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Geology topics

D.W. Kolpin

Publications and source records attributed to D.W. Kolpin.

At least 55 records · Page 3Linked to original sources
USGS2001

Occurrence of cyanazine compounds in groundwater: Degradates more prevalent than the parent compound

A recently developed analytical method using liquid chromatography/mass spectrometry was used to investigate the occurrence of cyanazine and its degradates cyanazine acid (CAC), cyanazine amide (CAM), deethylcyanazine (DEC), and deethylcyanazine acid (DCAC) in groundwater. This research represents some of the earliest data on the occurrence of cyanazine degradates in groundwater. Although cyanazine was infrequently detected in the 64 wells across Iowa sampled in 1999, cyanazine degradates were commonly found during this study. The most frequently detected cyanazine compound was DCAC (32.8%) followed by CAC (29.7%), CAM (17.2%), DEC (3.1%), and cyanazine (3.1%). The frequency of detection for cyanazine or one or more of its degradates (CYTOT) was more than 12-fold over that of cyanazine alone (39.1% for CYTOT versus 3.1% for cyanazine). Of the total measured concentration of cyanazine, only 0.2% was derived from its parent compound - with DCAC (74.1%) and CAC (18.4%) comprising 92.5% of this total. Thus, although DCAC and CAC had similar frequencies of detection, DCAC was generally present in higher concentrations. No concentrations of cyanazine compounds for this study exceeded water-quality criteria for the protection of human health. Only cyanazine, however, has such a criteria established. Nevertheless, because these cyanazine degradates are still chlorinated, they may have similar toxicity as their parent compound - similar to what has been found with the chlorinated degradates of atrazine. Thus, the results of this study documented that data on the degradates for cyanazine are critical for understanding its fate and transport in the hydrologic system. Furthermore, the prevalence of the chlorinated degradates of cyanazine found in groundwater suggests that to accurately determine the overall effect on human health and the environment from cyanazine its degradates should also be considered. In addition, because CYTOT was found in 57.6% of the samples collected from alluvial aquifers, about 2-5 times more frequently than the other major aquifer types (glacial drift, bedrock/karst, bedrock/nonkarst) under investigation, this finding has long-term implications for the occurrence of CYTOT in streams. It is anticipated that low-level concentrations of CYTOT will continue to be detected in streams for years after the use of cyanazine has terminated (scheduled for the year 2000 in the United States), primarily through its movement from groundwater into streams during base-flow conditions.

Iowa↗
USGS2001

Major herbicides in ground water: Results from the National Water-Quality Assessment

To improve understanding of the factors affecting pesticide occurrence in ground water, patterns of detection were examined for selected herbicides, based primarily on results from the National Water-Quality Assessment (NAWQA) program. The NAWQA data were derived from 2227 sites (wells and springs) sampled in 20 major hydrologic basins across the USA from 1993 to 1995. Results are presented for six high-use herbicides—atrazine (2-chloro-4-ethylamino-6-isopropylamino- s -triazine), cyanazine (2-[4-chloro-6-ethylamino-1,3,5-triazin-2-yl]amino]-2-methylpropionitrile), simazine (2-chloro-4,6-bis[ethylamino]- s -triazine), alachlor (2-chloro- N -[2,6-diethylphenyl]- N -[methoxymethyl]acetamide), acetochlor (2-chloro- N -[ethoxymethyl]- N -[2-ethyl-6-methylphenyl]acetamide), and metolachlor (2-chloro- N -[2-ethyl-6-methylphenyl]- N -[2-methoxy-1-methylethyl]acetamide)— as well as for prometon (2,4-bis[isopropylamino]-6-methoxy- s -triazine), a nonagricultural herbicide detected frequently during the study. Concentrations were <1 μg L −1 at 98% of the sites with detections, but exceeded drinking-water criteria (for atrazine) at two sites. In urban areas, frequencies of detection (at or above 0.01 μg L −1 ) of atrazine, cyanazine, simazine, alachlor, and metolachlor in shallow ground water were positively correlated with their nonagricultural use nationwide ( P < 0.05). Among different agricultural areas, frequencies of detection were positively correlated with nearby agricultural use for atrazine, cyanazine, alachlor, and metolachlor, but not simazine. Multivariate analysis demonstrated that for these five herbicides, frequencies of detection beneath agricultural areas were positively correlated with their agricultural use and persistence in aerobic soil. Acetochlor, an agricultural herbicide first registered in 1994 for use in the USA, was detected in shallow ground water by 1995, consistent with previous field-scale studies indicating that some pesticides may be detected in ground water within 1 yr following application. The NAWQA results agreed closely with those from other multistate studies with similar designs.

