Sources and flowpaths of dissolved organic carbon during storms in two forested watersheds of the Precambrian Shield

Dissolved organic carbon (DOC) concentrations and export were studied in two small catchments in central Ontario to examine DOC sources and to assess the hypothesis that organic matter adjacent to the stream is a significant contributor of DOC during storms. Different DOC dynamics and exports were observed according to the depth of the riparian water table. In Harp 4-21, riparian flowpaths were predominantly through A and upper B soil horizons and riparian soils contributed between 73 and 84% of the stream DOC export during an autumn storm. In Harp 3A, riparian flowpaths were predominantly through lower B horizons. Consequently, riparian soils were less important and hillslopes contributed more than 50% of the stream DOC export in subcatchments without wetlands during storms. Wetlands and adjacent soils contributed significantly to DOC export in Harp 3A; 8% of the total catchment area exported 32 to 46% of the storm runoff DOC. DOC export dynamics in wetlands and riparian soils were distinctly different. In wetlands, transport was affected by leaching and flushing of DOC at the wetland surface leading to lower DOC concentrations with successive storms. In riparian soils, groundwater flowpaths were more important and stronger positive relationships between discharge and DOC concentration were observed. Precipitation, throughfall and stemflow were minor sources of stream DOC during storms and contributed less than 20% of the total export.     

Contrasting nutrient exports from a forested and an agricultural catchment in south-eastern Australia

Dissolved organic carbon (DOC) and total and inorganic nitrogen and phosphorus concentrations were determined over 3 years in headwater streams draining two adjacent catchments. The catchments are currently under different land use; pasture/grazing vs plantation forestry. The objectives of the work were to quantify C and nutrient export from these landuses and elucidate the factors regulating export. In both catchments, stream water dissolved inorganic nutrient concentrations exhibited strong seasonal variations. Concentrations were highest during runoff events in late summer and autumn and rapidly declined as discharge increased during winter and spring. The annual variation of stream water N and P concentrations indicated that these nutrients accumulated in the catchments during dry summer periods and were flushed to the streams during autumn storm events. By contrast, stream water DOC concentrations did not exhibit seasonal variation. Higher DOC and NO₃ ⁻ concentrations were observed in the stream of the forest catchment, reflecting greater input and subsequent breakdown of leaf-litter in the forest catchment. Annual export of DOC was lower from the forested catchment due to the reduced discharge from this catchment. In contrast however, annual export of nitrate was higher from the forest catchment suggesting that there was an additional NO₃ ⁻ source or reduction of a NO₃ ⁻ sink. We hypothesize that the denitrification capacity of the forested catchment has been significantly reduced as a consequence of increased evapotranspiration and subsequent decrease in streamflow and associated reduction in the near stream saturated area.     

Export of dissolved organic carbon and nitrogen from Gleysol dominated catchments – the significance of water flow paths

In this study, we estimated whether changes in hydrological pathwaysduring storms could explain the large temporal variations of dissolvedorganic carbon (DOC) and nitrogen (DON) in the runoff of threecatchments: a forest and a grassland sub-catchment of 1600m² delineated by trenches, and a headwater catchment of 0.7km².The average annual DOC export from the sub-catchments was 185 kg DOCha^–1 y^–1 for the forest, 108 kg DOCha^–1 y^–1 for the grassland and 84 kgDOC ha^–1 y^–1 for the headwatercatchment. DON was the major form of the dissolved N in soil and streamwater. DON export from all catchments was approximately 6 kg Nha^–1 y^–1, which corresponded to 60% ofthe total N export and to 50% of the ambient wet N deposition. DOC andDON concentrations in weekly samples of stream water were positivelycorrelated with discharge. During individual storms, concentrations andproperties of DOC and DON changed drastically. In all catchments, DOCconcentrations increased by 6 to 7 mg DOC l^–1 comparedto base flow, with the largest relative increment in the headwatercatchment (+350%). Concentrations of DON, hydrolysable amino acids, andphenolics showed comparable increases, whereas the proportion ofcarbohydrates in DOC decreased at peak flow. Prediction of DOC and DONconcentrations by an end-member mixing analysis (EMMA) on the base ofinorganic water chemistry showed that changes in water flow pathslargely explained these temporal variability. According to the EMMA, thecontribution of throughfall to the runoff peaked in the initial phase ofthe storm, while water from the subsoil dominated during base flow only.EMMA indicated that the contribution of the DOC and DON-rich topsoil washighest in the later stages of the storm, which explained the highestDOC and DON concentrations as the hydrograph receded. Discrepanciesbetween observed and predicted concentrations were largest for thereactive DOC compounds such as carbohydrates and phenolics. Theyoccurred at base flow and in the initial phase of storms. This suggeststhat other mechanisms such as in-stream processes or a time-variantrelease of DOC also played an important role.     

