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K.M. Kuivila

Publications and source records attributed to K.M. Kuivila.

12 recordsLinked to original sources

Occurrence, distribution and transport of pesticides into the Salton Sea Basin, California, 2001-2002

The Salton Sea is a hypersaline lake located in southeastern California. Concerns over the ecological impacts of sediment quality and potential human exposure to dust emissions from exposed lakebed sediments resulting from anticipated shrinking of shoreline led to a study of pesticide distribution and transport within the Salton Sea Basin, California, in 2001-2002. Three sampling stations-upriver, river mouth, and offshore-were established along each of the three major rivers that discharge into the Salton Sea. Large-volume water samples were collected for analysis of pesticides in water and suspended sediments at the nine sampling stations. Samples of the bottom sediment were also collected at each site for pesticide analysis. Sampling occurred in October 2001, March-April 2002, and October 2002, coinciding with the regional fall and spring peaks in pesticide use in the heavily agricultural watershed. Fourteen current-use pesticides were detected in water and the majority of dissolved concentrations ranged from the limits of detection to 151 ng/l. Diazinon, EPTC and malathion were detected at much higher concentrations (940-3,830 ng/l) at the New and Alamo River upriver and near-shore stations. Concentrations of carbaryl, dacthal, diazinon, and EPTC were higher in the two fall sampling periods, whereas concentrations of atrazine, carbofuran, and trifluralin were higher during the spring, which matched seasonal use patterns of these pesticides. Current-use pesticides were also detected on suspended and bed sediments in concentrations ranging from detection limits to 106 ng/g. Chlorpyrifos, dacthal, EPTC, trifluralin, and DDE were the most frequently detected pesticides on sediments from all three rivers. The number of detections and concentrations of suspended sediment-associated pesticides were often similar for the river upriver and near-shore sites, consistent with downstream transport of pesticides via suspended sediment. While detectable suspended sediment pesticide concentrations were more sporadic than detected aqueous concentrations, seasonal trends were similar to those for dissolved concentrations. Generally, the pesticides detected on suspended sediments were the same as those on the bed sediments, and concentrations were similar, especially at the Alamo River upriver site. With a few exceptions, pesticides were not detected in suspended or bed sediments from the off-shore sites. The partitioning of pesticides between water and sediment was not predictable from solely the physical-chemical properties of individual pesticide compounds, but appear to be a complicated function of the quantity of pesticide applied in the watershed, residence time of sediments in the water, and compound solubility and hydrophobicity. Sediment concentrations of most pesticides were found to be 100-1,000 times lower than the low-effects levels determined in human health risk assessment studies. However, maximum concentrations of chlorpyrifos on suspended sediments were approximately half the low-effects level, suggesting the need for further sediment characterization of lake sediments proximate to riverine inputs. ?? 2008 Springer Science+Business Media B.V.

Hydrobiologia

A multi-residue method for the analysis of pesticides and pesticide degradates in water using HLB solid-phase extraction and gas chromatography-ion trap mass spectrometry

A method was developed for the analysis of over 60 pesticides and degradates in water by HLB solid-phase extraction and gas-chromatography/mass spectrometry. Method recoveries and detection limits were determined using two surface waters with different dissolved organic carbon (DOC) concentrations. In the lower DOC water, recoveries and detection limits were 80%–108% and 1–12 ng/L, respectively. In the higher DOC water, the detection limits were slightly higher (1–15 ng/L). Additionally, surface water samples from four sites were analyzed and 14 pesticides were detected with concentrations ranging from 4 to 1,200 ng/L.

Bulletin of Environmental Contamination and Toxico

Multi-residue method for the analysis of 85 current-use and legacy pesticides in bed and suspended sediments

A multi-residue method was developed for the simultaneous determination of 85 current-use and legacy organochlorine pesticides in a single sediment sample. After microwave-assisted extraction, clean-up of samples was optimized using gel permeation chromatography and either stacked carbon and alumina solid-phase extraction cartridges or a deactivated Florisil column. Analytes were determined by gas chromatography with ion-trap mass spectrometry and electron capture detection. Method detection limits ranged from 0.6 to 8.9 ??g/kg dry weight. Bed and suspended sediments from a variety of locations were analyzed to validate the method and 29 pesticides, including at least 1 from every class, were detected.

