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With loss of wetlands and their associated ecosystem services within landscapes, it is imperative to be able to understand the change in ecological functions underlying these services. Field-based functional assessments can produce a range of specific scores among a robust set of functions but are time and cost prohibitive as the number of wetlands assessed increases. Remote-based functional assessments are an alternative for broad scale assessments, but trade-off cost for limitations in scoring and functional assemblage. To address these concerns, we created a framework for the development of the Hydrogeomorphic Remote Assessment of Wetland Function (HGM-RAWF). Rooted in the hydrogeomorphic approach of an existing field-based functional assessment and its underlying models, this remote functional assessment substitutes field-based assessment methods with remotely assessed proxies. As potential remote proxies were determined through literature review and statistically screened for use in the remote assessment, a field-based reference wetland database of 222 freshwater wetlands in the Mid-Atlantic Region provided a baseline by which remote data could be compared and calibrated. The resulting HGM-RAWF protocol remotely assesses seven hydrology and biogeochemistry functions in the Mid-Atlantic with assessment scores similar to its field-based counterparts. With noted limitations, the HGM-RAWF framework provides the means to create desktop functional assessments across broad geographic scales with the diversity and specificity of field-based assessments at the reduced costs associated with remote assessments. Its basis in the HGM approach and use of public spatial datasets allows the framework to be adopted regionally and can be used as a model for national wetland functional assessment.
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Ecossistema , Áreas Alagadas , Monitoramento Ambiental/métodos , Hidrologia , Mid-Atlantic Region , Conservação dos Recursos NaturaisRESUMO
Estimating lateral carbon fluxes in agroecosystems presents challenges due to intricate anthropogenic and biophysical interactions. We used a modeling technique to enhance our comprehension of the determinants influencing lateral carbon fluxes and their significance in agroecosystem carbon budgets. The SWAT-C model was refined by incorporating a dynamic dissolved inorganic carbon (DIC) module, enhancing our ability to accurately quantify total lateral carbon fluxes. This improved model was calibrated using observed data on riverine particulate organic carbon (POC) and dissolved organic carbon (DOC) fluxes, as well as net ecosystem exchange (NEE) data monitored by a flux tower situated in a representative agricultural watershed, the Tuckahoe Watershed (TW) of the Chesapeake Bay's coastal plain. We assessed the losses of POC, DOC, and DIC across five primary rotation types: C (continuous carbon), CS (corn-soybean), CSS (corn-soybean-soybean), CWS (corn-wheat-soybean), and CWSCS (corn-wheat-soybean-corn-soybean). Our study revealed notable variations in the average annual fluxes of POC (ranging between 152 and 198 kg ha-1), DOC (74-85 kg ha-1), and DIC (93-156 kg ha-1) across the five rotation types. The primary influencing factor for annual POC fluxes was identified as sediment yield. While both annual DOC and DIC fluxes displayed a marked correlation with surface runoff across all crop rotation schemes, soil respiration also significantly influenced annual DIC fluxes. Total lateral carbon fluxes (POC + DOC+DIC) constituted roughly 11 % of both net ecosystem production (NEP) and NEE, yet they represented a striking 95 % of net biome production (NBP) in the TW's agroecosystem. Grain yield carbon accounted for 80 % of both NEP and NEE and was nearly seven times that of NBP. Our findings suggest that introducing soybeans into cornfields tends to reduce NEP, NEE, and also NBP. Conversely, integrating winter wheat into the corn-soybean rotation significantly boosted NEP, NEE, and NBP values, with NBP even surpassing the levels in continuous corn cultivation.