Stormflow Dynamics of Dissolved Organic Carbon and Total Dissolved Nitrogen in a Small Urban Watershed

We examined patterns of dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) loading to a small urban stream during baseflow and stormflow. We hypothesized that lower DOC and TDN contributions from impervious surfaces would dilute natural hydrologic flowpath (i.e., riparian) contributions during storm events in an urban watershed, resulting in lower concentrations of DOC and TDN during storms. We tested these hypotheses in a small urban watershed in Portland, Oregon, over a 3-month period during the spring of 2003. We compared baseflow and stormflow chemistry using Mann–Whitney tests (significant at p<0.05). We also applied a mass balance to the stream to compare the relative significance of impervious surface contributions versus riparian contributions of DOC and TDN. Results showed a significant increase in stream DOC concentrations during stormflows (median baseflow DOC = 2.00 mg l⁻¹ vs. median stormflow DOC = 3.46 mg l⁻¹). TDN streamwater concentrations, however, significantly decreased with stormflow (median baseflow TDN = 0.75 mg l⁻¹ vs. median stormflow TDN = 0.56 mg l⁻¹). During storms, remnant riparian areas contributed 70–74% of DOC export and 38–35% of TDN export to the stream. The observed pattern of increased DOC concentrations during stormflows in this urban watershed was similar to patterns found in previous studies of forested watersheds. Results for TDN indicated that there were relatively high baseflow nitrogen concentrations in the lower watershed that may have partially masked the remnant riparian signal during stormflows. Remnant riparian areas were a major source of DOC and TDN to the stream during storms. These results suggest the importance of preserving near-stream riparian areas in cities to maintain ambient carbon and nitrogen source contributions to urban streams.     

A stormflow/baseflow comparison of dissolved organic matter concentrations and bioavailability in an Appalachian stream

Patterns of dissolved organic carbon (DOC) and nitrogen (DON) delivery were compared between times of stormflow and baseflow in Paine Run, an Appalachian stream draining a 12.4 km² forested catchment in the Shenandoah National Park (SNP), Virginia. The potential in-stream ecological impact of altered concentrations and/or chemical composition of DOM during storms also was examined, using standardized bacterial bioassays. DOC and DON concentrations in Paine Run were consistently low during baseflow and did not show a seasonal pattern. During storms however, mean DOC and DON concentrations approximately doubled, with maximum concentrations occurring on the rising limb of storm hydrographs. The rapid response of DOM concentration to changes in flow suggests a near-stream or in-stream source of DOM during storms. Stormflow (4% of the time, 36% of the annual discharge) contributed >50% of DOC, DON and NO₃ ^– flux in Paine Run during 1997. In laboratory bacterial bioassays, growth rate constants were higher on Paine Run stormflow water than on baseflow water, but the fraction of total DOM which was bioavailable was not significantly different. The fraction of the total stream DOC pool taken up by water column bacteria was estimated to increase from 0.03 ± 0.02% h^–1 during baseflow, to 0.15 ± 0.04% h^–1 during storms. This uptake rate would have a minimal effect on bulk DOM concentrations in Paine Run, but storms may still have considerable impact on the bacterial stream communities by mobilizing them into the water column and by supplying a pulse of DOM.     

