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Pesticide and transformation product detections and age-dating relations from till and sand deposits

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. ?? 2007 American Water Resources Association.

Journal of the American Water Resources Associatio

Care of nestlings by wild female starlings exposed to an organophosphate pesticide

(1) Our objective was to determine the effect of exposure to an organophosphate pesticide (OP), dicrotophos (3-hydroxy- N,N -dimethyl- cis -scrotonamide dimethyl phosphate), on care of nestlings by wild female starlings ( Sturnus vulgaris ). (2) We selected twelve pairs of active nests based on synchrony in the reproductive cycle. When nestlings were 10 days old (day 10), adult males were captured and killed and brood size was adjusted to four. The frequency and temporal distribution of sorties made by each pair of females to feed their young were recorded for 2 h at 18.00 hours on day 11 and 06.00 hours on day 12. One female from each pair was given a single oral dose of dicrotophos (2.5 mg/kg of body weight) dissolved in corn oil; the second female received an equivalent exposure of pure corn oil. Birds were released and their nestlings weighed. Parental care was again monitored between 18.00 and 20.00 hours on day 12 and 06.00 and 08.00 hours on day 13. Females were then captured and they with their young were weighed and killed. Changes in parental care in OP-dosed and control females were compared using paired t-tests. (3) The OP-dosed females made significantly ( P < 0.5) fewer sorties to feed their young and remained away from their boxes for longer periods of time than controls. Nestlings of OP-treated females lost significantly more weight ( X̄ = 9.3%) than nestlings of controls ( X̄ = 3.2%). Brain ChE activity in OP-treated females was inhibited an average of 50.7% compared with controls. Weight changes in OP-dosed ( X̄ = -8.9%) and control females ( X̄ = -8.3%) were similar. (4) Results indicate that parental care may be significantly reduced in songbirds receiving severe but sublethal exposure to organophosphate pesticides. The potential for a reduction or modification in parental care to alter reproductive success in passerines is discussed. (5) Techniques utilized, or modifications thereof, may be useful in collecting the additional data needed to adequately assess the impact of OPs on songbird reproduction.

Journal of Applied Ecology

Chlorinated, brominated, and perfluorinated compounds, polycyclic aromatic hydrocarbons and trace elements in livers of sea otters from California, Washington, and Alaska (USA), and Kamchatka (Russia)

Concentrations of organochlorine pesticides (DDTs, HCHs, and chlordanes), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), perfluorinated compounds (PFCs), and 20 trace elements were determined in livers of 3- to 5-year old stranded sea otters collected from the coastal waters of California, Washington, and Alaska (USA) and from Kamchatka (Russia). Concentrations of organochlorine pesticides, PCBs, and PBDEs were high in sea otters collected from the California coast. Concentrations of DDTs were 10-fold higher in California sea otters than in otters from other locations; PCB concentrations were 5-fold higher, and PBDE concentrations were 2-fold higher, in California sea otters than in otters from other locations. Concentrations of PAHs were higher in sea otters from Prince William Sound than in sea otters from other locations. Concentrations of several trace elements were elevated in sea otters collected from California and Prince William Sound. Elevated concentrations of Mn and Zn in sea otters from California and Prince William Sound were indicative of oxidative stress-related injuries in these two populations. Concentrations of all of the target compounds, including trace elements, that were analyzed in sea otters from Kamchatka were lower than those found from the US coastal locations.

Alaska, California, Washington

Results of a prototype surface water network design for pesticides developed for the San Joaquin River Basin, California

A nested surface water monitoring network was designed and tested to measure variability in pesticide concentrations in the San Joaquin River and selected tributaries during the irrigation season. The network design an d sampling frequency necessary for determining the variability and distribution in pesticide concentrations were tested in a prototype study. The San Joaquin River Basin, California, was sampled from April to August 1992, a period during the irrigation season where there was no rainfall. Orestimba Creek, which drains a part of the western San Joaquin Valley, was sampled three times per week for 6 weeks, followed by a once per week sampling for 6 weeks, and the three times per week sampling for 6 weeks. A site on the San Joaquin River near the mouth of the basin, and an irrigation drain of the eastern San Joaquin Valley, were sampled weekly during the entire sampling period. Pesticides were most often detected in samples collected from Orestimba Creek. This suggests that the western valley was the principal source of pesticides to the San Joaquin River during the irrigation season. Irrigation drainage water was the source of pesticides to Orestimba Creek. Pesticide concentrations of Orestimba Creek showed greater temporal variability when sampled three times per week than when sampled once a week, due to variations in field management and irrigation. The implication for the San Joaquin River basin (an irrigation-dominated agricultural setting) is that frequent sampling of tributary sites is necessary to describe the variability in pesticides transported to the San Joaquin River.

