Relations from Till and Sand Deposits1

Abstract:  Pesticide and transformation product concentrations and frequencies in ground water from areas of similar crop and pesticide applications may vary substantially with differing lithologies. Pesticide analysis data for atrazine, metolachlor, alachlor, acetochlor, and cyanazine and their pesticide transformation products were collected at 69 monitoring wells in Illinois and northern Indiana to document occurrence of pesticides and their transformation products in two agricultural areas of differing lithologies, till, and sand. The till is primarily tile drained and has preferential fractured flow, whereas the sand primarily has surface water drainage and primary porosity flow. Transformation products represent most of the agricultural pesticides in ground water regardless of aquifer material – till or sand. Transformation products were detected more frequently than parent pesticides in both the till and sand, with metolachlor ethane sulfonic acid being most frequently detected. Estimated ground‐water recharge dates for the sand were based on chlorofluorocarbon analyses. These age‐dating data indicate that ground water recharged prior to 1990 is more likely to have a detection of a pesticide or pesticide transformation product. Detections were twice as frequent in ground water recharged prior to 1990 (82%) than in ground water recharged on or after 1990 (33%). The highest concentrations of atrazine, alachlor, metolachlor, and their transformation products, also were detected in samples from ground water recharged prior to 1990. These age/pesticide detection relations are opposite of what would normally be expected, and may be the result of preferential flow and/or ground‐water mixing between aquifers and aquitards as evident by the detection of acetochlor transformation products in samples with estimated ground‐water ages predating initial pesticide application.     

Effects of Groundwater-Flow Paths On Nitrate Concentrations Across Two Riparian Forest Corridors1

Speiran, Gary K., 2010. Effects of Groundwater-Flow Paths on Nitrate Concentrations Across Two Riparian Forest Corridors. Journal of the American Water Resources Association (JAWRA) 46(2):246-260. DOI: 10.1111/j.1752-1688.2010.00427.x Abstract: Groundwater levels, apparent age, and chemistry from field sites and groundwater-flow modeling of hypothetical aquifers collectively indicate that groundwater-flow paths contribute to differences in nitrate concentrations across riparian corridors. At sites in Virginia (one coastal and one Piedmont), lowland forested wetlands separate upland fields from nearby surface waters (an estuary and a stream). At the coastal site, nitrate concentrations near the water table decreased from more than 10 mg/l beneath fields to 2 mg/l beneath a riparian forest buffer because recharge through the buffer forced water with concentrations greater than 5 mg/l to flow deeper beneath the buffer. Diurnal changes in groundwater levels up to 0.25 meters at the coastal site reflect flow from the water table into unsaturated soil where roots remove water and nitrate dissolved in it. Decreases in aquifer thickness caused by declines in the water table and decreases in horizontal hydraulic gradients from the uplands to the wetlands indicate that more than 95% of the groundwater discharged to the wetlands. Such discharge through organic soil can reduce nitrate concentrations by denitrification. Model simulations are consistent with field results, showing downward flow approaching toe slopes and surface waters to which groundwater discharges. These effects show the importance of buffer placement over use of fixed-width, streamside buffers to control nitrate concentrations.     

Ground water stratification and delivery of nitrate to an incised stream under varying flow conditions

Ground water processes affecting seasonal variations of surface water nitrate concentrations were investigated in an incised first-order stream in an agricultural watershed with a riparian forest in the coastal plain of Maryland. Aquifer characteristics including sediment stratigraphy, geochemistry, and hydraulic properties were examined in combination with chemical and isotopic analyses of ground water, macropore discharge, and stream water. The ground water flow system exhibits vertical stratification of hydraulic properties and redox conditions, with sub-horizontal boundaries that extend beneath the field and adjacent riparian forest. Below the minimum water table position, ground water age gradients indicate low recharge rates (2-5 cm yr(-1)) and long residence times (years to decades), whereas the transient ground water wedge between the maximum and minimum water table positions has a relatively short residence time (months to years), partly because of an upward increase in hydraulic conductivity. Oxygen reduction and denitrification in recharging ground waters are coupled with pyrite oxidation near the minimum water table elevation in a mottled weathering zone in Tertiary marine glauconitic sediments. The incised stream had high nitrate concentrations during high flow conditions when much of the ground water was transmitted rapidly across the riparian zone in a shallow oxic aquifer wedge with abundant outflow macropores, and low nitrate concentrations during low flow conditions when the oxic wedge was smaller and stream discharge was dominated by upwelling from the deeper denitrified parts of the aquifer. Results from this and similar studies illustrate the importance of near-stream geomorphology and subsurface geology as controls of riparian zone function and delivery of nitrate to streams in agricultural watersheds.     

