Dissolved Organic Carbon Chemistry Research Articles

Molecular structure of dissolved organic carbon in a sandy soil receiving contrasting quality organic residues

Decomposing plant residues release plant-derived dissolved organic carbon (DOC) which can be transformed by microorganisms resulting in microbial-derived DOC (DOC biological function). The adsorbability of DOC to mineral surfaces, determined by DOC chemistry (DOC chemical function), can affect its vertical distribution down soil profiles (D). This study investigated the temporal characteristics (T) and functions (bioavailability, adsorbability) of DOC across the profile of a sandy soil by using chemically contrasting quality (Q) residues: 1) high-cellulose rice straw (RS), 2) nitrogen-rich groundnut stover (GN), 3) lignin-rich dipterocarp leaf litter (DP), and 4) medium-nitrogen and -lignin tamarind leaf litter (TM). Soil samples were collected at two depths (0–15 cm and 60–80 cm) two and eight weeks after residue application, and water-extractable DOC was determined. For the first time, the chemical structure of the extracted DOC was characterized using pyrolysis coupled with mid-infrared spectroscopy (Py-MIRS). The dominant functional groups found in all DOC samples were aromatic, carboxyl, and polysaccharide compounds. The interactive effects of Q, T, and D (soil depth) influenced DOC-polysaccharides, with the most pronounced effect observed in the RS treatment during the early stage, indicating that DOC-polysaccharides were mainly plant-derived. Evidence of partial adsorption of DOC-aromatics and DOC-carboxyls was found in topsoils. These high molecular weight-DOC functional groups may have displaced adsorbed polysaccharides, resulting in higher subsoil DOC-polysaccharides than topsoil, especially under DP and TM. During the later stage, topsoil DOC-polysaccharides were negatively related to microbial metabolic quotient (qCO2) (R2 = 0.938). This relationship led to our hypothesis that the dominant source of DOC-polysaccharides, particularly in the TM treatment, was of microbial origin. A novel discovery from this study is that the chemical quality of plant residues, which serve as the source of DOC, determines the origin of the polysaccharides in DOC. This origin transitioned from plant-derived to microbial-derived as decomposition progressed. Importantly, the presented findings were the first of its kind based on a field experiment.

Age and chemistry of dissolved organic carbon reveal enhanced leaching of ancient labile carbon at the permafrost thaw zone

Abstract. Climate change will alter the balance between frozen and thawed conditions in Arctic systems. Increased temperatures will make the extensive northern permafrost carbon stock vulnerable to decomposition and translocation. Production, cycling, and transport of dissolved organic carbon (DOC) are crucial processes for high-latitude ecosystem carbon loss that result in considerable export off the Arctic landscape. To identify where and under what conditions permafrost DOC is mobilized in an Arctic headwater catchment, we measured radiocarbon (14C) of DOC and assessed DOC composition with ultraviolet–visible spectroscopy (UV–Vis) of surface waters and shallow and deep subsurface porewaters from 17 drainages in the Barrow Environmental Observatory in Alaska. Samples were collected in July and September 2013 to assess changes in age and chemistry of DOC over time. DOC age was highly variable ranging from modern (19 ‰ Δ14C) to approximately 7000 BP (−583 ‰ Δ14C). DOC age increased with depth, over the summer as the active layer deepened, and with increasing drainage size. DOC quality indicators reflected a DOC source rich in high molecular-weight and aromatic compounds, characteristics consistent with vegetation-derived organic matter that had undergone little microbial processing, throughout the summer and a weak relationship with DOC age. In deep porewaters, DOC age was also correlated with several biogeochemical indicators (including dissolved methane concentration, δ13C, and the apparent fractionation factor), suggesting a coupling between carbon and redox biogeochemistry influencing methane production. In the drained thawed lake basins included in this study, DOC concentrations and contributions of vegetation-derived organic matter declined with increasing basin age. The weak relationship between DOC age and chemistry and consistency in DOC chemical indicators over the summer suggest a high lability of old DOC released by thawing permafrost.