Seasonal and hydrologic drivers of dissolved organic matter and nutrients in the upper Kuparuk River, Alaskan Arctic

As the planet warms, widespread changes in Arctic hydrology and biogeochemistry have been documented and these changes are expected to accelerate in the future. Improved understanding of the behavior of water-borne constituents in Arctic rivers with varying hydrologic conditions, including seasonal variations in discharge?Cconcentration relationships, will improve our ability to anticipate future changes in biogeochemical budgets due to changing hydrology. We studied the relationship between seasonal water discharge and dissolved organic carbon and nitrogen (DOC and DON) and nutrient concentrations in the upper Kuparuk River, Arctic Alaska. Fluxes of most constituents were highest during initial snowmelt runoff in spring, indicating that this historically under-studied period contributes significantly to total annual export. In particular, the initial snowmelt period (the stream is completely frozen during the winter) accounted for upwards of 35% of total export of DOC and DON estimated for the entire study period. DOC and DON concentrations were positively correlated with discharge whereas nitrate (NO₃ ^?) and silicate were negatively correlated with discharge throughout the study. However, discharge-specific DOC and DON concentrations (i.e. concentrations compared at the same discharge level) decreased over the summer whereas discharge-specific concentrations of NO₃ ^? and silicate increased. Soluble reactive phosphorus (SRP) and ammonium (NH₄ ⁺) were negatively correlated with discharge during the spring thaw, but were less predictable with respect to discharge thereafter. These data provide valuable information on how Arctic watershed biogeochemistry will be affected by future changes in temperature, snowfall, and rainfall in the Arctic. In particular, our results add to a growing body of research showing that nutrient export per unit of stream discharge, particularly NO₃ ^?, is increasing in the Arctic.     

The Role of Stream Water Carbon Dynamics and Export in the Carbon Balance of a Tropical Seasonal Rainforest,Southwest China

A two-year study (2009 ∼ 2010) was carried out to investigate the dynamics of different carbon (C) forms, and the role of stream export in the C balance of a 23.4-ha headwater catchment in a tropical seasonal rainforest at Xishuangbanna (XSBN), southwest China. The seasonal volumetric weighted mean (VWM) concentrations of total inorganic C (TIC) and dissolved inorganic C (DIC) were higher, and particulate inorganic C (PIC) and organic C (POC) were lower, in the dry season than the rainy season, while the VWM concentrations of total organic C (TOC) and dissolved organic C (DOC) were similar between seasons. With increased monthly stream discharge and stream water temperature (SWT), only TIC and DIC concentrations decreased significantly. The most important C form in stream export was DIC, accounting for 51.8% of the total C (TC) export; DOC, POC, and PIC accounted for 21.8%, 14.9%, and 11.5% of the TC export, respectively. Dynamics of C flux were closely related to stream discharge, with the greatest export during the rainy season. C export in the headwater stream was 47.1 kg C ha⁻¹ yr⁻¹, about 2.85% of the annual net ecosystem exchange. This finding indicates that stream export represented a minor contribution to the C balance in this tropical seasonal rainforest.     

Seasonal variability of dissolved organic carbon ina Mediterranean stream

The seasonal variability of dissolved organic carbon(DOC) flux in a Mediterranean stream subjected todischarges of wide range of intensities and variabledry period was studied as a function of the hydrologicconditions, and the relationship between surface andsubsurface (hyporheic and groundwater) DOCconcentration. DOC concentration in stream water(2.6 mg l^–1 ±1.5 SD) was higher thangroundwater (1.3 mg l^–1 ± 1.2 SD) and lower thanhyporheic water (3.8 mg l^–1 ±1.7 SD),suggesting that, at baseflow, stream DOC concentrationincreases when groundwater discharges through thehyporheic zone. Storms contributed to 39% of annualwater export and to 52% of the total annual DOCexport (220 kg km^–2). A positive relationship wasobserved between Discharge (Q) and stream DOCconcentration. Discharge explained only 40% of theannual variance in stream DOC, but explained up to93% of the variance within floods. The rate of streamDOC changes with discharge change during storms (dDOC/dQ), ranged between 0 and 0.0045 C mgl^–1 s l^–1, with minimum values during Springand Summer, and maxima values in Fall and Winter.These dynamics suggest that storm inputs ofterrigenous DOC vary between seasons. During floods inthe dormant season, DOC recession curves were alwayssteeper than discharge decline, suggesting shortflushing of DOC from the leaching of fresh detritusstored in the riparian zone.     

