Transport Of Dissolved Organic Matter Research Articles

Assessing inter-annual and seasonal patterns of DOC and DOM quality across a complex alpine watershed underlain by discontinuous permafrost in Yukon, Canada

Abstract. High-latitude environments store approximately half of the global organic carbon pool in peatlands, organic soils and permafrost, while large Arctic rivers convey an estimated 18–50 Tg C a−1 to the Arctic Ocean. Warming trends associated with climate change affect dissolved organic carbon (DOC) export from terrestrial to riverine environments. However, there is limited consensus as to whether exports will increase or decrease due to complex interactions between climate, soils, vegetation, and associated production, mobilization and transport processes. A large body of research has focused on large river system DOC and dissolved organic matter (DOM) lability and observed trends conserved across years, whereas investigation at smaller watershed scales show that thermokarst and fire have a transient impact on hydrologically mediated solute transport. This study, located in the Wolf Creek Research Basin situated ∼20 km south of Whitehorse, YT, Canada, utilizes a nested design to assess seasonal and annual patterns of DOC and DOM composition across diverse landscape types (headwater, wetland and lake) and watershed scales. Peak DOC concentration and export occurred during freshet, as is the case in most northern watersheds; however, peaks were lower than a decade ago at the headwater site Granger Creek. DOM composition was most variable during freshet with high A254 and SUVA254 and low FI and BIX. DOM composition was relatively insensitive to flow variation during summer and fall. The influence of increasing watershed scale and downstream mixing of landscape contributions was an overall dampening of DOC concentrations and optical indices with increasing groundwater contribution. Forecasted vegetation shifts, enhanced permafrost and seasonal thaw, earlier snowmelt, increased rainfall and other projected climate-driven changes will alter DOM sources and transport pathways. The results from this study support a projected shift from predominantly organic soils (high aromaticity and less fresh) to decomposing vegetation (more fresh and lower aromaticity). These changes may also facilitate flow and transport via deeper flow pathways and enhance groundwater contributions to runoff.

Quantity and quality variations of dissolved organic matter (DOM) in column leaching process from agricultural soil: Hydrochemical effects and DOM fractionation.

Leaching dynamics of dissolved organic matter (DOM) from agricultural soil are influenced by the chemistry of irrigation water. This study used multiple spectroscopy methods to investigate the dynamics of DOM in column leaching process by utilizing selected solutions. DOC was leached out by Na solutions more effectively than by Ca, despite the additional contributions of the ligand exchange of SO42- and the hydrolysis of HCO3-. The concentration ranking corresponding to solutions is Na2SO4 > NaHCO3 > NaCl > CaCl2. Furthermore, the aromaticity and molecular weights of DOM leached by Na solutions increased with the leaching, whereas contrary trends were reared by Ca. Thus, specific cation substantially affects DOM concentration and composition. Parallel factor analysis of the three-dimensional fluorescence spectra (EEM-PARAFAC) determined the characteristics of DOM components. (1) The long-wavelength, humic-like components (HLC, i.e., C1, C3, and C5) were largely accumulated at the early water saturating stage but attenuated toward dynamic stability in the salt-solution leaching (SSL) stage. (2) Reactive functional group-related HLC (i.e., C2, and C4) remarkably increased in response to the solutions chemistry. (3) The protein-like component (PLC, i.e., C6) was released with insignificant dynamic differences between the solutions. Despite approximately stable DOC concentration at the late stage of each SSL, HLC exhibited accelerating release in sodium salts but declining trend in calcium salt whereas PLC showed a roughly constant dynamic in the both. Ca-bridging reactions with the detachment of OM-Ca-clay complex prompting HLC release and its formation to stabilize the HLC well explain the contrast dynamics of HLC with Na or Ca leaching. The diffusion process that was defined for the slow, lasting and small concentration of leaching of inactive components could contribute to the steady dynamic of PLC, given its insensitivity to either the salt cation. This study identified distinct release kinetics of DOM compositions from those of DOC by EEM-PARAFAC and correspondingly the potential mechanisms, which offers promising advantages in monitoring DOM transport and fractionation in dynamic leaching process.