Journal of Environmental Quality↗
USGS2001

Soil characteristics and agrichemicals in groundwater of the Midwestern United States

A comprehensive set of soil characteristics were examined to determine the effect of soil on the transport of agrichemicals to groundwater. This paper examines the relation of soil characteristics to concentrations and occurrence nitrate, atrazine, and atrazine residue from 99 wells completed in unconsolidated aquifers across the Midwestern United States. Soil characteristics that determine the rate of water movement were directly related to the occurrence and concentrations of nitrate and atrazine in groundwater. The substantial differences in the relations found among soil characteristics and nitrate and atrazine in groundwater suggest that different processes affect the transformation, adsorption, and transport of these contaminants. A multi-variable analysis determined that the soil characteristics examined explained the amount of variability in concentrations for nitrate (19%), atrazine (33%), and atrazine residue (29%). These results document that, although soils do affect the transport of agrichemicals to groundwater, other factors such as hydrology, land use, and climate must also be considered to understand the occurrence of agrichemicals in groundwater.

Water Science and Technology↗
USGS2000

Finding minimal herbicide concentrations in ground water? Try looking for their degradates

Extensive research has been conducted regarding the occurrence of herbicides in the hydrologic system, their fate, and their effects on human health and the environment. Few studies, however, have considered herbicide transformation products (degradates). In this study of Iowa ground water, herbicide degradates were frequently detected. In fact, herbicide degradates were eight of the 10 most frequently detected compounds. Furthermore, a majority of a herbicide's measured concentration was in the form of its degradates &mdash; ranging from 55 to over 99%. The herbicide detection frequencies and concentrations varied significantly among the major aquifer types sampled. These differences, however, were much more pronounced when herbicide degradates were included. Aquifer types presumed to have the most rapid recharge rates (alluvial and bedrock/karst region aquifers) were those most likely to contain detectable concentrations of herbicide compounds. Two indirect estimates of ground-water age (depth of well completion and dissolved-oxygen concentration) were used to separate the sampled wells into general vulnerability classes (low, intermediate, and high). The results show that the herbicide detection frequencies and concentrations varied significantly among the vulnerability classes regardless of whether or not herbicide degradates were considered. Nevertheless, when herbicide degradates were included, the frequency of herbicide compound detection within the highest vulnerability class approached 90%, and the median total herbicide residue concentration increased over an order of magnitude, relative to the parent compounds alone, to 2 &mu;g/l. The results from this study demonstrate that obtaining data on herbicide degradates is critical for understanding the fate of herbicides in the hydrologic system. Furthermore, the prevalence of herbicide degradates documented in this study suggests that to accurately determine the overall effect on human health and the environment of a specific herbicide its degradates should also be considered.

Iowa↗
USGS1999

Assessing groundwater vulnerability to agrichemical contamination in the Midwest US

Agrichemicals (herbicides and nitrate) are significant sources of diffuse pollution to groundwater. Indirect methods are needed to assess the potential for groundwater contamination by diffuse sources because groundwater monitoring is too costly to adequately define the geographic extent of contamination at a regional or national scale. This paper presents examples of the application of statistical, overlay and index, and process-based modeling methods for groundwater vulnerability assessments to a variety of data from the Midwest U.S. The principles for vulnerability assessment include both intrinsic (pedologic, climatologic, and hydrogeologic factors) and specific (contaminant and other anthropogenic factors) vulnerability of a location. Statistical methods use the frequency of contaminant occurrence, contaminant concentration, or contamination probability as a response variable. Statistical assessments are useful for defining the relations among explanatory and response variables whether they define intrinsic or specific vulnerability. Multivariate statistical analyses are useful for ranking variables critical to estimating water quality responses of interest. Overlay and index methods involve intersecting maps of intrinsic and specific vulnerability properties and indexing the variables by applying appropriate weights. Deterministic models use process-based equations to simulate contaminant transport and are distinguished from the other methods in their potential to predict contaminant transport in both space and time. An example of a one-dimensional leaching model linked to a geographic information system (GIS) to define a regional metamodel for contamination in the Midwest is included.

