Incorporating the benefits of vegetative filter strips into risk assessment and risk management of pesticides.

The pesticide registration process in North America, including the USA and Canada, involves conducting a risk assessment based on relatively conservative modeling to predict pesticide concentrations in receiving waterbodies. The modeling framework does not consider some commonly adopted best management practices that can reduce the amount of pesticide that may reach a waterbody, such as vegetative filter strips (VFS). Currently, VFS are being used by growers as an effective way to reduce off-site movement of pesticides, and they are being required or recommended on pesticide labels as a mitigation measure. Given the regulatory need, a pair of multistakeholder workshops were held in Raleigh, North Carolina, to discuss how to incorporate VFS into pesticide risk assessment and risk management procedures within the North American regulatory framework. Because the risk assessment process depends heavily on modeling, one key question was how to quantitatively incorporate VFS into the existing modeling approach. Key outcomes from the workshops include the following: VFS have proven effective in reducing pesticide runoff to surface waterbodies when properly located, designed, implemented, and maintained; Vegetative Filter Strip Modeling System (VFSMOD), a science-based and widely validated mechanistic model, is suitable for further vetting as a quantitative simulation approach to pesticide mitigation with VFS in current regulatory settings; and VFSMOD parametrization rules need to be developed for the North American aquatic exposure assessment. Integr Environ Assess Manag 2024;20:454-464. © 2023 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Effectiveness and diurnal variations of vegetative environmental buffers (VEBs) for mitigating NH3 and PM emissions from poultry houses.

Air pollutants from poultry production, such as ammonia (NH3) and particulate matter (PM), have raised concerns due to their potential negative impacts on human health and the environment. Vegetative environmental buffers (VEBs), consisting of trees and/or grasses planted around poultry houses, have been investigated as a mitigation strategy for these emissions. Although previous research demonstrated that VEBs can reduce NH3 and PM emissions, these studies used a limited number of samplers and did not examine concentration profiles. Moreover, the differences between daytime and nighttime emissions have not been investigated. In this study, we characterized emission profiles from a commercial poultry house using an array with multiple sampling heights and explored the differences between daytime and nighttime NH3 and PM profiles. We conducted three sampling campaigns, each with ten sampling events (five daytime and five nighttime), at a VEB-equipped poultry production facility. NH3 and PM samples were collected downwind from the ventilation tunnel fans before, within, and after the VEB. Results showed that ground-level concentrations beyond the VEB decreased to 8.0% ± 2.7% for NH3, 13% ± 4% for TSP, 13% ± 4% for PM10, and 2.4% ± 2.8% for PM2.5 of the original concentrations from the exhaust tunnel fan, with greater reduction efficiency during daytime than nighttime. Furthermore, pollutant concentrations were positively intercorrelated. These findings will be valuable for developing more effective pollutant remediation strategies in poultry house emissions.

Overcoming Challenges of Incorporating Higher Tier Data in Ecological Risk Assessments and Risk Management of Pesticides in the United States: Findings and Recommendations from the 2017 Workshop on Regulation and Innovation in Agriculture.

Pesticide regulation requires regulatory authorities to assess the potential ecological risk of pesticides submitted for registration, and most risk assessment schemes use a tiered testing and assessment approach. Standardized ecotoxicity tests, environmental fate studies, and exposure models are used at lower tiers and follow well-defined methods for assessing risk. If a lower tier assessment indicates that the pesticide may pose an ecological risk, higher tier studies using more environmentally realistic conditions or assumptions can be performed to refine the risk assessment and inform risk management options. However, there is limited guidance in the United States on options to refine an assessment and how the data will be incorporated into the risk assessment and risk management processes. To overcome challenges to incorporation of higher tier data into ecological risk assessments and risk management of pesticides, a workshop was held in Raleigh, North Carolina. Attendees included representatives from the United States Environmental Protection Agency, United States Department of Agriculture, National Oceanic and Atmospheric Administration, universities, commodity groups, consultants, nonprofit organizations, and the crop protection industry. Key recommendations emphasized the need for 1) more effective, timely, open communication among registrants, risk assessors, and risk managers earlier in the registration process to identify specific protection goals, address areas of potential concern where higher tier studies or assessments may be required, and if a higher tier study is necessary that there is agreement on study design; 2) minimizing the complexity of study designs while retaining high value to the risk assessment and risk management process; 3) greater transparency regarding critical factors utilized in risk management decisions with clearly defined protection goals that are operational; and 4) retrospective analyses of success-failure learnings on the acceptability of higher tier studies to help inform registrants on how to improve the application of such studies to risk assessments and the risk management process. Integr Environ Assess Manag 2019;15:714-725. © 2019 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Using a Vegetative Environmental Buffer to Reduce the Concentrations of Volatile Organic Compounds in Poultry-House Atmospheric Emissions.

