Dynamic modeling of organophosphate pesticide load in surface water in the northern San Joaquin Valley watershed of California

The hydrology, sediment, and pesticide transport components of the Soil and Water Assessment Tool (SWAT) were evaluated on the northern San Joaquin Valley watershed of California. The Nash-Sutcliffe coefficients for monthly stream flow and sediment load ranged from 0.49 to 0.99 over the watershed during the study period of 1992-2005. The calibrated SWAT model was applied to simulate fate and transport processes of two organophosphate pesticides of diazinon and chlorpyrifos at watershed scale. The model generated satisfactory predictions of dissolved pesticide loads relative to the monitoring data. The model also showed great success in capturing spatial patterns of dissolved diazinon and chlorpyrifos loads according to the soil properties and landscape morphology over the large agricultural watershed. This study indicated that curve number was the major factor influencing the hydrology while pesticide fate and transport were mainly affected by surface runoff and pesticide application and in the study area.     

Mitigation of chlorpyrifos runoff using constructed wetlands

Constructed wetlands have been proposed as a potential best management practice (BMP) to mitigate effects of pesticide-associated agricultural runoff. Wetland mesocosms (14 m x 59-73 m) were amended with chlorpyrifos to simulate a storm runoff event at concentrations of 73, 147 and 733 microg/l. Water, sediment and plant samples collected weekly for 12 weeks indicated that chlorpyrifos rapidly sorbed to sediment and plant material, with approximately 47-65% of measured chlorpyrifos mass retained within the first 30-36 m of wetland mesocosms. Of the measured mass, approximately 55% and 25% were retained by sediments and plants, respectively. A field-scale evaluation of a constructed wetland's mitigation capability was performed in the Lourens River watershed of Cape Town, South Africa. Results indicate that the wetland was able to retain and considerably decrease the concentration (and hence toxicity) of chlorpyrifos and suspended sediment entering the receiving waterbody (Lourens River). This research provides fundamental answers concerning constructed wetland capabilities that are necessary for constructing field-scale systems within agricultural watersheds.     

Use of toxicity identification evaluations to determine the pesticide mitigation effectiveness of on-farm vegetated treatment systems

Evidence of ecological impacts from pesticide runoff has prompted installation of vegetated treatment systems (VTS) along the central coast of California, USA. During five surveys of two on-farm VTS ponds, 88% of inlet and outlet water samples were toxic to Ceriodaphnia dubia. Toxicity identification evaluations (TIEs) indicated water toxicity was caused by diazinon at VTS-1, and chlorpyrifos at VTS-2. Diazinon levels in VTS-1 were variable, but high pulse inflow concentrations were reduced through dilution. At VTS-2, chlorpyrifos concentrations averaged 52% lower at the VTS outlet than at the inlet. Water concentrations of most other pesticides averaged 20-90% lower at VTS outlets. All VTS sediment samples were toxic to amphipods (Hyalella azteca). Sediment TIEs indicated toxicity was caused by cypermethrin and lambda-cyhalothrin at VTS-1, and chlorpyrifos and permethrin at VTS-2. As with water, sediment concentrations were lower at VTS outlets, indicating substantial reductions in farm runoff pesticide concentrations.     

Management-oriented sensitivity analysis for pesticide transport in watershed-scale water quality modeling using SWAT

The Soil and Water Assessment Tool (SWAT) was calibrated for hydrology conditions in an agricultural watershed of Orestimba Creek, California, and applied to simulate fate and transport of two organophosphate pesticides chlorpyrifos and diazinon. The model showed capability in evaluating pesticide fate and transport processes in agricultural fields and instream network. Management-oriented sensitivity analysis was conducted by applied stochastic SWAT simulations for pesticide distribution. Results of sensitivity analysis identified the governing processes in pesticide outputs as surface runoff, soil erosion, and sedimentation in the study area. By incorporating sensitive parameters in pesticide transport simulation, effects of structural best management practices (BMPs) in improving surface water quality were demonstrated by SWAT modeling. This study also recommends conservation practices designed to reduce field yield and in-stream transport capacity of sediment, such as filter strip, grassed waterway, crop residue management, and tailwater pond to be implemented in the Orestimba Creek watershed.     

