The Effect of Natural Dissolved Organic Carbon on the Acute Toxicity of Copper to Larval Freshwater Mussels (\u3cem\u3eGlochidia\u3c/em\u3e)

The present study examined the effect of dissolved organic carbon (DOC), both added and inherent, on Cu toxicity in glochidia, the larvae of freshwater mussels. Using incremental additions of natural DOC concentrate and reconstituted water, a series of acute copper toxicity tests were conducted. An increase in DOC from 0.7 to 4.4 mg C/L resulted in a fourfold increase (36–150 μg Cu/L) in the 24-h median effective concentration (EC50) and a significant linear relationship (r2=0.98, p=0.0008) between the DOC concentration and the Cu EC50 of Lampsilis siliquoidea glochidia. The ameliorating effect of added DOC on Cu toxicity was confirmed using a second mussel species, the endangered (in Canada) Lampsilis fasciola. The effect of inherent (i.e., not added) DOC on Cu toxicity was also assessed in eight natural waters (DOC 5–15 mg C/L). These experiments revealed a significant relationship between the EC50 and the concentration of inherent DOC (r2=0.79, p=0.0031) with EC50s ranging from 27 to 111 μg Cu/L. These laboratory tests have demonstrated that DOC provides glochidia with significant protection from acute Cu toxicity. The potential risk that Cu poses to mussel populations was assessed by comparing Cu and DOC concentrations from significant mussel habitats in Ontario to the EC50s. Although overall mean Cu concentration in the mussel’s habitat was well below the acutely toxic level given the concentration of DOC, episodic Cu releases in low DOC waters may be a concern for the recovery of endangered freshwater mussels. The results are examined in the context of current Cu water quality regulations including the U.S. Environmental Protection Agency’s (U.S. EPA) biotic ligand model

Controls on dissolved organic carbon quantity and chemical character in temperate rivers of North America

Understanding the processes controlling the transfer and chemical composition of dissolved organic carbon (DOC) in freshwater systems is crucial to understanding the carbon cycle and the effects of DOC on water quality. Previous studies have identified watershed‐scale controls on bulk DOC flux and concentration among small basins but fewer studies have explored controls among large basins or simultaneously considered the chemical composition of DOC. Because the chemical character of DOC drives riverine biogeochemical processes such as metabolism and photodegradation, accounting for chemical character in watershed‐scale studies will improve the way bulk DOC variability in rivers is interpreted. We analyzed DOC quantity and chemical character near the mouths of 17 large North American rivers, primarily between 2008 and 2010, and identified watershed characteristics that controlled variability. We quantified DOC chemical character using both specific ultraviolet absorbance at 254 nm (SUVA254) and XAD‐resin fractionation. Mean DOC concentration ranged from 2.1 to 47 mg C L−1 and mean SUVA254 ranged from 1.3 to 4.7 L mg C−1 m−1. We found a significant positive correlation between basin wetland cover and both bulk DOC concentration (R2 = 0.78; p \u3c 0.0001) and SUVA254 (R2 = 0.91; p \u3c 0.0001), while other land use characteristics were not correlated. The strong wetland relationship with bulk DOC concentration is similar to that found by others in small headwater catchments. However, two watersheds with extremely long surface water residence times, the Colorado and St. Lawrence, diverged from this wetland relationship. These results suggest that the role of riverine processes in altering the terrestrial DOC signal at the annual scale was minimal except in river systems with long surface water residence times. However, synoptic DOC sampling of both quantity and character throughout river networks will be needed to more rigorously test this finding. The inclusion of DOC chemical character will be vital to achieving a more complete understanding of bulk DOC dynamics in large river systems

Challenges in modelling dissolved organic matter dynamics in agricultural soil using DAISY