Vertical dynamics of dissolved organic carbon in relation to organic input quality and microaggregate formation in a coarse– textured Ultisol

AbstractAgainst the background of current understanding of dissolved organic carbon (DOC) adsorption onto clay surfaces, it remains unclear if bulk DOC or its fractions contribute to microaggregate formation in the top layers of coarse‐textured soils. We therefore investigated the effects of long‐term inputs of biochemically contrasting organic residues on the chemical characteristics and vertical distribution of DOC in a coarse‐textured Ultisol. During 2007–2008, DOC samples were extracted from soil profiles of a long‐term residue quality field experiment initiated in 1995. In this field experiment, groundnut stover, dipterocarp and tamarind leaf litter, as well as rice straw of contrasting biochemical quality, were applied yearly at 10 Mg ha−1. Groundnut, dipterocarp and tamarind produced large amounts (7.1–11.8 g C m−2) of high‐molecular‐weight (HMW; > 10 kDa) DOC, which was found in high concentrations (30–50 mg C kg−1) in the topsoil (0–15 cm). Rice straw, however, produced large amounts (3.5 g C m−2) of low‐molecular‐weight (LMW; < 1 kDa) DOC during the initial stage of decomposition. Although the HMW DOC was retained in the topsoil (0–15 cm), the LMW DOC was rapidly translocated to lower soil depths (60–80 cm). This translocation was facilitated by the low adsorption potential of the rice straw‐derived LMW DOC on colloidal surfaces of the topsoil. There was a significant positive correlation of C in the HMW DOC with that in fine particles, indicating their contribution to microaggregate formation and thus C accumulation. It was concluded that biochemical quality of residues as a determinant of concentration and chemistry of DOC and its vertical dynamics along the soil profile must be considered for SOC accumulation in coarse‐textured soils. Furthermore, we found reasonable indications that HMW DOC contributes to microaggregate formation in topsoils.Highlights Residue quality determined vertical dynamics of DOC in coarse– textured Ultisols. Lignin‐ and polyphenol‐rich residues produced HMW DOC in topsoil. LMW DOC derived from cellulose‐rich residues was translocated to the subsoil. There were indications that HMW DOC supported microaggregate formation in topsoils.

Fluorescent DOC characteristics are related to streamflow and pasture cover in streams of a mixed landscape

A growing body of research suggests that different land use activities may alter both the quantity and quality of dissolved organic carbon (DOC) exported from terrestrial landscapes. However, little is known about DOC from mixed-use landscapes where hydrology varies seasonally. This study examined how DOC and chemical properties of stream water were related to land use, drainage area, and streamflow in mixed-use landscape in the Willamette River Basin, Oregon. Stream water samples were collected at roughly monthly intervals over three water years from 21 sites whose drainage areas ranged from 1 to > 11,000 km2 and included pasture, forest, and developed land uses. DOC properties were characterized using PARAFAC (parallel factor) analyses of 3-D excitation and emission matrices (EEMs). We used the Cory-McKnight (CM) model, and we also developed a model unique to our samples. Thirteen components were identified using the CM model, and these were highly correlated with, and similar with respect to excitation and emission to the three components identified in our site-specific model. Fluorescent components of DOC were related to discharge and land cover, but not to drainage area. In our model, one component (C1) appeared to be associated with terrestrial detritus and was greater in streamflow from sites with forest/developed cover than from sites with high pasture cover. A second component (C2) was greater in streamflow from high-pasture sites than from high-forest sites. C2 was strongly correlated with a protein component identified in the CM model, and therefore we attributed this second component to more microbially-processed DOC. C1 increased significantly with discharge for both land covers, suggesting that periods of high flow produce less microbially-processed DOC from more surficial flow. C2 decreased significantly with discharge for both land covers, suggesting that deeper hydrologic flow paths produce more soil-associated, microbially processed DOC. SUVA254, often used as an index of chemical quality and aromaticity of DOC, was related only to streamflow but not land use, suggesting that while the chemistry of DOC differed among land use types as detected by EEMs analysis, the aromaticity of the DOC did not differ. The CM model and our site-specific model provided consistent results: those components that were highest in high pasture sites were also highest at low flow and appeared to be more microbially processed; components that were highest in low pasture sites were also greatest at high flow and appeared to reflect less microbially processed DOC. Taken together, these findings are consistent with a conceptual model of how differences in DOC chemistry among landscape types reflect differences in plant litter input chemistry, hydrologic connectivity, and degree of microbial processing. Such changes in DOC quality with land-use change can affect foodweb dynamics in receiving waters and change the balance between carbon storage and carbon flux to the atmosphere, and they imply that even non-intensive agricultural land use can have significant effects on terrestrial-aquatic carbon processes.

