Sorption and fractionation of dissolved organic matter and associated phosphorus in agricultural soil

Molibility of dissolved organic matter (DOM) strongly affects the export of nitrogen (N) and phosphorus (P) from oils to surface waters. To study the sorption an mobility of dissolved organic C and P (DOC, DOP) in soil, the pH-dependent sorption of DOM to samples from Ap, EB, and Bt horizons from a Danish agircultural Humic Hapludult was investigated and a kinetic model applicable in field-scale model tested. Sorption experiments of 1 to 72 h duration were conducted at two pH levels (pH 5.0 and 7.0) and six initial DOC concentrtions (0-4.7 mmol L-1). Most sorption/desorption occurred during the first few hours. Dissolved organic carbon and DOP sorption decreased strongly with increased pH and desorption dominated at pH 7, especially for DOC. Due to fractionation during DOM sorption/desorption at DOC concentrations up to 2 mmol L-1, the solution fraction of DOM was enriched in P indicating preferred leaching of DOP. The kinetics of sorption was expressed as a function of how far the solution DOC or DOP concentrations deviate from "equilibrium". The model was able to simulate the kinetics of DOC and DOP sorption/desorption at all concentrations investigated and at both pH levels making it useful for incorporation in field-scale models for quantifying DOC and DOP dynamics

Patterns of dissolved organic carbon and nitrogen fluxes in deciduous and coniferous forests under historic high nitrogen deposition

Numerous recent studies have indicated that dissolved organic carbon (DOC) and nitrogen (DON) play an important role in C and N cycling in natural ecosystems, and have shown that N deposition alters the concentrations and fluxes of dissolved organic substances and may increase leaching losses from forests. Our study was set up to accurately quantify concentrations and flux patterns of DOC, DON and dissolved inorganic nitrogen (DIN) in deciduous and coniferous forest in Flanders, Belgium, under historical high nitrogen deposition. We measured DOC, DON and DIN concentrations at two weekly intervals in a silver birch (SB) stand, a corsican pine (CP) stand and a pine stand with higher N deposition (CPN), and used the SWAP model (calibrated with PEST) for generating accurate water and matter fluxes. The input with precipitation was an important source of DON, but not for DOC. Release of DOC from the forest floor was minimally affected by forest type, but higher N deposition (CPN stand) caused an 82% increase of DOC release from the forest floor. Adsorption to mineral soil material rich in iron and/or aluminum oxyhydroxides was suggested to be the most important process removing DOC from the soil solution, responsible for substantial retention (67–84%) of DOC entering the mineral soil profile with forest floor leachate. Generally, DON was less reactive (i.e. less removal from the soil solution) than DOC, resulting in decreasing DOC/DON ratios with soil depth. We found increased DOC retention in the mineral soil as a result of higher N deposition (84 kg ha−1 yr−1 additional DOC retention in CPN compared to CP). Overall DON leaching losses were 2.2, 3.3 and 5.0 kg N yr−1 for SB, CP and CPN, respectively, contributing between 9–28% to total dissolved N (TDN) leaching. The relative contribution to TDN leaching from DON loss from SB and CP was mainly determined by (large) differences in DIN leaching. The large TDN leaching losses are alarming, especially in the CPN stand that was N saturated

Leaching of organic nitrogen and carbon after cultivating grass-clover pastures

Leaching of organic nitrogen (DON) and carbon (DOC) was measured after cultivating grass-clover of different age. It was found that DON and escpecially DOC was lost in considerable amounts, and that the leaching depends upon crop and management. The highest concentrations of DON were measured in the bare soil treatment, whereas concen-trations in catch crop treatments were between 1.2 and 3.2 mg N L-1. The leaching of DOC showed opposite trends compared to leaching of DON with higher values in the catch crop treatments (296 - 310 kg DOC ha-1) than in bare soil treatments (174 - 217 kg DOC ha-1)

Water, rather than temperature, dominantly impacts how soil fauna affect dissolved carbon and nitrogen release from fresh litter during early litter decomposition

Longstanding observations suggest that dissolved materials are lost from fresh litter through leaching, but the role of soil fauna in controlling this process has been poorly documented. In this study, a litterbag experiment employing litterbags with different mesh sizes (3 mm to permit soil fauna access and 0.04 mm to exclude fauna access) was conducted in three habitats (arid valley, ecotone and subalpine forest) with changes in climate and vegetation types to evaluate the effects of soil fauna on the concentrations of dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) during the first year of decomposition. The results showed that the individual density and community abundance of soil fauna greatly varied among these habitats, but Prostigmata, Isotomidae and Oribatida were the dominant soil invertebrates. At the end of the experiment, the mass remaining of foliar litter ranged from 58% for shrub litter to 77% for birch litter, and the DOC and TDN concentrations decreased to 54%-85% and increased to 34%-269%, respectively, when soil fauna were not present. The effects of soil fauna on the concentrations of both DOC and TDN in foliar litter were greater in the subalpine forest (wetter but colder) during the winter and in the arid valley (warmer but drier) during the growing season, and this effect was positively correlated with water content. Moreover, the effects of fauna on DOC and TDN concentrations were greater for high-quality litter and were related to the C/N ratio. These results suggest that water, rather than temperature, dominates how fauna affect the release of dissolved substances from fresh litter