Sources of nitrate export during rain-on-snow events at forested catchments

Rain-on-snow (ROS) events are major drivers of nitrate (NO₃-N) export from seasonally snow-covered forested catchments and may cause episodic declines in stream pH. High intensity monitoring of throughfall, snow pack and stream water draining two proximal catchments (Harp 3A and Harp 6A) with very different NO₃-N export revealed that a very small percentage of ROS-induced stream discharge originates from throughfall and melting snow (new water; average = 6.4 %). However, this new water has a very high concentration of NO₃-N (throughfall/snowmelt average = 498 μg/L) compared with baseflow (average = 7.3 μg/L in Harp 6A; average = 41 μg/L in Harp 3A) and as a result, throughfall and snowmelt contribute the majority of NO₃-N export (average = 62 %) during ROS events. In contrast, concentrations of sulphate, dissolved organic carbon and calcium in rain and snowpack are similar to baseflow and therefore ROS-induced declines in pH (often to below pH 6.0) are attributed entirely to increases in NO₃-N concentration. Differences in absolute magnitude of ROS NO₃-N export between catchments are explained through differences in baseflow NO₃-N concentrations. The frequency and magnitude of ROS events in this region are affected by both NO₃-N deposition and winter temperature, and thus the impact of these events in the future depends on changes in both atmospheric deposition and winter climate.     

Seasonal Variations of Dissolved Nitrogen and DOC:DON Ratios in an Intermittent Mediterranean Stream

Seasonal variations of dissolved inorganic nitrogen (DIN) (NO₃–N and NH₄–N) and dissolved organic nitrogen (DON) were determined in Fuirosos, an intermittent stream draining an unpolluted Mediterranean forested catchment (10.5 km²) in Catalonia (Spain). The influence of flow on streamwater concentrations and seasonal differences in quality and origin of dissolved organic matter, inferred from dissolved organic carbon to nitrogen ratios (DOC:DON ratios), were examined. During baseflow conditions, nitrate and ammonium had opposite behaviour, probably controlled by biological processes such as vegetation uptake and mineralization activity. DON concentrations did not have a seasonal trend. During storms, nitrate and DON increased by several times but discharge was not a good predictor of nutrient concentrations. DOC:DON ratios in streamwater were around 26, except during the months following drought when DOC:DON ratios ranged between 42 and 20 during baseflow and stormflow conditions, respectively. Annual N export during 2000–2001 was 70 kg km⁻¹ year⁻¹, of which 75% was delivered during stormflow. The relative contribution of nitrogen forms to the total annual export was 57, 35 and 8% as NO₃–N, DON and NH₄–N, respectively.     

Hydrologic Drivers and Seasonality of Dissolved Organic Carbon Concentration, Nitrogen Content, Bioavailability, and Export in a Forested New England Stream