Homogenization of detrital leachate in an old-growth coniferous forest, OR: DOC fluorescence signatures in soils undergoing long-term litter manipulations

Characterizing the relationship between plant detrital inputs and the resulting dissolved organic carbon (DOC) leachate is vital to understanding the ultimate fate of root carbon, fallen wood and needles in forested watersheds. Similarly, elucidating chemical differences in the soil DOC pool may help to explain which DOC fractions are sorbed to mineral surfaces and contribute to accumulation of soil organic carbon, are respired as CO2, or are exported to nearby catchments. In order to test the hypothesis that soils with different detrital inputs impart a detectable signal on DOC in mineral soil, soil solution DOC was sampled from the Detrital Input and Removal Treatment (DIRT) plots located in the H.J. Andrews Experimental Forest, OR. Multiple types of fresh litter extracts, along with lysimeter and soil extracts from DIRT treatment plots were characterized using UV-Vis and fluorescence spectroscopy coupled with the Cory and McKnight (Environ Sci Technol 39:8142–8149, 2005) parallel factor analysis (PARAFAC) model. Principal component analysis of 13 unique fluorophores distinguished using PARAFAC show that litter and soil extracts (Douglas-fir needles, wood of decomposition Class 2, Class 3 and Class 5, O-horizon, and 0–5 cm A-horizon) each have distinct fluorescence signatures. However, while litter-leached DOC chemistry varies by litter type, neither lysimeter-collected DOC or soil extracts in the DIRT plots show statistically significant differences in fluorescence signatures among treatments, even after 17 years of litter manipulations. The lack of observed differences among DIRT treatments suggests that both abiotic interactions and microbial activity effectively homogenize organic carbon constituents within the dissolved pool. Minor but observable changes in PARAFAC components and optical indices during a 1-month biodegradation incubation of litter and soil extracts indicate that while biodegradation significantly alters DOC chemistry, abiotic mechanisms are also critical to DOC transformation in these soils with high sorption capacity. Although leachates from different plant detrital sources have distinct carbon chemical signatures, these DOC signatures are effectively homogenized after passage through mineral soil. These results highlight the dominant role of both biotic and abiotic interactions in controlling the chemistry of DOC in shallow soils.

Release of As, Ba, Cd, Cu, Pb, and Sr under pre-definite redox conditions in different rice paddy soils originating from the U.S.A. and Asia

The release dynamics of dissolved arsenic (As), barium (Ba), cadmium (Cd), copper (Cu), lead (Pb), and strontium (Sr) was determined in seven different paddy soils under controlled-redox conditions by using an automated biogeochemical microcosm apparatus. Seven surface soils were collected from five major rice-cultivating states in the United States (Arkansas, California, Louisiana, Mississippi, and Texas), and from two Asian regions: Hangzhou (China) and Java (Indonesia). The impact of redox potential (EH), pH, dissolved organic carbon (DOC), iron (Fe), manganese (Mn), and sulfur (S) on the release dynamics of the elements was quantified. The experiment was conducted stepwise from reducing (−270mV) to oxidizing (+676mV) soil conditions. Soil pH increased with decreasing soil EH. Concentrations of DOC and dissolved As, Fe, Mn were increased under reducing conditions as compared to oxidizing conditions. In opposite — the release of Ba, Cd, Cu, and Sr to soil solution increased under oxidizing conditions as compared to reducing conditions. The decrease of Ba, Cd, Cu, and Sr concentrations under reducing conditions could be caused by the relatively high pH and/or metal-sulfide precipitation. Lead showed an inconsistent trend with EH in the studied soils (All Soils). Factor analysis demonstrates that As, Fe, Mn, and DOC were associated in one group, while Ba, Sr, Cd, Cu, and EH were banded together in one cluster. These results indicate that the chemistry of DOC, Fe, and Mn might be stronger linked to the dynamics of As than to the dynamics of Ba, Cd, Cu, Pb, and Sr in these soils.The canonical discrimination analysis explained 85% of the variability of the geochemical behavior of the different soils and showed that the individual soils can clearly differentiate from each other. However, the Arkansas and Louisiana soils were relatively similar in their geochemical behavior, and the Indonesian and Texas soils were close, while and the California soil showed a different geochemical behavior. The behavior of Sr, Ba, S, DOC, and EH, respectively, was mainly responsible for the discrimination of the soils. In particular, our findings suggest that aerobic conditions can lead to a release of Ba, Cd, Cu, Pb, and Sr while a release of As under anaerobic conditions was observed. These results provide critical information on the potential risk of toxic elements for the sustainable management of paddy rice soils.

