Improving modeling of low-altitude particulate matter emission and dispersion: A cotton gin case study.

Monitoring and modeling of airborne particulate matter (PM) from low-altitude sources is becoming an important regulatory target as the adverse health consequences of PM become better understood. However, application of models not specifically designed for simulation of PM from low-altitude emissions may bias predictions. To address this problem, we describe the modification and validation of an air dispersion model for the simulation of low-altitude PM dispersion from a typical cotton ginning facility. We found that the regulatory recommended model (AERMOD) overestimated pollutant concentrations by factors of 64.7, 6.97 and 7.44 on average for PM2.5, PM10, and TSP, respectively. Pollutant concentrations were negatively correlated with height (p < 0.05), distance from source (p < 0.05) and standard deviation of wind direction (p < 0.001), and positively correlated with average wind speed (p < 0.001). Based on these results, we developed dispersion correction factors for AERMOD and cross-validated the revised model against independent observations, reducing overestimation factors to 3.75, 1.52 and 1.44 for PM2.5, PM10 and TSP, respectively. Further reductions in model error may be obtained from use of additional observations and refinement of dispersive correction factors. More generally, the correction permits the validated adjustment and application of pre-existing models for risk assessment and development of remediation techniques. The same approach may also be applied to improve simulations of other air pollutants and environmental conditions of concern.

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.

Use of organic amendments derived from biosolids for groundwater remediation of TCE.

Many groundwater aquifers around the world are contaminated with trichloroethene (TCE), which can be harmful to human and ecosystem health. Permeable Reactive Barriers (PRB) are commonly used to remediate TCE-contaminated groundwaters especially when a point source is ill defined. Using biosolids from wastewater treatment plants as a PRB filling material can provide a source of carbon and nutrients for dechlorinating bacterial activity. However, under the anaerobic conditions of the PRB, methanogenesis can also occur which can adversely affect reductive dechlorination. We conducted bench scale experiments to evaluate the effect of biosolids on TCE reductive dechlorination and found that methanogenesis was significantly higher in the reactors amended with biosolids, but that reductive dechlorination did not decrease. Furthermore, the microbial communities in the biosolid-enhanced reactors were more abundant with obligate dechlorinators, such as Dehalobacter and Dehalogenimonas, than the reactors amended only with the dechlorinating culture. The biosolids enhanced the presence and abundance of methanogens and acetogens, which had a positive effect on maintaining an efficient dechlorinating microbial community and provided the necessary enzymes, cofactors, and electron donors. These results indicate that waste materials such as biosolids can be turned into a valuable resource for bioremediation of TCE and likely other contaminants.

Trans enantiomeric separation of MESA and MOXA, two environmentally important metabolites of the herbicide, metolachlor.

Complete separation of the trans-enantiomers of the two most abundant, persistent polar metabolites of metolachlor, metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid (MOXA), was achieved using UPLC equipped with a reverse phase chiral column and trace detection with an electrospray triple quadrupole mass spectrometer. Various conditions that influenced the separation and instrumental signal were investigated to achieve the optimum separation and instrument response within an analysis time of less than 30 minutes. Different eluting solvent compositions for each metabolite were required for optimized separation of of the 4 enantiomers. Standard curves were responsive to less than 13 ng/mL and 8 ng/mL for the least plentiful MOXA and MESA enantiomers, respectively with a linear coefficient of determination greater than 0.998. Suitability of the method for quantification of the 4 mixed enantiomers of each was demonstrated using natural surface water samples collected from the Choptank River watershed in Eastern Maryland.•LC chiral separation parameters were varied to achieve optimal separation of the major enantiomers of the two metolachlor metabolites.•LC/MS-MS parameters were adjusted to maximize response and minimize analysis time.•Finished methods were used to quantitate enantiomers in archived stream water extracts from agricultural watersheds with corn/soybean production.

Conversations about the Future of Dicamba: The Science Behind Off-Target Movement.

Dicamba is an important herbicide for controlling post-emergent resistant weeds in soybean farming. Recently, the scientific community and general public have further examined off-target transport mechanisms (e.g., spray drift, volatilization, and tank contamination) and the visual responses of soybeans to ultralow dicamba concentrations. This paper synthesizes key chemical concepts and environmental processes associated with dicamba formulations, transport mechanisms, drift measurements, and plant responses. This paper proposes additional areas of research and actions to increase our understanding and communicate the science findings, which should provide farmers with more robust tools and practices for sustainable dicamba use.