Diapycnal dissolved organic matter supply into the upper Peruvian oxycline

Abstract. The eastern tropical South Pacific (ETSP) hosts the Peruvian upwelling system, which represents one of the most productive areas in the world ocean. High primary production followed by rapid heterotrophic utilization of organic matter supports the formation of one of the most intense oxygen minimum zones (OMZs) in the world ocean, where dissolved oxygen (O2) concentrations reach less than 1 µmol kg−1. The high productivity leads to an accumulation of dissolved organic matter (DOM) in the surface layers that may serve as a substrate for heterotrophic respiration. However, the importance of DOM utilization for O2 respiration in the Peruvian upwelling system in general and for shaping the upper oxycline in particular remains unclear so far. This study reports the first estimates of diapycnal fluxes and supply of O2, dissolved organic carbon (DOC), dissolved organic nitrogen, dissolved hydrolysable amino acids (DHAA) and dissolved combined carbohydrates (DCCHO) for the ETSP off Peru. Diapycnal flux and supply estimates were obtained by combining measured vertical diffusivities and solute concentration gradients. They were analysed together with the molecular composition of DCCHO and DHAA to infer the transport of labile DOM into the upper OMZ and the potential role of DOM utilization for the attenuation of the diapycnal O2 flux that ventilates the OMZ. The observed diapycnal O2 flux (50 mmol O2 m−2 d−1 at maximum) was limited to the upper 80 m of the water column; the O2 supply of ∼1 µmol kg−1 d−1 was comparable to previously published O2 consumption rates for the North and South Pacific OMZs. The diapycnal DOM flux (31 mmol C m−2 d−1 at maximum) was limited to ∼30 m water depth, suggesting that the labile DOM is extensively consumed within the upper part of the shallow oxycline off Peru. The analyses of DCCHO and DHAA composition support this finding, suggesting that DOM undergoes comprehensive remineralization within the upper part of the oxycline, as the DOM within the core of the OMZ was found to be largely altered. Estimated by a simple equation for carbon combustion, aerobic respiration of DCCHO and DHAA, supplied by diapycnal mixing (0.46 µmol kg−1 d−1 at maximum), could account for up to 38 % of the diapycnal O2 supply in the upper oxycline, which suggests that DOM utilization plays a significant role for shaping the upper oxycline in the ETSP.

Homogenization of dissolved organic matter within a river network occurs in the smallest headwaters

Understanding the drivers of variability in the concentration and composition of dissolved organic matter (DOM) in running waters is a fundamental challenge for aquatic biogeochemistry. Although multiple conceptual frameworks have been proposed to quantify expected changes in DOM within a river network, few studies have collected data to document the variability of DOM within such a network. We examine spatial and temporal variability in the concentration, optical properties, and biodegradability of DOM within a river network in New Hampshire, U.S.A. We examined dissolved organic carbon (DOC) concentration and DOM optical properties across 21 locations within the Lamprey River network (548 km2) with weekly to monthly sampling for 4 years, and biodegradable DOC (BDOC) at 7 mainstem locations for 1 year. DOC concentration and DOM character were highly heterogeneous at the scale of the smallest streams, where variability in land cover and nutrient concentrations were also greatest. At the landscape scale, DOC concentrations and DOM aromaticity increased with wetland cover and decreased with developed land cover and nitrate concentrations. Despite this heterogeneity across streams, we observed similar synchronous seasonal variation in DOC concentration and DOM character regardless of position within the river network, suggesting that broad environmental factors shape the sources and transport of DOM in river networks. In contrast, variation in BDOC over time or across sites was not strongly related to DOM quality or other predictors. Spatiotemporal patterns in DOM provide insight into the complex processes that influence terrestrial carbon export, in-stream processes, and DOM delivery to downstream ecosystems.