Journal of Hydrology

Prevalence and potential for biological effects of several chemicals of interest in Lake Superior tributaries

Lake Superior is typically assumed to have excellent water quality, but its tributaries have been understudied for contaminants relative to other Great Lakes. This study monitored polycyclic aromatic hydrocarbons (PAHs), alkylphenols (AP) and alkylphenol ethoxylates (APEs), bisphenols, and neonicotinoid pesticides in 18 sites on 17 United States tributaries to Lake Superior in 2022. Contaminants were analyzed from 54 surface water and 17 stream bed sediment samples. PAHs were the most prevalent contaminant class. Among 17 PAHs in 17 samples (289 instances), 71 % were positive detections. Surface water samples were not analyzed for PAHs. Next, among 4 APs and APEs analyzed, 35 % of sediment sample instances and 21 % of instances in 54 water samples were positive detections. Bisphenol analogues were detected in 2 % of sediment sample instances and 4 % of water sample instances. Bisphenol A (BPA) was not quantified due to field blank contamination, but bisphenol AF (BPAF), bisphenol E (BPE), bisphenol F (BPF), and bisphenol S (BPS) were detected in environmental samples. Neonicotinoids were detected in 0.5 % of sediment sample instances and 0.4% of water samples instances. Low detection frequencies for contaminants precluded analyses with watershed land use characteristics, but four sites (Tischer Creek, Miller Creek, Carp River and Iron River) emerged as locations with relatively elevated contaminant concentrations. Comparison of concentrations with ToxCast and other water quality guidelines suggested potential for biological effects from some samples. This study provides a baseline of low contaminant prevalence in Lake Superior tributaries while identifying a few locations that may warrant further monitoring.

Michigan, Minnesota, Wisconsin

A seasonal electric barrier blocks invasive adult sea lamprey (Petromyzon marinus) and reduces production of larvae

Sea lamprey ( Petromyzon marinus ) control is achieved in the Laurentian Great Lakes by applying lamprey-specific pesticides (lampricides) to habitats containing larval sea lamprey. Lampricide treatments cost less and are more effective in watersheds where dams block adult sea lamprey migration and limit larval distribution relative to watersheds with no barriers to migration. However, dams impound water and can block movement of valued fishes, outcomes that are untenable for some stakeholders. Here, a seasonal and non-physical barrier of pulsed direct electrical current was tested to block adult sea lamprey while also monitoring the movement and mortality of non-target fish species. The electric barrier was operated in the Black Mallard River, a tributary to northern Lake Huron, March through August 2016–2018. The electric field blocked adult sea lamprey; 1056 adult sea lamprey were captured downstream of the electric field and two were captured upstream of the electric barrier over the three-year study. In 2018, larval sea lamprey abundance upstream of the barrier was about 50% less than historical averages, and genetic analysis found that roughly 98% of larvae upstream of the barrier were spawned in years prior to barrier installation. When the barrier was electrified, non-target fish species were blocked, and a small percentage (<3%) were killed. This study demonstrated that a seasonally deployed electric barrier can reduce the abundance of larval sea lamprey upstream without impounding water, but effects on the movements and survival of other fish species remain a concern.