Because dissolved organic matter (DOM) plays an important role is terrestrial C-,N-and P-balances and transport of these three components to aquatic environments, there is a need to include it in models. This paper presents the concept of the newly developed DOM modules implemented in the DAISY model with focus on the quantification of DOM sorption/desorption and microbial-driven DOM turnover. The kinetics of DOM sorption/desorption is described by the deviation of the actual DOM concentration in solution from the equilibrium concentration, Ceq. The Ceq is soil specific and estimated from pedotransfer functions taking into account the soil content of organic matter, Al and Fe oxides. The turnover of several organic matter pools including one DOM pool are described by first-order kinetics. The DOM module was tested at field scale for three soil treatments applied after cultivating grass–clover swards. Suction cups were installed at depths 30, 60 and 90 cm and soil solution was sampled for quantification of dissolved organic C (DOC) and dissolved organic N (DON). In the topsoil, the observed fluctuations in DOC were successfully simulated when the sorption/desorption rate coefficient k was low. In the subsoil, the observed concentrations of DOC were steadier and the best simulations were obtained using a high k. The model shows that DOC and DON concentrations are levelled out in the subsoils due to soil buffering. The steady concentration levels were based on the Ceq for each horizon and the kinetic concept for sorption/desorption of DOC appeared aviable approach. If Ceq was successfully estimated by the pedotransfer function it was possible to simulate the DOC concentration in the subsoil. In spite of difficulties in describing the DOC dynamics of the topsoil, the DOM module simulates the subsoil concentration level of DOC well, and also — but with more uncertainty — the DON concentration level

Removal of Refractory Dissolved Organic Carbon in the Amundsen Sea, Antarctica.

The removal mechanism of refractory deep-ocean dissolved organic carbon (deep-DOC) is poorly understood. The Amundsen Sea Polynya (ASP) serves as a natural test basin for assessing the fate of deep-DOC when it is supplied with a large amount of fresh-DOC and exposed to strong solar radiation during the polynya opening in austral summer. We measured the radiocarbon content of DOC in the water column on the western Amundsen shelf. The radiocarbon content of DOC in the surface water of the ASP reflected higher primary production than in the region covered by sea ice. The radiocarbon measurements of DOC, taken two years apart in the ASP, were different, suggesting rapid cycling of DOC. The increase in DOC concentration was less than expected from the observed increase in radiocarbon content from those at the greatest depths. Based on a radiocarbon mass balance, we show that deep-DOC is consumed along with fresh-DOC in the ASP. Our observations imply that water circulation through the surface layer, where fresh-DOC is produced, may play an important role in global DOC cycling

Spatial and temporal variation in degradation of dissolved organic carbon on the main stem of the Lamprey River

Degradation of dissolved organic carbon by microbial and photolytic processes was examined along the main stem of the Lamprey River Watershed located in southeastern New Hampshire. Eight sites were chosen and sampled biweekly throughout the seasonal hydrograph. Lab incubations were employed to assess microbial degradation of dissolved organic carbon (DOC) where one set of samples was exposed to natural sunlight for a day to assess photolytic degradation. Mean biodegradable dissolved organic carbon (BDOC) throughout the study period was 5.8% with no significant variation observed between sites. Temporal variation was found to be a much stronger driver of DOC composition with summer showing the highest degradation of 8.6% and winter the lowest. Initial DOC concentration was found to be the only significant positive predictor of BDOC on both an annual and seasonal scale. Photolysis had no significant effect on DOC degradation or availability of DOC to the microbial pool. Findings suggest that temporal variation is a significant driver of DOC composition via DOC sources that change throughout the season

Assessing connectivity between an overlying aquifer and a coal seam gas resource using methane isotopes, dissolved organic carbon and tritium