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Remotely sensed products are often used in watershed modeling as additional constraints to improve model predictions and reduce model uncertainty. Remotely sensed products also enabled the spatial evaluation of model simulations due to their spatial and temporal coverage. However, their usability is not extensively explored in various regions. This study evaluates the effectiveness of incorporating remotely sensed evapotranspiration (RS-ET) and leaf area index (RS-LAI) products to enhance watershed modeling predictions. The objectives include reducing parameter uncertainty at the watershed scale and refining the model's capability to predict the spatial distribution of ET and LAI at sub-watershed scale. Using the Soil and Water Assessment Tool (SWAT) model, a systematic calibration procedure was applied. Initially, solely streamflow data was employed as a constraint, gradually incorporating RS-ET and RS-LAI thereafter. The results showed that while 14 parameter sets exhibit satisfactory performance for streamflow and RS-ET, this number diminishes to six with the inclusion of RS-LAI as an additional constraint. Furthermore, among these six sets, only three effectively captured the spatial patterns of ET and LAI at the sub-watershed level. Our findings showed that leveraging multiple remotely sensed products has the potential to diminish parameter uncertainty and increase the credibility of intra-watershed process simulations. These results contributed to broadening the applicability of remotely sensed products in watershed modeling, enhancing their usefulness in this field.
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The hydrologic connectivity of non-floodplain wetlands (NFWs) with downstream water (DW) has gained increased importance, but connectivity via groundwater (GW) is largely unknown owing to the high complexity of hydrological processes and climatic seasonality. In this study, a causal inference method, convergent cross mapping (CCM), was applied to detect the hydrologic causality between upland NFW and DW through GW. CCM is a nonlinear inference method for detecting causal relationships among environmental variables with weak or moderate coupling in nonlinear dynamical systems. We assumed that causation would exist when the following conditions were observed: (1) the presence of two direct causal (NFW â GW and GW â DW) and one indirect causal (NFW â DW) relationship; (2) a nonexistent opposite causal relationship (DW â NFW); (3) the two direct causations with shorter lag times relative to indirect causation; and (4) similar patterns not observed with pseudo DW. The water levels monitored by a well and piezometer represented NFW and GW measurements, respectively, and the DW was indicated by the baseflow at the outlet of the drainage area, including NFW. To elucidate causality, the DW taken at the adjacent drainage area with similar climatic seasonality was also tested as pseudo DW. The CCM results showed that the water flow from NFW to GW and then DW was only present, and any opposite flows did not exist. In addition, direct causations had shorter lag time than indirect causation, and 3-day lag time was shown between NFW and DW. Interestingly, the results with pseudo DW did not show any lagged interactions, indicating non-causation. These results provide the signals for the hydrologic connectivity of NFW and DW with GW. Therefore, this study would support the importance of NFW protection and management.
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Despite the extensive application of the Soil and Water Assessment Tool (SWAT) for water quality modeling, its ability to simulate soil inorganic nitrogen (SIN) dynamics in agricultural landscapes has not been directly verified. Here, we improved and evaluated the SWAT-Carbon (SWAT-C) model for simulating long-term (1984-2020) dynamics of SIN for 40 cropping system treatments in the U.S. Midwest. We added one new nitrification and two new denitrification algorithms to the default SWAT version, resulting in six combinations of nitrification and denitrification options with varying performance in simulating SIN. The combination of the existing nitrification method in SWAT and the second newly added denitrification method performed the best, achieving R, NSE, PBIAS, and RMSE of 0.63, 0.29, -4.7 %, and 16.0 kg N ha-1, respectively. This represents a significant improvement compared to the existing methods. In general, the revised SWAT-C model's performance was comparable to or better than other agroecosystem models tested in previous studies for assessing the availability of SIN for plant growth in different cropping systems. Sensitivity analysis showed that parameters controlling soil organic matter decomposition, nitrification, and denitrification were most sensitive for SIN simulation. Using SWAT-C for improved prediction of plant-available SIN is expected to better inform agroecosystem management decisions to ensure crop productivity while minimizing the negative environmental impacts caused by fertilizer application.
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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.â¢LC chiral separation parameters were varied to achieve optimal separation of the major enantiomers of the two metolachlor metabolites.â¢LC/MS-MS parameters were adjusted to maximize response and minimize analysis time.â¢Finished methods were used to quantitate enantiomers in archived stream water extracts from agricultural watersheds with corn/soybean production.