Water Science and Technology↗
USGS1999

Agrichemicals in ground water of the midwestern USA: Relations to soil characteristics

A comprehensive set of soil characteristics were examined to determine the effect of soil on the transport of agrichemicals to ground water. This paper examines the relation of local soil characteristics to concentrations and occurrence of nitrate, atrazine (2-chloro-4 ethylamino-6-isopropylamino- s -trazine), and atrazine residue [atrazine + deethylatrazine (2-amino-4-chloro-6-isopropylamino- s -triazine) + deisopropylatrazine (2-amino-4-chloro-6-ethylamino- s -triazine)] from 99 wells completed in unconsolidated aquifers across the midwestern USA. The occurrence and concentrations of nitrate and atrazine in ground water were directly related to soil characteristics that determine the rate of water movement. The substantial differences in the relations found among soil characteristics and nitrate and atrazine in ground water suggest that different processes affect the transformation, adsorption, and transport of these contaminants. A multivariate analysis determined that the soil characteristics examined explained the amount of variability in concentrations for nitrate (19.0%), atrazine (33.4%), and atrazine residue (28.6%). These results document that, although soils do affect the transport of agrichemicals to ground water, other factors such as hydrology, land use, and climate must also be considered to understand the occurrence of agrichemicals in ground water.

Journal of Environmental Quality↗
USGS1998

The environmental occurrence of herbicides: The importance of degradates in ground water

Numerous studies are being conducted to investigate the occurrence, fate, and effects on human health and the environment from the extensive worldwide use of herbicides to control weeds. Few studies, however, are considering the degradates of these herbicides in their investigations. Our study of herbicides in aquifers across Iowa found herbicide degradates to be prevalent in ground water, being detected in about 75% of the wells sampled. With the exception of atrazine, the frequencies of detection in ground water for a given herbicide increased multifold when its degradates were considered. Furthermore, a majority of the measured concentration for a given herbicide was in the form of its degradates&mdash;even for a relatively persistent compound such as atrazine. For this study, degradates comprised from 60 to over 99% of a herbicide's measured concentration. Because herbicide degradates can have similar acute and chronic toxicity as their parent compounds, these compounds have environmental significance as well as providing a more complete understanding of the fate and transport of a given herbicide. Thus, it is essential that degradates are included in any type of herbicide investigation.

Iowa↗
USGS1997

Analysis of environmental data with censored observations

The potential threats to humans and to terrestrial and aquatic ecosystems from environmental contamination could depend on the sum of the concentrations of different chemicals. However, direct summation of environmental data is not generally feasible because it is common for some chemical concentrations to be recorded as being below the analytical reporting limit. This creates special problems in the analysis of the data. A new model selection procedure, named forward censored regression, is introduced for selecting an appropriate model for environmental data with censored observations. The procedure is demonstrated using concentrations of atrazine (2-chloro-4-ethylamino-6-isopropylamino- s -triazine), deethylatrazine (DEA, 2-amino-4-chloro-6-isopropylamino- s -triazine), and deisopropylatrazine (DIA, 2-amino-4-chloro-6-ethylamino- s -triazine) in groundwater in the midwestern United States by using the data derived from a previous study conducted by the U.S. Geological Survey. More than 80% of the observations for each compound for this study were left censored at 0.05 &mu;g/L. The values for censored observations of atrazine, DEA, and DIA are imputed with the selected models. The summation of atrazine residue (atrazine + DEA + DIA) can then be calculated using the combination of observed and imputed values to generate a pseudo-complete data set. The all-subsets regression procedure is applied to the pseudo-complete data to select the final model for atrazine residue. The methodology presented can be used to analyze similar cases of environmental contamination involving censored data.