We present the results of a full year of high-resolution monitoring of hydrologic event-driven export of stream dissolved organic matter (DOM) from the forested Bigelow Brook watershed in Harvard Forest, Massachusetts, USA. A combination of in situ fluorescent dissolved organic matter (FDOM) measurement, grab samples, and bioassays was utilized. FDOM was identified as a strong indicator of concentration for dissolved organic carbon (DOC, r ² = 0.96), dissolved organic nitrogen (DON, r ² = 0.81), and bioavailable DOC (BDOC, r ² = 0.81). Relationships between FDOM and concentration were utilized to improve characterization of patterns of hydrological event-driven export and the quantification of annual export. This characterization was possible because DOM composition remained relatively consistent seasonally; however, a subtle shift to increased fluorescence per unit absorbance was observed for summer and fall seasons and percent BDOC did increase slightly with increasing concentrations. The majority of export occurred during pulsed hydrological events, so the greatest impact of bioavailable exports may be on downstream aquatic ecosystems. Export from individual events was highly seasonal in nature with the highest flow weighted mean concentrations (DOC_FW) being observed in late summer and fall months, but the highest total export being observed for larger winter storms. Seasonal trends in DOC export coincide with weather driven changes in surface and subsurface flow paths, potential for depletion and rebuilding of a flushable soil organic matter pool, and the availability of terrestrial carbon sources such as leaf litter. Our approach and findings demonstrate the utility of high frequency FDOM measurement to improve estimates of intra-annual temporal trends of DOM export.     

Changes in the character of DOC in streams during storms in two Midwestern watersheds with contrasting land uses

Dissolved organic carbon (DOC) dynamics in streams is important, yet few studies focus on DOC dynamics in Midwestern streams during storms. In this study, stream DOC dynamics during storms in two Midwestern watersheds with contrasting land uses, the change in character of stream DOC during storms, and the usability of DOC as a hydrologic tracer in artificially drained landscapes of the Midwest are investigated. Major cation/DOC concentrations, and DOC specific UV absorbance (SUVA) and fluorescence index (FI) were monitored at 2–4 h intervals during three spring storms. Although DOC is less aromatic in the mixed land use watershed than in the agricultural watershed, land use has little impact on stream DOC concentration during storms. For both watersheds, DOC concentration follows discharge, and SUVA and FI values indicate an increase in stream DOC aromaticity and lignin content during storms. The comparison of DOC/major cation flushing dynamics indicates that DOC is mainly exported via overland flow/macropore flow. In both watersheds, the increase in DOC concentration in the streams during storms corresponds to a shift in the source of DOC from DOC originating from mineral soil layers of the soil profile at baseflow, to DOC originating from surficial soil layers richer in aromatic substances and lignin during storms. Results also suggest that DOC, SUVA and FI could be used as hydrologic tracers in artificially drained landscapes of the Midwest. These results underscore the importance of sampling streams for DOC during high flow periods in order to understand the fate of DOC in streams.     

Seasonal variation of DOC concentration and annual loss of DOC from an Atlantic blanket bog in South Western Ireland

This paper represents the first continuous dissolved organic carbon (DOC) record, measured in a stream draining an Atlantic blanket bog in South West Ireland for the calendar year 2007. At 30-min intervals, the DOC concentration was automatically measured using an in-stream spectroanalyser whose variation compared well with laboratory analysed samples taken by a 24-bottle auto-sampler. The concentration of DOC ranged from 2.7 to 11.5 mg L^?1 with higher values during the summer and lower values during the winter. A simple linear regression model of DOC concentration versus air temperature of the previous day was found, suggesting that temperature more than discharge was controlling the DOC concentration in the stream. The change in DOC concentration with storm events showed two patterns: (1) in the colder period: the DOC concentration seemed to be independent of changes in stream flow; (2) in the warmer period: the DOC concentration was found to rise with increases in stream flow on some occasions and to decrease with increasing stream flow on other occasions. The annual export of DOC for 2007 was 14.1 (±1.5) g C m^?2. This value was calculated using stream discharge data that were determined by continuously recorded measurements of stream height. The flux of DOC calculated with the 30-min sampling was compared with that calculated based on lower sampling frequencies. We found that sampling frequency of weekly or monthly were adequate to calculate the annual flux of DOC in our study site in 2007.     