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BACKGROUND: Despite the widely recognized importance of aquatic processes for bridging gaps in the global carbon cycle, there is still a lack of understanding of the role of riverbed processes for carbon flows and stocks in aquatic environments. Here, we added a sediment diagenesis and sediment carbon (C) resuspension module into the SWAT-C model and tested it for simulating both particulate organic C (POC) and dissolved organic C (DOC) fluxes using 4 years of monthly observations (2014-2017) in the Tuckahoe watershed (TW) in the U.S. Mid-Atlantic region. RESULTS: Sensitivity analyses show that parameters that regulate POC deposition in river networks are more sensitive than those that determine C resuspension from sediments. Further analyses indicate that allochthonous contributions to POC and DOC are about 36.6 and 46 kgC ha-1 year-1, respectively, while autochthonous contributions are less than 0.72 kgC ha-1 year-1 for both POC and DOC (less than 2% of allochthonous sources). The net deposition of POC on the riverbed (i.e., 11.4 kgC ha-1 year-1) retained ca. 31% of terrestrial inputs of POC. In addition, average annual buried C was 0.34 kgC ha-1 year-1, accounting for only 1% of terrestrial POC inputs or 3% of net POC deposition. The results indicate that about 79% of deposited organic C was converted to inorganic C (CH4 and CO2) in the sediment and eventually released into the overlying water column. CONCLUSION: This study serves as an exploratory study on estimation of C fluxes from terrestrial to aquatic environments at the watershed scale. We demonstrated capabilities of the SWAT-C model to simulate C cycling from uplands to riverine ecosystems and estimated C sinks and sources in aquatic environments. Overall, the results highlight the importance of including carbon cycle dynamics within the riverbed in order to accurately estimate aquatic carbon fluxes and stocks. The new capabilities of SWAT-C are expected to serve as a useful tool to account for those processes in watershed C balance assessment.
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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.
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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.
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Acetamidas/química , Alcanossulfonatos/química , Monitoramento Ambiental/métodos , Água Subterrânea/química , Herbicidas/química , Compostos Orgânicos/química , Poluentes Químicos da Água/química , Cromatografia Líquida de Alta Pressão/métodos , Estereoisomerismo , Espectrometria de Massas em Tandem/métodosRESUMO
Headwater wetlands affect ecosystem integrity of downstream waters; however, many wetlands - particularly geographically isolated wetlands (GIWs) - continue to be at risk. A significant portion of US federal policy is based on the jurisdictional status of wetlands, which is partly determined by the relationship between wetlands and downstream waters, including the cumulative impact of wetlands on those waters. We present a novel multi-phase geospatial modeling method to help elucidate hydrological relationship between GIWs and downstream waters at the landscape scale. The presented approach in this study used inundation maps derived from time series remotely sensed data between 1985 and 2010, weather and hydrological records, and ancillary geospatial data including information from the US Fish and Wildlife Service National Wetlands Inventory (NWI). The study site was a headwater catchment (292â¯km2) of the Choptank River Basin, located in the Mid-Atlantic region of USA, which contained a large number of Delmarva bays. The results showed inundation extent within GIWs varied, in aggregate, in response to weather variability (râ¯=â¯0.58; p-valueâ¯=â¯0.05), and was well correlated with streamflow (râ¯=â¯0.81; p-valueâ¯<â¯0.01) and base flow (râ¯=â¯0.57; p-valueâ¯<â¯0.1) conditions. The relationship between inundation patterns and stream discharge also varied with NWI hydrologic modifiers. The GIWs with water regime characterized by longer durations of flooding exhibited stronger correlations with stream discharge, but those GIWs with shorter durations of flooding were less correlated with stream discharge. This analysis suggests the mutual reliance (i.e., connection) of wetlands and streams on groundwater. GIWs appeared to function in aggregate, and it is likely that the combined effect of these wetlands significantly influenced the functioning of downstream waters.