Understanding particulate matter formation in the California San Joaquin Valley: conceptual model and data needs

Quantitative information from the 1995 Integrated Monitoring Study (IMS95) is used to develop a conceptual model, which describes the chemical characteristics and the physical processes responsible for the accumulation of PM in the San Joaquin Valley of California. One significant finding of the conceptual model is the sensitivity of ammonium nitrate (46% of winter PM_2.5) and nitric acid to oxidants, which may be VOC-sensitive rather than NO_x-sensitive. Key gaps in current knowledge are identified using the conceptual model, e.g., the relative sensitivity of winter oxidants to VOC and NO_x, mechanistic details of secondary organic aerosol formation, mechanisms of dispersion under calm conditions, and the importance of dry deposition. Some recommendations are also provided for the formulation of air quality models suitable to address the accumulation of PM in the San Joaquin Valley.     

Integrated assessment of the impacts of agricultural drainwater in the Salinas River (California,USA)

The Salinas River is the largest of the three rivers that drain into the Monterey Bay National Marine Sanctuary in central California. Large areas of this watershed are cultivated year-round in row crops and previous laboratory studies have demonstrated that acute toxicity of agricultural drainwater to Ceriodaphnia dubia is caused by the organophosphate (OP) pesticides chlorpyrifos and diazinon. In the current study, we used a combination of ecotoxicologic tools to investigate incidence of chemical contamination and toxicity in waters and sediments in the river downstream of a previously uncharacterized agricultural drainage creek system. Water column toxicity was investigated using a cladoceran C. dubia while sediment toxicity was investigated using an amphipod Hyalella azteca. Ecological impacts of drainwater were investigated using bioassessments of macroinvertebrate community structure. The results indicated that Salinas River water downstream of the agricultural drain is acutely toxic to Ceriodaphnia, and toxicity to this species was highly correlated with combined toxic units (TUs) of chlorpyrifos and diazinon. Laboratory tests were used to demonstrate that sediments in this system were acutely toxic to H. azteca, which is a resident genus. Macroinvertebrate community structure was moderately impacted downstream of the agricultural drain input. While the lowest macroinvertebrate abundances were measured at the station demonstrating the greatest water column and sediment toxicity and the highest concentrations of pesticides, macroinvertebrate metrics were more significantly correlated with bank vegetation cover than any other variable. Results of this study suggest that pesticide pollution is the likely cause of laboratory-measured toxicity in the Salinas River samples and that this factor may interact with other factors to impact the macroinvertebrate community in the system.     

Degradation of chlorpyrifos and its hydrolysis product, 3,5,6‐trichloro‐2‐pyridinol,in soil

Abstract

The degradation of ¹⁴C‐chlorpyrifos and its hydrolysis product, 3,5,6‐trichloro‐2‐pyridinol (TCP), was investigated in soil in laboratory experiments. Between 12 and 57% of the applied chlorpyrifos persisted in a variety of agricultural soils after a 4‐week incubation. Concentrations of TCP present in these soils ranged from 1 to 34% of the applied dose. Two patterns of persistence were observed. In some soils, significant quantities of TCP and soil‐bound residues were produced, but little ¹⁴CO₂. In other soils, neither TCP nor soil‐bound residues accumulated, but large quantities of ¹⁴CO₂ were evolved. Direct treatment of fresh samples of each of these soils with ¹⁴C‐TCP resulted in rapid mineralization of TCP to ¹⁴CO₂ only in those soils in which TCP had not accumulated after chlorpyrifos treatment. The rapid mineralization of TCP in these soils was microbially mediated, but populations of soil microorganisms capable of using TCP as a sole carbon‐energy source were not detected.     

Determination of vapor pressure-temperature relationships of current–use pesticides and transformation products

Sub-cooled liquid vapor pressures (P_L ⁰) of current–use organochlorine and organophosphate pesticides (chlorothalonil, chlorpyrifos methyl, diazinon, fipronil) and selected transformation products (chlorpyrifos oxon, heptachlor epoxide, oxychlordane, 3,5,6-trichloro-2-pyridinol) were determined at multiple temperatures using the gas chromatography retention time technique. Results were utilized to determine vapor pressure-temperature relationships and to calculate enthalpies of vaporization (ΔH_vap). While results for chlorothalonil and diazinon were comparable with published values, the measured value for fipronil (1.82 × 10^{? 6} Pa) is almost an order of magnitude higher than the reported literature value (3.7 × 10^{? 7} Pa). The availability of vapor pressure temperature relationships for these chemicals will aid in pesticide risk assessment development and improve the effectiveness of mitigation and remediation efforts.     