Michigan

Organochlorine pesticides and thiamine in eggs of largemouth bass and American alligators and their relationship with early life-stage mortality

Thiamine deficiency has been linked to early mortality syndrome in salmonids in the Great Lakes. This study was conducted to compare thiamine concentrations in American alligators ( Alligator mississippiensis ) and Florida largemouth bass ( Micropterus salmoides floridanus ) eggs from sites with high embryo mortality and high exposure to organochlorine pesticides (OCPs) (Lakes Apopka and Griffin, and Emeralda Marsh, Florida, USA) to those from sites that have historically exhibited low embryo mortality and low OCPs (Lakes Woodruff and Orange, Florida). During June-July 2000, 20 alligator clutches were collected from these sites, artificially incubated, and monitored for embryo mortality. Thiamine and OCPs were measured in one egg/clutch. During February 2002, 10 adult female bass were collected from Emeralda Marsh and Lake Woodruff and mature ovaries analyzed for thiamine and OCP concentrations. Although ovaries from the Emeralda Marsh bass contained almost 1,000-fold more OCPs compared with the reference site, Lake Woodruff, there were no differences in thiamine concentrations between sites (11,710 vs. 11,857 pmol/g). In contrast, alligator eggs from the reference site had five times the amount of thiamine compared with the contaminated sites (3,123 vs. 617 pmol/g). Similarly, clutches with > 55% hatch rates had significantly higher concentrations of thiamine compared with clutches with <54% hatch rates (1,119 vs. 201 pmol/g). These results suggest that thiamine deficiency might be playing an important role in alligator embryo survival but not in reproductive failure and recruitment of largemouth bass. The cause(s) of this thiamine deficiency are unknown but might be related to differences in the nutritional value of prey items across the sites studied and/or to the presence of high concentration of contaminants in eggs.

Florida

Managing individual nests promotes population recovery of a top predator

Threatened species are managed using diverse conservation tactics implemented at multiple scales ranging from protecting individuals, to populations, to entire species. Individual protection strives to promote recovery at the population‐ or species‐level, although this is seldom evaluated. After decades of widespread declines, bald eagles, Haliaeetus leucocephalus , are recovering throughout their range due to legal protection and pesticide bans. However, like other raptors, their recovery remains threatened by human activities. Bald eagle nests are commonly managed using buffer zones to minimize human disturbance, but the benefits of this practice remain unquantified. Within Voyageurs National Park (VNP), Minnesota, USA, managers have monitored bald eagle populations for over 40 years, and since 1991, have protected at‐risk nests from human disturbance using buffer zones (200 and 400 m radius). We aimed to (1) quantify the recovery of bald eagles in VNP (1973–2016), and (2) provide a first‐ever evaluation of the individual‐ and population‐level effects of managing individual nests. To do so, we developed Bayesian Integrated Population Models combining observations of nest occupancy and reproductive output (metrics commonly collected for raptors) to estimate nest‐level probabilities of occupancy, nest success, and high productivity (producing ≥2 nestlings), as well as population‐level estimates of abundance and growth. The breeding population of bald eagles at VNP increased steadily from <10 pairs in the late 1970s to 48 pairs by 2016. At the nest‐level, management significantly improved occupancy and success. At the population‐level, management led to 8% and 13% increases in nest success and productivity rates, respectively, resulting in a 37% increase in breeding pair abundance. Synthesis and applications . There is a clear need to evaluate how management approaches at multiple scales assist in species recovery. Our study uses an Integrated Population Model to reveal the population‐level benefits of a widely used, individual‐based management action (protecting nests using buffer zones) on a recovering raptor.

Minnesota

Land management impacts on dairy-derived dissolved organic carbon in ground water

Dairy operations have the potential to elevate dissolved organic carbon (DOC) levels in ground water, where it may interact with organic and inorganic contaminants, fuel denitrification, and may present problems for drinking water treatment. Total and percent bioavailable DOC and total and carbon-specific trihalomethane (THM) formation potential (TTHMFP and STHMFP, respectively) were determined for shallow ground water samples from beneath a dairy farm in the San Joaquin Valley, California. Sixteen wells influenced by specific land management areas were sampled over 3 yr. Measured DOC concentrations were significantly elevated over the background as measured at an upgradient monitoring well, ranging from 13 to 55 mg L-1 in wells downgradient from wastewater ponds, 8 to 30 mg L-1 in corral wells, 5 to 12 mg L-1 in tile drains, and 4 to 15 mg L-1 in wells associated with manured fields. These DOC concentrations were at the upper range or greatly exceeded concentrations in most surface water bodies used as drinking water sources in California. DOC concentrations in individual wells varied by up to a factor of two over the duration of this study, indicating a dynamic system of sources and degradation. DOC bioavailability over 21 d ranged from 3 to 10%, comparable to surface water systems and demonstrating the potential for dairy-derived DOC to influence dissolved oxygen concentrations (nearly all wells were hypoxic to anoxic) and denitrification. TTHMFP measurements across all management units ranged from 141 to 1731 ??g L-1, well in excess of the maximum contaminant level of 80 ??g L-1 established by the Environmental Protection Agency. STHMFP measurements demonstrated over twofold variation (???4 to ???8 mmol total THM/mol DOC) across the management areas, indicating the dependence of reactivity on DOC composition. The results indicate that land management strongly controls the quantity and quality of DOC to reach shallow ground water and hence should be considered when managing ground water resources and in any efforts to mitigate contamination of ground water with carbon-based contaminants, such as pesticides and pharmaceuticals. Copyright ?? 2008 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Journal of Environmental Quality

