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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.

Science of the Total Environment

Nitrogen reductions have decreased hypoxia in the Chesapeake Bay: Evidence from empirical and numerical modeling

Seasonal hypoxia is a characteristic feature of the Chesapeake Bay due to anthropogenic nutrient input from agriculture and urbanization throughout the watershed. Although coordinated management efforts since 1985 have reduced nutrient inputs to the Bay, oxygen concentrations at depth in the summer still frequently fail to meet water quality standards that have been set to protect critical estuarine living resources. To quantify the impact of watershed nitrogen reductions on Bay hypoxia during a recent period including both average discharge and extremely wet years (2016–2019), this study employed both statistical and three-dimensional (3-D) numerical modeling analyses. Numerical model results suggest that if the nitrogen reductions since 1985 had not occurred, annual hypoxic volumes (O 2 < 3 mg L −1 ) would have been ~50–120% greater during the average discharge years of 2016–2017 and ~20–50% greater during the wet years of 2018–2019. The effect was even greater for O 2 < 1 mg L −1 , where annual volumes would have been ~80–280% greater in 2016–2017 and ~30–100% greater in 2018–2019. These results were supported by statistical analysis of empirical data, though the magnitude of improvement due to nitrogen reductions was greater in the numerical modeling results than in the statistical analysis. This discrepancy is largely accounted for by warming in the Bay that has exacerbated hypoxia and offset roughly 6–34% of the improvement from nitrogen reductions. Although these results may reassure policymakers and stakeholders that their efforts to reduce hypoxia have improved ecosystem health in the Bay, they also indicate that greater reductions are needed to counteract the ever-increasing impacts of climate change.

Chesapeake Bay

Watershed export of fine sediment, organic carbon, and chlorophyll-a to Chesapeake Bay: Spatial and temporal patterns in 1984–2016

Chesapeake Bay has long experienced nutrient enrichment and water clarity deterioration. This study provides new quantification of loads and yields for sediment (fine and coarse grained), organic carbon (total, dissolved, and particulate), and chlorophyll-a from the monitored nontidal Chesapeake Bay watershed (MNTCBW), all of which are expected to drive estuarine water clarity. We conducted an integrated analysis of nine major tributaries to the Bay to understand spatial and temporal export patterns over the last thirty years (1984–2016). In terms of spatial pattern, export of these constituents from the MNTCBW was strongly dominated (~ 90%) by the three largest tributaries (i.e., Susquehanna, Potomac, and James). Among the nine tributaries, the ranking of constituent export generally follows the order of their watershed sizes, with other factors such as land use and reservoir playing important roles in some exceptions. In terms of partitioning, suspended sediment (SS) export was dominated by fine-grained sediment (SS fine ) in all nine tributaries; overall, ~ 90% of the MNTCBW SS is SS fine . Total organic carbon (TOC) export was dominated by dissolved organic carbon (DOC) in all tributaries except Potomac River; overall, ~ 60% of the MNTCBW TOC is DOC. A comparison with literature shows that the MNTCBW SS and TOC yields were ~ 80% and ~ 60% of the respective medians of worldwide watersheds. In terms of temporal pattern, flow-normalized yields from the MNTCBW show overall increases in SS (both long-term [1984–2016] and short-term [2004–2016]), SS fine (long-term and short-term), TOC (long-term), and chlorophyll-a (short-term). The rises in SS, SS fine , and TOC were largely driven by Susquehanna River where Conowingo Reservoir's trapping efficiency has greatly diminished in the last twenty years. Overall, these new results on the status and trends of sediment, organic carbon, and chlorophyll-a provide the foundation for building potential linkages between riverine inputs and estuarine water clarity patterns.

