Laura L. McConnell

Evidence of currently-used pesticides in air, ice, fog, seawater and surface microlayer in the Bering and Chukchi Seas

Abstract Investigation of currently-used pesticides (triazines, acetanilides, organophosphates and organochlorines) was carried out in the Bering and Chukchi marine ecosystems in the summer of 1993. Chlorpyrifos and trace levels of endosulphan were the most frequently identified contaminants in seawater, chlorpyrifos and atrazine were found in marine ice, and chlorothalonil and trifluralin were found in surface microlayer samples. Concentrations of chlorpyrifos were highest (170 ng l−1) in marine ice and higher in seawater (19–67 ng l−1) at locations which were closest to the ice edge. Endosulphan was found as a widely distributed currently used pesticide in the polar atmosphere. The greatest concentration of any one single agrochemical was trifluralin (1.15 μg l−1) in a Bristol Bay surface microlayer sample. Arctic marine fog was sampled and for the first time, several currently-used pesticides (chlorpyrifos, trifluralin, metolachlor, chlorothalonil, terbufos and endosulphan) were detected at concentrations several times higher than in adjacent waters or ice.

Pesticides in mountain yellow‐legged frogs (Rana muscosa) from the Sierra Nevada Mountains of California, USA

In 1997, pesticide concentrations were measured in mountain yellow-legged frogs (Rana muscosa) from two areas in the Sierra Nevada Mountains of California, USA. One area (Sixty Lakes Basin, Kings Canyon National Park) had large, apparently healthy populations of frogs. A second area (Tablelands, Sequoia National Park) once had large populations, but the species had been extirpated from this area by the early 1980s. The Tablelands is exposed directly to prevailing winds from agricultural regions to the west. When an experimental reintroduction of R. muscosa in 1994 to 1995 was deemed unsuccessful in 1997, the last 20 (reintroduced) frogs that could be found were collected from the Tablelands, and pesticide concentrations in both frog tissue and the water were measured at both the Tablelands and at reference sites at Sixty Lakes. In frog tissues, dichlorodiphenyldichloroethylene (DDE) concentration was one to two orders of magnitude higher than the other organochlorines (46+/-20 ng/g wet wt at Tablelands and 17+/-8 Sixty Lakes). Both gamma-chlordane and trans-nonachlor were found in significantly greater concentrations in Tablelands frog tissues compared with Sixty Lakes. Organophosphate insecticides, chlorpyrifos, and diazinon were observed primarily in surface water with higher concentrations at the Tablelands sites. No contaminants were significantly higher in our Sixty Lakes samples.

Hydrolysis of chlorpyrifos in natural waters of the Chesapeake Bay.

Chlorpyrifos is the most widely used insecticide in the Chesapeake Bay region. Recent studies show that this organophospate chemical is consistently present in the air, rain and surface waters of the Chesapeake Bay region, suggesting a long environmental half-life. Hydrolytic degradation of chlorpyrifos is likely a dominant removal process, but existing hydrolysis data do not reflect conditions in the Chesapeake Bay. In this project, hydrolysis rates of chlorpyrifos were measured in sterilized, ambient water from the mouth of four Chesapeake Bay tributaries ranging in salinity from 0 to 17 ppt. The measured hydrolysis half-lives varied from 24 d in the Patuxent River to 126 d in the Susquehanna River. These results indicate that pH alone cannot be used as a single parameter to predict hydrolysis under field conditions. The influence of copper concentration, and other water constituents, need to be further evaluated as they may emerge as independent predictors to assess the fate of pesticides in natural systems.

A review of field experiments to determine air-water gas exchange of persistent organic pollutants

Abstract Field experiments to determine air-water exchange of gas-phase persistent organic pollutants (POPs) in lakes and oceans are reviewed. Evidence for exchange comes from mass balancing total inputs and outputs of POPs in lakes, and experiments to determine air-water fugacity gradients. Several of these investigations in the Great Lakes demonstrate a net volatilization of polychlorinated biphenyls (PCBs). The annual cycle of hexachlorocyclohexanes (HCHs) in the Great Lakes, predicted from average monthly air concentrations, shows invasion for most of the year, with short periods of evasion during summer. Volatilization of HCHs takes place in some estuarine regions. Gas-phase fluxes of organochlorine pesticides to oceans and large lakes are of equal or greater magnitude than those due to precipitation and dry particle deposition.

