Review of Pesticide Retention Processes Occurring in Buffer Strips Receiving Agricultural Runoff1

Arora, Kapil, Steven K. Mickelson, Matthew J. Helmers, and James L. Baker, 2010. Review of Pesticide Retention Processes Occurring in Buffer Strips Receiving Agricultural Runoff. Journal of the American Water Resources Association (JAWRA) 46(3):618-647. DOI: 10.1111/j.1752-1688.2010.00438.x Abstract: Review of the published results shows that the retention of the two pesticide carrier phases (runoff volume and sediment mass) influences pesticide mass transport through buffer strips. Data averaged across different studies showed that the buffer strips retained 45% of runoff volume (ranging between 0 and 100%) and 76% of sediment mass (ranging between 2 and 100%). Sorption (soil sorption coefficient, K_oc) is one key pesticide property affecting its transport with the two carrier phases through buffer strips. Data from different studies for pesticide mass retention for weakly (K_oc < 100), moderately (100 < K_oc < 1,000), and strongly sorbed pesticides (K_oc > 1,000) averaged (with ranges) 61 (0-100), 63 (0-100), and 76 (53-100) %, respectively. Because there are more data for runoff volume and sediment mass retention, the average retentions of both carrier phases were used to calculate that the buffer strips would retain 45% of weakly to moderately sorbed and 70% of strongly sorbed pesticides on an average basis. As pesticide mass retention presented is only an average across several studies with different experimental setups, the application of these results to actual field conditions should be carefully examined.     

Factors Influencing Prymnesium parvum Population Dynamics During Bloom Initiation: Results from In-lake Mesocosm Experiments1

Roelke, Daniel L., Leslie Schwierzke, Bryan W. Brooks, James P. Grover, Reagan M. Errera, Theodore W. Valenti, Jr., and James L. Pinckney, 2010. Factors Influencing Prymnesium parvum Population Dynamics During Bloom Initiation: Results from In-Lake Mesocosm Experiments. Journal of the American Water Resources Association (JAWRA) 46(1):76-91. DOI: 10.1111/j.1752-1688.2009.00392.x Abstract: The alga Prymnesium parvum forms large fish-killing blooms in many Texas lakes. In some of these lakes, however, P. parvum occurs but does not develop blooms. In this study, we investigated factors that may influence bloom initiation by conducting a series of in-lake experiments involving mixing of waters from Lake Whitney, which has a history of P. parvum blooms, with waters from Lake Waco where no blooms have occurred. In all experiments, the addition of Lake Waco waters resulted in a poorer performance of P. parvum. Various experimental treatments and field data show that differences in grazing, pathogens, nutrients, and salts between the two lakes were not likely factors that contributed to this observation. Industrial and agricultural contaminants, allelochemicals and algicidal chemicals were not measured as a part of this research. However, anthropogenic contaminants other than nutrients were not observed at levels exceeding water quality standards in Lake Waco in recent years. On the other hand, nuisance cyanobacteria are common in Lake Waco, where Microcystis sp. and Anabaena sp. were abundant during the initiation of our experiments, both taxa are known to produce chemicals with allelopathic properties. In addition, the emergent field of algal-heterotrophic bacteria interactions suggests that chemicals produced by heterotrophic bacteria should not be overlooked. Further research focusing on the chemical interactions between cyanobacteria and P. parvum, as well as the potential role of algicidal bacteria, in the initiation of P. parvum blooms is necessary, as it may be important to the management of these blooms.     

Source apportionment of wintertime secondary organic aerosol during the California regional PM10/PM2.5 air quality study

The UCD/CIT air quality model with the Caltech Atmospheric Chemistry Mechanism (CACM) was used to predict source contributions to secondary organic aerosol (SOA) formation in the San Joaquin Valley (SJV) from December 15, 2000 to January 7, 2001. The predicted 24-day average SOA concentration had a maximum value of 4.26 μg m^?3 50 km southwest of Fresno. Predicted SOA concentrations at Fresno, Angiola, and Bakersfield were 2.46 μg m^?3, 1.68 μg m^?3, and 2.28 μg m^?3, respectively, accounting for 6%, 37%, and 4% of the total predicted organic aerosol. The average SOA concentration across the entire SJV was 1.35 μg m^?3, which accounts for approximately 20% of the total predicted organic aerosol. Averaged over the entire SJV, the major SOA sources were solvent use (28% of SOA), catalyst gasoline engines (25% of SOA), wood smoke (16% of SOA), non-catalyst gasoline engines (13% of SOA), and other anthropogenic sources (11% of SOA). Diesel engines were predicted to only account for approximately 2% of the total SOA formation in the SJV because they emit a small amount of volatile organic compounds relative to other sources. In terms of SOA precursors within the SJV, long-chain alkanes were predicted to be the largest SOA contributor, followed by aromatic compounds. The current study identifies the major known contributors to the SOA burden during a winter pollution episode in the SJV, with further enhancements possible as additional formation pathways are discovered.     