Lignin Dimers as Potential Markers for 14C-young Terrestrial Dissolved Organic Matter in the Critical Zone

The origin, molecular composition and fate of dissolved organic matter (DOM) provides essential information that links surface and subsurface processes and explores the functioning of the Critical Zone. Therefore it is important to identify specific marker compounds that provide information on the temporal and spatial linkages in the Critical Zone. Here we used ultra-high resolution mass spectrometry and accelerator mass spectrometry in order to identify markers for fast transport of surface-derived DOM through the Critical Zone. We assessed the molecular composition and radiocarbon age of solid phase extracted DOM (SPE-DOM) from forest top soils. The 14C ages of SPE-DOM in our study were similar to that of bulk DOM. Calibrated ages ranged from 0 to 49 years and the within-site variability was larger than between sampling sites. Spearman rank correlation between the 14C ages and the DOM composition identified 129 sum formulae that were significantly correlated to 14C age. We found that molecular entities with younger 14C ages had lower molecular weight, higher unsaturation and less oxygen and heteroatoms than those associated with older 14C ages. A chemical library search suggested that phenylpropanoids and compounds, which are known to be lignin derived, are key molecular species for terrestrial DOM with young 14C ages. Among them, lignin dimers emerged as prominent surface-derived compounds that can potentially be used as markers for fast transport of water and DOM into the subsurface and groundwater.

Biochar's impact on dissolved organic matter (DOM) export from a cropland soil during natural rainfalls

Although biochar amendment to soil has achieved widely recognized benefits such as plant growth improvement and carbon sequestration, what impact it would have on soil carbon cycling, especially on the behavior of the active dissolved organic matter (DOM), is still unclear. This study evaluated biochar's effects on soil properties and the characteristics of DOM exporting from a cropland Entisol. The soil is the major arable land resource in the upper reaches of the Yangtze River, China and noted for its low soil organic matter and prevalence of preferential flow. Surface runoff, soil pore water and leachate were collected from the field upon a series of natural rainfall. Concentration of dissolved organic carbon (DOC) of soil pore water was found to respond strongly toward the rainfalls. Biochar application led to relatively higher DOC levels within the soil (p > 0.05). Despite apparent increase of DOC and EEM intensities for the freshly-amended soil, PARAFAC analyses indicated no changes in DOM's fluorophore compositions after two years of ageing. The identified DOM components (C1 and C2) showed similar dynamics with the DOCs in responding to the rainfalls. On the other hand, total flux of DOM leaching from biochar-amended plots during three monitored storms was on average 59% higher than the control (p > 0.05), whereas DOM export via surface runoff was slightly diminished. Noticeably, biochar amendment had caused a significant increase of >1000 μm macropores and thus the enhanced infiltration of soil water. Such changes led to increased flow discharge, which in turn resulted in elevated leaching of organic carbon during rainfalls. The results therefore implies that changes of soil structure and hydraulic properties that will take place after biochar application merits attention as they may play a continuous role in influencing the transport of DOM and possibly other solutes via runoff processes.

Characterizing dissolved organic matter in eroded sediments from a loess hilly catchment using fluorescence EEM-PARAFAC and UV–Visible absorption: Insights from source identification and carbon cycling

The chemical characteristics of dissolved organic matter (DOM) in soils that experience erosion and deposition are key to the biogeochemical cycle of carbon on the earth's surface. However, data related to the transport and fate of DOM from soils that experience erosion and different management practices are scarce, particularly at catchment scales. In this study, soil samples (uppermost 10 cm) were collected from uplands representing four land use types (cropland, fallow, grassland, and forests) as well as gullies, and sediment samples (100 cm sampled at 10 depths) were collected from sediments retained by a check dam. Chemical characteristics of DOM in soils and sediments, as well as subsequent source identification, were inferred from UV–Visible absorption and fluorescence excitation emission matrix (EEM)-parallel factor analysis (PARAFAC) as well as principal component analysis (PCA). The results indicated higher aromaticity, hydrophobic fraction, and molecular size in DOM from forest soils than those from other land use types and gullies. These factors were also higher in soils at the eroding sites than in sediments. EEM-PARAFAC analysis demonstrated that more protein-like components (tyrosine-like and tryptophan-like combined, accounting for >42.77%) were present in sediments compared to soils with terrestrial humic-like substances. PCA results revealed that approximately 72% of the variance in the DOM characteristics was explained by the first two principal components and that the DOM in upland and gully soils had a negligible contribution to DOM in sediments. Combined our results indicate that, despite the large amount of sediment-associated carbon that is transported by erosion and trapped in check dams, DOM is likely mineralized during soil transport. Furthermore, biological production of new organic compounds (autochthonous sources) are likely the major source of sediment DOM in depositional settings.