Chesapeake Bay watershed

Chesapeake Bay impact structure: Morphology, crater fill, and relevance for impact structures on Mars

The late Eocene Chesapeake Bay impact structure (CBIS) on the Atlantic margin of Virginia is one of the largest and best-preserved "wet-target" craters on Earth. It provides an accessible analog for studying impact processes in layered and wet targets on volatile-rich planets. The CBIS formed in a layered target of water, weak clastic sediments, and hard crystalline rock. The buried structure consists of a deep, filled central crater, 38 km in width, surrounded by a shallower brim known as the annular trough. The annular trough formed partly by collapse of weak sediments, which expanded the structure to ???85 km in diameter. Such extensive collapse, in addition to excavation processes, can explain the "inverted sombrero" morphology observed at some craters in layered targets. The distribution of crater-fill materials i n the CBIS is related to the morphology. Suevitic breccia, including pre-resurge fallback deposits, is found in the central crater. Impact-modified sediments, formed by fluidization and collapse of water-saturated sand and silt-clay, occur in the annular trough. Allogenic sediment-clast breccia, interpreted as ocean-resurge deposits, overlies the other impactites and covers the entire crater beneath a blanket of postimpact sediments. The formation of chaotic terrains on Mars is attributed to collapse due to the release of volatiles from thick layered deposits. Some flat-floored rimless depressions with chaotic infill in these terrains are impact craters that expanded by collapse farther than expected for similar-sized complex craters in solid targets. Studies of crater materials in the CBIS provide insights into processes of crater expansion on Mars and their links to volatiles. ?? The Meteoritical Society, 2006.

Meteoritics and Planetary Science

Point sources and agricultural practices control spatial-temporal patterns of orthophosphate in tributaries to Chesapeake Bay

Orthophosphate (PO 4 ) is the most bioavailable form of phosphorus (P). Excess PO 4 may cause harmful algal blooms in aquatic ecosystems. A major restoration effort is underway for Chesapeake Bay (CB) to reduce P, nitrogen, and sediment loading to CB. Although PO 4 cycling and delivery to streams has been characterized in small-scale studies, regional drivers of PO 4 patterns remain poorly understood because most water quality trend assessment focus on total P. Moreover, these trend assessments are usually at an annual timestep. To address this research gap, we analyzed PO 4 patterns over a 9-year period at 53 monitoring stations across the CB watershed to: 1) characterize the role of PO 4 in total P fluxes and trends; 2) describe spatial and temporal patterns of PO 4 concentrations across seasons and streamflow ; and 3) explore factors explaining these patterns. Agricultural watersheds exported the most total P compared with watersheds under different land uses (e.g., urban or forest), with PO 4 comprising up to 50% of those exports. Although PO 4 exports are declining at many sites, some agricultural regions are experiencing increasing trends at a rate sufficient to drive total P trends. Regression modeling results suggest that point source load reductions are likely responsible for decreasing PO 4 concentrations observed at many sites. Watersheds with more Conservation Reserve Program enrollment had lower summer PO 4 concentrations, highlighting the effectiveness of this practice. Manure inputs strongly predicted PO 4 concentrations at high flows across all seasons. Both manure applications and conservation tillage were correlated with changes in PO 4 concentrations at high flow, suggesting these activities could contribute to increasing PO 4 concentrations. This study highlights the effectiveness of point source control for reducing PO 4 exports and underscores the need for management strategies to target sources, practices, and landscape factors determining PO 4 loss from soils where manure inputs remain high.

Delaware, Maryland, New York, Pennsylvania, Virgin

Legacy sediment as a potential source of orthophosphate: Preliminary conceptual and geochemical models for the Susquehanna River, Chesapeake Bay watershed, USA

