Watershed carbon yield derived from gauge observations and river network connectivity in the United States.

River networks play a critical role in the global carbon cycle. Although global/continental scale riverine carbon cycle studies demonstrate the significance of rivers and streams for linking land and coastal regions, the lack of spatially distributed riverine carbon load data represents a gap for quantifying riverine carbon net gain or net loss in different regions, understanding mechanisms and factors that influence the riverine carbon cycle, and testing simulations of aquatic carbon cycle models at fine scales. Here, we (1) derive the riverine load of particulate organic carbon (POC) and dissolved organic carbon (DOC) for over 1,000 hydrologic stations across the Conterminous United States (CONUS) and (2) use the river network connectivity information for over 80,000 catchment units within the National Hydrography Dataset Plus (NHDPlus) to estimate riverine POC and DOC net gain or net loss for watersheds controlled between upstream-downstream hydrologic stations. The new riverine carbon load and watershed net gain/loss represent a unique contribution to support future studies for better understanding and quantification of riverine carbon cycles.

Bioavailability of dissolved organic matter varies with anthropogenic landcover in the Upper Mississippi River Basin.

Anthropogenic conversion of forests and wetlands to agricultural and urban landcovers impacts dissolved organic matter (DOM) within streams draining these catchments. Research on how landcover conversion impacts DOM molecular level composition and bioavailability, however, is lacking. In the Upper Mississippi River Basin (UMRB), water from low-order streams and rivers draining one of three dominant landcovers (forest, agriculture, urban) was incubated for 28 days to determine bioavailable DOC (BDOC) concentrations and changes in DOM composition. The BDOC concentration averaged 0.49 ± 0.30 mg L-1 across all samples and was significantly higher in streams draining urban catchments (0.72 ± 0.34 mg L-1) compared to streams draining agricultural (0.28 ± 0.15 mg L-1) and forested (0.47 ± 0.17 mg L-1) catchments. Percent BDOC was significantly greater in urban (10% ± 4.4%) streams compared to forested streams (5.6% ± 3.2%), corresponding with greater relative abundances of aliphatic and N-containing aliphatic compounds in urban streams. Aliphatic compound relative abundance decreased across all landcovers during the bioincubation (average -4.1% ± 10%), whereas polyphenolics and condensed aromatics increased in relative abundance across all landcovers (average of +1.4% ± 5.9% and +1.8% ± 10%, respectively). Overall, the conversion of forested to urban landcover had a larger impact on stream DOM bioavailability in the UMRB compared to conversion to agricultural landcover. Future research examining the impacts of anthropogenic landcover conversion on stream DOM composition and bioavailability needs to be expanded to a range of spatial scales and to different ecotones, especially with continued landcover alterations.

Challenges in Quantifying Air-Water Carbon Dioxide Flux Using Estuarine Water Quality Data: Case Study for Chesapeake Bay.

Estuaries play an uncertain but potentially important role in the global carbon cycle via CO2 outgassing. The uncertainty mainly stems from the paucity of studies that document the full spatial and temporal variability of estuarine surface water partial pressure of carbon dioxide ( pCO2). Here, we explore the potential of utilizing the abundance of pH data from historical water quality monitoring programs to fill the data void via a case study of the mainstem Chesapeake Bay (eastern United States). We calculate pCO2 and the air-water CO2 flux at monthly resolution from 1998 to 2018 from tidal fresh to polyhaline waters, paying special attention to the error estimation. The biggest error is due to the pH measurement error, and errors due to the gas transfer velocity, temporal sampling, the alkalinity mixing model, and the organic alkalinity estimation are 72%, 27%, 15%, and 5%, respectively, of the error due to pH. Seasonal, interannual, and spatial variability in the air-water flux and surface pCO2 is high, and a correlation analysis with oxygen reveals that this variability is driven largely by biological processes. Averaged over 1998-2018, the mainstem bay is a weak net source of CO2 to the atmosphere of 1.2 (1.1, 1.4) mol m-2 yr-1 (best estimate and 95% confidence interval). Our findings suggest that the abundance of historical pH measurements in estuaries around the globe should be mined in order to constrain the large spatial and temporal variability of the CO2 exchange between estuaries and the atmosphere.