Differences in N loading affect DOM dynamics during typhoon events in a forested mountainous catchment

The dissolved organic matter (DOM) and nutrient dynamics in small mountainous rivers (SMRs) strongly depend on hydrologic conditions, and especially on extreme events. Here, we investigated the quantity and quality of DOM and inorganic nutrients during base-flow and typhoon events, in a chronically N-saturated mainstream and low N-loaded tributaries of a forested small mountainous reservoir catchment in Taiwan. Our results suggest that divergent transport mechanisms were triggered in the mainstream vs. tributaries during typhoons. The mainstream DON increased from 3.4 to 34.7% of the TDN pool with a static DOC:NO3-N ratio and enhanced DOM freshness, signalling a N-enriched DOM transport. Conversely, DON decreased from 46 to 6% of the TDN pool in the tributaries and was coupled with a rapid increase of the DOC:NO3-N ratio and humified DOM signals, suggesting the DON and DOC were passively and simultaneously transported. This study confirmed hydrology and spatial dimensions being the main drivers shaping the composition and concentration of DOM and inorganic nutrients in small mountainous catchments subject to hydrologic extremes. We highlighted that the dominant flow paths largely controlled the N-saturation status and DOM composition within each sub-catchment, the effect of land-use could therefore be obscured. Furthermore, N-saturation status and DOM composition are not only a result of hydrologic dynamics, but potential agents modifying the transport mechanism of solutes export from fluvial systems. We emphasize the importance of viewing elemental dynamics from the perspective of a terrestrial-aquatic continuum; and of taking hydrologic phases and individual catchment characteristics into account in water quality management.

Multiple exchange processes on mineral surfaces control the transport of dissolved organic matter through soil profiles

Organic topsoil layers are important sources of dissolved organic matter (DOM) transported to deeper soil layers. During passage through the mineral soil, both organic matter (OM) quality and quantity change markedly. Whether these alterations are due to sorption processes alone or to additional stepwise exchange processes of OM on mineral surfaces (“cascade model”) is not fully understood. To test the “cascade model”, we conducted a laboratory flow cascade experiment with undisturbed soil columns from three depths of two different soil profiles (Dystric and Eutric Cambisol) using carbon (C) isotope labelling. Each of the connected topsoil and subsoil columns contained a goethite (α-FeOOH) layer either with or without sorbed 13C-labelled OM to assess the importance of OM immobilization/mobilization reactions with reactive soil minerals. By using a multiple method approach including 13C analysis in the solid and solution phases, nanometer scale secondary ion mass spectrometry (NanoSIMS), and quantitative polymerase chain reaction (qPCR), we quantified organic carbon (OC) adsorption and desorption and net OC exchange at goethite surfaces as well as the associated microbial community patterns at every depth step of the column experiment. The gross OC exchange between OM-coated goethite and the soil solution was in the range of 15–32%. This indicates that a considerable proportion of the mineral associated OM was mobilized and replaced by percolating DOM. We showed that specific groups of bacteria play an important role in processing organic carbon compounds in the mineral micro-environment. Whereas bulk soils were dominated by oligotrophic bacteria such as Acidobacteria, the goethite layers were specifically enriched with copiotrophic bacteria such as Betaproteobacteria. This group of microorganisms made use of labile carbon derived either from direct DOM transport or from OM exchange processes at goethite surfaces. Specific microorganisms appear to contribute to the cascade process of OM transport within soils. Our study confirms the validity of the postulated “cascade model”, featuring the stepwise transport of OM within the soil profile.