Aerosol speciation and mass prediction from toluene oxidation under high NOx conditions

A kinetically based gas-particle partitioning box model is used to highlight the importance of parameter representation in the prediction of secondary organic aerosol (SOA) formation following the photo-oxidation of toluene. The model is initialized using experimental data from York University's indoor smog chamber and provides a prediction of the total aerosol yield and speciation. A series of model sensitivity experiments were performed to study the aerosol speciation and mass prediction under high NO_x conditions (VOC/NO_x = 0.2). Sensitivity experiments indicate vapour pressure estimation to be a large area of weakness in predicting aerosol mass, creating an average total error range of 70 μg m^?3 (range of 5–145 μg m^?3), using two different estimation methods. Aerosol speciation proved relatively insensitive to changes in vapour pressure. One species, 3-methyl-6-nitro-catechol, dominated the aerosol phase regardless of the vapour pressure parameterization used and comprised 73–88% of the aerosol by mass. The dominance is associated with the large concentration of 3-methyl-6-nitro-catechol in the gas-phase. The high NO_x initial conditions of this study suggests that the predominance of 3-methyl-6-nitro-catechol likely results from the cresol-forming branch in the Master Chemical Mechanism taking a significant role in secondary organic aerosol formation under high NO_x conditions. Further research into the yields and speciation leading to this reaction product is recommended.     

Use of CALPUFF for exposure assessment in a near-field,complex terrain setting

CALPUFF is an atmospheric source-receptor model recommended by the U.S. Environmental Protection Agency for use on a case-by-case basis in complex terrain and wind conditions. The ability of the model to provide useful information for exposure assessments in areas with those topographical and meteorological conditions has received little attention. This is an important knowledge gap for use of CALPUFF outside of regulatory applications, such as exposure analyses conducted in support of risk assessments and health studies. We compared deposition of cadmium (Cd), lead (Pb), and zinc (Zn) calculated with CALPUFF as a result of emissions from a zinc smelter with corresponding concentrations of the metals measured in attic dust and soil samples obtained from the surrounding area. On a point-by-point analysis, predictions from CALPUFF explained 11% (lead) to 53% (zinc) of the variability in concentrations measured in attic dust. Levels of heavy metals in soil interpolated to 100 residential addresses from the distribution of concentrations measured in soil samples also agreed well with deposition predicted with CALPUFF: R² of 0.46, 0.76, and 079 for Pb, Cd, and Zn, respectively. Community-average concentrations of Cd, Pb, and Zn measured in soil were significantly (p < 0.0001) and strongly correlated (R² ranged from 0.77 to 0.98) with predicted deposition rates. These findings demonstrate that CALPUFF can provide reasonably accurate predictions of the patterns of long-term air pollutant deposition in the near-field associated with emissions from a discrete source in complex terrain. Because deposition estimates are calculated as a linear function of air concentrations, CALPUFF is expected to be reliable model for prediction of long-term average, near-field ambient air concentrations in complex terrain as well.     

Improvements to lawn and garden equipment emissions estimates for Baltimore, Maryland