Resolving the interactions between population density and air pollution emissions controls in the San Joaquin Valley,USA

The effectiveness of emissions control programs designed to reduce concentrations of airborne particulate matter with an aerodynamic diameter <2.5 μm (PM_2.5) in California's San Joaquin Valley was studied in the year 2030 under three growth scenarios: low, medium, and high population density. Base-case inventories for each choice of population density were created using a coupled emissions modeling system that simultaneously considered interactions between land use and transportation, area source, and point source emissions. The ambient PM_2.5 response to each combination of population density and emissions control was evaluated using a regional chemical transport model over a 3-week winter stagnation episode. Comparisons between scenarios were based on regional average and population-weighted PM_2.5 concentrations. In the absence of any emissions control program, population-weighted concentrations of PM_2.5 in the future San Joaquin Valley are lowest under growth scenarios that emphasize low population density. A complete ban on wood burning and a 90% reduction in emissions from food cooking operations and diesel engines must occur before medium- to high-density growth scenarios result in lower population-weighted concentrations of PM_2.5. These trends partly reflect the fact that existing downtown urban cores that naturally act as anchor points for new high-density growth in the San Joaquin Valley are located close to major transportation corridors for goods movement. Adding growth buffers around transportation corridors had little impact in the current analysis, since the 8-km resolution of the chemical transport model already provided an artificial buffer around major emissions sources.

Assuming that future emissions controls will greatly reduce or eliminate emissions from residential wood burning, food cooking, and diesel engines, the 2030 growth scenario using “as-planned” (medium) population density achieves the lowest population-weighted average PM_2.5 concentration in the future San Joaquin Valley during a severe winter stagnation event.

Implications: The San Joaquin Valley is one of the most heavily polluted air basins in the United States that are projected to experience strong population growth in the coming decades. The best plan to improve air quality in the region combines medium- or high-density population growth with rigorous emissions controls. In the absences of controls, high-density growth leads to increased population exposure to PM_2.5 compared with low-density growth scenarios (urban sprawl).     

晋江西溪流域茶园降雨径流产污特征

在野外模拟降雨条件下,开展了晋江西溪流域茶园和裸地的径流产沙及氮磷养分流失过程对比实验,研究结果表明,在相同降雨强度下,3种下垫面径流和产沙量顺序均为:裸地＞2年茶园＞4年茶园,径流量与产沙量之间呈显著正相关.对地表径流水相而言,2年茶园、4年茶园和裸地的TN流失量分别为:461.29、129.38和107.86 mg/m2;NO3-N流失量分别为:286.42、98.58和103.00 mg/m2,均占TN流失量的60％以上;NH4-N流失量分别为:48.67、16.19和4.42 mg/m2;Tp流失量分别为:34.71、16.47和23.88 mg/m2.对径流泥沙相而言,2年茶园、4年茶园和裸地的TN流失量分别为:379.28、44.81和747.16 mg/m2,占流失总量的比重在25.72％～87.93％之间;TP流失量分别为:27.94、4.17和58.85 mg/m2,占流失总量的比重在53.42％ ～68.36％之间.茶园的N、P主要随径流流失,而裸地以泥沙迁移为主.这说明茶叶种植具有一定的水土保持效应,且种植年限较长的茶园可显著减少随径流泥沙进入水体中的N、P元素.     

Capturing the lost phosphorus

Minable phosphorus (P) reserves are being depleted and will need to be replaced by recovering P that currently is lost from the agricultural system, causing water-quality problems. The largest two flows of lost P are in agricultural runoff and erosion (∼46% of mined P globally) and animal wastes (∼40%). These flows are quite distinct. Runoff has a very high volumetric flow rate, but a low P concentration; animal wastes have low flow rates, but a high P concentration together with a high concentration of organic material. Recovering the lost P in animal wastes is technically and economically more tractable, and it is the focus for this review of promising P-capture technologies. P capture requires that organic P be transformed into inorganic P (phosphate). For high-strength animal wastes, P release can be accomplished in tandem with anaerobic treatment that converts the energy value in the organic matter to CH₄, H₂, or electricity. Once present as phosphate, the P can be captured in a reusable form by four approaches. Most well developed is precipitation as magnesium or calcium solids. Less developed, but promising are adsorption to iron-based adsorbents, ion exchange to phosphate-selective solids, and uptake by photosynthetic microorganisms or P-selective proteins.     

