Developmental framework for a desktop hydrogeomorphic wetland functional assessment derived from field-based data.

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.

Modeling lateral carbon fluxes for agroecosystems in the Mid-Atlantic region: Control factors and importance for carbon budget.

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.

Detecting causal relationship of non-floodplain wetland hydrologic connectivity using convergent cross mapping.

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 → GW and GW → DW) and one indirect causal (NFW → DW) relationship; (2) a nonexistent opposite causal relationship (DW → 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.

Simulating agroecosystem soil inorganic nitrogen dynamics under long-term management with an improved SWAT-C model.

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.

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.

Modeling sediment diagenesis processes on riverbed to better quantify aquatic carbon fluxes and stocks in a small watershed of the Mid-Atlantic region.

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.

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.

Mapping landscape-level hydrological connectivity of headwater wetlands to downstream waters: A geospatial modeling approach - Part 1.

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 (292 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 (r = 0.58; p-value = 0.05), and was well correlated with streamflow (r = 0.81; p-value < 0.01) and base flow (r = 0.57; p-value < 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.

Mapping landscape-level hydrological connectivity of headwater wetlands to downstream waters: A catchment modeling approach - Part 2.

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 (30 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.

A watershed-scale model for depressional wetland-rich landscapes.

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.

Impacts of Watershed Characteristics and Crop Rotations on Winter Cover Crop Nitrate-Nitrogen Uptake Capacity within Agricultural Watersheds in the Chesapeake Bay Region.

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.

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.

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.

Evaluation of three field-based methods for quantifying soil carbon.

Three advanced technologies to measure soil carbon (C) density (g C m(-2)) are deployed in the field and the results compared against those obtained by the dry combustion (DC) method. The advanced methods are: a) Laser Induced Breakdown Spectroscopy (LIBS), b) Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS), and c) Inelastic Neutron Scattering (INS). The measurements and soil samples were acquired at Beltsville, MD, USA and at Centro International para el Mejoramiento del Maíz y el Trigo (CIMMYT) at El Batán, Mexico. At Beltsville, soil samples were extracted at three depth intervals (0-5, 5-15, and 15-30 cm) and processed for analysis in the field with the LIBS and DRIFTS instruments. The INS instrument determined soil C density to a depth of 30 cm via scanning and stationary measurements. Subsequently, soil core samples were analyzed in the laboratory for soil bulk density (kg m(-3)), C concentration (g kg(-1)) by DC, and results reported as soil C density (kg m(-2)). Results from each technique were derived independently and contributed to a blind test against results from the reference (DC) method. A similar procedure was employed at CIMMYT in Mexico employing but only with the LIBS and DRIFTS instruments. Following conversion to common units, we found that the LIBS, DRIFTS, and INS results can be compared directly with those obtained by the DC method. The first two methods and the standard DC require soil sampling and need soil bulk density information to convert soil C concentrations to soil C densities while the INS method does not require soil sampling. We conclude that, in comparison with the DC method, the three instruments (a) showed acceptable performances although further work is needed to improve calibration techniques and (b) demonstrated their portability and their capacity to perform under field conditions.

Potential pollutant sources in a Choptank River (USA) subwatershed and the influence of land use and watershed characteristics.

Row-crop and poultry production have been implicated as sources of water pollution along the Choptank River, an estuary and tributary of the Chesapeake Bay. This study examined the effects of land use, subwatershed characteristics, and climatic conditions on the water quality parameters of a subwatershed in the Choptank River watershed. The catchments within the subwatershed were defined using advanced remotely-sensed data and current geographic information system processing techniques. Water and sediment samples were collected in May-October 2009 and April-June 2010 under mostly baseflow conditions and analyzed for select bacteria, nitrate-N, ammonium-N, total arsenic, total phosphorus (TP), orthophosphate (ortho-P), and particle-phase phosphorus (PP); n=96 for all analytes except for arsenic, n=136, and for bacteria, n=89 (aqueous) and 62 (sediment). Detections of Enterococci and Escherichia coli concentrations were ubiquitous in this subwatershed and showed no correlation to location or land use, however larger bacterial counts were observed shortly after precipitation. Nitrate-N concentrations were not correlated with agricultural lands, which may reflect the small change in percent agriculture and/or the similarity of agronomic practices and crops produced between catchments. Concentration data suggested that ammonia emission and possible deposition to surface waters occurred and that these processes may be influenced by local agronomic practices and climatic conditions. The negative correlation of PP and arsenic concentrations with percent forest was explained by the stronger signal of the head waters and overland flow of particulate phase analytes versus dissolved phase inputs from groundwater. Service roadways at some poultry production facilities were found to redirect runoff from the facilities to neighboring catchment areas, which affected water quality parameters. Results suggest that in this subwatershed, catchments with poultry production facilities are possible sources for arsenic and PP as compared to catchment areas where these facilities were not present.

Relating nutrient and herbicide fate with landscape features and characteristics of 15 subwatersheds in the Choptank River watershed.