Ground-level ozone is formed when volatile organic compounds (VOCs) react with hydroxyl radicals and nitrogen oxides in the presence of ultraviolet light. Research has typically focused on the release and control of VOCs from hydrocarbon processing; however, agricultural activities, such as poultry production, can also be VOC sources and potentially contribute to ozone pollution. Therefore, this study examines the emission of C2-C6 VOCs from poultry houses and the use of a vegetative environmental buffer (VEB) as a potential mitigation strategy. Sampling campaigns were conducted at two farms, one with and one without a VEB. Of the nine compounds measured, methanol, ethanol, and acetone were the primary VOCs emitted and had the largest ozone-formation potential (OFP). A significantly larger decrease in the OFP for methanol as a function of distance from the poultry house was observed at the farm with the VEB as compared with at the farm without the VEB. These results suggest that besides being a visual barrier and particulate screen, VEBs can provide some control of VOCs emitted from poultry production.

Assessment of particulate matter and ammonia emission concentrations and respective plume profiles from a commercial poultry house.

Poultry-emitted air pollutants, including particulate matter (PM) and ammonia, have raised concerns due to potential negative effects on human health and the environment. However, developing and optimizing remediation technologies requires a better understanding of air pollutant concentrations, the emission plumes, and the relationships between the pollutants. Therefore, we conducted ten field experiments to characterize PM (total suspended particulate [TSP], particulate matter less than 10 µm in aerodynamic diameter [PM10], and particulate matter less than 2.5 µm in aerodynamic diameter [PM2.5]) and ammonia emission-concentration profiles from a typical commercial poultry house. The emission factors of the poultry house, which were calculated using the concentrations and fan speed, were 0.66 (0.29-0.99) g NH3-N bird-1d-1 for ammonia, 52 (44-168) g d-1AU-1 (AU = animal unit = 500 kg) for TSP, 3.48 (1.16-9.03) g d-1AU-1 for PM10, and 0.07 (0.00-0.36) g d-1AU-1 for PM2.5. PM and ammonia emission concentrations decreased as distance from the fan increased. Although emission concentrations were similar in the daytime and nighttime, diurnal and nocturnal plume shapes were different due to the increased stability of the atmosphere at night. Particle size distribution analysis revealed that, at a given height, the percentage of PM10 and PM2.5 was consistent throughout the plume, indicating that the larger particles were not settling out of the airstream faster than the smaller particles. Overall, the direction of the measured air pollutant emission plumes was dominated by the tunnel fan ventilation airflow rate and direction instead of the ambient wind speed and direction. This is important because currently-available air dispersion models use ambient or modeled wind speed and direction as input parameters. Thus, results will be useful in evaluating dispersion models for ground-level, horizontally-released, point sources and in developing effective pollutant remediation strategies for emissions.

Using a high-organic matter biowall to treat a trichloroethylene plume at the Beaver Dam Road landfill.