Ammonium,Nitrate and Nitrite Nitrogen and Nitrate Reductase Enzyme Activity in Groundnut (Arachis hypogaea L.) Fields After Diazinon,Imidacloprid and Lindane Treatments

Impacts of diazinon (O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate), imidacloprid [1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] and lindane (1,2,3,4,5.6-hexachlorocyclohexane) treatments on ammonium, nitrate, and nitrite nitrogen and nitrate reductase enzyme activities were determined in groundnut (Arachis hypogaea L.) field for three consecutive years (1997 to 1999). Diazinon was applied for both seed- and soil-treatments but imidacloprid and lindane were used for seed treatments only at recommended rates. Diazinon residues persisted for 60 days in both the cases. Average half-lives (t_1/2) of diazinon were found 29.3 and 34.8 days respectively in seed and soil treatments. In diazinon seed treatment, NH₄ ⁺, NO₃ ^?, and NO₂ ^? nitrogen and nitrate reductase activity were not affected. Whereas, diazinon soil treatment indicated significant increase in NH₄ ⁺-N in a 1-day sample, which continued until 90 days. Some declines in NO₃ ^?N were found from 15 to 60 days. Along with this decline, significant increases in NO₂ ^?N and nitrate reductase activity were found between 1 and 30 days. Imidacloprid and lindane persisted for 90 and 120 days with average half-lives (t_1/2) of 40.9 and 53.3 days, respectively. Within 90 days, imidacloprid residues lost by 73.17% to 82.49% while such losses for lindane residues were found 78.19% to 79.86 % within 120 days. In imidacloprid seed-treated field, stimulation of NO₃ ^?N and the decline in NH₄ ⁺NO₂ ^?-N and nitrate reductase enzyme activity were observed between 15 to 90 days. However, lindane seed treatment indicated significant increases in NH₄ ⁺-N, NO₂ ^?-N and nitrate reductase activity and some adverse effects on NO₃ ^?N between 15 and 90 days.     

Effects of land use and land cover, stream discharge, and interannual climate on the magnitude and timing of nitrogen, phosphorus, and organic carbon concentrations in three coastal plain watersheds.

In-stream nitrogen, phosphorus, organic carbon, and suspended sediment concentrations were measured in 18 subbasins over 2 annual cycles to assess how land use and land cover (LULC) and stream discharge regulate water quality variables. The LULC was a primary driver of in-stream constituent concentrations and nutrient speciation owing to differences in dominant sources and input pathways associated with agricultural, urban, and forested land uses. Stream discharge was shown to be a major factor that dictated not only the magnitude of constituent concentrations, but also the chemical form. In high discharge agricultural subbasins, where nitrate was the dominant nitrogen form, there was a negative correlation between discharge and nitrate concentration indicating groundwater inputs as the dominant pathway. In urban settings, however, nitrate was positively correlated with discharge, and, in forested subwatersheds, where dissolved organic nitrogen (DON) was the dominant nitrogen form, there was a positive correlation between discharge and DON, indicating washoff from the watershed as the dominant input pathway. Similarly, phosphorus concentrations were strongly regulated by LULC, discharge, and seasonality. This comparative study highlights that different mechanisms regulate different forms of nitrogen, phosphorus, and carbon, and thus field programs or water quality models used for regulatory purposes must assess these nutrient forms to accurately apply management plans for nutrient reductions.     