Transport of dissolved organic matter in Boom Clay: Size effects

A coupled experimental-modelling approach was developed to evaluate the effects of molecular weight (MW) of dissolved organic matter (DOM) on its transport through intact Boom Clay (BC) samples. Natural DOM was sampled in-situ in the BC layer. Transport was investigated with percolation experiments on 1.5cm BC samples by measuring the outflow MW distribution (MWD) by size exclusion chromatography (SEC). A one-dimensional reactive transport model was developed to account for retardation, diffusion and entrapment (attachment and/or straining) of DOM. These parameters were determined along the MWD by implementing a discretisation of DOM into several MW points and modelling the breakthrough of each point. The pore throat diameter of BC was determined as 6.6–7.6nm. Below this critical size, transport of DOM is MW dependent and two major types of transport were identified. Below MW of 2kDa, DOM was neither strongly trapped nor strongly retarded. This fraction had an averaged capacity factor of 1.19±0.24 and an apparent dispersion coefficient ranging from 7.5×10−11 to 1.7× 10−11m2/s with increasing MW. DOM with MW>2kDa was affected by both retardation and straining that increased significantly with increasing MW while apparent dispersion coefficients decreased. Values ranging from 1.36 to 19.6 were determined for the capacity factor and 3.2×10−11 to 1.0×10−11m2/s for the apparent dispersion coefficient for species with 2.2kDa<MW<9.3kDa. Straining resulted in an immobilisation of in average 49±6% of the injected 9.3kDa species. Our findings show that an accurate description of DOM transport requires the consideration of the size effects.

Quality and reactivity of dissolved organic matter in a Mediterranean river across hydrological and spatial gradients

Understanding DOM transport and reactivity in rivers is essential to having a complete picture of the global carbon cycle. In this study, we explore the effects of hydrological variability and downstream transport on dissolved organic matter (DOM) dynamics in a Mediterranean river. We sampled the main stem of the river Tordera from the source to the sea, over a range of fifteen hydrological conditions including extreme events (flood and drought). By exploring spatial and temporal gradients of DOM fluorescence properties, river hydrology was found to be a significant predictor of DOM spatial heterogeneity. An additional space-resolved mass balance analysis performed on four contrasting hydrological conditions revealed that this was due to a shift in the biogeochemical function of the river. Flood conditions caused a conservative transport of DOM, generating a homogeneous, humic-like spatial profile of DOM quality. Lower flows induced a non-conservative, reactive transport of DOM, which enhanced the spatial heterogeneity of DOM properties. Moreover, the downstream evolution of DOM chemostatic behaviour revealed that the role of hydrology in regulating DOM properties increased gradually downstream, indicating an organised inter-dependency between the spatial and the temporal dimensions. Overall, our findings reveal that riverine DOM dynamics is in constant change owing to varying hydrological conditions, and emphasize that in order to fully understand the role of rivers in the global carbon cycle, it is necessary to take into account the full range of hydrological variability, from floods to droughts.

Importance of lateral flux and its percolation depth on organic carbon export in Arctic tundra soil: Implications from a soil leaching experiment

AbstractTemperature rise in the Arctic is causing deepening of active layers and resulting in the mobilization of deep permafrost dissolved organic matter (DOM). However, the mechanisms of DOM mobilization from Arctic soils, especially upper soil horizons which are drained most frequently through a year, are poorly understood. Here we conducted a short‐term leaching experiment on surface and deep organic active layer soils, from the Yukon River basin, to examine the effects of DOM transport on bulk and molecular characteristics. Our data showed a net release of DOM from surface soils equal to an average of 5% of soil carbon. Conversely, deep soils percolated with surface leachates retained up to 27% of bulk DOM while releasing fluorescent components (up to 107%), indicating selective release of aromatic components (e.g., lignin and tannin), while retaining nonchromophoric components, as supported by spectrofluorometric and ultrahigh‐resolution mass spectroscopic techniques. Our findings highlight the importance of the lateral flux of DOM on ecosystem carbon balance as well as processing of DOM transport through organic active layer soils en route to rivers and streams. This work also suggests the potential role of leachate export as an important mechanism of C losses from Arctic soils, in comparison with the more traditional pathway from soil to atmosphere in a warming Arctic.

Transport and humification of dissolved organic matter within a semi-arid floodplain