Coal seam gas (CSG) production can have an impact on groundwater quality and quantity in adjacent or overlying aquifers. To assess this impact we need to determine the background groundwater chemistry and to map geological pathways of hydraulic connectivity between aquifers. In south-east Queensland (Qld), Australia, a globally important CSG exploration and production province, we mapped hydraulic connectivity between the Walloon Coal Measures (WCM, the target formation for gas production) and the overlying Condamine River Alluvial Aquifer (CRAA), using groundwater methane (CH4) concentration and isotopic composition (δ13C-CH4), groundwater tritium (3H) and dissolved organic carbon (DOC) concentration. A continuous mobile CH4 survey adjacent to CSG developments was used to determine the source signature of CH4 derived from the WCM. Trends in groundwater δ13C-CH4 versus CH4 concentration, in association with DOC concentration and 3H analysis, identify locations where CH4 in the groundwater of the CRAA most likely originates from the WCM. The methodology is widely applicable in unconventional gas development regions worldwide for providing an early indicator of geological pathways of hydraulic connectivity

The biogeochemical influence of nitrate, dissolved oxygen, and dissolved organic carbon on stream nitrate uptake

Streams are potential hotspots for retention and removal of NO3−, and understanding the mechanisms that enhance NO3− reactivity in stream systems is critical for predicting and preventing eutrophication. Both dissolved organic C (DOC) and dissolved O2 (DO) influence NO3− removal processes. Assessing the individual impacts of NO3−, DO, and DOC concentrations on stream NO3− removal is difficult because these factors covary and are coupled through the C and N cycles. We used an experimental approach to quantify the influences of NO3−, DOC, and DO on NO3− transport in headwater streams of the Ipswich and Parker River watersheds (Massachusetts, USA) with contrasting levels of DOC and DO. In a 1st set of experiments, we added NO3− to address how uptake kinetics differed between a low-DO/high-DOC stream (Cedar Swamp Creek) and a high-DO/low-DOC stream (Cart Creek). In a 2nd set of experiments, we manipulated, for the first time at the reach scale, both DO and DOC in a factorial experiment. DO was added to the low-DO stream by injecting O2 and was removed from the high-DO stream by adding sodium sulfite. DOC was added both alone and in combination with the DO manipulations. NO3− concentration was an important control of NO3− uptake velocity in our study streams, consistent with previous findings. The results of the DOC and DO manipulations suggested that DO determines whether a stream has net NO3− uptake or production and that the presence of DOC magnifies the DO response processes. Addition of DOC by itself did not lead to increased NO3− uptake. In addition, we observed organic matter priming effects, wherein the addition of labile organic matter resulted in accelerated metabolism of naturally occurring DOC in the water column. Priming effects have not been reported previously in stream systems. Results from our experiments suggest that NO3− uptake in streams might arise from complex interactions among DOC, DO, and NO3−, and ultimately, from the influence of DO on dominant stream processes

Spatial and Temporal Patterns in Atmospheric Deposition of Dissolved Organic Carbon

Atmospheric deposition of dissolved organic carbon (DOC) to terrestrial ecosystems is a small, but rarely studied component of the global carbon (C) cycle. Emissions of volatile organic compounds (VOC) and organic particulates are the sources of atmospheric C and deposition represents a major pathway for the removal of organic C from the atmosphere. Here, we evaluate the spatial and temporal patterns of DOC deposition using 70 data sets at least one year in length ranging from 40° south to 66° north latitude. Globally, the median DOC concentration in bulk deposition was 1.7 mg L$^{−1}$. The DOC concentrations were significantly higher in tropical (25°) latitudes. DOC deposition was significantly higher in the tropics because of both higher DOC concentrations and precipitation. Using the global median or latitudinal specific DOC concentrations leads to a calculated global deposition of 202 or 295 Tg C yr$^{−1}$ respectively. Many sites exhibited seasonal variability in DOC concentration. At temperate sites, DOC concentrations were higher during the growing season; at tropical sites, DOC concentrations were higher during the dry season. Thirteen of the thirty-four long-term (>10 years) data sets showed significant declines in DOC concentration over time with the others showing no significant change. Based on the magnitude and timing of the various sources of organic C to the atmosphere, biogenic VOCs likely explain the latitudinal pattern and the seasonal pattern at temperate latitudes while decreases in anthropogenic emissions are the most likely explanation for the declines in DOC concentration