Lawn and garden equipment are a significant source of emissions of volatile organic compounds (VOCs) and other pollutants in suburban and urban areas. Emission estimates for this source category are typically prepared using default equipment populations and activity data contained in emissions models such as the U.S. Environmental Protection Agency's (EPA) NONROAD model or the California Air Resources Board's (CARB) OFFROAD model. Although such default data may represent national or state averages, these data are unlikely to reflect regional or local differences in equipment usage patterns because of variations in climate, lot sizes, and other variables. To assess potential errors in lawn and garden equipment emission estimates produced by the NONROAD model and to demonstrate methods that can be used by local planning agencies to improve those emission estimates, this study used bottom-up data collection techniques in the Baltimore metropolitan area to develop local equipment population, activity, and temporal data for lawn and garden equipment in the area. Results of this study show that emission estimates of VOCs, particulate matter (PM), carbon monoxide (CO), carbon dioxide (CO2), and nitrogen oxides (NO(x)) for the Baltimore area that are based on local data collected through surveys of residential and commercial lawn and garden equipment users are 24-56% lower than estimates produced using NONROAD default data, largely because of a difference in equipment populations for high-usage commercial applications. Survey-derived emission estimates of PM and VOCs are 24 and 26% lower than NONROAD default estimates, respectively, whereas survey-derived emission estimates for CO, CO2, and NO(x) are more than 40% lower than NONROAD default estimates. In addition, study results show that the temporal allocation factors applied to residential lawn and garden equipment in the NONROAD model underestimated weekend activity levels by 30% compared with survey-derived temporal profiles.     

Theoretical versus observed gas-particle partitioning of carbonyl emissions from motor vehicles

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120-580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

WRF-Chem simulation of East Asian air quality: Sensitivity to temporal and vertical emissions distributions

This study develops fine temporal (seasonal, day-of-week, diurnal) and vertical allocations of anthropogenic emissions for the TRACE-P inventory and evaluates their impacts on the East Asian air quality prediction using WRF-Chem simulations in July 2001 at 30-km grid spacing against available surface measurements from EANET and NEMCC. For NO₂ and SO₂, the diurnal and vertical redistributions of emissions play essential roles, while the day-of-week variation is less important. When all incorporated, WRF-Chem best simulates observations of surface NO₂ and SO₂ concentrations, while using the default emissions produces the worst result. The sensitivity is especially large over major cities and industrial areas, where surface NO₂ and SO₂ concentrations are reduced by respectively 3–7 and 6–12 ppbv when using the scaled emissions. The incorporation of all the three redistributions of emissions simulates surface O₃ concentrations higher by 4–8 ppbv at night and 2–4 ppbv in daytime over broad areas of northern, eastern and central China. To this sensitivity, the diurnal redistribution contributes more than the other two.     

Influence of regional development policies and clean technology adoption on future air pollution exposure

Future air pollution emissions in the year 2030 were estimated for the San Joaquin Valley (SJV) in central California using a combined system of land use, mobile, off-road, stationary, area, and biogenic emissions models. Four scenarios were developed that use different assumptions about the density of development and level of investment in transportation infrastructure to accommodate the expected doubling of the SJV population in the next 20 years. Scenario 1 reflects current land-use patterns and infrastructure while scenario 2 encouraged compact urban footprints including redevelopment of existing urban centers and investments in transit. Scenario 3 allowed sprawling development in the SJV with reduced population density in existing urban centers and construction of all planned freeways. Scenario 4 followed currently adopted land use and transportation plans for the SJV. The air quality resulting from these urban development scenarios was evaluated using meteorology from a winter stagnation event that occurred on December 15th, 2000 to January 7th 2001. Predicted base-case PM2.5 mass concentrations within the region exceeded 35 μg m^?3 over the 22-day episode. Compact growth reduced the PM2.5 concentrations by ～1 μg m^?3 relative to the base-case over most of the SJV with the exception of increases (～1 μg m^?3) in urban centers driven by increased concentrations of elemental carbon (EC) and organic carbon (OC). Low-density development increased the PM2.5 concentrations by 1–4 μg m^?3 over most of the region, with decreases (0.5–2 μg m^?3) around urban areas. Population-weighted average PM2.5 concentrations were very similar for all development scenarios ranging between 16 and 17.4 μg m^?3. Exposure to primary PM components such as EC and OC increased 10–15% for high density development scenarios and decreased by 11–19% for low-density scenarios. Patterns for secondary PM components such as nitrate and ammonium ion were almost exactly reversed, with a 10% increase under low-density development and a 5% decrease under high density development. The increased human exposure to primary pollutants such as EC and OC could be predicted using a simplified analysis of population-weighted primary emissions. Regional planning agencies should develop thresholds of population-weighted primary emissions exposure to guide the development of growth plans. This metric will allow them to actively reduce the potential negative impacts of compact growth while preserving the benefits.