Trichloroethylene (TCE) is a highly effective industrial degreasing agent and known carcinogen. It was frequently buried improperly in landfills and has subsequently become one of the most common groundwater and soil contaminants in the USA. A common strategy to remediate TCE-contaminated sites and to prevent movement of the TCE plumes into waterways is to construct biowalls which consist of biomaterials and amendments to enhance biodegradation. This approach was chosen to contain a TCE plume emanating from a closed landfill in Maryland. However, predicting the effectiveness of biowalls is often site specific. Therefore, we conducted an extensive series of batch reactor studies at 12 °C as opposed to the typical room temperature to examine biowall fill-material combinations including the effects of zero-valent iron (ZVI) and glycerol amendments. No detectable TCE was observed after several months in the laboratory study when using the unamended 4:3 mulch-to-compost combination. In the constructed biowall, this mixture reduced the upstream TCE concentration by approximately 90% and generated ethylene downstream, an indication of successful reductive dechlorination. However, the more toxic degradation product vinyl chloride (VC) was also detected downstream at levels approximately ten times greater than the maximum contaminant level. This indicates that incomplete degradation also occurred. In the laboratory, ZVI reduced VC formation. A hazard quotient was calculated for the landfill site with and without the biowall. The addition of the biowall decreased the hazard quotient by 88%.

Evaluation of an electronic nose for odorant and process monitoring of alkaline-stabilized biosolids production.

Electronic noses have been widely used in the food industry to monitor process performance and quality control, but use in wastewater and biosolids treatment has not been fully explored. Therefore, we examined the feasibility of an electronic nose to discriminate between treatment conditions of alkaline stabilized biosolids and compared its performance with quantitative analysis of key odorants. Seven lime treatments (0-30% w/w) were prepared and the resultant off-gas was monitored by GC-MS and by an electronic nose equipped with ten metal oxide sensors. A pattern recognition model was created using linear discriminant analysis (LDA) and principal component analysis (PCA) of the electronic nose data. In general, LDA performed better than PCA. LDA showed clear discrimination when single tests were evaluated, but when the full data set was included, discrimination between treatments was reduced. Frequency of accurate recognition was tested by three algorithms with Euclidan and Mahalanobis performing at 81% accuracy and discriminant function analysis at 70%. Concentrations of target compounds by GC-MS were in agreement with those reported in literature and helped to elucidate the behavior of the pattern recognition via comparison of individual sensor responses to different biosolids treatment conditions. Results indicated that the electronic nose can discriminate between lime percentages, thus providing the opportunity to create classes of under-dosed and over-dosed relative to regulatory requirements. Full scale application will require careful evaluation to maintain accuracy under variable process and environmental conditions.

Polybrominated diphenyl ethers: Residence time in soils receiving biosolids application.

Polybrominated diphenyl ethers (PBDEs) may enter the environment because of accumulation in biosolids followed by application to agricultural lands. No published dissipation studies are available for PBDEs in agricultural soils after biosolids application. Therefore, we conducted a 3-year study to examine the fate of PBDEs in a small-scale 0.24-ha continuously cropped field after a single biosolids application at 72.3 wet tons/ha and determined dissipation half-lives for BDE-47+BDE-99 and BDE-209. In addition, we conducted a large-scale survey of soils from 26 mostly pasture fields at 10 farms with detailed information on timing and rate of biosolids applications. In the small-scale experiment, maximum soil PBDE concentrations of 43.7 ± 42.7 µg kg-1 d.w. for BDE-209 and 6.05 ± 7.15 µg kg-1 d.w. for BDE-47+BDE-99 were reached 1 year after application. We hypothesized that PBDEs were slowly released from the biosolids matrix into the soil over the first year. After 3 years, median BDE-47+BDE-99 concentrations were approximately equal to preapplication levels, whereas median BDE-209 concentrations remained ∼129% above preapplication levels. The estimated residence time from the small-scale experiment was 342 d for BDE-47+BDE-99 and 861 d for BDE-209. In the large-scale study, a subset of fields that received a single biosolids application was used to generate another estimate of residence time: 704 d for BDE-47+BDE-99 and 1440 d for BDE-209. These longer residence time estimates were used in three different first-order decay dissipation scenarios (continuous, limited, and no dissipation) to predict PBDE concentration in fields with single and multiple biosolids applications. Results indicate that dissipation occurs primarily in the first 2 years after application, but residues remaining in the soil after this period are likely to be much more tightly bound and less available for degradation.