Environmental Science & Technology↗
USGS1997

Temporal trends of selected agricultural chemicals in Iowa's groundwater, 1982-1995: Are things getting better?

Since 1982, the Iowa Groundwater Monitoring (IGWM) Program has been used to sample untreated groundwater from Iowa municipal wells for selected agricultural chemicals. This long-term database was used to determine if concentrations of select agricultural chemicals in groundwater have changed with time. Nitrate, alachlor [2-chloro-2&prime;-6&prime;-diethyl- N -(methoxymethyl)-acetanilide], atrazine (2-chloro-4-ethylamino-6-isopropylamino- s -triazine), cyanazine [2-[[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino]-2-methylpropionitrile)], and metolachlor [2-chloro- N -(2-ethyl-6-methylphenyl)- N -(2-methoxy-1-methylethyl) acetamide] were selected for this temporal analysis of the data. Conclusive temporal changes in frequency of detection and median chemical concentrations were found only for atrazine (decrease) and metolachlor (increase). The greatest temporal chemical changes occurred in the shallowest wells and in alluvial aquifers&mdash;both relating to groups of wells generally having the youngest groundwater age. The temporal patterns found for atrazine and metolachlor are consistent with their patterns of chemical use and/or application rates and are suggestive of a causal relation. Only continued data collection, however, will indicate if the trends in chemical concentrations described here represent long-term temporal patterns or only short-term changes in groundwater. No definitive answers could be made in regards to the question of overall improvements in groundwater quality with respect to agricultural chemical contamination and time, due to the inherent problems with the simplistic measurement of overall severity (summation of alachlor + atrazine + cyanazine + metolachlor concentrations) examined for this study. To adequately determine if there is an actual decreasing trend in the overall severity of contamination (improving groundwater quality), the collection of additional water-chemistry data and the investigation of other measures of severity are needed.

Iowa↗
USGS1997

Agricultural chemicals in groundwater of the midwestern United States: Relations to land use

To determine the relations between land use and concentrations of selected agricultural chemicals (nitrate, atrazine residue [atrazine (2-chloro-4-ethylamino-6-isopropylamino- s -triazine) + deethylatrazinc (2-amino-4-chloro-6-isopropylamino- s -triazine) + deisopropylatrazine (2-amino-4-chloro-6-ethylamino- s -triazine)], and alachlor residue [alachlor, [2-chloro-2&prime;,6&prime;-diethyl- N -(methoxymethyl) acetanilide] + alachlor ethanesulfonic acid (alachlor-ESA; 2-[(2,6-diethylphenyl)(methoxymethyl)amino]-2-oxoethanesulfonic acid)] in groundwater, detailed land use information based on accurate measurements from aerial photographs for the 1991 growing season was obtained within a 2-km radius surrounding 100 wells completed in near-surface unconsolidated aquifers in the midwestern USA. The most significant land use factors to the agricultural chemicals examined were: nitrate (amount of irrigated crop production, positive relation), atrazine residue (amount of irrigated crop production, positive relation), and alachlor residue (amount of highly erodible land, inverse relation). The investigation of smaller buffer sizes (size of circular area around sampled wells) proved insightful for this study. Additional land use factors having significant relations to all three agricultural chemicals were identified using these smaller buffer radii. The most significant correlations (correlation maxima) generally occurred at &le;500-m for nitrate and &ge;1000-m for atrazine residue and alachlor residue. An attempt to improve the statistical relations to land use by taking hydrologic considerations into account (removing land outside the estimated most probable recharge area from the statistical analysis) was not as successful as anticipated. Only 45% of the nitrate, 32% of the atrazine residue, and 20% of the alachlor residue correlations were improved by a consideration of the estimated most probable recharge area.