Changes in dissolved organic carbon quality in soils and discharge 10 years after peatland restoration

Summary Peatlands are large sources of dissolved organic carbon (DOC) to downstream ecosystems and DOC losses account for an important portion of peatland carbon balance. Disturbance and restoration of peatland ecosystems alters ecohydrological conditions that are likely to affect DOC chemistry in both soil water and discharge, although the direction of change and controls on DOC chemistry post-restoration remain unclear. We investigated DOC chemistry (concentration, SUVA254, E2:E3, E4:E6, pentose and hexose concentration) during the growing season (May to October) in soil and discharge of a peatland restored for 10 years and compared the results to those measured at neighboring unrestored and natural peatland sites. Controls on the spatial and temporal variability of DOC chemistry, including pH, water table, temperature, plant cover and type, and carbon dioxide and methane flux were also investigated. After 10 years, restoration increased DOC concentration in soils compared to both natural and unrestored sites. This high DOC concentration likely resulted from high plant productivity post-restoration and a mean water table position deeper than the natural site. Ecohydrological conditions were also correlated to DOC chemistry. High vascular plant cover and photosynthesis rates were correlated to lower SUVA254 and higher pentose concentration, while deeper water table position was correlated to higher E2:E3 and E4:E6. DOC concentration in discharge was lower, and E2:E3 higher, at the restored compared to the unrestored site. Differences in DOC chemistry in discharge water were minimal between the sites except when water was likely sourced from the near surface layer at the restored site, which represents new peat accumulated post-restoration. These results suggest that DOC dynamics 10 years post-restoration remain intermediate between natural and unrestored peatland.

Abiotic and biotic controls of organic matter cycling in a managed stream

[1] Urbanization often alters the physical, chemical, and biological structure of aquatic ecosystems embedded within them, creating managed ecosystems with different structure and functioning as compared to their unmanaged counterparts. Our work focused on patterns in dissolved organic carbon (DOC) along a managed stream in Phoenix, Arizona. We documented longitudinal changes in DOC concentrations and quality (defined as chemical complexity and measured as specific ultraviolet absorbance at 254 nm, SUVA) along a 66 km stream dominated by treated wastewater effluent. DOC concentrations along the stream declined by an average of 64%, and chemical complexity increased substantially. We posed four hypotheses to explain changes in downstream water chemistry; including hydrologic dilution, microbial mineralization, abiotic sorption to suspended sediments, and photodegradation by ultraviolet (UV) radiation. Only the second and fourth hypotheses represent permanent removal mechanisms. Our data most strongly supported predictions from the dilution hypothesis and microbial mineralization as an explanation for the changes in DOC chemistry. Surface-subsurface water linkages were important but altered from unmanaged streams, as deep groundwater was used to augment surface flows. Variation in the use of groundwater was linked to human decision making and engineering related to water management. Reduction in geomorphic complexity increased the importance of dilution in explaining patterns but also increased the importance of UV oxidation as a mechanism influencing DOC chemistry. Our findings suggest urban stream management has shifted dependence on microbially mediated C removal mechanisms to hydrologic dilution to reduce output concentrations. This shift lowers contaminant removal potential and increases dependence on limited groundwater resources.

Source water controls on the character and origin of dissolved organic matter in streams of the Yukon River basin, Alaska