Agricultural pesticide residues in oysters and water from two Chesapeake Bay tributaries

Abstract Little is known of the impact of agricultural activity on oysters in Chesapeake Bay tributaries. As a preliminary assessment of pesticide residues in oyster tissues, this study monitored more than 60 pesticides in oysters and overlying water in two tributaries of the Chesapeake Bay. Paired water and oyster samples were collected throughout 1997 from the Patuxent and Choptank Rivers which discharge into opposite shores of the Chesapeake Bay in Maryland. In water, herbicides such as atrazine, simazine, cyanazine, and metolachlor were present throughout the year with individual water concentrations peaking as high as 430 ng/1 in the late spring and summer and subsiding in the fall. These herbicides were not detected in the oysters even when concentrations were highest in the water. Another herbicide, trifluralin, was detected throughout the year at concentrations of less than 0.6 ng/1 and 0.4 ng/g (wet weight) in water and oyster samples, respectively. Several insecticides, such as endosulfans I and II, endosulfan sulfate, chlorpyrifos, α- and γ-HCH, p,p′-DDE, o,p′-DDT, trans-nonachlor, and trans-chlordane were also measured in both oysters and water at low concentrations.

Air concentrations of organochlorine insecticides and polychlorinated biphenyls over Green Bay, WI, and the four lower Great Lakes

Abstract Organochlorine pesticides and polychlorinated biphenyls were determined in high volume air samples collected in Green Bay from the University of Wisconsin (1989), and from shipboard over the four lower Great Lakes (1990). Average concentrations of Σchlordane, DDT, DDE, toxaphene and ΣPCBs in Green Bay were 35, 8.7, 15, 59 and 330 pg m−3, respectively. Air concentrations of the pesticides were positively correlated to each other (R2=0.896–0.997), and analysis of back trajectory data from Green Bay showed that higher atmospheric concentrations of organochlorine insecticides were associated with air masses originating in southern USA. Average concentrations from the Great Lakes were: Σchlordane, 187 pg m−3; DDT, 38 pg m−3; pg m−3; DDE, 59 pg m−3; toxaphene, 33 pg m−3; and ΣPCBs, 385 pg m−3. Higher air concentrations of PCBs were found in areas of industrial and urban development. There was no strong positive correlation of concentration values between any pesticides, with the exception of the chlordane isomers, or between any pesticide and ΣPCB from the Great Lakes cruise. Results from 5-day air mass back trajectory data suggest that, at the time of the cruise, atmospheric sources of organochlorines were not long-range transport from southern USA, but local or regional volatilization.

Persistence of polybrominated diphenyl ethers in agricultural soils after biosolids applications.

This study examines polybrominated diphenyl ethers (PBDE) levels, trends in biosolids from a wastewater treatment plant, and evaluates potential factors governing PBDE concentrations and the fate in agricultural soils fertilized by biosolids. The mean concentration of the most abundant PBDE congeners in biosolids ( summation operatorBDE-47, BDE-99, and BDE-209) generated by one wastewater treatment plant was 1250 +/- 134 microg/kg d.w. with no significant change in concentration over 32 months (n = 15). In surface soil samples from the Mid-Atlantic region, average PBDE concentrations in soil from fields receiving no biosolids (5.01 +/- 3.01 microg/kg d.w.) were 3 times lower than fields receiving one application (15.2 +/- 10.2 microg/kg d.w.) and 10 times lower than fields that had received multiple applications (53.0 +/- 41.7 microg/kg d.w.). The cumulative biosolids application rate and soil organic carbon were correlated with concentrations and persistence of PBDEs in soil. A model to predict PBDE concentrations in soil after single or multiple biosolids applications provides estimates which fall within a factor of 2 of observed values.

Characterizing the isotopic composition of atmospheric ammonia emission sources using passive samplers and a combined oxidation‐bacterial denitrifier approach