Effects of carbaryl,chlorpyrifos and endosulfan on growth,reproduction and respiration of tropical epigeic earthworm,Perionyx excavatus (Perrier)

Effects of sub-lethal doses of carbaryl (1-Naphthyl-methylcarbamate), chlorpyrifos (O,O-diethyl O-3,5,6-trichloro-2-pyridinyl-phosphorothioate) and endosulfan (6,7,8,9,10,10-Hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin-3-oxide), respectively a carbamate, an organophosphate and an organochlorine insecticide on growth, reproduction and respiration of the tropical earthworm, Perionyx excavatus (Perrier) were investigated under laboratory conditions. The results showed significant reduction in biomass, production and hatching of cocoon and production of juveniles of the worms exposed to 0.75 to 3.03 mg/kg soil of carbaryl, 0.91 to 3.65 mg/kg soil of chlorpyrifos and 3.75 to 15.0 μg/kg soil of endosulfan corresponding to 12.5 to 50 % of LC₅₀ value of the respective insecticide for P. excavatus. Endosulfan was found most dangerous among the three insecticides followed by carbaryl and chlorpyrifos. There was no hatching of the worms at endosulfan treatment 5.0 μg/kg soil (25 % LC₅₀) or above while the highest dose of carbaryl and chlorpyrifos (50 % of LC₅₀) rendered respectively 87.13 and 24.84 % reductions in hatching as compared to control. Chlorpyrifos produced no change in respiration of the worms except at the highest dose, while the worms showed an increase in evolution of CO₂ at all doses of carbaryl and endosulfan. Based on the recommended agricultural dose of each insecticide, it was concluded that application of endosulfan and carbaryl was potentially dangerous to earthworms.     

Membrane bioreactor treatment of commonly used organophosphate pesticides

Five pesticide formulations registered for use in Canada containing organophosphate-insecticide active ingredients azinphos-methyl, chlorpyrifos, diazinon, malathion and phorate were subjected to treatment by membrane bioreactor (MBR) technology. The target active ingredients were introduced to the MBR at ppm level concentrations. The biodegradation of these compounds was analyzed daily using selected ion monitoring gas chromatography-mass spectrometry (GC/MS-SIM) following extraction of the analytes using solid-phase extraction (SPE). Amounts measuring 83 % to 98 % of the target analytes were removed with steady-state concentrations being reached within 5 days of their introduction. The dissolved oxygen, temperature, pH, and total heterotrophic bacterial population were monitored daily to ensure optimal conditions for biodegradation. The quality of the effluent from the MBR was assessed daily through spectrophotometric methods. Measurements were conducted for the concentration of ammonia, nitrate, nitrite, total and reactive phosphorus, as well as the chemical oxygen demand (COD) of the effluent. This study demonstrated that the MBR technology is feasible and efficient for treatment of organophosphate pesticides without introducing additional chemical additives.     

Analysis of ozone in the San Joaquin Valley of California

The dynamics of ozone in the San Joaquin Valley of central California are studied by systematic diagnostic runs of the three-dimensional SARMAP Air Quality Model. Air quality in the San Joaquin Valley is the result of a complex combination of local and transported emissions. Simulations show that relatively brisk winds at points of inflow to the Valley produce a strong dependence of ozone in the Valley on upwind conditions. Furthermore, NO_x influx from boundaries and local emissions has significantly greater impact on ozone production than ROG influx and emissions.     

Removal mechanisms and fate of insecticides in constructed wetlands

Constructed wetlands (CWs), along with other vegetative systems, are increasingly being promoted as a mitigation practice to treat non-point source runoff to reduce contaminants such as pesticides. However, studies so far have mostly focused on demonstrating contaminant removal efficiency. In this study, using two operational CWs located in the Central Valley of California, we explored the mechanisms underlying the removal of pyrethroids and chlorpyrifos from agricultural runoff water, and further evaluated the likelihood for the retained pesticides to accumulate within the CWs over time.In the runoff water passing through the CWs, pyrethroids were associated overwhelmingly with suspended solids >0.7 μm, and the sorbed fraction accounted for 38-100% of the total concentrations. The derived K_d values for the suspended solids were in the order of 10⁴-10⁵, substantially greater than those reported for bulk soils and sediments. Distribution of pyrethroids in the wetland sediments was found to mimic organic carbon distribution, and was enriched in large particles that were partially decomposed plant materials, and clay-size particles (<2 μm). Retention of suspended particles, especially the very large particles (>250 μm) and the very fine particles, is thus essential in removing pyrethroids and chlorpyrifos in CWs. Under flooded and anaerobic conditions, most pyrethroids and chlorpyrifos showed moderate persistence, with DT₅₀ values between 106-353 d. However, the retained pyrethroids were very stable in dry and aerobic sediments between irrigation seasons, suggesting a possibility for accumulation over time. Therefore, the long-term ecological risks of CWs should be further understood before their wide adoption.     