In order to understand the transport and humification processes of dissolved organic matter (DOM) within sediments of a semi-arid floodplain at Rifle, Colorado, fluorescence excitation–emission matrix (EEM) spectroscopy, humification index (HIX) and specific UV absorbance (SUVA) at 254nm were applied for characterizing depth and seasonal variations of DOM composition. Results revealed that late spring snowmelt leached relatively fresh DOM from plant residue and soil organic matter down into the deeper vadose zone (VZ). More humified DOM is preferentially adsorbed by upper VZ sediments, while non- or less-humified DOM was transported into the deeper VZ. Interestingly, DOM at all depths undergoes rapid biological humification process evidenced by the products of microbial by-product-like (i.e., tyrosine-like and tryptophan-like) matter in late spring and early summer, particularly in the deeper VZ, resulting in more humified DOM (e.g., fulvic-acid-like and humic-acid-like substances) at the end of year. This indicates that DOM transport is dominated by spring snowmelt, and DOM humification is controlled by microbial degradation, with seasonal variations. It is expected that these relatively simple spectroscopic measurements (e.g., EEM spectroscopy, HIX and SUVA) applied to depth- and temporally-distributed pore-water samples can provide useful insights into transport and humification of DOM in other subsurface environments as well.

Small scale variability of vertical water and dissolved organic matter fluxes in sandy Cambisol subsoils as revealed by segmented suction plates

Dissolved organic matter (DOM) is considered as a major carbon source in subsoils. As soil water fluxes are highly variable at small scale, and transport versus sorptive retention of DOM is related to water flux and associated contact time with minerals, knowledge of the small scale spatial variability of the dissolved organic carbon (DOC) concentrations and fluxes into the subsoil is decisive for a solid estimation of organic carbon (OC) translocation into the subsoil. Here, we made advantage of novel segmented suction plates (4 × 4 segments, each 36 cm2) to analyze the small scale spatial and temporal variability of DOC transport at 10, 50 and 150 cm depth of three subsoil observatories (approximately 50 m apart) in a sandy Dystric Cambisol under beech in the Grinderwald, 40 km northwest from Hannover, Germany. Water fluxes, DOC concentrations and fluxes as well as the specific UV absorbance (SUVA) at 280 nm were determined in weekly samples from August 2014 to November 2015 for each individual segment. The DOC fluxes decreased with depth (19.6 g C m−2 year−1, 10 cm; 1.2 g C m−2 year−1, 150 cm) and were strongly related to the water fluxes. The SUVA at 280 nm also decreased with depth (0.03 L mg C−1 cm−1, 10 cm; 0.01 L mg C−1 cm−1, 150 cm), indicating a selective retention of aromatic moieties, that was eased with increasing water flux at least in the subsoil. The proportion of temporal fluctuations and small scale variability on the total variance of each parameter where determined by the calculation of intra class correlations. The seasonal heterogeneity and the small scale spatial heterogeneity were identified to be of major importance. The importance of the small scale spatial heterogeneity strongly increased with depth, pointing towards the stability of flow paths and suggesting that at a given substrate hydrological processes rather than physicochemical processes are decisive for the sorptive retention of DOM and the variability of OC accumulation in the subsoil. Our results clearly show the demand of small scale sampling for the identification of processes regarding carbon cycling in the subsoil.

Variation of organic matter quantity and quality in streams at Critical Zone Observatory watersheds

The quantity and chemical composition of dissolved organic matter (DOM) in surface waters influence ecosystem processes and anthropogenic use of freshwater. However, despite the importance of understanding spatial and temporal patterns in DOM, measures of DOM quality are not routinely included as part of large-scale ecosystem monitoring programs and variations in analytical procedures can introduce artifacts. In this study, we used consistent sampling and analytical methods to meet the objective of defining variability in DOM quantity and quality and other measures of water quality in streamflow issuing from small forested watersheds located within five Critical Zone Observatory sites representing contrasting environmental conditions. Results show distinct separations among sites as a function of water quality constituents. Relationships among rates of atmospheric deposition, water quality conditions, and stream DOM quantity and quality are consistent with the notion that areas with relatively high rates of atmospheric nitrogen and sulfur deposition and high concentrations of divalent cations result in selective transport of DOM derived from microbial sources, including in-stream microbial phototrophs. We suggest that the critical zone as a whole strongly influences the origin, composition, and fate of DOM in streams. This study highlights the value of consistent DOM characterization methods included as part of long-term monitoring programs for improving our understanding of interactions among ecosystem processes as controls on DOM biogeochemistry.