Climate warming and permafrost degradation at high latitudes will likely impact watershed hydrology, and consequently, alter the concentration and character of dissolved organic carbon (DOC) in northern rivers. We examined seasonal variation of DOC chemistry in 16 streams of the Yukon River basin, Alaska. Our primary objective was to evaluate the relationship between source water (shallow versus deep groundwater flow paths) and DOC chemical composition. Using base cation chemistry and principal component analysis, we observed high contributions of deep groundwater to glacial and clearwater streams, whereas blackwater streams received larger contributions from shallow groundwater sources. DOC concentration and specific ultraviolet absorbance peaked during spring snowmelt in all streams, and were consistently higher in blackwater streams than in glacial and clearwater streams. The hydrophobic acid fraction of DOC dominated across all streams and seasons, comprising between 35% and 56% of total DOC. The hydrophilic acid fraction of DOC was more prominent in glacial (23% ± 3%) and clearwater streams (19% ± 1%) than in blackwater streams (16% ± 1%), and was enriched during winter base flow (29% ± 1%) relative to snowmelt and summer base flow. We observed that an increase in the contribution of deep groundwater to streamflow resulted in decreased DOC concentration, aromaticity, and DOC‐to‐dissolved organic nitrogen ratio, and an increase in the proportion of hydrophilic acids relative to hydrophobic acids. Our findings suggest that future permafrost degradation and higher contributions of groundwater to streamflow may result in a higher fraction of labile DOM in streams of the Yukon basin.

Humic substances—part 7: the biogeochemistry of dissolved organic carbon and its interactions with climate change

Background, aim, and scope Dissolved organic matter, measured as dissolved organic carbon (DOC), is an important component of aquatic ecosystems and of the global carbon cycle. It is known that changes in DOC quality and quantity are likely to have ecological repercussions. This review has four goals: (1) to discuss potential mechanisms responsible for recent changes in aquatic DOC concentrations; (2) to provide a comprehensive overview of the interactions between DOC, nutrients, and trace metals in mainly boreal environments; (3) to explore the impact of climate change on DOC and the subsequent effects on nutrients and trace metals; and (4) to explore the potential impact of DOC cycling on climate change.

Dissolved organic carbon chemistry and dynamics in contrasting forest and grassland soils

In this study, we examined changes in isotopic (13C and 14C) and spectroscopic (UV and 13C NMR) properties of dissolved organic carbon (DOC) in relation to soil organic matter (SOM) to elucidate the sources and sinks of DOC as water percolates through the soils of two contrasting upland coastal California ecosystems—a redwood forest and a coastal prairie. Despite differences in the distribution of C stocks and litter chemistry at these two sites, we found similar shifts in DOC chemistry with soil depth. DOC concentrations dropped rapidly with increasing depth, with an accompanying decrease in the C:N ratio, an increase in the δ13C value and an decrease in specific UV adsorption. In the grassland soil, Δ14C values declined from current atmospheric values (+70‰) in the surface horizon to −75‰ at 100 cm. In the redwood soil, the Δ14C value of 111‰ in O horizon leachates was indicative of OM with a residence time of 8–10 yrs, with a decrease in Δ14C values to −80‰ at 100 cm. Solid-state CP/MAS 13C NMR spectra were generally most similar to highly humified OM, with a general decrease in the relative abundance of aromatic compounds and an increase in the alkyl C/O-alkyl C ratio with increasing depth. All of these trends are consistent with the shifts in SOM properties with increasing depth, which are interpreted to mean a shift from fresh plant material to older, highly altered OM. In this Mediterranean climate, we found distinct seasonal shifts in the quantity and composition of DOC found in soil solution during the winter rainy period that was also consistent with a shift from recent labile substrates to older, highly altered OM. These results fit in with a growing body of literature suggesting that the source of much of the DOC within mineral soils is the local soil OM, and the 14C data, in particular, indicate that DOC at depth is not simply the fraction of surficial leachates that have not been adsorbed or decomposed. Rather, exchange reactions with a portion of the more stabilized SOM pool exert the strongest control on both the concentration and composition of DOC found in these soils.

Dissolved Organic Carbon in Alaskan Boreal Forest: Sources, Chemical Characteristics, and Biodegradability