Fluxes of agricultural nitrogen and metolachlor metabolites are highly correlated in a first order stream in Maryland, USA.

Nitrogen pollution in watersheds containing significant cropland area is generally problematic. Conservation practices intended to reduce nitrate-N (NO3--N) export from watersheds are being implemented by many regions without necessary tools to assess effectiveness of abatement. A commonly used herbicide metolachlor degrades in the vadose zone of croplands to form two metabolites (metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid (MOXA)) which are both highly soluble in soils. Study of metabolite fates in a first order watershed provided evidence that transport of these metabolites to stream water is highly correlated to transport of agricultural NO3--N that also forms in the cropland vadose zone. Linear models describing the relationships of stream flux of MESA and MOXA to NO3--N flux generated goodness of fit values of 0.93 and 0.81, respectively. These findings support a conclusion that both MESA and MOXA act as excellent transport analogs of NO3--N and become strongly correlated to agricultural NO3--N leaching from the cropland vadose zone. Moreover, their use as conservative tracers in agricultural watersheds can provide valuable information concerning movement and fate of agricultural nitrogen at watershed scales of observation.

Method to Evaluate the Age of Groundwater Inputs to Surface Waters by Determining the Chirality Change of Metolachlor Ethanesulfonic Acid (MESA) Captured on a Polar Organic Chemical Integrative Sampler (POCIS).

We previously discovered a method to estimate the groundwater mean residence time using the changes in the enantiomeric ratio of metolachlor ethanesulfonic acid (MESA), (2-[(2-ethyl-6-methylphenyl)(2-methoxy-1-methylethyl)amino]-2-oxoethanesulfonic acid), a metabolite of the herbicide metolachlor. However, many grab samples would be needed for each watershed over an extended period, and this is not practical. Thus, we examined the use of a polar organic chemical integrative sampler (POCIS) deployed for 28 days combined with a modified liquid chromatography-mass spectrometry LC-MS/MS method to provide a time-weighted average of the MESA enantiomeric ratio. POCISs equipped with hydrophilic-lipophilic-balanced (HLB) discs were deployed at five sites across the United States where metolachlor was used before and after 1999 and compared the effectiveness of the POCIS to capture MESA versus grab samples. In addition, an in situ POCIS sampling rate (Rs) for MESA was calculated (0.15 L/day), the precision of MESA extraction from stored POCIS discs was determined, and the effectiveness of HLB to extract MESA was examined. Finally, using molecular modeling, the influence of the asymmetric carbon of metolachlor degradation on the MESA enantiomeric ratio was predicted to be negligible. Results of this work will be used in projects to discern the groundwater mean residence times, to evaluate the delivery of nitrate-N from groundwater to surface waters under various soil, agronomic, and land use conditions, and to examine the effectiveness of conservation practices.

Impacts and interactions of organic compounds with chlorine sanitizer in recirculated and reused produce processing water.

Water conservation and economics dictate that fresh produce processors reuse/recirculate the process water. However, the ensuing accumulation of organic matter in water depletes the chlorine sanitizer required for food safety. In this study, we comprehensively investigated chemical compounds that are responsible for water quality in relation to chemical oxygen demand (COD) and chlorine demand (CLD), the two most critical factors associated with water treatment and chlorine replenishment. Simulating commercial fresh-cut wash operations, multiple batches of diced cabbage (0.3 x 0.3 cm2) were washed in the same tank of water. The major components were isolated from the wash water and analyzed by HPLC. Sugars were the predominant compounds (82.7% dry weight) and the major contributor to COD (81.6%), followed by proteins/peptides (7.3% dry weight, 5.3% COD), organic acids (6.2% dry weight, 3.6% COD), and phenolics (0.5% dry weight, 0.5% COD). By repeated time course measures, the effect of these chemicals on CLD are dependent on the chemical structure, concentration in the wash water, and their rate of reaction. Proteins/peptides accounted for about 50% of the total CLD over a 120-min period and phenolics was 21% at 5 min, but diminished with time. The contribution by organic acids and sugars increased continuously, reaching 22% and 16% of total CLD at 120 min of chlorination, respectively. Collectively, these compounds represented 86% of the CLD in cabbage wash water at 5 min and greater than 94% CLD afterwards. This is the first systematic report on the source of COD and CLD during fresh produce washing. It provides essential information for the produce processors to develop safe, effective, and economical wash water treatment/reuse and chlorine replenishment strategies.