Transport and fate of nitrate and pesticides: hydrogeology and riparian zone processes

There is continuing concern over potential impacts of widespread application of nutrients and pesticides on ground- and surface-water quality. Transport and fate of nitrate and pesticides were investigated in a shallow aquifer and adjacent stream, Cow Castle Creek, in Orangeburg County, South Carolina. Pesticide and pesticide degradate concentrations were detected in ground water with greatest frequency and largest concentrations directly beneath and downgradient from the corn (Zea mays L.) field where they were applied. In almost all samples in which they were detected, concentrations of pesticide degradates greatly exceeded those of parent compounds, and were still present in ground waters that were recharged during the previous 18 yr. The absence of both parent and degradate compounds in samples collected from deeper in the aquifer suggests that this persistence is limited or that the ground water had recharged before use of the pesticide. Concentrations of NO(-)(3) in ground water decreased with increasing depth and age, but denitrification was not a dominant controlling factor. Hydrologic and chemical data indicated that ground water discharges to the creek and chemical exchange takes place within the upper 0.7 m of the streambed. Ground water had its greatest influence on surface-water chemistry during low-flow periods, causing a decrease in concentrations of Cl(-), NO(-)(3), pesticides, and pesticide degradates. Conversely, shallow subsurface drainage dominates stream chemistry during high-flow periods, increasing stream concentrations of Cl(-), NO(-)(3), pesticides, and pesticide degradates. These results point out the importance of understanding the hydrogeologic setting when investigating transport and fate of contaminants in ground water and surface water.     

Changes in Shallow Groundwater Quality Beneath Recently Urbanized Areas in the Memphis,Tennessee Area1

Barlow, Jeannie R.B., James A. Kingsbury, and Richard H. Coupe, 2012. Changes in Shallow Groundwater Quality Beneath Recently Urbanized Areas in the Memphis, Tennessee Area. Journal of the American Water Resources Association (JAWRA) 48(2): 336‐354. DOI: 10.1111/j.1752‐1688.2011.00616.x Abstract: Memphis, the largest city in the state of Tennessee, and its surrounding suburbs depend on a confined aquifer, the Memphis aquifer, for drinking water. Concern over the potential for downward movement of water from an overlying shallow aquifer to the underlying Memphis aquifer provided impetus for monitoring groundwater quality within the shallow aquifer. The occurrence of volatile organic compounds (VOCs), nitrate, and pesticides in samples from the shallow well network indicate a widespread affect on water quality from the overlying urban land use. Total pesticide concentration was generally higher in more recently recharged groundwater indicating that as the proportion of recent water increases, the occurrence of pesticides related to the current urban land use also increases. Groundwater samples with nitrate concentrations greater than 1.5 mg/l and detectable concentrations of the pesticides atrazine and simazine also had higher concentrations of chloroform, a VOC primarily associated with urban land use, than in other samples. The age of the water from these wells indicates that these concentrations are most likely not representative of past agricultural use, but of more recent urban use of these chemicals. Given that the median age of water represented by the shallow well network was 21 years, a lag time likely exists between changes in land use and the occurrence of constituents related to urbanization in shallow groundwater.     

Physical and Temporal Isolation of Mountain Headwater Streams in the Western Mojave Desert,Southern California1

Abstract: Streams draining mountain headwater areas of the western Mojave Desert are commonly physically isolated from downstream hydrologic systems such as springs, playa lakes, wetlands, or larger streams and rivers by stream reaches that are dry much of the time. The physical isolation of surface flow in these streams may be broken for brief periods after rainfall or snowmelt when runoff is sufficient to allow flow along the entire stream reach. Despite the physical isolation of surface flow in these streams, they are an integral part of the hydrologic cycle. Water infiltrated from headwater streams moves through the unsaturated zone to recharge the underlying ground‐water system and eventually discharges to support springs, streamflow, isolated wetlands, or native vegetation. Water movement through thick unsaturated zones may require several hundred years and subsequent movement through the underlying ground‐water systems may require many thousands of years – contributing to the temporal isolation of mountain headwater streams.     