Clothianidin in agricultural soils and uptake into corn pollen and canola nectar after multiyear seed treatment applications.

Limited data are available on the fate of clothianidin under realistic agricultural production conditions. The present study is the first large-scale assessment of clothianidin residues in soil and bee-relevant matrices from corn and canola fields after multiple years of seed-treatment use. The average soil concentration from 50 Midwest US corn fields with 2 yr to 11 yr of planting clothianidin-treated seeds was 7.0 ng/g, similar to predicted concentrations from a single planting of Poncho 250-treated corn seeds (6.3 ng/g). The water-extractable (i.e., plant-bioavailable) clothianidin residues in soil were only 10% of total residues. Clothianidin concentrations in soil reached a plateau concentration (amount applied equals amount dissipated) in fields with 4 or more application years. Concentrations in corn pollen from these fields were low (mean: 1.8 ng/g) with no correlation to total years of use or soil concentrations. For canola, soil concentrations from 27 Canadian fields with 2 yr to 4 yr of seed treatment use (mean = 5.7 ng/g) were not correlated with use history, and plant bioavailability was 6% of clothianidin soil residues. Average canola nectar concentrations were 0.6 ng/g and not correlated to use history or soil concentrations. Under typical cropping practices, therefore, clothianidin residues are not accumulating significantly in soil, plant bioavailability of residues in soil is limited, and exposure to pollinators will not increase over time in fields receiving multiple applications of clothianidin.

Organic amendments for risk mitigation of organochlorine pesticide residues in old orchard soils.

Performance of compost and biochar amendments for in situ risk mitigation of aged DDT, DDE and dieldrin residues in an old orchard soil was examined. The change in bioavailability of pesticide residues to Lumbricus terrestris L. relative to the unamended control soil was assessed using 4-L soil microcosms with and without plant cover in a 48-day experiment. The use of aged dairy manure compost and biosolids compost was found to be effective, especially in the planted treatments, at lowering the bioavailability factor (BAF) by 18-39%; however, BAF results for DDT in the unplanted soil treatments were unaffected or increased. The pine chip biochar utilized in this experiment was ineffective at lower the BAF of pesticides in the soil. The US EPA Soil Screening Level approach was used with our measured values. Addition of 10% of the aged dairy manure compost reduced the average hazard quotient values to below 1.0 for DDT + DDE and dieldrin. Results indicate this sustainable approach is appropriate to minimize risks to wildlife in areas of marginal organochlorine pesticide contamination. Application of this remediation approach has potential for use internationally in areas where historical pesticide contamination of soils remains a threat to wildlife populations.

13th IUPAC International Congress of Pesticide Chemistry: Crop, Environment, and Public Health Protection, Technologies for a Changing World.

This introductory paper provides an overview of Perspectives papers written by plenary speakers from the 13th IUPAC International Congress of Pesticide Chemistry held in San Francisco, CA, USA, in August 2014. This group of papers emphasizes some of the emerging issues and challenges at the forefront of agricultural research: sustainability; agriculture's response to climate change and population growth; pollinator health and risk assessment; and global food production and food security. In addition, as part of the Congress, a workshop on "Developing Global Leaders for Research, Regulation, and Stewardship of Crop Protection Chemistry in the 21st Century" identified specific recommendations to attract the best scientists to agricultural science, to provide opportunities to study and conduct research on crop protection chemistry topics, and to improve science communication skills.

Climate Change, Carbon Dioxide, and Pest Biology: Monitor, Mitigate, Manage.