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In Part 1 of this two-part manuscript series, we presented an effective assessment method for mapping inundation of geographically isolated wetlands (GIWs) and quantifying their cumulative landscape-scale hydrological connectivity with downstream waters using time series remotely sensed data (Yeo et al., 2018). This study suggested strong hydrological coupling between GIWs and downstream waters at the seasonal timescale via groundwater. This follow-on paper investigates the hydrological connectivity of GIWs with downstream waters and cumulative watershed-scale hydrological impacts over multiple time scales. Modifications were made to the representation of wetland processes within the Soil and Water Assessment Tool (SWAT). A version of SWAT with improved wetland function, SWAT-WET, was applied to Greensboro Watershed, which is located in the Mid-Atlantic Region of USA, to simulate hydrological processes over 1985-2015 under two contrasting land use scenarios (i.e., presence and absence of GIWs). Comparative analysis of simulation outputs elucidated how GIWs could influence partitioning of precipitation between evapotranspiration (ET) and terrestrial water storage, and affect water transport mechanisms and routing processes that generate streamflow. Model results showed that GIWs influenced the watershed water budget and stream flow generation processes over the long-term (30â¯year), inter-annual, and monthly time scales. GIWs in the study watershed increased terrestrial water storage during the wet season, and buffered the dynamics of shallow groundwater during the dry season. The inter-annual modeling analysis illustrated that densely distributed GIWs can exert strong hydrological influence on downstream waters by regulating surface water runoff, while maintaining groundwater recharge and ET under changing (wetter) climate conditions. The study findings highlight the hydrological connectivity of GIWs with downstream waters and the cumulative hydrological influence of GIWs as hydrologic sources to downstream ecosystems through different runoff processes over multiple time scales.
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Fires in terrestrial ecosystems produce large amounts of charcoal that persist in the environment and represent a substantial pool of sequestered carbon in soil. The objective of this research was to investigate the effect of charring on mid-infrared spectra of materials likely to be present in forest fires in order to determine the feasibility of determining charred organic matter in soils. Four materials (cellulose, lignin, pine bark, and pine wood) and char from these materials, created by charring for various durations (1 to 168 h) and at various temperatures (200 to 450 degrees C), were studied. Mid-infrared spectra and measures of acidity (total acids, carboxylic acids, lactones, and phenols as determined by titration) were determined for 56 different samples (not all samples were charred at all temperatures/durations). Results showed spectral changes that varied with the material, temperature, and duration of charring. Despite the wide range of spectral changes seen with the differing materials and length/temperature of charring, partial least squares calibrations for total acids, carboxylic acids, lactones, and phenols were successfully created (coefficient of determination and root mean squared deviation of 0.970 and 0.380; 0.933 and 0.227; 0.976 and 0.120; and 0.982 and 0.101 meq/g, respectively), indicating that there is a sufficient commonality in the changes to develop calibrations without the need for unique calibrations for each specific material or condition of char formation.
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Celulose/química , Carvão Vegetal/análise , Lignina/química , Casca de Planta/química , Solo/análise , Madeira/química , Incêndios , Pinus ponderosa/química , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
Depending on management, soil organic carbon (SOC) is a potential source or sink for atmospheric CO(2). We used the EPIC model to study impacts of soil and crop management on SOC in corn (Zea mays L.) and soybean (Glycine max L. Merr.) croplands of Iowa. The National Agricultural Statistics Service crops classification maps were used to identify corn-soybean areas. Soil properties were obtained from a combination of SSURGO and STATSGO databases. Daily weather variables were obtained from first order meteorological stations in Iowa and neighboring states. Data on crop management, fertilizer application and tillage were obtained from publicly available databases maintained by the NRCS, USDA-Economic Research Service (ERS), and Conservation Technology Information Center. The EPIC model accurately simulated state averages of crop yields during 1970-2005 (R(2) = 0.87). Simulated SOC explained 75% of the variation in measured SOC. With current trends in conservation tillage adoption, total stock of SOC (0-20 cm) is predicted to reach 506 Tg by 2019, representing an increase of 28 Tg with respect to 1980. In contrast, when the whole soil profile was considered, EPIC estimated a decrease of SOC stocks with time, from 1835 Tg in 1980 to 1771 Tg in 2019. Hence, soil depth considered for calculations is an important factor that needs further investigation. Soil organic C sequestration rates (0-20 cm) were estimated at 0.50 to 0.63 Mg ha(-1) yr(-1) depending on climate and soil conditions. Overall, combining land use maps with EPIC proved valid for predicting impacts of management practices on SOC. However, more data on spatial and temporal variation in SOC are needed to improve model calibration and validation.