Journal of Environmental Quality↗
USGS1996

Acetochlor in the hydrologic system in the midwestern United States, 1994

The herbicide acetochlor [2-chloro- N -(ethoxymethyl)- N -(2-ethyl-6-methylphenyl)acetamide] was given conditional registration in the United States by the U.S. Environmental Protection Agency in March 1994. This registration provided a rare opportunity to investigate the occurrence of a pesticide during its first season of extensive use in the midwestern United States. Water samples collected and analyzed by the U.S. Geological Survey during 1994 documented the distribution of acetochlor in the hydrologic system; it was detected in 29% of the rain samples from four sites in Iowa, 17% of the stream samples from 51 sites across nine states, and 0% of the groundwater samples from 38 wells across eight states. Acetochlor exhibited concentration increases in rain and streams following its application to corn in the midwestern United States, with 75% of the rainwater and 35% of the stream samples having acetochlor detected during this time period. Acetochlor concentrations in rain decreased as the growing season progressed. Based on the limited data collected for this study, it is anticipated that acetochlor concentrations will have a seasonal pattern in rain and streams similar to those of other acetanilide herbicides examined. Possible explanations for the absence of acetochlor in groundwater for this study include the rapid degradation of acetochlor in the soil zone, insufficient time for this first extensive use of acetochlor to have reached the aquifers sampled, and the possible lack of acetochlor use in the recharge areas for the wells examined.

Environmental Science & Technology↗
USGS1996

Atrazine concentrations in near-surface aquifers: A censored regression approach

In 1991, the U.S. Geological Survey (USGS) conducted a study to investigate the occurrence of atrazine (2-chloro-4-ethylamino-6- isopropylamino-s-triazine) and other agricultural chemicals in near-surface aquifers in the midcontinental USA. Because about 83% of the atrazine concentrations from the USGS study were censored, standard statistical estimation procedures could not be used. To determine factors that affect atrazine concentrations in groundwater while accommodating the high degree of data censoring. Tobit models were used (normal homoscedastic, normal heteroscedastic, lognormal homoscedastic, and lognormal heteroscedastic). Empirical results suggest that the lognormal heteroscedastic Tobit model is the model of choice for this type of study. This model determined the following factors to have the strongest effect on atrazine concentrations in groundwater: percent of pasture within 3.2 km, percent of forest within 3.2 km (2 mi), mean open interval of the well, primary water use of a well, aquifer class (unconsolidated or bedrock), aquifer type (unconfined or confined), existence of a stream within 30 m (100 ft), existence of a stream within 30 m to 0.4 km (0.25 mi), and existence of a stream within 0.4 to 3.2 km. Examining the elasticities of the continuous explanatory factors provides further insight into their effects on atrazine concentrations in groundwater. This study documents a viable statistical method that can be used to accommodate the complicating presence of censured data, a feature that commonly occurs in environmental data.

Journal of Environmental Quality↗
USGS1996

Water-quality data for nutrients, pesticides, and volatile organic compounds in near-surface aquifers of the midcontinental United States, 1992-1994

Water samples were collected from 175 wells in 12 Midcontinental States (Illinois, Indiana, Iowa, Kansas, Michigan, Minnesota, Missouri, Nebraska, North Dakota, Ohio, South Dakota, Wisconsin) from 1992 through 1994 to determine the spatial distribution of nutrients, pesticides, and volatile organic compounds in ground water, and to document the potential effects of the historic flooding that occurred during 1993 on ground- water quality. Concentrations of nitrate greater than the 0.05 mg/L reporting limit were found in 69.1 percent of the water samples, and nitrate concentrations exceeded the U.S. Environmental Protection Agency maximum contaminant limit of 10 mg/L in 9.6 percent of the 249 samples analyzed for nitrate. Pesticides or pesticide metabolites were detected in 72.4 percent of the 210 pesticide analyses, and 28 different compounds were found. Concentrations of multiple pesticide compounds above analytical reporting limits were found in water from about 60 percent of the wells sampled. Although pesticides were frequently detected, only one sample had a pesticide concentration that exceeded a maximum contaminant level for drinking water. The most frequently detected compounds, however, were pesticide metabolites for which maximum contaminant levels have not yet been established. Volatile organic compounds were detected in 13.5 percent of the 155 samples analyzed for these compounds. Only one sample had concentrations of volatile organic compounds that exceeded a maximum contaminant level for drinking water.

Open-File Report↗