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

Dissolved organic carbon uptake in streams: A review and assessment of reach‐scale measurements

Quantifying the role that freshwater ecosystems play in the global carbon cycle requires accurate measurement and scaling of dissolved organic carbon (DOC) removal in river networks. We reviewed reach‐scale measurements of DOC uptake from experimental additions of simple organic compounds or leachates to inform development of aquatic DOC models that operate at the river network, regional, or continental scale. Median DOC uptake velocity (vf) across all measurements was 2.28 mm min−1. Measurements using simple compound additions resulted in faster vf (2.94 mm min−1) than additions of leachates (1.11 mm min−1). We also reviewed published data of DOC bioavailability for ambient stream water and leaf leachate DOC from laboratory experiments. We used these data to calculate and apply a correction factor to leaf leachate uptake velocity to estimate ambient stream water DOC uptake rates at the reach scale. Using this approach, we estimated a median ambient stream DOC vf of 0.26 mm min−1. Applying these DOC vf values (0.26, 1.11, 2.28, and 2.94 mm min−1) in a river network inverse model in seven watersheds revealed that our estimated ambient DOC vf value is plausible at the network scale and 27 to 45% of DOC input was removed. Applying the median measured simple compound or leachate vf in whole river networks would require unjustifiably high terrestrial DOC inputs to match observed DOC concentrations at the basin mouth. To improve the understanding and importance of DOC uptake in fluvial systems, we recommend using a multiscale approach coupling laboratory assays, with reach‐scale measurements, and modeling

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

Dry-season length and runoff control annual variability in stream DOC dynamics in a small, shallowgroundwater-dominated agricultural watershed

International audienceAs a phenomenon integrating climate conditions and hydrological control of the connection betweenstreams and terrestrial dissolved organic carbon (DOC) sources, groundwater dynamics controlpatterns of stream DOC characteristics (concentrations and fluxes). Influence of intra-annualvariations in groundwater level, discharge and climatic factors on DOC concentrations and fluxeswere assessed over 13 years at the headwater watershed of Kervidy-Naizin (5 km²) in westernFrance. Four seasonal periods were delineated within each year according to groundwaterfluctuations (A: rewetting, B: high flow, C: recession, and D: drought). Annual and seasonal baseflow vs stormflow DOC concentrations were defined based on daily hydrograph readings. Highinter-annual variability of annual DOC fluxes (5.4-39.5 kg.ha-1.yr-1) indicates that several years ofdata are required to encompass variations in water flux to evaluate the actual DOC export capacity ofa watershed. Inter-annual variability of mean annual DOC concentrations was much lower (4.9-7.5mg C.l-1), with concentrations decreasing within each year from ca. 9.2 mg C.l-1 in A to ca. 3.0 mgC.l-1 in C. This indicates an intra-annual pattern of stream DOC concentrations controlled by DOCsource characteristics and groundwater dynamics very similar across years. Partial least squareregressions combined with multiple linear regressions showed that the dry season characteristics(length and drawdown) determine the mean annual DOC concentration while annual runoffdetermines the annual flux. Antagonistic mechanisms of production-accumulation and dilution depletioncombined with an unlimited DOC supply from riparian wetland soils can mitigate theresponse of stream concentrations to global changes and climatic variations

The biogeochemistry of carbon across a gradient of streams and rivers within the Congo Basin

Dissolved organic carbon (DOC) and inorganic carbon (DIC and pCO2), lignin biomarkers and the optical properties of dissolved organic matter (DOM) were measured in a gradient of streams and rivers within the Congo Basin (Republic of Congo), with the aim of examining how vegetation cover and hydrology influences the composition and concentration of exported fluvial carbon (C). Three sampling campaigns (February 2010, November 2010 and August 2011) spanning 56 sites are compared by sub-basin watershed land cover type (savannah, tropical forest, and swamp) and hydrologic regime (high, intermediate, and low). Land cover properties predominately controlled the amount and quality of DOC, chromophoric DOM (CDOM) and lignin phenol concentrations (∑8) exported in streams and rivers throughout the Congo Basin. Higher DIC concentrations and changing DOM composition (lower molecular weight, less aromatic C) during periods of low hydrologic flow indicated a shift from rapid overland supply pathways in wet conditions to deeper groundwater inputs during drier periods. Lower DOC concentrations in forest and swamp sub-basins were apparent with increasing catchment area, indicating enhanced DOC loss with extended water residence time. Surface water pCO2 in savannah and tropical forest catchments ranged between 2600 and 11922 µatm, and swamp regions contained extremely high pCO2 (10598-15802 µatm), highlighting their potential as significant pathways for water-air efflux. Our data suggest that the quantity and quality of DOM exported to streams and rivers is largely driven by terrestrial ecosystem structure and that anthropogenic land-use or climate change may impact the composition and reactivity of fluvial C, with ramifications for regional C budgets and future climate scenarios