RESIDENCE TIME OF WATER DISCHARGING FROM THE HANGING GARDENS OF ZION PARK1

ABSTRACT: The Hanging Gardens are a unique feature of Zion National Park. Knowledge of the source and residence time of water discharging from the Hanging Gardens is necessary to help preserve these features. Ground-water chemical and isotopic data distinguish the discharge from seeps and springs into two groups, one of low and one of high conductivity. Water with low conductivity likely originates as recharge near the seeps and springs, and it only interacts with the Navajo Sandstone. High conductivity water, on the other hand, originates as recharge on the tops of plateaus to the east, where it interacts with marine rocks of the Carmel Formation. Carbon dating of these ground waters indicates that the low conductivity water is essentially modern recharge, while the high conductivity water was recharged 1,000 to 4,000 years ago.     

INTERACTIONS BETWEEN GROUND WATER AND SURFACE WATER IN THE SUWANNEE RIVER BASIN,FLORIDA1

ABSTRACT: Ground water and surface water constitute a single dynamic system in most parts of the Suwannee River basin due to the presence of karst features that facilitate the interaction between the surface and subsurface. Low radon-222 concentrations (below background levels) and enriched amounts of oxygen-18 and deuterium in ground water indicate mixing with surface water in parts of the basin. Comparison of surface water and regional ground water flow patterns indicate that boundaries for ground water basins typically do not coincide with surface water drainage subbasins. There are several areas in the basin where ground water flow that originates outside of the Suwannee River basin crosses surface water basin boundaries during both low-flow and high-flow conditions. In a study area adjacent to the Suwannee River that consists predominantly of agricultural land use, 18 wells tapping the Upper Floridan aquifer and 7 springs were sampled three times during 1990 through 1994 for major dissolved inorganic constituents, trace elements, and nutrients. During a period of above normal rainfall that resulted in high river stage and high ground water levels in 1991, the combination of increased amounts of dissolved organic carbon and decreased levels of dissolved oxygen in ground water created conditions favorable for the natural reduction of nitrate by denitrification reactions in the aquifer. As a result, less nitrate was discharged by ground water to the Suwannee River.     

GEOCHEMICAL CHARACTERIZATION OF SHALLOW GROUND WATER IN THE EUTAW AQUIFER,MONTGOMERY, ALABAMA1

ABSTRACT: Ground water samples were collected from 30 wells located in, or directly down gradient from, recharge areas of the Eutaw aquifer in Montgomery, Alabama. The major ion content of the water evolves from calcium‐sodium‐chloride‐dominated type in the recharge area to calcium‐bicarbonate‐dominated type in the confined portion of the aquifer. Ground water in the recharge area was under saturated with respect to aluminosilicate and carbonate minerals. Ground water in the confined portion of the aquifer was at equilibrium levels for calcite and potassium feldspar. Dissolved oxygen and nitrite‐plus‐nitrate concentrations decreased as ground water age increased; pH, iron, and sulfate concentrations increased as ground water age increased. Aluminum, copper, and zinc concentrations decreased as ground water age and pH increased. These relations indicate that nitrate, aluminum, copper, and zinc are removed from solution as water moves from recharge areas to the confined areas of the Eutaw aquifer. The natural evolution of ground water quality, which typically increases the pH and decreases the dissolved oxygen content, may be an important limiting factor to the migration of nitrogen based compounds and metals.     

DROUGHT EFFECTS ON WATER QUALITY IN THE SOUTH PLATTE RIVER BASIN,COLORADO1

ABSTRACT: Twenty‐three stream sites representing a range of forested, agricultural, and urban land uses were sampled in the South Platte River Basin of Colorado from July through September 2002 to characterize water quality during drought conditions. With a few exceptions, dissolved ammonia, Kjeldahl nitrogen, total phosphorus, and dissolved orthophosphate concentrations were similar to seasonal historical levels in all land use areas during the drought. At some agricultural sites, decreased dilution of irrigation return flow may have contributed to higher concentrations of some nutrient species, increased primary productivity, and higher dissolved oxygen concentrations. At some urban sites, decreased dilution of base flow and wastewater treatment plant effluent may have contributed to higher dissolved nitrite‐plus‐nitrate concentrations, increased primary productivity, and higher dissolved oxygen concentrations. Total pesticide concentrations in urban and agricultural areas were not consistently higher or lower during the drought. At most forested sites, decreased dilution of ground water‐derived calcium bicarbonate type base flow likely led to elevated pH and specific‐conductance values. Water temperatures at many of the forested sites also were higher, contributing to lower dissolved oxygen concentrations during the drought.     