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Produtos Agrícolas , Modelos Teóricos , Solo/análise , Calibragem , IowaRESUMO
Wetlands are often dominant features in low relief, depressional landscapes and provide an array of hydrologically driven ecosystem services. However, contemporary models do not adequately represent the role of spatially distributed wetlands in watershed-scale water storage and flows. Such tools are critical to better understand wetland hydrological, biogeochemical, and biological functions and predict management and policy outcomes at varying spatial scales. To develop a new approach for simulating depressional landscapes, we modified the Soil and Water Assessment Tool (SWAT) model to incorporate improved representations of depressional wetland structure and hydrological processes. Specifically, we refined the model to incorporate: (1) water storage capacity and surface flowpaths of individual wetlands and (2) local wetland surface and subsurface exchange. We utilized this model, termed SWAT-DSF (DSF for Depressional Storage and Flows), to simulate the ~289 km2 Greensboro watershed within the Delmarva Peninsula of the US Coastal Plain. Model calibration and verification used both daily streamflow observations and remotely sensed surface water extent data (ca. 2-week temporal resolution), allowing us to assess model performance with respect to both streamflow and watershed inundation patterns. Our findings demonstrate that SWAT-DSF can successfully replicate distributed wetland processes and resultant watershed-scale hydrology. SWAT-DSF provides improved temporal and spatial characterization of watershed-scale water storage and flows in depressional landscapes, providing a new tool to quantify wetland functions at broad spatial scales.
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A common management practice for the production of fresh-market vegetables utilizes polyethylene (plastic) mulch because it increases soil temperature, decreases weed pressure, maintains soil moisture, and minimizes soil contact with the product. However, rain events afford much more erosion and runoff because 50-75% of the field is covered with an impervious surface. A plot study was conducted to compare and to quantify the off-site movement of soil, insecticides, and fungicides associated with runoff from plots planted with Sunbeam tomatoes (Lycopersicon esculentum Mill) using the conventional polyethylene mulch management practice vs an alternative management practice-polyethylene mulch-covered beds with cereal rye (Secale cereale) planted in the furrows between the beds. The use of cereal rye-covered furrows with the conventional polyethylene system decreased runoff volume by more than 40%, soil erosion by more than 80%, and pesticide loads by 48-74%. Results indicate that vegetative furrows are critical to minimizing the negative aspects of this management practice.
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Agricultura/métodos , Fungicidas Industriais/análise , Inseticidas/análise , Plásticos , Chuva , Solanum lycopersicum/crescimento & desenvolvimento , Polietileno , Secale/crescimento & desenvolvimento , Solo , Água/químicaRESUMO
Perchlorate has been detected in U.S. milk samples from many different states. Applying data from a recently reported 9-week experiment in which 16 Holstein dairy cows were administered perchlorate allowed us to derive an equation for the dose-response relationship between perchlorate concentrations in feed/drinking water and its appearance in milk. Examination of background concentrations of perchlorate in the total mixed ration (TMR) fed in addition to the variable dose supplied to treated cows as a ruminal infusate revealed that cows receive significant and variable exposure to perchlorate from the TMR. Weekly examination of the TMR disclosed that a change in ingredients midway through the experiment caused a significant (78%) change in TMR perchlorate concentration. Analyses of the ingredients comprising the TMR revealed that 41.9% of the perchlorate came from corn silage, 22.9% came from alfalfa hay and 11.7% was supplied by sudan grass. Finally, USDA Food and Nutrition Survey data on fluid milk consumption were used to predict potential human exposure from milk that contained concentrations of perchlorate observed in our previous dosing study. The study suggests that reducing perchlorate concentration in dairy feed may reduce perchlorate concentrations in milk as well as the potential to reduce human exposure to perchlorate in milk.