Solute Sources in Stream Water during Consecutive Fall Storms in a Northern Hardwood Forest Watershed: A Combined Hydrological, Chemical and Isotopic Approach

Understanding the effects of climate change including precipitation patterns has important implications for evaluating the biogeochemical responses of watersheds. We focused on four storms in late summer and early fall that occurred after an exceptionally dry period in 2002. We analyzed not only the influence of these storms on episodic chemistry and the role of different water sources in affecting surface water chemistry, but also the relative contributions of these storms to annual biogeochemical mass balances. The study site was a well studied 135-ha watershed in the Adirondack Park of New York State (USA). Our analyses integrated measurements on hydrology, solute chemistry and the isotopic composition of NO₃⁻(δ¹⁵N and δ¹⁸O) and SO₄²⁻(δ³⁴S and δ¹⁸O) to evaluate how these storms affected surface water chemistry. Precipitation amounts varied among the storms (Storm 1: Sept. 14–18, 18.5 mm; Storm 2: Sept. 21–24, 33 mm; Storm 3: Sept. 27–29, 42.9 mm; Storm 4: Oct. 16–21, 67.6 mm). Among the four storms, there was an increase in water yields from 2 to 14%. These water yields were much less than in studies of storms in previous years at this same watershed when antecedent moisture conditions were higher. In the current study, early storms resulted in relatively small changes in water chemistry. With progressive storms the changes in water chemistry became more marked with particularly major changes in C_b (sum of base cations), Si, NO₃⁻, and SO₄²⁻, DOC and pH. Analyses of the relationships between Si, DOC, discharge and water table height clearly indicated that there was a decrease in ground water contributions (i.e., lower Si concentrations and higher DOC concentrations) as the watershed wetness increased with storm succession. The marked changes in chemistry were also reflected in changes in the isotopic composition of SO₄²⁻ and NO₃⁻. There was a strong inverse relationship between SO₄²⁻ concentrations and δ³⁴S values suggesting the importance of S biogeochemical redox processes in contributing to SO₄²⁻ export. The isotopic composition of NO₃⁻ in stream water indicated that this N had been microbially processed. Linkages between SO₄²⁻ and DOC concentrations suggest that wetlands were major sources of these solutes to drainage waters while the chemical and isotopic response of NO₃⁻ suggested that upland sources were more important. Although these late summer and fall storms did not play a major role in the overall annual mass balances of solutes for this watershed, these events had distinctive chemistry including depressed pH and therefore have important consequences to watershed processes such as episodic acidification, and the linkage of these processes to climate change.     

Influence of drought-induced acidification on the mobility of dissolved organic carbon in peat soils

A strong relationship between dissolved organic carbon (DOC) and sulphate (SO₄^2?) dynamics under drought conditions has been revealed from analysis of a 10‐year time series (1993–2002). Soil solution from a blanket peat at 10 cm depth and stream water were collected at biweekly and weekly intervals, respectively, by the Environmental Change Network at Moor House‐Upper Teesdale National Nature Reserve in the North Pennine uplands of Britain. DOC concentrations in soil solution and stream water were closely coupled, displaying a strong seasonal cycle with lowest concentrations in early spring and highest in late summer/early autumn. Soil solution DOC correlated strongly with seasonal variations in soil temperature at the same depth 4‐weeks prior to sampling. Deviation from this relationship was seen, however, in years with significant water table drawdown (>?25 cm), such that DOC concentrations were up to 60% lower than expected. Periods of drought also resulted in the release of SO₄^2?, because of the oxidation of inorganic/organic sulphur stored in the peat, which was accompanied by a decrease in pH and increase in ionic strength. As both pH and ionic strength are known to control the solubility of DOC, inclusion of a function to account for DOC suppression because of drought‐induced acidification accounted for more of the variability of DOC in soil solution (R²=0.81) than temperature alone (R²=0.58). This statistical model of peat soil solution DOC at 10 cm depth was extended to reproduce 74% of the variation in stream DOC over this period. Analysis of annual budgets showed that the soil was the main source of SO₄^2? during droughts, while atmospheric deposition was the main source in other years. Mass balance calculations also showed that most of the DOC originated from the peat. The DOC flux was also lower in the drought years of 1994 and 1995, reflecting low DOC concentrations in soil and stream water. The analysis presented in this paper suggests that lower concentrations of DOC in both soil and stream waters during drought years can be explained in terms of drought‐induced acidification. As future climate change scenarios suggest an increase in the magnitude and frequency of drought events, these results imply potential for a related increase in DOC suppression by episodic acidification.     