Journal of Chromatography A

Diversity, composition, and geographical distribution of microbial communities in California salt marsh sediments

The Pacific Estuarine Ecosystem Indicators Research Consortium seeks to develop bioindicators of toxicant-induced stress and bioavailability for wetland biota. Within this framework, the effects of environmental and pollutant variables on microbial communities were studied at different spatial scales over a 2-year period. Six salt marshes along the California coastline were characterized using phospholipid fatty acid (PLFA) analysis and terminal restriction fragment length polymorphism (TRFLP) analysis. Additionally, 27 metals, six currently used pesticides, total polychlorinated biphenyls and polycyclic aromatic hydrocarbons, chlordanes, nonachlors, dichlorodiphenyldichloroethane, and dichlorodiphenyldichloroethylene were analyzed. Sampling was performed over large (between salt marshes), medium (stations within a marsh), and small (different channel depths) spatial scales. Regression and ordination analysis suggested that the spatial variation in microbial communities exceeded the variation attributable to pollutants. PLFA analysis and TRFLP canonical correspondence analysis (CCA) explained 74 and 43% of the variation, respectively, and both methods attributed 34% of the variation to tidal cycles, marsh, year, and latitude. After accounting for spatial variation using partial CCA, we found that metals had a greater effect on microbial community composition than organic pollutants had. Organic carbon and nitrogen contents were positively correlated with PLFA biomass, whereas total metal concentrations were positively correlated with biomass and diversity. Higher concentrations of heavy metals were negatively correlated with branched PLFAs and positively correlated with methyl- and cyclo-substituted PLFAs. The strong relationships observed between pollutant concentrations and some of the microbial indicators indicated the potential for using microbial community analyses in assessments of the ecosystem health of salt marshes. Copyright ?? 2006, American Society for Microbiology. All Rights Reserved.

Applied and Environmental Microbiology

Potential exposure of larval and juvenile delta smelt to dissolved pesticides in the Sacramento-San Joaquin Delta, California

The San Francisco Estuary is critical habitat for delta smelt Hypomesus transpacificus, a fish whose abundance has declined greatly since 1983 and is now listed as threatened. In addition, the estuary receives drainage from the Central Valley, an urban and agricultural region with intense and diverse pesticide usage. One possible factor of the delta smelt population decline is pesticide toxicity during vulnerable larval and juvenile stages, but pesticide concentrations are not well characterized in delta smelt spawning and nursery habitat. The objective of this study was to estimate the potential exposure of delta smelt during their early life stages to dissolved pesticides. For 3 years (1998-2000), water samples from the Sacramento-San Joaquin Delta were collected during April-June in coordination with the California Department of Fish and Game's delta smelt early life stage monitoring program. Samples were analyzed for pesticides using solid-phase extraction and gas chromatography/mass spectrometry. Water samples contained multiple pesticides, ranging from 2 to 14 pesticides in each sample. In both 1999 and 2000, elevated concentrations of pesticides overlapped in time and space with peak densities of larval and juvenile delta smelt. In contrast, high spring outflows in 1998 transported delta smelt away from the pesticide sampling sites so that exposure could not be estimated. During 2 years, larval and juvenile delta smelt were potentially exposed to a complex mixture of pesticides for a minimum of 2-3 weeks. Although the measured concentrations were well below short-term (96-h) LC50 values for individual pesticides, the combination of multiple pesticides and lengthy exposure duration could potentially have lethal or sublethal effects on delta smelt, especially during early larval development.

American Fisheries Society Symposium

Genetic variation among interconnected populations of Catostomus occidentalis: Implications for distinguishing impacts of contaminants from biogeographical structuring