Nutrient pollution from agriculture and urban areas plus acid mine drainage (AMD) from legacy coal mines are primary causes of water-quality impairment in the Susquehanna River, which is the predominant source of freshwater and nutrients entering the Chesapeake Bay. Recent increases in the delivery of dissolved orthophosphate (PO 4 ) from the river to the bay may be linked to long-term increases in pH, decreased acidity of precipitation, and decreased acidity, iron, and aluminum loading from widespread AMD. Since the 1950s, baseline pH increased from ~6.5 to ~8 in the West Branch and “North Branch” of the Susquehanna River, which drain bituminous and anthracite coalfields of Pennsylvania. A current baseline pH of ~8 and daily maxima exceeding 9 have been documented along the lower Susquehanna River. In response to improved river quality, bioavailable PO 4 now may be released into solution from legacy sediment that has filled major impoundments in lower reaches of the river. At typical pH (5–8) of natural water, aqueous PO 4 species tend to be adsorbed by hydrous iron, aluminum, and manganese oxides that coat soil and sediment particles; however, PO 4 may be substantially desorbed at pH >8. We created a geochemical model that simulates equilibrium aqueous/solid distributions of PO 4 as pH and other solution characteristics change. Considering current conditions in the lower Susquehanna River, the model demonstrates potential for extensive release of adsorbed PO 4 at pH >8. Empirical data from laboratory experiments corroborate model results. The transfer of PO 4 into the water column may increase algae growth, which removes CO 2 and drives pH to higher values, facilitating additional PO 4 release and exacerbating the potential for harmful algal blooms. Thus, legacy sediment is a currently unquantified source of PO 4 that warrants consideration by resource managers and programs collaborating to reduce phosphorus loads to the bay and similar settings worldwide.

Chesapeake Bay watershed

Evidence that watershed nutrient management practices effectively reduce estrogens in environmental waters

We evaluate the impacts of different nutrient management strategies on the potential for co-managing estrogens and nutrients in environmental waters of the Potomac watershed of the Chesapeake Bay. These potential co-management approaches represent agricultural and urban runoff, wastewater treatment plant effluent, and combined sewer overflow replacements. Twelve estrogenic compounds and their metabolites were analysed by gas chromatography–mass spectrometry. Estrogenic activity (E 2 Eq) was measured by in vitro bioassay. We detected estrone E 1 (0.05–6.97 ng L −1 ) and estriol E 3 (below detection-8.13 ng L −1 ) and one conjugated estrogen (estrone-3-sulfate E 1 -3S; below detection-8.13 ng L −1 ). E 1 was widely distributed and positively correlated with E 2 Eq, water temperature, and dissolved organic carbon (DOC). Among nonpoint sources, E 2 Eq, and concentrations of E 1 , soluble reactive phosphorus (SRP) and total dissolved nitrogen (TDN) decreased by 51–61%, 77–82%, 62–64%, 4–16% in restored urban and agricultural streams with best management practices (BMPs) relative to unrestored streams without BMPs. In a wastewater treatment plant (Blue Plains WWTP), >94% of E 1 , E 1 -3S, E 3 , E 2 Eq and TDN were removed while SRP increased by 305% during nitrification/denitrification as a part of advanced wastewater treatment. Consequently, E 1 and TDN concentrations in WWTP effluents were comparable or even lower than those observed in the receiving stream or river waters, and the effects of wastewater discharges on downstream E 1 and TDN concentrations were minor. Highest E 2 Eq value and concentrations of E1, E3, and TDN were detected in combined sewer overflow (CSO). This study suggests that WWTP upgrades with biological nutrient removal, CSO management, and certain agricultural and urban BMPs for nutrient controls have the potential to remove estrogens from point and nonpoint sources along with other contaminants in streams and rivers.

Maryland

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&ndash;October 2009 and April&ndash;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.