Presence of organohalide-respiring bacteria in and around a permeable reactive barrier at a trichloroethylene-contaminated Superfund site.

Trichloroethylene (TCE) is one of the most common groundwater contaminants in the United States; however clean-up efforts are a challenge due to its physical and chemical properties. TCE and several of its degradation products were detected in the groundwater of the Beaver Dam Road Landfill site (Beltsville, MD) at concentrations above accepted maximum contaminant levels. A permeable reactive barrier (i.e., biowall) was installed to remediate the groundwater. Microbial infiltration and colonization of the biowall with native site bacteria was expected to occur. An array of molecular biological tools was applied to survey the microbial community for presence of organohalide-respiring microorganisms at the site. Microorganisms belonging to methanogens, acetogens, sulfate-reducing bacteria, and chlorinated aliphatic hydrocarbon-metabolizing bacteria were identified, thus making way for the application of the microbial populations in the biowall bioaugmentation efforts. In concomitant laboratory studies, molecular approaches were used to monitor continuously-fed column reactors containing saturated biowall material spiked with a commercially-available, Dehalococcoides-containing culture (SDC-9), with or without zero-valent iron (ZVI) shavings. The column without ZVI had the highest abundance of Dehalococcoides spp. (2.7 × 106 cells g-1 material, S.D. = 3.8 × 105 cells g-1 material), while the addition of ZVI did not affect the overall population. Although the addition of ZVI and biostimulation did change ratios of the Dehalococcoides strains, the results suggests that if ZVI would be applied as a biowall material amendment, biostimulation would not be required to maintain a Dehalococcoides population. These experimental results will be utilized in future remediation and/or biowall expansion plans to utilize the natural resources most effectively at the biowall site.

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.

Analysis of metolachlor ethane sulfonic acid (MESA) chirality in groundwater: A tool for dating groundwater movement in agricultural settings.

UNLABELLED: To better address how much groundwater contributes to the loadings of pollutants from agriculture we developed a specific dating tool for groundwater residence times. This tool is based on metolachlor ethane sulfonic acid, which is a major soil metabolite of metolachlor. The chiral forms of metolachlor ethane sulfonic acid (MESA) and the chiral forms of metolachlor were examined over a 6-year period in samples of groundwater and water from a groundwater-fed stream in a riparian buffer zone. This buffer zone bordered cropland receiving annual treatments with metolachlor. Racemic (rac) metolachlor was applied for two years in the neighboring field, and subsequently S-metolachlor was used which is enriched by 88% with the S-enantiomer. Chiral analyses of the samples showed an exponential increase in abundance of the S-enantiomeric forms for MESA as a function of time for both the first order riparian buffer stream (R(2)=0.80) and for groundwater within the riparian buffer (R(2)=0.96). However, the S-enrichment values for metolachlor were consistently high indicating different delivery mechanisms for MESA and metolachlor. A mean residence time of 3.8years was determined for depletion of the initially-applied rac-metolachlor. This approach could be useful in dating groundwater and determining the effectiveness of conservation measures. ONE SENTENCE SUMMARY: A mean residence time of 3.8years was calculated for groundwater feeding a first-order stream by plotting the timed-decay for the R-enantiomer of metolachlor ethane sulfonic acid.

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.

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.

Continuous temperature-dependent Raman spectroscopy of melamine and structural analog detection in milk powder.

Hyperspectral Raman imaging has the potential for rapid screening of solid-phase samples for potential adulterants. We can improve mixture analysis algorithms by defining a temperature range in which the contaminant spectrum changes dramatically and uniquely compared with unadulterated material. Raman spectra were acquired for urea, biuret, cyanuric acid, and melamine (pure and at 1% in dried milk powder) from 50 to 310 °C with a gradient of 1 °C min(-1). Adulterants were clearly indentified in the milk powder. Specific frequencies that were mainly associated with ring breathing, stretching, and in-plane deformation shifted with respect to temperature up to 12 cm(-1) in all four molecules. Specific frequencies significantly increased/decreased in intensity within narrow temperature ranges independent of whether the amine was mixed in milk. Correlation of Raman and differential scanning calorimetry data identified structural components and vibrational modes, which concur with or trigger phase transitions.

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.