WALNUT CREEK WATERSHED MONITORING PROJECT,IOWA MONITORING WATER QUALITY IN RESPONSE TO PRAIRIE RESTORATION1

ABSTRACT: Land use and surface water data for nitrogen and pesticides (1995 to 1997) are reported for the Walnut Creek Watershed Monitoring Project, Jasper County Iowa. The Walnut Creek project was established in 1995 as a nonpoint source monitoring program in relation to watershed habitat restoration and agricultural management changes implemented at the Neal Smith National Wildlife Refuge by the U.S. Fish and Wildlife Service. The monitoring project utilizes a paired‐watershed approach (Walnut and Squaw creeks) as well as upstream/downstream comparisons on Walnut for analysis and tracking of trends. From 1992 to 1997, 13.4 percent of the watershed was converted from row crop to native prairie in the Walnut Creek watershed. Including another 6 percent of watershed farmed on a cash‐rent basis, land use changes have been implemented on 19.4 percent of the watershed by the USFWS. Nitrogen and pesticide applications were reduced an estimated 18 percent and 28 percent in the watershed from land use changes. Atrazine was detected most often in surface water with frequencies of detection ranging from 76–86 percent. No significant differences were noted in atrazine concentrations between Walnut and Squaw Creek. Nitrate‐N concentrations measured in both watersheds were similar; both basins showed a similar pattern of detection and an overall reduction in nitrate‐N concentrations from upstream to downstream monitoring sites. Water quality improvements are suggested by nitrate‐N and chloride ratios less than one in the Walnut Creek watershed and low nitrate‐N concentrations measured in the subbasin of Walnut Creek containing the greatest amount of land use changes. Atrazine and nitrate‐N concentrations from the lower portion of the Walnut Creek watershed (including the prairie restoration area) may be decreasing in relation to the upstream untreated component of the watershed. The frequencies of pesticide detections and mean nitrate‐N concentrations appear related to the percentage of row crop in the basins and subbasins. Although some results are encouraging, definitive water quality improvements have not been observed during the first three years of monitoring. Possible reasons include: (1) more time is needed to adequately detect changes; (2) the size of the watershed is too large to detect improvements; (3) land use changes are not located in the area of the watershed where they would have greatest effect; or (4) water quality improvements have occurred but have been missed by the project monitoring design. Longer‐term monitoring will allow better evaluation of the impact of restoration activities on water quality.     

Simulated fate and transport of metolachlor in the unsaturated zone, Maryland, USA

An unsaturated-zone transport model was used to examine the transport and fate of metolachlor applied to an agricultural site in Maryland, USA. The study site was instrumented to collect data on soil-water content, soil-water potential, ground water levels, major ions, pesticides, and nutrients from the unsaturated zone during 2002-2004. The data set was enhanced with site-specific information describing weather, soils, and agricultural practices. The Root Zone Water Quality Model was used to simulate physical, chemical, and biological processes occurring in the unsaturated zone. Model calibration to bromide tracer concentrations indicated flow occurred through the soil matrix. Simulated recharge rates were within the measured range of values. The pesticide transport model was calibrated to the intensive data collection period (2002-2004), and the calibrated model was then used to simulate the period 1984 through 2004 to examine the impact of sustained agricultural management practices on the concentrations of metolachlor and its degradates at the study site. Simulation results indicated that metolachlor degrades rapidly in the root zone but that the degradates are transported to depth in measurable quantities. Simulations indicated that degradate transport is strongly related to the duration of sustained use of metolachlor and the extent of biodegradation.     