The fate of terrestrially-derived dissolved organic carbon (DOC) is important to carbon (C) cycling in both terrestrial and aquatic environments, and recent evidence suggests that climate warming is influencing DOC dynamics in northern ecosystems. To understand what determines the fate of terrestrial DOC, it is essential to quantify the chemical nature and potential biodegradability of this DOC. We examined DOC chemical characteristics and biodegradability collected from soil pore waters and dominant vegetation species in four boreal black spruce forest sites in Alaska spanning a range of hydrologic regimes and permafrost extents (Well Drained, Moderately Well Drained, Poorly Drained, and Thermokarst Wetlands). DOC chemistry was characterized using fractionation, UV–Vis absorbance, and fluorescence measurements. Potential biodegradability was assessed by incubating the samples and measuring CO2 production over 1 month. Soil pore water DOC from all sites was dominated by hydrophobic acids and was highly aromatic, whereas the chemical composition of vegetation leachate DOC varied significantly with species. There was no seasonal variability in soil pore water DOC chemical characteristics or biodegradability; however, DOC collected from the Poorly Drained site was significantly less biodegradable than DOC from the other three sites (6% loss vs. 13–15% loss). The biodegradability of vegetation-derived DOC ranged from 10 to 90% loss, and was strongly correlated with hydrophilic DOC content. Vegetation such as Sphagnum moss and feathermosses yielded DOC that was quickly metabolized and respired. In contrast, the DOC leached from vegetation such as black spruce was moderately recalcitrant. Changes in DOC chemical characteristics that occurred during microbial metabolism of DOC were quantified using fractionation and fluorescence. The chemical characteristics and biodegradability of DOC in soil pore waters were most similar to the moderately recalcitrant vegetation leachates, and to the microbially altered DOC from all vegetation leachates.

Controls on surface water chemistry in two lake‐watersheds in the Adirondack region of New York: differences in nitrogen solute sources and sinks

AbstractThe southwestern Adirondack region of New York receives among the highest rates of atmospheric nitrogen (N) deposition in the USA. Atmospheric N deposition to sensitive ecosystems, like the Adirondacks, may increase the acidification of soils through losses of exchangeable nutrient cations, and the acidification of surface waters associated with enhanced mobility of nitrate (NO3−). However, watershed attributes, including surficial terrestrial characteristics, in‐lake processing, and geological settings, have been found to complicate the relationships between atmospheric N deposition and N drainage losses. We studied two lake‐watersheds in the southwestern Adirondacks, Grass Pond and Constable Pond, which are located in close proximity (∼26 km) and receive similarly high N deposition, but have contrasting watershed attributes (e.g. wetland area, geological settings). Since the difference in the influence of N deposition was minimal, we were able to examine both within‐ and between‐watershed influences of land cover, the contribution of glacial till groundwater inputs, and in‐lake processes on surface water chemistry with particular emphasis on N solutes and dissolved organic carbon (DOC). Monthly samples at seven inlets and one outlet of each lake were collected from May to October in 1999 and 2000. The concentrations of NO3− were high at the Grass Pond inlets, especially at two inlets, and NO3− was the major N solute at the Grass Pond inlets. The concentrations of likely weathering products (i.e. dissolved Si, Ca2+, Mg2+, Na+) as well as acid neutralizing capacity and pH values, were also particularly high at those two Grass Pond inlets, suggesting a large contribution of groundwater inputs. Dissolved organic N (DON) was the major N solute at the Constable Pond inlets. The higher concentrations of DON and DOC at the Constable Pond inlets were attributed to a large wetland area in the watershed. The DOC/DON ratios were also higher at the Constable Pond inlets, possibly due to a larger proportion of coniferous forest area. Although DON and DOC were strongly related, the stronger relationship of the proportion of wetland area with DOC suggests that additional factors regulate DON. The aggregated representation of watershed physical features (i.e. elevation, watershed area, mean topographic index, hypsometric‐analysis index) was not clearly related to the lake N and DOC chemistry. Despite distinctive differences in inlet N chemistry, NO3− and DON concentrations at the outlets of the two lakes were similar. The lower DOC/DON ratios at the lake outlets and at the inlets having upstream ponds suggest the importance of N processing and organic N sources within the lakes. Although an inverse relationship between NO3− and DOC/DON has been suggested to be indicative of a N deposition gradient, the existence of this relationship for sites that receive similar atmospheric N deposition suggest that the relationship between NO3− and the DOC/DON ratio is derived from environmental and physical factors. Our results suggest that, despite similar wet N deposition at the two watershed sites, N solutes entering lakes were strongly affected by hydrology associated with groundwater contribution and the presence of wetlands, whereas N solutes leaving lakes were strongly influenced by in‐lake processing. Copyright © 2006 John Wiley & Sons, Ltd.