Rising concentrations of atmospheric carbon dioxide ([CO2]) and subsequent changes in climate, including temperature and precipitation extremes, are very likely to alter pest pressures in both managed and unmanaged plant communities. Such changes in pest pressures can be positive (migration from a region) or negative (new introductions), but are likely to be accompanied by significant economic and environmental consequences. Recent studies indicate the range of invasive weeds such as kudzu and insects such as mountain pine beetle have already expanded to more northern regions as temperatures have risen. To reduce these consequences, a better understanding of the link between CO2/climate and pest biology is needed in the context of existing and new strategies for pest management. This paper provides an overview of the probable biological links and the vulnerabilities of existing pest management (especially chemical control) and provides a preliminary synthesis of research needs that could potentially improve the ability to monitor, mitigate, and manage pest impacts.

Long-term trends of PBDEs, triclosan, and triclocarban in biosolids from a wastewater treatment plant in the Mid-Atlantic region of the US.

In the US, land application of biosolids has been utilized in government-regulated programs to recycle valuable nutrients and organic carbon that would otherwise be incinerated or buried in landfills. While many benefits have been reported, there are concerns that these practices represent a source of organic micropollutants to the environment. In this study, biosolids samples from a wastewater treatment plant in the Mid-Atlantic region of the US were collected approximately every 2 months over a 7-year period and analyzed for brominated diphenyl ethers (BDE-47, BDE-99, and BDE-209), triclosan, and triclocarban. During the collection period of 2005-2011, concentrations of the brominated diphenyl ethers BDE-47+BDE-99 decreased by 42%, triclocarban decreased by 47%, but BDE-209 and triclosan remained fairly constant. Observed reductions in contaminant concentrations could not be explained by different seasons or by volumetric changes of wastewaters arriving at the treatment plant and instead may be the result of the recent phaseout of BDE-47 and BDE-99 as well as potential reductions in the use of triclocarban.

Fate of microconstituents in biosolids composted in an aerated silage bag.

Although most composting studies report pathogen concentrations, little is known about the fate of Endocrine Disruptor Chemicals (EDCs) during composting. In this study, a positively aerated polyethylene bag composting system was filled with a mixture of woodchips and limed biosolids from a large Waste Water Treatment Plant (WWTP) to study the removal efficiency of two different groups of EDCs. Two antibacterial compounds, Triclocarban (TCC) and Triclosan (TCS), and a TCS byproduct, Methyltriclosan (MeTCS), as well as seven congeners of flame retardants known as PBDEs (Polybrominated Diphenyl Ethers) were studied during two phases of composting: 1) a thermophilic phase, in which positive mechanical aeration, pushing air into and through the materials matrix, was conducted for 2 months; and 2) a curing and stabilization phase in which no mechanical aeration was provided and the bag was opened to ambient passive aeration to simulate storage conditions for seven months. Our results showed that while TCC concentrations remained constant, TCS degradation took place during both phases. The degradation of TCS was corroborated by the formation of MeTCS in both phases. The TCS concentrations decreased from 18409 ± 1,877 to 11955 ± 288 ng g(-1) dry wt. during the thermophilic phase and declined from 11,955 ± 288 to 7,244 ± 909. ng g(-1) dry wt. by the end of the curing phase. Thus, slightly greater TCS transformation occurred during the second than during the first (35.1 vs. 39.4%). MeTCS concentrations increased from 189.3 ± 8.6 to 364.6 ± 72.5 ng g(-1) dry wt. during the first phase and reached 589.0 ± 94.9 ng g(-1) dry wt. at the end of the second phase. PBDEs concentrations were below quantification limits for all but two of the congeners analyzed (BDE-47 and BDE-99). PBDE concentrations were measured at the end of the first phase only and were comparable to initial concentrations.

Temperature-dependent Raman spectroscopic evidence of and molecular mechanism for irreversible isomerization of ß-endosulfan to α-endosulfan.