Yellowstone grizzly bear investigations: Annual report of the Interagency Grizzly Bear Study Team, 2004

The contents of this Annual Report summarize results of monitoring and research from the 2004 field season. The report also contains a summary of nuisance grizzly bear ( Ursus arctos horribilis ) management actions. The study team continues to work on issues associated with counts of unduplicated females with cubs-of-the-year (COY). These counts are used to establish a minimum population size, which is then used to establish mortality thresholds for the Recovery Plan (U.S. Fish and Wildlife Service [USFWS] 1993). A computer program that defines the rule set used by Knight et al. (1995) to differentiate unique family groups was completed in spring 2005. We will use an improved version of this model to verify the accuracy of the rules using known bears and their telemetry locations in test runs. We hope to have this work complete by the end of 2005. The grizzly bear recovery plan (USFWS 1993) established mortality quotas at 4% of the minimum population estimate derived from female with COY data and no more than 30% of the 4% (1.2%) could be female bears. Simulation modeling (Harris 1984) established sustainable mortality at around 6% of the population. We used the latest information on reproduction and survival to estimate population trajectory in the same simulation model originally used by Harris. A Wildlife Monograph has been accepted for publication and should be available by summer 2005. Our project addressing the potential application of stable isotopes and trace elements to quantify consumption rates of whitebark pine ( Pinus albicaulis ) and cutthroat trout ( Oncorhynchus clarki ) by grizzly bears was completed. Our manuscript on consumption rates of whitebark pine has been published (Canadian Journal of Zoology 81:763-770). The manuscript on fish consumption rates was also accepted and is published in the Canadian Journal of Zoology 82:493-501. Both can be found on the Interagency Grizzly Bear Study Team (IGBST) website http://www.nrmsc.usgs.gov/research/igbst-home.htm. We began a new study in Grand Teton National Park evaluating habitat use both temporally and spatially between grizzly and black ( Ursus americanus ) bears. We will employ a new form of Global Positioning System (GPS) technology that incorporates a spread spectrum communication system. Spread spectrum allows for transfer of stored GPS locations from the collar to a remote receiving station. Results of our first yea r&rsquo;s field season are summarized in this report. Whitebark pine (WBP) has been identified as one of the import ant fall foods of the Yellowstone grizzly bear. Previous efforts to map the distribution of WBP were for the Cumulative Effects Model. Consequently the only coverage of WBP distribution was for the grizzly bear Recovery Zone. We were successful in getting financial support through the U.S. Geological Survey Land Remote Sensing Program and Interdisciplinary Science Support Activities Project to create an ecosystem-wide map of the distribution of WBP. The results of that project are reported in Appendix A. The study team annually estimates WBP cone production on a series of transects. That information is reported annually in our reports. Concern over the long-term health of WBP prompted us to investigate the usefulness of cone counts as an indirect index of WBP health. Results of this analysis (Appendix B) indicated that cone production is too variable to serve this purpose. Consequently, we partnered with several 2 other agencies and embarked on a program to develop a long-term monitoring program directed specifically at WBP health in the Greater Yellowstone Ecosystem (GYE). Our team (Greater Yellowstone Whitebark Pine Monitoring Working Group) was successful in obtaining funds to develop and implement a WBP health monitoring program. Results of our first years work are presented in Appendix C. We also successfully competed for funds in 2005 and will continue to collect information on WBP health. Army cutworm moths ( Euxoa auxiliaris ) are also a very important food for a segment of the GYE grizzly bear population. Hillary Robison, graduate student at University of Nevada, Reno, is nearing completion of her program. In this report, we post her annual work summary, and abstracts of her most recently submitted publications. These include one on the levels of pesticides in cutworm moths and their potential affect on grizzly bears (Appendix D), a spatial analysis to identify army cutworm moth habitat (Appendix E), and the results of a preliminary analysis of pollen grains on the mouth parts of moths (Appendix F) to help identify which plant species are commonly fed upon. Other study team members have also been working on various aspects of grizzly bear science. Study team member Kerry Gunther hosted a workshop on habituated grizzly bears in North America. A copy of the abstract of that report can be found in Appendix G. Additionally, Kerry Gunther and Doug Smith, wolf researcher in Yellowstone National Park (YNP), reported on the interactions between gray wolves ( Canis lupus ) and female grizzly bears with young. They report that of 15 interactions between these 2 carnivores, 8 involve d females with COY. They observed 2 incidents where cubs were killed by wolves at ungulate carcasses (Appendix H). The annual reports of the IGBST summarize annual data collection. Because additional information can be obtained after publication, data summaries are subject to change. For that reason, data analyses and summaries presented in this report supersede all previously published data. The study area and sampling techniques are reported by Blanchard (1985), Mattson et al. (1991 a ), and Haroldson et al. (1998).