Exposure to contaminants can affect survivorship, recruitment, reproductive success, mutation rates and migration, and may play a significant role in the partitioning of genetic variation among exposed and nonexposed populations. However, the application of molecular population genetic data to evaluate such influences has been uncommon and often flawed. We tested whether patterns of genetic variation among native fish populations (Sacramento sucker, Catostomus occidentalis) in the Central Valley of California were consistent with long-term pesticide exposure history, or primarily with expectations based on biogeography. Field sampling was designed to rigorously test for both geographical and contamination influences. Fine-scale structure of these interconnected populations was detected with both amplified fragment length polymorphisms (AFLP) and microsatellite markers, and patterns of variation elucidated by the two marker systems were highly concordant. Analyses indicated that biogeographical hypotheses described the data set better than hypotheses relating to common historical pesticide exposure. Downstream populations had higher genetic diversity than upstream populations, regardless of exposure history, and genetic distances showed that populations from the same river system tended to cluster together. Relatedness among populations reflected primarily directions of gene flow, rather than convergence among contaminant-exposed populations. Watershed geography accounted for significant partitioning of genetic variation among populations, whereas contaminant exposure history did not. Genetic patterns indicating contaminant-induced selection, increased mutation rates or recent bottlenecks were weak or absent. We stress the importance of testing contaminant-induced genetic change hypotheses within a biogeographical context. Strategic application of molecular markers for analysis of fine-scale structure, and for evaluating contaminant impacts on gene pools, is discussed.

Molecular Ecology

Work plan for determining the occurrence of glyphosate, its transformation product AMPA, other herbicide compounds, and antibiotics in midwestern United States streams, 2002

Changes in herbicide use in the Midwestern United States have been substantial over the last 5 years. Most significant is a tripling in the use of glyphosate (N-[phosphonomethyl]glycin). Over this same time period (1997­2001), atrazine use increased by 20 percent and acetochlor use increased by 10 percent, while cyanazine use decreased by 99 percent, alachlor use decreased by 70 percent, and metolachlor use decreased by 55 percent. Previous studies have documented that herbicide flushes occur in midwestern streams during runoff events for several weeks to several months following application, and that herbicide concentrations in midwestern streams during flushing events are related to rates of herbicide use. The objective of this study is to determine the distribution of glyphosate and its primary transformation product aminomethylphosphonic acid (AMPA) in midwestern streams during post-application and harvest-season runoff events. Water samples will be collected in 2002 during two post-herbicide-application runoff events and one harvest-season runoff event from 53 sites on streams in the Midwestern United States. All samples will be analyzed at the U.S. Geological Survey Organic Geochemistry Research Laboratory in Lawrence, Kansas, for glyphosate and 20 other herbicides. Samples will also be analyzed for a glyphosate transformation product (AMPA) and 26 other herbicide transformation products, using GC/MS or HPLC/MS. Selected samples will be analyzed for 36 antibiotics or antibiotic transformational products. Results from this study will represent the first broad-scale investigation of glyphosate and AMPA in U.S. water resources.

Midwest region

Rice pesticide concentrations in the Colusa Basin Drain and the Sacramento River, California, 1990-1993

The pesticides molinate, thiobencarb, and carbofuran are applied to rice (Oryza sativa L.) fields in the Sacramento Valley, California, each year during April through June. These pesticides are of concern because of their adverse effects on water quality and their potential adverse effects on aquatic life. Therefore, the California Regional Water Quality Control Board (CRWQCB) mandated the holding of irrigation-return water in rice fields to increase pesticide degradation and dissipation before the water is released to the Sacramento River. The CRWQCB also established performance goals to maintain drinking Water quality for the city of Sacramento and to protect the habitat for aquatic life. The objectives of this study were to determine the effects of increased irrigation-return water holding times on rice pesticide concentrations and loads in the Colusa Basin Drain and the Sacramento River. Dissolved pesticide concentrations were measured in water samples collected in May through July during 1990-1993 at the Colusa Basin Drain at Road 99E near Knights Landing (Colusa Basin Drain) and at the Sacramento River at Sacramento. Pesticide concentrations and loads at both sites showed a decrease from 1990-1992 and an increase in 1993. This trend cannot be explained by the yearly holding time regulations but can be explained by the amount of yearly emergency releases. The yearly changes in pesticide concentration detected demonstrate that continued monitoring and management of pesticides is necessary to maintain water quality.