Leaf Litter as a Source of Dissolved Organic Carbon in Streams

Dissolved organic carbon (DOC) is an abundant form of organic matter in stream ecosystems. Most research has focused on the watershed as the source of DOC in streams, but DOC also comes from leaching of organic matter stored in the stream channel. We used a whole-ecosystem experimental approach to assess the significance of leaching of organic matter in the channel as a source of DOC in a headwater stream. Inputs of leaf litter were excluded from a forested Appalachian headwater stream for 3 years. Stream-water concentration, export, and instream generation of DOC were reduced in the litter-excluded stream as compared with a nearby untreated reference stream. The proportion of high molecular weight (HMW) DOC (more than 10,000 daltons) in stream water was not altered by litter exclusion. Mean DOC concentration in stream water was directly related to benthic leaf-litter standing stock. Instream generation of DOC from leaf litter stored in the stream channel contributes approximately 30% of daily DOC exports in this forested headwater stream. This source of DOC is greatest during autumn and winter and least during spring and summer. It is higher during increasing discharge than during base flow. We conclude that elimination of litter inputs from a forested headwater stream has altered the biogeochemistry of DOC in this ecosystem. Received 2 September 1997; accepted 27 January 1998.     

Long-term trends in dissolved organic carbon concentration: a cautionary note

Dissolved organic carbon (DOC) plays an important role in surface water chemistry and ecology and trends in DOC concentration have been also associated with shifts in terrestrial carbon pools. Numerous studies have reported long-term trends in DOC concentration; however, some studies consider changes in average measured DOC whereas other compute discharge weighted concentrations. Because of differences in reporting methods and variable record lengths it is difficult to compare results among studies and make regional generalizations. Furthermore, changes in stream discharge may impact long-term trends in DOC concentration and the potentially subtle effect of shifts in stream flow may be missed if only measured DOC concentrations are considered. In this study we compare trends in volume-weighted vs. average measured DOC concentration between 1980 and 2001 at seven headwater streams in south-central Ontario, Canada that vary in wetland coverage and DOC (22-year mean vol. wt.) from 3.4 to 10.6 mg l⁻¹. On average, annual measured DOC concentrations were 13–34% higher than volume-weighted values, but differences of up to 290% occurred in certain years. Estimates of DOC flux were correspondingly higher using measured concentration values. Both measured and volume-weighted DOC concentrations increased significantly between 1980 and 2001, but slopes were larger in measured data (0.04–0.35 mg l⁻¹ year⁻¹ compared with 0.05–0.15 mg l⁻¹ year⁻¹) and proportional increases at the most wetland-influenced sites ranged from 32 to 43% in volume-weighted DOC and from 52 to 75% in measured DOC. In contrast, DOC flux did not change with time when estimated using either method, because of the predominant influence of stream flow on DOC export. Our results indicate that changes in stream flow have an important impact on trends in DOC concentration, and extrapolation of trend results from one region to another should be made cautiously and consider methodological and reporting differences among sites.     