Endosulfan (6,7,8, 9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) is a broad-spectrum, organochlorine insecticide used on numerous crops since the 1950s. It is has been identified as a persistent organic pollutant (POP) due to its persistence, bioaccumulation, long-range transport, and adverse effects to human health and aquatic ecosystems; it will be phased out in the United States in 2016. Endosulfan consists of two diastereomers, α and ß; α-endosulfan exists as two asymmetrical, twist-chair enantiomers which interchange, while ß-endosulfan has a symmetrical-chair conformation. ß-Endosulfan has been shown to isomerize to α-endosulfan. Here we document the previously proposed isomerization mechanism using temperature-dependent Raman (TDR) spectroscopy. The bending frequencies in the fingerprint region were assigned to specific bonds. Changes in the signal intensity as a function of temperature were used to identify detailed ring movements and thus conversion of ß to α. These movements cannot occur simultaneously nor symmetrically, precluding conversion of α-endosulfan to ß-endosulfan.

Metolachlor metabolite (MESA) reveals agricultural nitrate-N fate and transport in Choptank River watershed.

Over 50% of streams in the Chesapeake Bay watershed have been rated as poor or very poor based on the index of biological integrity. The Choptank River estuary, a Bay tributary on the eastern shore, is one such waterway, where corn and soybean production in upland areas of the watershed contribute significant loads of nutrients and sediment to streams. We adopted a novel approach utilizing the relationship between the concentration of nitrate-N and the stable, water-soluble herbicide degradation product MESA {2-[2-ethyl-N-(1-methoxypropan-2-yl)-6-methylanilino]-2-oxoethanesulfonic acid} to distinguish between dilution and denitrification effects on the stream concentration of nitrate-N in agricultural subwatersheds. The ratio of mean nitrate-N concentration/(mean MESA concentration * 1000) for 15 subwatersheds was examined as a function of percent cropland on hydric soil. This inverse relationship (R(2)=0.65, p<0.001) takes into consideration not only dilution and denitrification of nitrate-N, but also the stream sampling bias of the croplands caused by extensive drainage ditch networks. MESA was also used to track nitrate-N concentrations within the estuary of the Choptank River. The relationship between nitrate-N and MESA concentrations in samples collected over three years was linear (0.95 ≤ R(2) ≤ 0.99) for all eight sampling dates except one where R(2)=0.90. This very strong correlation indicates that nitrate-N was conserved in much of the Choptank River estuary, that dilution alone is responsible for the changes in nitrate-N and MESA concentrations, and more importantly nitrate-N loads are not reduced in the estuary prior to entering the Chesapeake Bay. Thus, a critical need exists to minimize nutrient export from agricultural production fields and to identify specific conservation practices to address the hydrologic conditions within each subwatershed. In well drained areas, removal of residual N within the cropland is most critical, and practices such as cover crops which sequester the residual N should be strongly encouraged. In poorly drained areas where denitrification can occur, wetland restoration and controlled drained structures that minimize ditch flow should be used to maximize denitrification.

Utilizing thin-film solid-phase extraction to assess the effect of organic carbon amendments on the bioavailability of DDT and dieldrin to earthworms.

Improved approaches are needed to assess bioavailability of hydrophobic organic compounds in contaminated soils. Performance of thin-film solid-phase extraction (TF-SPE) using vials coated with ethylene vinyl acetate was compared to earthworm bioassay (Lumbricus terrestris). A DDT and dieldrin contaminated soil was amended with four organic carbon materials to assess the change in bioavailability. Addition of organic carbon significantly lowered bioavailability for all compounds except for 4,4'-DDT. Equilibrium concentrations of compounds in the polymer were correlated with uptake by earthworms after 48d exposure (R(2) = 0.97; p < 0.001), indicating TF-SPE provided an accurate uptake simulation. Bioavailability of residues in soil was compared with a spiked soil aged for 90d in laboratory. Dieldrin and DDX were respectively 18% and 11% less bioavailable in contaminated soil relative to spiked soil despite >40yr of aging. Results show that TF-SPE can be useful in examining potential risks associated with contaminated soils and to test effectiveness of remediation efforts.