DIN Retention‐Transport Through Four Hydrologically Connected Zones in a Headwater Catchment of the Upper Mississippi River1

Abstract: Dissolved inorganic nitrogen (DIN) retention‐transport through a headwater catchment was synthesized from studies encompassing four distinct hydrologic zones of the Shingobee River Headwaters near the origin of the Mississippi River. The hydrologic zones included: (1) hillslope ground water (ridge to bankside riparian); (2) alluvial riparian ground water; (3) ground water discharged through subchannel sediments (hyporheic zone); and (4) channel surface water. During subsurface hillslope transport through Zone 1, DIN, primarily nitrate, decreased from ～3 mg‐N/l to <0.1 mg‐N/l. Ambient seasonal nitrate:chloride ratios in hillslope flow paths indicated both dilution and biotic processing caused nitrate loss. Biologically available organic carbon controlled biotic nitrate retention during hillslope transport. In the alluvial riparian zone (Zone 2) biologically available organic carbon controlled nitrate depletion although processing of both ambient and amended nitrate was faster during the summer than winter. In the hyporheic zone (Zone 3) and stream surface water (Zone 4) DIN retention was primarily controlled by temperature. Perfusion core studies using hyporheic sediment indicated sufficient organic carbon in bed sediments to retain ground water DIN via coupled nitrification‐denitrification. Numerical simulations of seasonal hyporheic sediment nitrification‐denitrification rates from perfusion cores adequately predicted surface water ammonium but not nitrate when compared to 5 years of monthly field data (1989‐93). Mass balance studies in stream surface water indicated proportionally higher summer than winter N retention. Watershed DIN retention was effective during summer under the current land use of intermittently grazed pasture. However, more intensive land use such as row crop agriculture would decrease nitrate retention efficiency and increase loads to surface water. Understanding DIN retention capacity throughout the system, including special channel features such as sloughs, wetlands and floodplains that provide surface water‐ground water connectivity, will be required to develop effective nitrate management strategies.     

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

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

Evaluation of Three Watershed‐Scale Pesticide Environmental Transport and Fate Models1

Abstract: The U.S. Environmental Protection Agency (USEPA) Office of Pesticide Programs (OPP) has completed an evaluation of three watershed‐scale simulation models for potential use in Food Quality Protection Act pesticide drinking water exposure assessments. The evaluation may also guide OPP in identifying computer simulation tools that can be used in performing aquatic ecological exposure assessments. Models selected for evaluation were the Soil Water Assessment Tool (SWAT), the Nonpoint Source Model (NPSM), a modified version of the Hydrologic Simulation Program‐Fortran (HSPF), and the Pesticide Root Zone Model‐Riverine Water Quality (PRZM‐RIVWQ) model. Simulated concentrations of the pesticides atrazine, metolachlor, and trifluralin in surface water were compared with field data monitored in the Sugar Creek watershed of Indiana’s White River basin by the National Water Quality Assessment (NAWQA) program. The evaluation not only provided USEPA with experience in using watershed models for estimating pesticide concentration in flowing water but also led to the development of improved statistical techniques for assessing model accuracy. Further, it demonstrated the difficulty of representing spatially and temporally variable soil, weather, and pesticide applications with relatively infrequent, spatially fixed, point estimates. It also demonstrated the value of using monitoring and modeling as mutually supporting tools and pointed to the need to design monitoring programs that support modeling.     

Comparison of Two Parametric Methods to Estimate Pesticide Mass Loads in California’s Central Valley1

Saleh, Dina K., David L. Lorenz, and Joseph L. Domagalski, 2010. Comparison of Two Parametric Methods to Estimate Pesticide Mass Loads in California’s Central Valley. Journal of the American Water Resources Association (JAWRA) 00(0):1‐11. DOI: 10.1111/j.1752‐1688.2010.00506.x Abstract: Mass loadings were calculated for four pesticides in two watersheds with different land uses in the Central Valley, California, by using two parametric models: (1) the Seasonal Wave model (SeaWave), in which a pulse signal is used to describe the annual cycle of pesticide occurrence in a stream, and (2) the Sine Wave model, in which first‐order Fourier series sine and cosine terms are used to simulate seasonal mass loading patterns. The models were applied to data collected during water years 1997 through 2005. The pesticides modeled were carbaryl, diazinon, metolachlor, and molinate. Results from the two models show that the ability to capture seasonal variations in pesticide concentrations was affected by pesticide use patterns and the methods by which pesticides are transported to streams. Estimated seasonal loads compared well with results from previous studies for both models. Loads estimated by the two models did not differ significantly from each other, with the exceptions of carbaryl and molinate during the precipitation season, where loads were affected by application patterns and rainfall. However, in watersheds with variable and intermittent pesticide applications, the SeaWave model is more suitable for use on the basis of its robust capability of describing seasonal variation of pesticide concentrations.     