Riparian alder fens — Source or sink for nutrients and dissolved organic carbon? — 1. Effects of water level fluctuations

The biogeochemistry of riparian alder wetlands was studied from 1995 to 1997. Nutrient and DOC chemistry was related to water level changes. The spatial and temporal patterns of nutrients (P and N) and dissolved organic carbon (DOC) were measured in the surface water flowing through a riparian alder fen and in the adjacent creek. Nutrient and DOC concentrations were extremely variable temporally but not spatially within the wetland. In the wetland and the adjacent creek concentrations of NO 3-N, PO 4-P and DOC were homogenous during high-flow periods and frozen conditions. After low-flow conditions water bodies were isolated from the creek. The concentration of NH 4-N, PO 4-P and DOC in these isolated water bodies was significantly higher than in the adjacent creeks due to low oxygen levels. Enclosures of different sizes were installed in the wetland to study possible release rates. A large enclosure experiment in the flooded alder fen showed the same concentrations as after high-flood conditions except for DOC. The DOC concentrations were enriched in the large enclosure after decomposition from leaf litter during fall season. Small enclosures with low oxygen levels confirmed data obtained from low-flow conditions. The release rates were calculated for low-flow conditions from small enclosure experiments for 2 months a year when the alder fen is not flooded. The rates for July and August were 11.6 kg/ha NH 4-N, 8.6 kg/ha PO 4-P and 57.6 kg/ha DOC. The DOC concentrations for fall estimated from the large enclosure-experiments were 168.2 kg/ha for the months September and October. This means possible output rates of N, P and DOC during the summer and DOC during fall in the adjacent river system. This can cause eutrophication and organic pollution depending on the length of the low-flow conditions and the size of the alder fen. Water level changes must be regarded as important for the management of riparian wetlands such as alder fens. The riparian alder system may vary from a nutrient sink to a nutrient source at different times of a year depending on high or low water levels.

The influence of source on the sorption of dissolved organic carbon by soils

We examined the influence of dissolved organic carbon (DOC) source on the sorption of DOC by two clayey and two sandy soils using seven extracts from plant tissues and organic soil horizons. Sorption characteristics, such as null-point DOC concentration, partition coefficient and intercept, were determined over the initial solution concentration range of 0–50 mg DOC L−1. The clayey soils had larger partition coefficients and higher null points than the sandy soils. There was an average threefold variation in null-point DOC concentration and partition coefficient amongst the seven DOC extracts. Fractionation of the DOC samples into humic acid and hydrophobic and hydrophilic acids, bases and neutrals revealed weak relationships between the sorption characteristics and DOC chemistry. Key words: Dissolved organic carbon, sorption, fractionation, humic acid, fulvic acid

Concentration and composition of dissolved organic carbon in streams in relation to catchment soil properties

Two adjacent catchments in the Otway Ranges of Victoria, Australia (Redwater and Clearwater) produce water with markedly different concentrations of dissolved organic carbon (DOC) during summer. Water from Redwater Creek had a DOC concentration of 32 mg L-l, while water from Clearwater Creek had a DOC concentration of 3.8 mg L-l. Examination of the catchments revealed that while climate, topography, vegetation and land use were similar, the soils were different. The objective of this study was to examine the relationship between the concentration and chemical composition of DOC in stream waters and the nature of soils in the two catchments. Soil mapping determined that clayey soils formed on Cretaceous sediments (Cretaceous soils) occurred throughout both catchments, but that Redwater Catchment also contained a large area (39%) of sandy soils formed on Tertiary sediments (Tertiary soils). The concentration of DOC in forest floor leachate was high in both the Tertiary and Cretaceous areas; however, the concentration of DOC in water draining areas dominated by Tertiary soils was greater than that in water draining areas dominated by Cretaceous soils. Laboratory experiments showed that the Cretaceous soils had higher adsorption capacities for forest floor leachate DOC than the Tertiary soils. The difference in DOC concentrations of the streams was therefore attributed to the difference in adsorption capacity of catchment soils for DOC. Adsorption capacities of the soils were found to be a function of their clay contents and specific surface areas. Solid-state 13C nuclear magnetic resonance spectroscopy and pyrolysis-mass spectrometry were used to determine the chemical structure of DOC found in streams and forest floor leachate samples and that remaining in solution after interaction with soil. Chemistry of DOC in forest floor leachate was similar before and after interaction with soil, indicating no preferential adsorption of a particular type of carbon. Thus, differences between the chemical structure of stream DOC and forest floor leachate DOC could be attributed to microbial modifications during its movement through soils and into the streams, rather than losses by adsorption.