Choptank River

Patterns of diel variation in nitrate concentrations in the Potomac River

The Potomac River is a large source of N to Chesapeake Bay, where reducing nutrient loads is a focus of efforts to improve trophic status. Better understanding of NO 3 – loss, reflected in part by diel variation in NO 3 – concentrations, may refine model predictions of N loads to the Bay. We analyzed 2 y of high-frequency NO 3 – sensor data in the Potomac to quantify seasonal variation in the magnitude and timing of diel NO 3 – loss. Diel patterns were evident, especially during low flow, despite broad seasonal and flow-driven variation in NO 3 – concentrations. Diel variation was ~0.01 mg N/L in winter and 0.02 to 0.03 mg N/L in summer with intermediate values in spring and autumn, equivalent to <1% of the daily mean NO 3 – concentration in winter and ~2 to 4% in summer. Maximum diel NO 3 – values generally occurred in mid- to late morning, with more repeatable patterns in summer and wider variation in autumn and winter. Diel NO 3 – loss reduced loads by 0.7% in winter and 3% in summer. These losses were less than estimates of total in-stream NO 3 – load loss across the basin that averaged 33% of the annual groundwater contribution to the river. Water temperature and discharge had stronger relationships to the daily magnitude of diel NO 3 – variation than did photosynthetically active radiation. Estimated diel areal NO 3 – loss rates were generally >1000 mg N m –2 d –1 , greater than most published values because measurements in this large river integrate over a greater depth/unit stream bottom area than do those from smaller rivers. These diel NO 3 – patterns are consistent with the influence of photoautotrophic uptake and related denitrification, but we cannot attribute these patterns to assimilation alone because the magnitude and timing of diel dynamics were affected to an unknown extent by processes, such as evapotranspiration, transient storage, and hydrodynamic dispersion. Improvements to diel loss estimates will require additional high-frequency measures, such as dissolved O 2 , dissolved organic N, and NH 4 + , and deployment of 2 measurement stations.

Potomac River

Petrography, mineralogy, and geochemistry of deep gravelly sands in the Eyreville B core, Chesapeake Bay impact structure

The ICDP–USGS Eyreville drill cores in the Chesapeake Bay impact structure reached a total depth of 1766 m and comprise (from the bottom upwards) basement-derived schists and granites/pegmatites, impact breccias, mostly poorly lithified gravelly sand and crystalline blocks, a granitic slab, sedimentary breccias, and postimpact sediments. The gravelly sand and crystalline block section forms an approximately 26 m thick interval that includes an amphibolite block and boulders of cataclastic gneiss and suevite. Three gravelly sands (basal, middle, and upper) are distinguished within this interval. The gravelly sands are poorly sorted, clast supported, and generally massive, but crude size-sorting and subtle, discontinuous layers occur locally. Quartz and K-feldspar are the main sand-size minerals and smectite and kaolinite are the principal clay minerals. Other mineral grains occur only in accessory amounts and lithic clasts are sparse (only a few vol%). The gravelly sands are silica rich (~80 wt% SiO 2 ). Trends with depth include a slight decrease in SiO 2 and slight increase in Fe 2 O 3 . The basal gravelly sand (below the cataclasite boulder) has a lower SiO 2 content, less K-feldspar, and more mica than the higher sands, and it contains more lithic clasts and melt particles that are probably reworked from the underlying suevite. The middle gravelly sand (below the amphibolite block) is finer-grained, contains more abundant clay minerals, and displays more variable chemical compositions than upper gravelly sand (above the block). Our mineralogical and geochemical results suggest that the gravelly sands are avalanche deposits derived probably from the nonmarine Potomac Formation in the lower part of the target sediment layer, in contrast to polymict diamictons higher in the core that have been interpreted as ocean-resurge debris flows, which is in agreement with previous interpretations. The mineralogy and geochemistry of the gravelly sands are typical for a passive continental margin source. There is no discernible mixing with marine sediments (no glauconite or Paleogene marine microfossils noted) during the impact remobilization and redeposition. The unshocked amphibolite block and cataclasite boulder might have originated from the outer parts of the transient crater.