Effects of natural organic matter on the microporous sorption sites of black carbon in a Yangtze River sediment

Black carbon (BC), characterized by high microporosity and high specific surface area (SSA), has been demonstrated to have substantial contributions to the sorption of hydrophobic organic chemicals in soils and sediments. Other naturally occurring organic matters provide soft and penetrable sorption domains while may cling to BC and affect its original surface properties. In this work, we studied the sorption sites of a Yangtze River sediment sample with organic carbon (OC) content of 3.3 % and the preheated sediment (combusted at 375 °C) with reduced OC content (defined as BC) of 0.4 % by gas and pyrene sorption. The SSA and microporosity of the pristine and preheated sediments were characterized by N₂ and CO₂ adsorption. The results suggest that the adsorption of N₂ was hindered by amorphous organic carbon (AOC) in the pristine sediment but CO₂ was not. Instead, the uptake of CO₂ was higher in the presence of AOC, likely due to the partition of CO₂ molecules into the organic matter. The pyrene adsorptions to BC in pristine and preheated sediments show a similar adsorption capacity at high concentration, suggesting that AOC of ca. 2.9 % in the pristine sediment does not reduce the accessibility to the sorption sites on BC for pyrene.     

Wintertime Vertical Variations in Particulate Matter (PM) and Precursor Concentrations in the San Joaquin Valley during the California Regional Coarse PM/Fine PM Air Quality Study

Abstract

Air quality monitoring was conducted at a rural site with a tower in the middle of California’s San Joaquin Valley (SJV) and at elevated sites in the foothills and mountains surrounding the SJV for the California Regional PM₁₀/M_2.5 Air Quality Study. Measurements at the surface and on a tower at 90 m were collected in Angiola, CA, from ecember 2000 through February 2001 and included hourly black carbon (BC), particle counts from optical particle counters, nitric oxide, ozone, temperature, relative humidity, wind speed, and direction. Boundary site measurements were made primarily using 24-hr integrated particulate matter (PM) samples. These measurements were used to understand the vertical variations of PM and PM precursors, the effect of stratification in the winter on concentrations and chemistry aloft and at the surface, and the impact of aloft-versus-surface transport on PM concentrations. Vertical variations of concentrations differed among individual species. The stratification may be important to atmospheric chemistry processes, particularly nighttime nitrate formation aloft, because NO₂ appeared to be oxidized by ozone in the stratified aloft layer. Additionally, increases in accumulation-mode particle concentrations in the aloft layer during a fine PM (PM_2.5) episode corresponded with increases in aloft nitrate, demonstrating the likelihood of an aloft nighttime nitrate formation mechanism. Evidence of local transport at the surface and regional transport aloft was found; transport processes also varied among the species. The distribution of BC appeared to be regional, and BC was often uniformly mixed vertically. Overall, the combination of time-resolved tower and surface measurements provided important insight into PM stratification, formation, and transport.     

Comparison of summer and winter California central valley aerosol distributions from lidar and MODIS measurements

Aerosol distributions from two aircraft lidar campaigns conducted in the California Central Valley are compared in order to identify seasonal variations. Aircraft lidar flights were conducted in June 2003 and February 2007. While the ground PM_2.5 (particulate matter with diameter ≤ 2.5 μm) concentration was highest in the winter, the aerosol optical depth (AOD) measured from the MODIS and lidar instruments was highest in the summer. A multiyear seasonal comparison shows that PM_2.5 in the winter can exceed summer PM_2.5 by 68%, while summer AOD from MODIS exceeds winter AOD by 29%. Warmer temperatures and wildfires in the summer produce elevated aerosol layers that are detected by satellite measurements, but not necessarily by surface particulate matter monitors. Temperature inversions, especially during the winter, contribute to higher PM_2.5 measurements at the surface. Measurements of the mixing layer height from lidar instruments provide valuable information needed to understand the correlation between satellite measurements of AOD and in situ measurements of PM_2.5. Lidar measurements also reflect the ammonium nitrate chemistry observed in the San Joaquin Valley, which may explain the discrepancy between the MODIS AOD and PM_2.5 measurements.