Hydrological conditions control in situ DOM retention and release along a Mediterranean river

Uncertainties exist regarding the magnitude of in situ dissolved organic matter (DOM) processing in lotic systems. In addition, little is known about the effects of extreme hydrological events on in-stream DOM retention or release during downriver transport.This study quantified the net in-stream retention/release efficiencies (η) of dissolved organic carbon (DOC) and its humic and protein-like fluorescent fractions along a Mediterranean river during drought, baseflow and flood conditions. High performance size exclusion chromatography was used to describe the apparent size distributions of the humic and protein-like DOM moieties. A snapshot mass balance allowed estimating the η values of DOC and humic and protein-like fractions. Significant DOM net retention (η < 0) was detected during the drought condition and the protein-like fraction was more retained than the humic-like fraction and bulk DOC. In addition, small substances were more efficiently retained than larger substances. DOC retention decreased under baseflow conditions, but it remained significant. The humic and protein-like net efficiencies exhibited high variability, but the net retention were not significant. From a longitudinal perspective, the entire fluvial corridor contributed net retention of DOC and humic and protein-like moieties net retention during drought condition. In contrast, net retention/release efficiencies exhibited spatial variability during baseflow condition. The flood preferentially mobilized large size DOM molecules and the fluvial corridor behaved as a homogeneous passive DOM (η = 0) conduit.This research highlights the relevance of hydrological extreme events on the magnitude of DOM retention/release mass balance and emphasizes the need to perform measurements during these conditions to quantify the impact of fluvial corridors on DOM fate and transport.

Spatial and temporal variation of dissolved organic matter in the Changjiang: Fluvial transport and flux estimation

AbstractThe Changjiang is the most important source of freshwater and dissolved organic matter (DOM) for the East China Sea. However, knowledge regarding the sources, seasonal fluxes, and fluvial transport of terrigenous DOM (tDOM) in the Changjiang is lacking. To fill this knowledge gap, we measured dissolved organic carbon (DOC) and dissolved lignin in water samples collected in the middle and lower Changjiang under different hydrological conditions. Additional samples were collected biweekly in the lower Changjiang. Through comparisons with other rivers, we found that the DOC in the Changjiang is mainly from soil organic matter and has a higher fraction of tDOM during flood. Mass balance model results indicate that approximately 33% of the dissolved lignin discharged into the middle and lower Changjiang is removed during its transport to the lower reach during both low‐discharge and flood periods. Based on a comparison of the removal rates under these two contrasting hydrological conditions and considering the lower organic carbon content and fine grain size of the Changjiang's suspended particles, we speculate that the major process for the removal of dissolved lignin is sorption, and potentially flocculation by suspended particles. Changjiang discharges 1.4 ± 0.10 Tg yr−1 and 8.6 ± 0.30 Gg yr−1 DOC and dissolved lignin to the estuary during the period of July 2010 to June 2011, respectively. Seasonal distributions of DOC and dissolved lignin fluxes are controlled by water discharge, which will be affected by future climate change and the Three Gorges Dam.

Partitioning of organic matter in Boom Clay: Leachable vs mobile organic matter

Boom Clay (BC) is considered in Belgium as a potential host rock for nuclear waste disposal. The formation contains up to 5 wt% of natural organic matter and the presence of dissolved organic matter (DOM) may have a strong impact on radionuclide mobility. However, due to physical constraints, only a fraction of DOM is mobile through the BC layer and the extent of DOM-facilitated radionuclide transport is controlled by the distribution of OM over the mobile and immobile pools. In this work, we investigate 1/the concentration and the size distribution of leachable organic matter in BC, 2/the variability along the BC layer of the concentration and the size distribution of mobile DOM, 3/the parameters controlling the concentration and the size distribution of the leachable OM pool and of the mobile OM pool. Size exclusion chromatography with UV detection at 280 nm is chosen as the reference technique. The UV response of BC DOM is investigated as a function of MW. In pore waters, i.e for mobile DOM, the SUVA280 is dependent on the OM size/MW with the lowest value measured for low MW species (<1 kDa). The use of dynamic light scattering permits to also estimate the hydrodynamic radius (RH) distribution of BC DOM. In the investigated part of BC, the concentration of mobile DOM represents only 0.15 ± 0.8% of the total organic matter content (TOC) and is mostly <20 kDa (RH < 2.8 nm). In contrast, the OM leached from solid samples is dominated by species with MW > 50 kDa and RH > 5.3 nm and accounts for about 12 TOC%. While the concentration of the leachable OM pool is mostly controlled by the TOC content of the rock and to a lower extent by the hydrogen index of the kerogen, the mineralogy plays a significant role in the concentration and the size distribution of the mobile DOM. Filtration and sorption are promoted by clay minerals that preferentially preserves large organic species and leave only small species mobile in pore waters. Inversely, coarser minerals like silt and/or sand facilitate the transport of DOM and increase both the concentration and the MW/RH of the mobile species. The threshold of 20 kDa (RH = 2.8 nm) is considered as a cut-off over which DOM species are hardly mobile in BC. A large part of OM is showed insoluble or immobile but the distribution of OM over the mobile and immobile/insoluble pools, characterised by an average Kd¯ of 140 L kg−1 is found to rather favour the transport of radionuclides than to act as an additive sorbent phase.