Conference Paper

Determination of pesticides associated with suspended sediments in the San Joaquin River, California, USA, using gas chromatography-ion trap mass spectrometry

An analytical method useful for the quantification of a range of pesticides and pesticide degradation products associated with suspended sediments was developed by testing a variety of extraction and cleanup schemes. The final extraction and cleanup methods chosen for use are suitable for the quantification of the listed pesticides using gas chromatography-ion trap mass spectrometry and the removal of interfering coextractable organic material found in suspended sediments. Methylene chloride extraction followed by Florisil cleanup proved most effective for separation of coextractives from the pesticide analytes. Removal of elemental sulfur was accomplished with tetrabutylammonium hydrogen sulfite. The suitability of the method for the analysis of a variety of pesticides was evaluated, and the method detection limits (MDLs) were determined (0.1-6.0 ng/g dry weight of sediment) for 21 compounds. Recovery of pesticides dried onto natural sediments averaged 63%. Analysis of duplicate San Joaquin River suspended-sediment samples demonstrated the utility of the method for environmental samples with variability between replicate analyses lower than between environmental samples. Eight of 21 pesticides measured were observed at concentrations ranging from the MDL to more than 80 ng/g dry weight of sediment and exhibited significant temporal variability. Sediment-associated pesticides, therefore, may contribute to the transport of pesticides through aquatic systems and should be studied separately from dissolved pesticides.

Toxicological and Environmental Chemistry

Concentrations, transport and biological effects of dormant spray pesticides in the San Francisco Estuary, California

The transport and biological effects of dormant spray pesticides were examined in the San Francisco Estuary, California, by measuring dissolved- pesticide concentrations and estimating toxicity using bioassays at a series of sites in January and February 1993. Distinct pulses of pesticides, including diazinon, methidathion, and chlorpyrifos, were detected in the San Joaquin River in January and February and in the Sacramento River in February following rainfall. The higher pesticide loads in the Sacramento River compared with those in the San Joaquin River can be attributed to the greater amount of rainfall in the Sacramento Valley. The use patterns and water solubility of the pesticides can account for the observed temporal and spatial distributions in the two rivers. The pesticide pulses detected at Sacramento were followed through the northern embayment of San Francisco Estuary. In contrast, the pesticide distribution in the Sacramento-San Joaquin Delta changed from distinct pulses to steady increases in concentration over time. Seven-day bioassays indicated that Sacramento River water at Rio Vista was acutely toxic to Ceriodaphnia dubia (water flea) for 3 consecutive d and San Joaquin River water at Vernalis for 12 consecutive d. These water samples all had the highest diazinon concentrations. Examination of 96-h LC50 values (lethal concentration that kills 50% of test organisms in 96 H) indicates that measured diazinon concentrations could account for most but not all the observed toxicity. Other pesticides present could contribute to the toxicity.

Environmental Toxicology and Chemistry

Distributions of pesticides and organic contaminants between water and suspended sediment, San Francisco Bay, California

Suspended-sediment and water samples were collected from San Francisco Bay in 1991 during low river discharge and after spring rains. All samples were analyzed for organophosphate, carbamate, and organochlorine pesticides; petroleum hydrocarbons; biomarkers; and polynuclear aromatic hydrocarbons. The objectives were to determine the concentrations of these contaminants in water and suspended sediment during two different hydrologic conditions and to determine partition coefficients of the contaminants between water and sediment. Concentrations of hydrophobic contaminants, such as polynuclear aromatic hydrocarbons, varied with location of sample collection, riverine discharge, and tidal cycle. Concentrations of hydrophobic contaminants in suspended sediments were highest during low river discharge but became diluted as agricultural soils entered the bay after spring rains. Polynuclear aromatic hydrocarbons defined as dissolved in the water column were not detected. The concentrations sorbed on suspended sediments were variable and were dependent on sediment transport patterns in the bay. In contrast, the relatively hydrophilic organophosphate pesticides, such as chlorpyrifos and diazinon, has a more uniform concentration in suspended sediment. These pesticides were detected only after spring rains. Most of the measured diazinon, at least 98% for all samples, was in the dissolved phase. Measured partition coefficients for diazinon generally were uniform, which suggests that suspended-sediment concentrations were close to equilibrium with dissolved concentrations. The concentration of diazinon sorbed to suspended sediments, at any given sampling site, was driven primarily by the more abundant solution concentration. The concentrations of diazinon sorbed to suspended sediments, therefore, were independent of the patterns of sediment movement.

California

Methane cycling in the sediments of Lake Washington

About half of the methane flux from depth is oxidized to CO2 in the upper 0.7 cm of the sediments and the remainder escapes into the water column. In terms of the total carbon budget of the lake, the upward flux of methane is insignificant with only about 2% of the carbon fixed by primary production being returned as methane. The upward flux of methane, however, does represent about 20% of the organic carbon decomposed within the sediments. -from Authors

Limnology and Oceanography