Virginia

Assessing winter cover crop nutrient uptake efficiency using a water quality simulation model

Winter cover crops are an effective conservation management practice with potential to improve water quality. Throughout the Chesapeake Bay Watershed (CBW), which is located in the Mid-Atlantic US, winter cover crop use has been emphasized and federal and state cost-share programs are available to farmers to subsidize the cost of winter cover crop establishment. The objective of this study was to assess the long-term effect of planting winter cover crops at the watershed scale and to identify critical source areas of high nitrate export. A physically-based watershed simulation model, Soil and Water Assessment Tool (SWAT), was calibrated and validated using water quality monitoring data and satellite-based estimates of winter cover crop species performance to simulate hydrological processes and nutrient cycling over the period of 1991&ndash;2000. Multiple scenarios were developed to obtain baseline information on nitrate loading without winter cover crops planted and to investigate how nitrate loading could change with different winter cover crop planting scenarios, including different species, planting times, and implementation areas. The results indicate that winter cover crops had a negligible impact on water budget, but significantly reduced nitrate leaching to groundwater and delivery to the waterways. Without winter cover crops, annual nitrate loading was approximately 14 kg ha &minus;1 , but it decreased to 4.6&ndash;10.1 kg ha &minus;1 with winter cover crops resulting in a reduction rate of 27&ndash;67% at the watershed scale. Rye was most effective, with a potential to reduce nitrate leaching by up to 93% with early planting at the field scale. Early planting of winter cover crops (~30 days of additional growing days) was crucial, as it lowered nitrate export by an additional ~2 kg ha &minus;1 when compared to late planting scenarios. The effectiveness of cover cropping increased with increasing extent of winter cover crop implementation. Agricultural fields with well-drained soils and those that were more frequently used to grow corn had a higher potential for nitrate leaching and export to the waterways. This study supports the effective implement of winter cover crop programs, in part by helping to target critical pollution source areas for winter cover crop implementation.

Chesapeake Bay Watershed

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 &mu;g/L and 0.19 &mu;g/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.

Delaware, Maryland

Comparative analyses of hydrological responses of two adjacent watersheds to climate variability and change using the SWAT model

Water quality problems in the Chesapeake Bay Watershed (CBW) are expected to be exacerbated by climate variability and change. However, climate impacts on agricultural lands and resultant nutrient loads into surface water resources are largely unknown. This study evaluated the impacts of climate variability and change on two adjacent watersheds in the Coastal Plain of the CBW, using the Soil and Water Assessment Tool (SWAT) model. We prepared six climate sensitivity scenarios to assess the individual impacts of variations in CO 2 concentration (590 and 850 ppm), precipitation increase (11 and 21 %), and temperature increase (2.9 and 5.0 °C), based on regional general circulation model (GCM) projections. Further, we considered the ensemble of five GCM projections (2085–2098) under the Representative Concentration Pathway (RCP) 8.5 scenario to evaluate simultaneous changes in CO 2 , precipitation, and temperature. Using SWAT model simulations from 2001 to 2014 as a baseline scenario, predicted hydrologic outputs (water and nitrate budgets) and crop growth were analyzed. Compared to the baseline scenario, a precipitation increase of 21 % and elevated CO 2 concentration of 850 ppm significantly increased streamflow and nitrate loads by 50 and 52 %, respectively, while a temperature increase of 5.0 °C reduced streamflow and nitrate loads by 12 and 13 %, respectively. Crop biomass increased with elevated CO 2 concentrations due to enhanced radiation- and water-use efficiency, while it decreased with precipitation and temperature increases. Over the GCM ensemble mean, annual streamflow and nitrate loads showed an increase of ∼ 70 % relative to the baseline scenario, due to elevated CO 2 concentrations and precipitation increase. Different hydrological responses to climate change were observed from the two watersheds, due to contrasting land use and soil characteristics. The watershed with a larger percent of croplands demonstrated a greater increased rate of 5.2 kg N ha −1 in nitrate yield relative to the watershed with a lower percent of croplands as a result of increased export of nitrate derived from fertilizer. The watershed dominated by poorly drained soils showed increased nitrate removal due do enhanced denitrification compared to the watershed dominated by well-drained soils. Our findings suggest that increased implementation of conservation practices would be necessary for this region to mitigate increased nitrate loads associated with predicted changes in future climate.

Greensboro Watershed, Tuckahoe Creek Watershed