Soil carbon and litter development along a reconstructed biodiverse forest chronosequence of South-Western Australia

We performed a meta-data analysis to investigate the importance of event based fluxes to DOC export from forested watersheds. A total of 30 small eastern United States forested watersheds with no wetland component, with a total of 5,176 DOC and accompanying discharge measurements were used in this analysis. There is a clear increase in DOC concentration during hydrologic events (storms and snow melt) that follows a power relationship. We estimate that 86% of DOC is exported during events. The majority (70%) of this event based DOC flux occurs during the rising hydrograph and during large events. Events with a discharge greater than 1.38 cm day^?1 make up only 4.8% of the annual hydrograph, yet are responsible for 57% of annual DOC flux. The relationship between event discharge and both DOC concentration and flux is also regulated by temperature and antecedent conditions, with a larger response in both fluxes and concentrations to events during warmer periods and periods where the preceding discharge was low. The temperature relationship also shows seasonality indicating a potential link to the size or reactivity of watershed OM pools. The 86% of DOC lost during events represents a conservative estimate of the amount of allochthonous forested DOC transported laterally to streams. Future research on watershed cycling of DOC should take into account the importance of events in regulating the transport of DOC to downstream ecosystems, determine the relative importance of abiotic versus biotic processes for the temperature regulation of event-associated DOC fluxes, and elucidate the interactions between processes that respond to climate on event versus longer time scales.     

A long-term perspective of dissolved organic carbon transport in Sycamore Creek, Arizona, USA

Dissolved organic carbon (DOC) dynamics were examined over five years (1989–1993) in Sycamore Creek, a Sonoran Desert stream, specifically focusing on DOC concentration in surface and hyporheic waters, and rates of export. In 1989 and 1990, the years of lowest stream discharge (0.08 and 0.04 m³ s^–1 annual mean of daily discharge, respectively), DOC was high, averaging 7.37 and 6.22 mgC l^–1 (weighted annual means). In contrast, from 1991 through 1993, a period of increased flow (1.1, 1.2 and 4.3 m³ s^–1), concentration was significantly lower (P<0.001) with annual mean concentrations of 3.54, 3.49 and 3.39 mgC l^–1. Concentration exhibited little spatial variation between two sampling stations located 6 km apart along the mainstem or between surface and hyporheic waters. Annual export of DOC from Sycamore Creek varied 100-fold over the five-year period from a mean rate of only 24 kgC d^–1 in 1990 to 2100 kgC d^–1 in 1993. Ninety percent of DOC was exported by flows greater than 2.8 m³ s^–1, and 50% during flows greater than 27 m³ s^–1; flows of 2.8 and 24 m³ s^–1 occurred only 9 and 1% of the time. The export of organic matter in Sycamore Creek appears to be coupled to El Niño-Southern Oscillation phenomena. The years of highest export, 1991–1993, had El Niño conditions while 1989 and 1990 had medial conditions.     

Dissolved organic carbon and its utilization in a riverine wetland ecosystem

Variations in dissolved organic carbon (DOC) concentrations of surface waters and subsurface interstitial groundwater of riparian and wetland soils to 1.2 m depth were evaluated in a riverine wetland ecosystem over one year. DOC was monitored at seven sites within the wetland pond, two sites on the inflow stream, and one site on the outflow stream. Surface concentrations in the inflow stream ranged from 0.74 to 11.6 mg C L^–1 and those of the outflow from 2.1 to 8.0 mg C L^–1 Average DOC from stream floodplain hydrosoils (3.1 to 32.1 mg C L^–1 was greater than DOC from the sediments below the stream channel (1.6 to 6.8 mg C L^–1 Surface DOC within the wetland varied seasonally, with greatest fluctuations in concentrations through the summer and autumn (range 4.8 to 32.6 mg C L^–1 ) during intensive macrophyte growth and bacterial production. DOC was less variable during the winter months (1.7 to 3.3 mg C L^–1 Within the wetland pond, average DOC concentrations (7.1 to 48.2 mg C L^–1) in the subsurface waters were significantly greater (p < 0.05) than average surface concentrations. The microbial availability of surface and subsurface DOC to bacteria was evaluated from losses of DOC by wetland bacteria grown on the DOC. Bacterial growth efficiencies ranged from 5 to 20% and were negatively correlated to the percentage of DOC removed by bacteria (r²=0.93). Throughout the ecosystem, DOC concentrations were greatest in the subsurface waters, but at most depths this DOC was a less suitable substrate than surface DOC for utilization by bacteria.