Excess nutrients and agrochemicals from non-point sources contribute to water quality impairment in the Chesapeake Bay watershed and their loading rates are related to land use, agricultural practices, hydrology, and pollutant fate and transport processes. In this study, monthly baseflow stream samples from 15 agricultural subwatersheds of the Choptank River in Maryland USA (2005 to 2007) were characterized for nutrients, herbicides, and herbicide transformation products. High-resolution digital maps of land use and forested wetlands were derived from remote sensing imagery. Examination of landscape metrics and water quality data, partitioned according to hydrogeomorphic class, provided insight into the fate, delivery, and transport mechanisms associated with agricultural pollutants. Mean Nitrate-N concentrations (4.9 mg/L) were correlated positively with percent agriculture (R(2)=0.56) and negatively with percent forest (R(2)=0.60). Concentrations were greater (p=0.0001) in the well-drained upland (WDU) hydrogeomorphic region than in poorly drained upland (PDU), reflecting increased denitrification and reduced agricultural land use intensity in the PDU landscape due to the prevalence of hydric soils. Atrazine and metolachlor concentrations (mean 0.29 µg/L and 0.19 µg/L) were also greater (p=0.0001) in WDU subwatersheds than in PDU subwatersheds. Springtime herbicide concentrations exhibited a strong, positive correlation (R(2)=0.90) with percent forest in the WDU subwatersheds but not in the PDU subwatersheds. In addition, forested riparian stream buffers in the WDU were more prevalent than in the PDU where forested patches are typically not located near streams, suggesting an alternative delivery mechanism whereby volatilized herbicides are captured by the riparian forest canopy and subsequently washed off during rainfall. Orthophosphate, CIAT (6-chloro-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine), CEAT (6-chloro-N-ethyl-1,3,5-triazine-2,4-diamine), and MESA (2-[(2-ethyl-6-methylphenyl) (2-methoxy-1-methylethyl)amino]-2-oxoethanesulfonic acid) were also analyzed. These findings will assist efforts in targeting implementation of conservation practices to the most environmentally-critical areas within watersheds to achieve water quality improvements in a cost-effective manner.

Pollutant fate and spatio-temporal variability in the choptank river estuary: factors influencing water quality.

Restoration of the Chesapeake Bay, the largest estuary in the United States, is a national priority. Documentation of progress of this restoration effort is needed. A study was conducted to examine water quality in the Choptank River estuary, a tributary of the Chesapeake Bay that since 1998 has been classified as impaired waters under the Federal Clean Water Act. Multiple water quality parameters (salinity, temperature, dissolved oxygen, chlorophyll a) and analyte concentrations (nutrients, herbicide and herbicide degradation products, arsenic, and copper) were measured at seven sampling stations in the Choptank River estuary. Samples were collected under base flow conditions in the basin on thirteen dates between March 2005 and April 2008. As commonly observed, results indicate that agriculture is a primary source of nitrate in the estuary and that both agriculture and wastewater treatment plants are important sources of phosphorus. Concentrations of copper in the lower estuary consistently exceeded both chronic and acute water quality criteria, possibly due to use of copper in antifouling boat paint. Concentrations of copper in the upstream watersheds were low, indicating that agriculture is not a significant source of copper loading to the estuary. Concentrations of herbicides (atrazine, simazine, and metolachlor) peaked during early-summer, indicating a rapid surface-transport delivery pathway from agricultural areas, while their degradation products (CIAT, CEAT, MESA, and MOA) appeared to be delivered via groundwater transport. Some in-river processing of CEAT occurred, whereas MESA was conservative. Observed concentrations of herbicide residues did not approach established levels of concern for aquatic organisms. Results of this study highlight the importance of continued implementation of best management practices to improve water quality in the estuary. This work provides a baseline against which to compare future changes in water quality and may be used to design future monitoring programs needed to assess restoration strategy efficacy.

Size distributions of manure particles released under simulated rainfall.

Manure and animal waste deposited on cropland and grazing lands serve as a source of microorganisms, some of which may be pathogenic. These microorganisms are released along with particles of dissolved manure during rainfall events. Relatively little if anything is known about the amounts and sizes of manure particles released during rainfall, that subsequently may serve as carriers, abode, and nutritional source for microorganisms. The objective of this work was to obtain and present the first experimental data on sizes of bovine manure particles released to runoff during simulated rainfall and leached through soil during subsequent infiltration. Experiments were conducted using 200 cm long boxes containing turfgrass soil sod; the boxes were designed so that rates of manure dissolution and subsequent infiltration and runoff could be monitored independently. Dairy manure was applied on the upper portion of boxes. Simulated rainfall (ca. 32.4 mm h(-1)) was applied for 90 min on boxes with stands of either live or dead grass. Electrical conductivity, turbidity, and particle size distributions obtained from laser diffractometry were determined in manure runoff and soil leachate samples. Turbidity of leachates and manure runoff samples decreased exponentially. Turbidity of manure runoff samples was on average 20% less than turbidity of soil leachate samples. Turbidity of leachate samples from boxes with dead grass was on average 30% less than from boxes with live grass. Particle size distributions in manure runoff and leachate suspensions remained remarkably stable after 15 min of runoff initiation, although the turbidity continued to decrease. Particles had the median diameter of 3.8 microm, and 90% of particles were between 0.6 and 17.8 microm. The particle size distributions were not affected by the grass status. Because manure particles are known to affect transport and retention of microbial pathogens in soil, more information needs to be collected about the concurrent release of pathogens and manure particles during rainfall events.