IDENTIFYING DISCHARGE ZONES OF ARSENIC IN THE GOOSE RIVER BASIN,MAINE1

ABSTRACT: Water balance modeling and the analysis of stable water isotopes in ground water were conducted to aid the location of ground water discharge areas within the Goose River basin, in mid‐coastal Maine. Previous investigations of drinking water from wells in the fractured crystalline bedrock encountered persistent elevated total arsenic. Such contamination may be related to discharging ground water from fractured zones in the basin. Modeled discharge rates greater than +10 cm/yr and ¹⁸O values lighter than‐9.5 per mil VSMOW may indicate recent recharge is mixing with deeper ground water and is focused along some fractured zones in arsenic bearing crystalline rocks.     

WATER QUALITY OF AN INTENSWE AGRICULTURAL WATERSHED IN QUEBEC1

ABSTRACT: . Under a watershed based approach being examined by the Quebec Ministry of Agriculture to accelerate the adoption of conservation practices, a study on the impacts of agricultural practices on the St. Esprit watershed was initiated in the fall of 1993. The water quality of this 26 km² intensive agricultural watershed was studied over an 18 month period. Water samples taken at the outlet of the watershed were analyzed for nitrate, phosphate, suspended sediment, and atrazine. Water quality data were analyzed to establish seasonal trends in pollutant concentration and load in the watercourse. Spring snowmelt was identified as a significant period of pollutant material export. All pollutant materials displayed seasonal variability in the export process. Peak pollutant concentrations were associated with high flow events. Mean observed pollutant concentrations did not exceed drinking water quality standards.     

CHARACTERIZING GROUND WATER FLOW IN THE MUNICIPAL WELL FIELDS OF CEDAR RAPIDS,IOWA, WITH SELECTED ENVIRONMENTAL TRACERS1

ABSTRACT: Cedar Rapids obtains its municipal water supply from a shallow alluvial aquifer along the Cedar River in east-central Iowa. Water samples were collected and analyzed for selected isotopes and chlorofluorocarbons to characterize the ground-water flow system near the municipal well fields. Analyses of deuterium and oxygen-18 indicate that water in the alluvial aquifer and in the underlying carbonate bedrock aquifer was recharged from precipitation during modern climatic conditions. Analyses of tritium indicate modern, post-1952, water in the alluvial aquifer and older, pre-1952, water in the bedrock aquifer. Mixing of the modern and older waters occurs in areas where (1) the confining layer between the two aquifers is discontinuous, (2) the bedrock aquifer is fractured, or (3) pumping of supply wells induces the flow of water between aquifers. Analyses of chlorofluorocarbons were used to determine the date of recharge of water samples. Water in the bedrock aquifer likely was recharged prior to the 1950s. Water in the alluvial aquifer likely was recharged from the 1960s to 1990s. Biodegradation or sorption probably affected some of the ground water analyzed for chlorofluorocarbons. These processes reduce the concentrations of CFCs, which results in older than actual calculated dates of recharge.     

Seasonal Flushing of Pollutant Concentrations and Loads in Urban Stormwater1

Schiff, Kenneth C. and Liesl L. Tiefenthaler, 2011. Seasonal Flushing of Pollutant Concentrations and Loads in Urban Stormwater. Journal of the American Water Resources Association (JAWRA) 47(1):136‐142. DOI: 10.1111/j.1752‐1688.2010.00497.x Abstract: Despite broad observations of first flush within storms, the scientific understanding of seasonal flushing remains incomplete. Seasonal flushing occurs when initial storms of the season have greater concentrations or loads than storms later in the season. The goal of this study was to census stormwater concentrations and loads from an arid, urban watershed to quantify seasonal flushing. Samples were collected every 15 min during the 1997‐1998 wet season from the Santa Ana River and analyzed for total suspended solids. Initial storms of the season generated event mean concentrations 3‐10 times the event mean concentration of storms later in the season. Cumulative flow‐weighted mean concentrations were calculated as the season progressed. Early season storms discharged only 6% of the annual volume, but influenced flow‐weighted mean concentrations well past the midpoint of the wet season. Mass‐based estimates also indicated a disproportionate load in the early portion of the year; over 52% of the annual load was discharged in the first 30% of the annual volume from the highly urbanized lower watershed. Other stormwater pollutants, including six trace metals (Cd, Cr, Cu, Pb, Ni, Zn), were highly correlated with total suspended solids and also exhibited a significant seasonal flush.