Tracking litter-derived dissolved organic matter along a soil chronosequence using 14C imaging: Biodegradation, physico-chemical retention or preferential flow?

The cycling of dissolved organic matter (DOM) in soils is controversial. While DOM is believed to be a C source for soil microorganisms, DOM sorption to the mineral phase is regarded as a key stabilization mechanism of soil organic matter (SOM). In this study, we added 14C-labelled DOM derived from Leucanthemopsis alpina to undisturbed soil columns of a chronosequence ranging from initial unweathered soils of a glacier forefield to alpine soils with thick organic layers. We traced the 14C label in mineralized and leached DOM and quantified the spatial distribution of DO14C retained in soils using a new autoradiographic technique. Leaching of DO14C through the 10 cm-long soil columns amounted up to 28% of the added DO14C in the initial soils, but to less than 5% in the developed soils. Biodegradation hardly contributed to the removal of litter-DO14C as only 2–9% were mineralized, with the highest rates in mature soils. In line with the mass balance of 14C fluxes, measured 14C activities in soils indicated that the major part of litter DO14C was retained in soils (>80% on average). Autoradiographic images showed an effective retention of almost all DO14C in the upper 3 cm of the soil columns. In the deeper soil, the 14C label was concentrated along soil pores and textural discontinuities with similarly high 14C activities than in the uppermost soil. These findings indicate DOM transport via preferential flow, although this was quantitatively less important than DOM retention in soils. The leaching of DO14C correlated negatively with oxalate-extractable Al, Fe, and Mn. In conjunction with the rapidity of DO14C immobilization, this strongly suggests that sorptive retention DOM was the dominating pathway of litter-derived DOM in topsoils, thereby contributing to SOM stabilization.

Correction: Self-Organising Maps and Correlation Analysis as a Tool to Explore Patterns in Excitation-Emission Matrix Data Sets and to Discriminate Dissolved Organic Matter Fluorescence Components

Dissolved organic matter (DOM) is a complex mixture of organic compounds, ubiquitous in marine and freshwater systems. Fluorescence spectroscopy, by means of Excitation-Emission Matrices (EEM), has become an indispensable tool to study DOM sources, transport and fate in aquatic ecosystems. However the statistical treatment of large and heterogeneous EEM data sets still represents an important challenge for biogeochemists. Recently, Self-Organising Maps (SOM) has been proposed as a tool to explore patterns in large EEM data sets. SOM is a pattern recognition method which clusterizes and reduces the dimensionality of input EEMs without relying on any assumption about the data structure. In this paper, we show how SOM, coupled with a correlation analysis of the component planes, can be used both to explore patterns among samples, as well as to identify individual fluorescence components. We analysed a large and heterogeneous EEM data set, including samples from a river catchment collected under a range of hydrological conditions, along a 60-km downstream gradient, and under the influence of different degrees of anthropogenic impact. According to our results, chemical industry effluents appeared to have unique and distinctive spectral characteristics. On the other hand, river samples collected under flash flood conditions showed homogeneous EEM shapes. The correlation analysis of the component planes suggested the presence of four fluorescence components, consistent with DOM components previously described in the literature. A remarkable strength of this methodology was that outlier samples appeared naturally integrated in the analysis. We conclude that SOM coupled with a correlation analysis procedure is a promising tool for studying large and heterogeneous EEM data sets.