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 (PO4) 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 PO4 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 PO4 species tend to be adsorbed by hydrous iron, aluminum, and manganese oxides that coat soil and sediment particles; however, PO4 may be substantially desorbed at pH >8. We created a geochemical model that simulates equilibrium aqueous/solid distributions of PO4 as pH and other solution characteristics change. Considering current conditions in the lower Susquehanna River, the model demonstrates potential for extensive release of adsorbed PO4 at pH >8. Empirical data from laboratory experiments corroborate model results. The transfer of PO4 into the water column may increase algae growth, which removes CO2 and drives pH to higher values, facilitating additional PO4 release and exacerbating the potential for harmful algal blooms. Thus, legacy sediment is a currently unquantified source of PO4 that warrants consideration by resource managers and programs collaborating to reduce phosphorus loads to the bay and similar settings worldwide.

Advancing estuarine ecological forecasts: seasonal hypoxia in Chesapeake Bay.

Ecological forecasts are quantitative tools that can guide ecosystem management. The coemergence of extensive environmental monitoring and quantitative frameworks allows for widespread development and continued improvement of ecological forecasting systems. We use a relatively simple estuarine hypoxia model to demonstrate advances in addressing some of the most critical challenges and opportunities of contemporary ecological forecasting, including predictive accuracy, uncertainty characterization, and management relevance. We explore the impacts of different combinations of forecast metrics, drivers, and driver time windows on predictive performance. We also incorporate multiple sets of state-variable observations from different sources and separately quantify model prediction error and measurement uncertainty through a flexible Bayesian hierarchical framework. Results illustrate the benefits of (1) adopting forecast metrics and drivers that strike an optimal balance between predictability and relevance to management, (2) incorporating multiple data sources in the calibration data set to separate and propagate different sources of uncertainty, and (3) using the model in scenario mode to probabilistically evaluate the effects of alternative management decisions on future ecosystem state. In the Chesapeake Bay, the subject of this case study, we find that average summer or total annual hypoxia metrics are more predictable than monthly metrics and that measurement error represents an important source of uncertainty. Application of the model in scenario mode suggests that absent watershed management actions over the past decades, long-term average hypoxia would have increased by 7% compared to 1985. Conversely, the model projects that if management goals currently in place to restore the Bay are met, long-term average hypoxia would eventually decrease by 32% with respect to the mid-1980s.

Factors driving nutrient trends in streams of the Chesapeake Bay watershed.

Despite decades of effort toward reducing nitrogen and phosphorus flux to Chesapeake Bay, water-quality and ecological responses in surface waters have been mixed. Recent research, however, provides useful insight into multiple factors complicating the understanding of nutrient trends in bay tributaries, which we review in this paper, as we approach a 2025 total maximum daily load (TMDL) management deadline. Improvements in water quality in many streams are attributable to management actions that reduced point sources and atmospheric nitrogen deposition and to changes in climate. Nutrient reductions expected from management actions, however, have not been fully realized in watershed streams. Nitrogen from urban nonpoint sources has declined, although water-quality responses to urbanization in individual streams vary depending on predevelopment land use. Evolving agriculture, the largest watershed source of nutrients, has likely contributed to local nutrient trends but has not affected substantial changes in flux to the bay. Changing average nitrogen yields from farmland underlain by carbonate rocks, however, may suggest future trends in other areas under similar management, climatic, or other influences, although drivers of these changes remain unclear. Regardless of upstream trends, phosphorus flux to the bay from its largest tributary has increased due to sediment infill in the Conowingo Reservoir. In general, recent research emphasizes the utility of input reductions over attempts to manage nutrient fate and transport at limiting nutrients in surface waters. Ongoing research opportunities include evaluating effects of climate change and conservation practices over time and space and developing tools to disentangle and evaluate multiple influences on regional water quality.

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

Orthophosphate (PO4) is the most bioavailable form of phosphorus (P). Excess PO4 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 PO4 cycling and delivery to streams has been characterized in small-scale studies, regional drivers of PO4 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 PO4 patterns over a 9-year period at 53 monitoring stations across the CB watershed to: 1) characterize the role of PO4 in total P fluxes and trends; 2) describe spatial and temporal patterns of PO4 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 PO4 comprising up to 50% of those exports. Although PO4 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 PO4 concentrations observed at many sites. Watersheds with more Conservation Reserve Program enrollment had lower summer PO4 concentrations, highlighting the effectiveness of this practice. Manure inputs strongly predicted PO4 concentrations at high flows across all seasons. Both manure applications and conservation tillage were correlated with changes in PO4 concentrations at high flow, suggesting these activities could contribute to increasing PO4 concentrations. This study highlights the effectiveness of point source control for reducing PO4 exports and underscores the need for management strategies to target sources, practices, and landscape factors determining PO4 loss from soils where manure inputs remain high.

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 (SSfine) in all nine tributaries; overall, ~90% of the MNTCBW SS is SSfine. 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]), SSfine (long-term and short-term), TOC (long-term), and chlorophyll-a (short-term). The rises in SS, SSfine, 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.

Modeling drivers of phosphorus loads in Chesapeake Bay tributaries and inferences about long-term change.

Causal attribution of changes in water quality often consists of correlation, qualitative reasoning, listing references to the work of others, or speculation. To better support statements of attribution for water-quality trends, structural equation modeling was used to model the causal factors of total phosphorus loads in the Chesapeake Bay watershed. By transforming, scaling, and standardizing variables, grouping similar sites, grouping some causal factors into latent variable models, and using methods that correct for assumption violations, we developed a structural equation model to show how causal factors interact to produce total phosphorus loads. Climate (in the form of annual total precipitation and the Palmer Hydrologic Drought Index) and anthropogenic inputs are the major drivers of total phosphorus load in the Chesapeake Bay watershed. Increasing runoff due to natural climate variability is offsetting purposeful management actions that are otherwise decreasing phosphorus loading; consequently, management actions may need to be reexamined to achieve target reductions in the face of climate variability.