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Ração Animal/análise , Exposição Ambiental , Leite/química , Percloratos/análise , Animais , Bovinos , Feminino , Contaminação de Alimentos/análise , HumanosRESUMO
The ability of agricultural management practices to reduce the ecological risks of pesticides was evaluated. Risk quotients, a mathematical description of the relationship between exposure and toxicity, and hazard ratings, a rank of the potential risk of pesticides to aquatic environments, were calculated for conventional and alternative cultivation practices for tomatoes: Poly-Bare, raised beds covered with polyethylene mulch with bare-soil furrows; Poly-Rye, raised beds covered with polyethylene mulch with cereal rye (Secale cereale) grown in the furrows; and Vetch, raised beds and furrows planted with hairy vetch seed (Vicia villosa). Evaluations were conducted using measured pesticide concentrations in runoff at the edge-of-field and estimated environmental concentrations in an adjacent creek and a theoretical pond receiving the runoff. Runoff from Poly-Bare presented the greatest risk to ecosystem health and to sensitive organisms, whereas the use of Vetch minimized these risks. Previous studies have shown that harvest yields were maintained and that runoff volume, soil loss, and off-site transport of pesticides measured in runoff were reduced using the alternative management practices (Poly-Rye and Vetch). Together, these results indicate that the alternative management practices (Poly-Rye and Vetch) have a less adverse impact on the environment than the conventional management practice (Poly-Bare) while providing growers with an acceptable economic return. In addition, the present study demonstrates the need to consider the management practice when assessing the potential risks and hazards for certain pesticides.
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Conservação dos Recursos Naturais/métodos , Saúde Ambiental , Praguicidas/toxicidade , Verduras/efeitos dos fármacos , Gerenciamento de Resíduos/métodos , Poluentes Químicos da Água/toxicidade , Abastecimento de Água/normas , Agricultura , Ecologia , Modelos Biológicos , Praguicidas/análise , Medição de Risco , Verduras/crescimento & desenvolvimento , Poluentes Químicos da Água/análise , Abastecimento de Água/análiseRESUMO
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.
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Acetamidas/análise , Monitoramento Ambiental/métodos , Água Subterrânea/química , Herbicidas/análise , Ácidos Sulfônicos/análise , Poluentes Químicos da Água/análise , Agricultura , Etano/análiseRESUMO
The adoption rate of winter cover crops (WCCs) as an effective conservation management practice to help reduce agricultural nutrient loads in the Chesapeake Bay (CB) is increasing. However, the WCC potential for water quality improvement has not been fully realized at the watershed scale. This study was conducted to evaluate the long-term impact of WCCs on hydrology and NO3-N loads in two adjacent watersheds and to identify key management factors that affect the effectiveness of WCCs using the Soil and Water Assessment Tool (SWAT) and statistical methods. Simulation results indicated that WCCs are effective for reducing NO3-N loads and their performance varied based on planting date, species, soil characteristics, and crop rotations. Early-planted WCCs outperformed late-planted WCCs on the reduction of NO3-N loads and early-planted rye (RE) reduced NO3-N loads by ~49.3% compared to the baseline (no WCC). The WCCs were more effective in a watershed dominated by well-drained soils with increased reductions in NO3-N fluxes of ~2.5 kg N·ha-1 delivered to streams and ~10.1 kg N·ha-1 leached into groundwater compared to poorly-drained soils. Well-drained agricultural lands had higher transport of NO3-N in the soil profile and groundwater due to increased N leaching. Poorly-drained agricultural lands had lower NO3-N due to extensive drainage ditches and anaerobic soil conditions promoting denitrification. The performance of WCCs varied by crop rotations (i.e., continuous corn and corn-soybean), with increased N uptake following soybean crops due to the increased soil mineral N availability by mineralization of soybean residue compared to corn residue. The WCCs can reduce N leaching where baseline NO3-N loads are high in well-drained soils and/or when residual and mineralized N availability is high due to the cropping practices. The findings suggested that WCC implementation plans should be established in watersheds according to local edaphic and agronomic characteristics for reducing N leaching.