Vertical Habitat Gradients: Comparing Phytoplankton Dynamics in Lakes with Low to Moderate Dissolved Organic Carbon Concentration

Concentrations of dissolved organic carbon (DOC) increased across lakes of Maine for several decades before stabilizing or decreasing in recent years. To investigate the seasonal effects of DOC on phytoplankton habitat structure, I assessed vertical gradients of temperature, oxygen, light, and chlorophyll in four lakes in Acadia National Park from under ice through fall turnover in 2020. Lake DOC concentrations ranged from low (~2 mg L-1) to moderate (~4 mg L-1). Low-DOC lakes were clearer, with greater mean Secchi depths (9-15 m) than moderate-DOC lakes (5-6 m). Moderate-DOC lakes experienced hypolimnetic anoxia in the summer and had more variable concentrations and vertical gradients of chlorophyll a. Seasonal variance of vertical habitat gradients were similar between low- and moderate-DOC lakes, but there was greater stability of chlorophyll a biomass and consistently deeper chlorophyll fluorescence peaks in the low-DOC lakes. Phytoplankton community structure was also assessed at three depths in one low- and one moderate-DOC lake on four dates over the sampling period. While the concentration and depth of chlorophyll a varied more in the moderate-DOC lake, there was greater turnover of phytoplankton community in the low-DOC lake, with Morisita-Horn dissimilarity slightly higher in low-DOC Jordan Pond (r2 = 0.66, p \u3c 0.01) than in moderate-DOC Seal Cove Pond (r2 = 0.61, p \u3c 0.01). Long-term trends in DOC concentration were correlated with Secchi depth across several lakes in Acadia National Park (r2 = 0.76, p \u3c 0.001), and DOC concentration was also related to changes in phytoplankton pigment assemblages in the sediment record of Seal Cove Pond (r2 = -0.38, p = 0.09). DOC concentration was not related to diatom-inferred mixing depth in Seal ii Cove Pond’s sediment record, suggesting that DOC has a greater impact on light environment than on mixing depth in the moderate-DOC lake. Differences in the vertical habitat gradients and phytoplankton community structure of lakes ranging in DOC concentration from 2-4 mg L-1 indicates that lakes are highly sensitive to changes in light environment, thermal structure, and other environmental drivers, particularly at low DOC concentrations. The greater sensitivity of low- to moderate-DOC lakes has important implications for broader ecosystem processes, including nutrient cycling, productivity, and water quality

Controls on the composition and lability of dissolved organic matter in Siberia's Kolyma River basin

High-latitude northern rivers export globally significant quantities of dissolved organic carbon (DOC) to the Arctic Ocean. Climate change, and its associated impacts on hydrology and potential mobilization of ancient organic matter from permafrost, is likely to modify the flux, composition, and thus biogeochemical cycling and fate of exported DOC in the Arctic. This study examined DOC concentration and the composition of dissolved organic matter (DOM) across the hydrograph in Siberia's Kolyma River, with a particular focus on the spring freshet period when the majority of the annual DOC load is exported. The composition of DOM within the Kolyma basin was characterized using absorbance-derived measurements (absorbance coefficienta330, specific UV absorbance (SUVA254), and spectral slope ratio SR) and fluorescence spectroscopy (fluorescence index and excitation-emission matrices (EEMs)), including parallel factor analyses of EEMs. Increased surface runoff during the spring freshet led to DOM optical properties indicative of terrestrial soil inputs with high humic-like fluorescence, SUVA254, and low SRand fluorescence index (FI). Under-ice waters, in contrast, displayed opposing trends in optical properties representing less aromatic, lower molecular weight DOM. We demonstrate that substantial losses of DOC can occur via biological (∼30% over 28 days) and photochemical pathways (>29% over 14 days), particularly in samples collected during the spring freshet. The emerging view is therefore that of a more dynamic and labile carbon pool than previously thought, where DOM composition plays a fundamental role in controlling the fate and removal of DOC at a pan-Arctic scale