Idaho, Montana, Wyoming

Effect of flood-induced chemical load on filtrate quality at bank filtration sites

Riparian municipal wells, that are located on riverbanks, are specifically designed to capture a portion of the river water through induced infiltration. Runoff from agricultural watersheds is found to carry enormous amounts of pesticides and nitrate. While the risk of contamination for a vast majority of sites with small-capacity vertical wells is low, potential exists for medium to large capacity collector wells to capture a fraction of the surface water contaminants during flood. Prior monitoring and current modeling results indicate that a small-capacity (peak pumpage 0.0315 m3/s) vertical bank filtration well may not be affected by river water nitrate and atrazine even during flood periods. For a medium capacity (0.0875-0.175 m3/s) hypothetical collector well at the same site, potential exists for a portion of the river water nitrate and atrazine to enter the well during flood periods. Various combinations of hydraulic conductivity of the riverbed or bank material were used. For nitrate, it was assumed either no denitrification occurred during the period of simulation or a half-life of 2 years. Equilibrium controlled sorption (organic carbon partition coefficient of 52 ml/g) and a half-life of between 7.5 and 15 weeks were considered for atrazine. Combinations of these parameters were used in various simulations. Peak concentrations of atrazine or nitrate in pumped water could vary from less than 1% to as high as 90% of that in the river. It was found that a combination of river stage, pumping rates, hydraulic properties of the riverbed and bank, and soil/pesticide properties could affect contaminant entry from river water to any of these wells. If the hydraulic conductivity of the bed and bank material were low, atrazine would not reach the pumping well with or without sorption and degradation. However, for moderately low permeable bank and bed materials, some atrazine from river water could enter a hypothetical collector well while pumping at 0.0875 m3/s. It was interesting to note that doubling the pumpage of this collector well would bring in more ground water from the aquifer (with no atrazine) and thus have a lower concentration of atrazine in the filtrate. For highly conductive banks, it is possible to find some atrazine at a vertical well for a sustained pumpage rate of 0.0125 m3/s if the effect of sorption is neglected. However, with equilibrium sorption, the concentration would be below the detection limit. On the other hand, if a collector well of capacity 0.0875 m3/s is used at the place of the vertical well with highly conductive banks, atrazine concentration in the filtrate would be about 80% of river water even assuming equilibrium sorption and a half-life of 7.5 weeks. Remediation of river water contamination of the aquifer using 'scavenger' wells between the river and the pumping well(s) was not a feasible option due to the contact of the aquifer with a highly conductive bank at the site. However, moving the existing pumping well(s) 100 m upstream would have negligible impact from the bank-stored water. ?? 2002 Elsevier Science B.V. All rights reserved.

Journal of Hydrology