RATIONALE Ammonia (NH3) emissions are a substantial source of nitrogen pollution to sensitive terrestrial, aquatic, and marine ecosystems and dependable quantification of NH3 sources is of growing importance due to recently observed increases in ammonium (NH4(+)) deposition rates. While determination of the nitrogen isotopic composition of NH3 (δ(15)N-NH3) can aid in the quantification of NH3 emission sources, existing methods have precluded a comprehensive assessment of δ(15)N-NH3 values from major emission sources. METHODS We report an approach for the δ(15)N-NH4(+) analysis of low concentration NH4(+) samples that couples the bromate oxidation of NH4(+) to NO2(-) and the microbial denitrifier method for δ(15)N-NO2(-) analysis. This approach reduces the required sample mass by 50-fold relative to standard elemental analysis (EA) procedures, is capable of high throughput, and eliminates toxic chemicals used in a prior method for the analysis of low concentration samples. Using this approach, we report a comprehensive inventory of δ(15)N-NH3 values from major emission sources (including livestock operations, marine sources, vehicles, fertilized cornfields) collected using passive sampling devices. RESULTS The δ(15)N-NH4(+) analysis approach developed has a standard deviation of ±0.7‰ and was used to analyze passively collected NH3 emissions with a wide range of ambient NH3 concentrations (0.2 to 165.6 µg/m(3)). The δ(15)N-NH3 values reveal that the NH3 emitted from volatilized livestock waste and fertilizer has relatively low δ(15)N values (-56 to -23‰), allowing it to be differentiated from NH3 emitted from fossil fuel sources that are characterized by relatively high δ(15)N values (-15 to +2‰). CONCLUSIONS The isotopic source signatures presented in this emission inventory can be used as an additional tool in identifying NH3 emission sources and tracing their transport across localized landscapes and regions. The insight into the transport of NH3 emissions provided by isotopic investigation is an important step in devising strategies to reduce future NH3 emissions, a mounting concern for air quality scientists, epidemiologists, and policy-makers.

Water quality and conservation practice effects in the Choptank River watershed

The Choptank River is an estuary, tributary of the Chesapeake Bay, and an ecosystem in decline due partly to excessive nutrient and sediment loads from agriculture. The Conservation Effects Assessment Project for the Choptank River watershed was established to evaluate the effectiveness of conservation practices on water quality within this watershed. Several measurement frameworks are being used to assess conservation practices. Nutrients (nitrogen and phosphorus) and herbicides (atrazine and metolachlor) are monitored within 15 small, agricultural subwatersheds and periodically in the lower portions of the river estuary. Initial results indicate that land use within these subwatersheds is a major determinant of nutrient concentration in streams. In addition, the 18O isotope signature of nitrate was used to provide a landscape assessment of denitrification processes in the presence of the variable land use. Herbicide concentrations were not correlated to land use, suggesting that herbicide delivery to the streams is influenced by other factors and/or processes. Remote sensing technologies have been used to scale point measurements of best management practice effectiveness from field to subwatershed and watershed scales. Optical satellite (SPOT-5) data and ground-level measurements have been shown to be effective for monitoring nutrient uptake by winter cover crops in fields with a wide range of management practices. Synthetic Aperture Radar (RADARSAT-1) data have been shown to detect and to characterize accurately the hydrology (hydroperiod) of forested wetlands at landscape and watershed scales. These multiple approaches are providing actual data for assessment of conservation practices and to help producers, natural resource managers, and policy makers maintain agricultural production while protecting this unique estuary.

Pesticide distributions and population declines of California, USA, alpine frogs, Rana muscosa and Rana sierrae

Atmospherically deposited pesticides from the intensively cultivated Central Valley of California, USA, have been implicated as a cause for population declines of several amphibian species, with the strongest evidence for the frogs Rana muscosa and Rana sierrae at high elevation in the Sierra Nevada mountains. Previous studies on these species have relied on correlations between frog population status and either a metric for amount of upwind pesticide use or limited measurements of pesticide concentrations in the field. The present study tested the hypothesis that pesticide concentrations are negatively correlated with frog population status (i.e., fraction of suitable water bodies occupied within 2 km of a site) by measuring pesticide concentrations in multiple media twice at 28 sites at high elevation in the southern Sierra Nevada. Media represented were air, sediment, and Pseudacris sierra tadpoles. Total cholinesterase (ChE), which has been used as an indicator for organophosphorus and carbamate pesticide exposure, was also measured in P. sierra tadpoles. Results do not support the pesticide-site occupancy hypothesis. Among 46 pesticide compounds analyzed, nine were detected with ≥ 30% frequency, representing both historically and currently used pesticides. In stepwise regressions with a chemical metric and linear distance from the Central Valley as predictor variables, no negative association was found between frog population status and the concentration of any pesticide or tadpole ChE activity level. By contrast, frog population status showed a strong positive relationship with linear distance from the Valley, a pattern that is consistent with a general west-to-east spread across central California of the amphibian disease chytridiomycosis observed by other researchers.