Landscape Drivers of Dynamic Change in Water Quality of U.S. Rivers.

Water security is a top concern for social well-being, and dramatic changes in the availability of freshwater have occurred as a result of human uses and landscape management. Elevated nutrient loading and perturbations to major ion composition have resulted from human activities and have degraded freshwater resources. This study addresses the emerging nature of streamwater quality in the 21st century through analysis of concentrations and trends in a wide variety of constituents in streams and rivers of the U.S. Concentrations of 15 water quality constituents including nutrients, major ions, sediment, and specific conductance were analyzed over the period 1982-2012 and a targeted trend analysis was performed from 1992 to 2012. Although environmental policy is geared toward addressing the long-standing problem of nutrient overenrichment, these efforts have had uneven success, with decreasing nutrient concentrations at urbanized sites and little to no change at agricultural sites. Additionally, freshwaters are being salinized rapidly in all human-dominated land use types. While efforts to control nutrients are ongoing, rapid salinity increases are ushering in a new set of poorly defined issues. Increasing salinity negatively affects biodiversity, mobilizes sediment-bound contaminants, and increases lead contamination of drinking water, but its effects are not well integrated into current paradigms of water management.

Influence of land use and region on glyphosate and aminomethylphosphonic acid in streams in the USA.

Glyphosate is the most widely used herbicide in the United States for agricultural and non-agricultural weed control. Many studies demonstrate possible effects of glyphosate and its degradate AMPA on human and ecological health. Although glyphosate is thought to have limited mobility in soil, it is found year-round in many rivers and streams throughout the world in both agricultural and developed environments. It is vitally important to continue to increase the knowledge base of glyphosate use, distribution, transport, and impacts on human health and the environment. Here we show that glyphosate and AMPA are found in nearly all of 70 streams throughout the United States at concentrations far below human health or ecological benchmarks, with less occurrence in the Northeast and that undeveloped land, classified as such by land use near the sampling station, has lower concentrations compared to other types of land. Results also show that sites with large watersheds tend to have more AMPA than glyphosate and the opposite is true for small watersheds. Travel times and opportunity for glyphosate to degrade to AMPA and for reservoirs of AMPA to grow are greater in large watersheds. Factors that promoted quick movement of glyphosate to streams, such as subsurface tile or storm drains, sewers, overland flow from developed landscapes, and arid landscapes were associated with sites that had greater concentrations of glyphosate compared to AMPA. These results contribute contemporary information and generalized interpretations adding to the knowledge base of the fate of glyphosate on a national scale and provide a springboard for further exploration of technical processes controlling transport to streams.

Variable impacts of contemporary versus legacy agricultural phosphorus on US river water quality.

Phosphorus (P) fertilizer has contributed to the eutrophication of freshwater ecosystems. Watershed-based conservation programs aiming to reduce external P loading to surface waters have not resulted in significant water-quality improvements. One factor that can help explain the lack of water-quality response is remobilization of accumulated legacy (historical) P within the terrestrial-aquatic continuum, which can obscure the beneficial impacts of current conservation efforts. We examined how contemporary river P trends (between 1992 and 2012) responded to estimated changes in contemporary agricultural P balances [(fertilizer + manure inputs)-crop uptake and harvest removal] for 143 watersheds in the conterminous United States, while also developing a proxy estimate of legacy P contribution, which refers to anthropogenic P inputs before 1992. We concluded that legacy sources contributed to river export in 49 watersheds because mean contemporary river P export exceeded mean contemporary agricultural P balances. For the other 94 watersheds, agricultural P balances exceeded river P export, and our proxy estimate of legacy P was inconclusive. If legacy contributions occurred in these locations, they were likely small and dwarfed by contemporary P sources. Our continental-scale P mass balance results indicated that improved incentives and strategies are needed to promote the adoption of nutrient-conserving practices and reduce widespread contemporary P surpluses. However, a P surplus reduction is only 1 component of an effective nutrient plan as we found agricultural balances decreased in 91 watersheds with no consistent water-quality improvements, and balances increased in 52 watersheds with no consistent water-quality degradation.

Recent trends in nutrient and sediment loading to coastal areas of the conterminous U.S.: Insights and global context.

Coastal areas in the U.S. and worldwide have experienced massive population and land-use changes contributing to significant degradation of coastal ecosystems. Excess nutrient pollution causes coastal ecosystem degradation, and both regulatory and management efforts have targeted reducing nutrient and sediment loading to coastal rivers. Decadal trends in flow-normalized nutrient and sediment loads were determined for 95 monitoring locations on 88 U.S. coastal rivers, including tributaries of the Great Lakes, between 2002 and 2012 for nitrogen (N), phosphorus (P), and sediment. N and P loading from urban watersheds generally decreased between 2002 and 2012. In contrast, N and P trends in agricultural watersheds were variable indicating uneven progress in decreasing nutrient loading. Coherent decreases in N loading from agricultural watersheds occurred in the Lake Erie basin, but limited benefit is expected from these changes because P is the primary driver of degradation in the lake. Nutrient loading from undeveloped watersheds was low, but increased between 2002 and 2012, possibly indicating degradation of coastal watersheds that are minimally affected by human activities. Regional differences in trends were evident, with stable nutrient loads from the Mississippi River to the Gulf of Mexico, but commonly decreasing N loads and increasing P loads in Chesapeake Bay. Compared to global rivers, coastal rivers of the conterminous U.S have somewhat lower TN yields and slightly higher TP yields, but similarities exist among land use, nutrient sources, and changes in nutrient loads. Despite widespread decreases in N loading in coastal watersheds, recent N:P ratios remained elevated compared to historic values in many areas. Additional progress in reducing N and P loading to U.S. coastal waters, particularly outside of urban areas, would benefit coastal ecosystems.

The metabolic regimes of 356 rivers in the United States.

A national-scale quantification of metabolic energy flow in streams and rivers can improve understanding of the temporal dynamics of in-stream activity, links between energy cycling and ecosystem services, and the effects of human activities on aquatic metabolism. The two dominant terms in aquatic metabolism, gross primary production (GPP) and aerobic respiration (ER), have recently become practical to estimate for many sites due to improved modeling approaches and the availability of requisite model inputs in public datasets. We assembled inputs from the U.S. Geological Survey and National Aeronautics and Space Administration for October 2007 to January 2017. We then ran models to estimate daily GPP, ER, and the gas exchange rate coefficient for 356 streams and rivers across the continental United States. We also gathered potential explanatory variables and spatial information for cross-referencing this dataset with other datasets of watershed characteristics. This dataset offers a first national assessment of many-day time series of metabolic rates for up to 9 years per site, with a total of 490,907 site-days of estimates.

Thiol methylation potential in anoxic, low-pH wetland sediments and its relationship with dimethylsulfide production and organic carbon cycling.

Dimethylsulfide (CH(3)SCH(3)) is formed in anoxic freshwater sediments by biological methylation of methanethiol (CH(3)SH). We measured thiol methylation potential in low-pH, Sphagnum peat sediments from Alaska and Alabama by adding ethanethiol (CH(3)CH(2)SH) to peat slurries and quantifying the rate of ethylmethylsulfide (CH(3)CH(2)SCH(3)) formation. Thiol methylation potential ranged from 12 to 154 nM h(-1) and was significantly related to dimethylsulfide accumulation rates (P=0.0007; r(2)=0.48). Addition of methanol or syringic acid stimulated thiol methylation potential and dimethylsulfide accumulation rate, suggesting that these compounds could be methyl donors. Addition of acetate or its metabolic precursors (glucose or Sphagnum plant material) inhibited thiol methylation potential, but not carbon dioxide or methane production. Inhibition of methanogenesis with either 2-bromoethanesulfonic acid or KNO(3) consistently inhibited thiol methylation potential and dimethylsulfide accumulation. These results suggest that methanogens play a role in thiol methylation and therefore dimethylsulfide formation.