Temporal and spatial distributions of dissolved organic carbon and nitrogen in two small lakes on the Southwestern China Plateau

Temporal and spatial distributions of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), chlorophyll-a and inorganic nitrogen were investigated in two small mountainous lakes (Lake Hongfeng and Baihua), on the Southwestern China Plateau, based on almost 2 years’ field observation. DOC concentrations ranged from 163 μM to 248 μM in Lake Hongfeng and from 143 μM to 308 μM in Lake Baihua, respectively, during the study period. DON concentrations ranged from 7 μM to 26 μM in Lake Hongfeng and from 14 μM to 47 μM in Lake Baihua. DOC showed vertical heterogeneity with higher concentrations in the epilimnion than in the hypolimnion during the stratification period. The DON concentration profiles appeared to be more variable than the DOC profiles. Apparent DON maxima occurred in the upper layer of water. In Lake Hongfeng, DOC concentration in the surface water was highest at the end of spring and early summer. DON concentration was 2–5 μM higher in May 2003 and in June 2004 than in adjacent months. DOC and chlorophyll-a concentrations were significantly correlated (r = 0.79, P < 0.05). The period of highest concentrations of DOC in Lake Hongfeng was also the season of concentrated rainfall. Algae activity and allochthonous input might result in an increase of DOC and DON concentrations together. In Lake Baihua, the maximum concentrations of DOC and DON in the surface water occurred simultaneously in May 2003 and February 2004. DOC concentrations were significantly correlated with DON (r = 0.90, P < 0.01), indicating the common sources. Allochthonous input, biological processes, stratification and mixing were the most important factors controlling the distributions and cycling of dissolved organic matter (DOM) and inorganic nitrogen in these two lakes. Inference from the corresponding vertical distributions of DOM and inorganic nitrogen indicated that DOM played potential roles in the internal loading of nitrogen and metabolism in the water body in these small lakes. The carbon/nitrogen (C/N) ratio showed a potential significance for tracing the source and biogeochemical processes of DOM in the lakes. These results are of significance in the further understanding of biogeochemical cycling and environmental effects of DOM and nitrogen in lake ecosystems.     

Factors controlling concentration, export, and decomposition of dissolved organic nutrients in the Everglades of Florida

Water draining from the Everglades marshes of southern Florida containshigh concentrations of dissolved organic C (DOC), N (DON), and in somelocations, P (DOP). These dissolved organic nutrients carry over 90% of the Nand organic C, and about 25% of the P exported downstream in the Everglades.Ourobjectives were to describe the most important aspects of the origin and fateofdissolved organic matter (DOM) in the Everglades, and to describe the processescontrolling its concentration and export. Concentrations of dissolved organicnutrients are influenced by local plant production, decomposition, and sorptionequilibrium with peat. The drained peat soils of the Everglades AgriculturalArea and the more productive marshes of the northern Everglades produce some ofthe highest concentrations of DOC and DON in the Everglades watershed. Inportions of the marshes of the northern Everglades, P enrichment was correlatedwith higher local DOC and DON concentrations and greater production of solubleplant matter. Microbial degradation of Everglades DOM was very slow; less than10% of the DOC was lost after 6 months of incubation in the laboratory andsupplements of inorganic nutrients failed to speed the decomposition. Exposureto solar radiation increased the subsequent decay rate of the remaining DOC(25%in 6 mo.). Solar radiation alone mineralized 20.5% of the DOC, 7%of the DON, and degraded about 50% of the humic substances over 21 days insterile porewater samples and thus degraded DOM faster than microbialdegradation. The humic substances appeared to inhibit biodegradation of theother fractions of the DOC since hydrophilic organic acids decomposed fasterwhen isolated from the humic substances.The fate of DOC and DON is closely linked as indicated by a generally narrowrange of C/N ratios. In contrast, high concentrations of DOP were associatedwith P enrichment (at least in pore water). The DOC was composed of about 50%humic substances, 33% hydrophilic acids, and 15% hydrophilic neutralsubstances,typical of DOC from other environments, despite the fact that it originatesfroma neutral to slightly alkaline peatland. Despite high exports of DON (3.9g m^–2 y^–1 from one area), themarshes of the northern Everglades are a sink for DON on a landscape scale. Theagricultural fields of the Everglades Agricultural Area, however, exported netquantities of DON. High concentrations of DOC desorbed from the agriculturalsoils when water with no DOC was added. Sorption experiments indicated thathighconcentrations of dissolved organic matter flowing into the marshes from theEverglades Agricultural Area could suppress the further desorption ofadditionalsoluble organic matter through physicochemical mechanisms. While biologicalfactors, plant production and microbial decomposition are important inproducingpotentially soluble organic nutrients, physicochemical sorption equilibria,hydrology, and degradation by solar radiation are also likely to control theexport of this material on the landscape scale.     

Fluorescence characteristics and biodegradability of dissolved organic matter in forest and wetland soils from coastal temperate watersheds in southeast Alaska

Understanding how the concentration and chemical quality of dissolved organic matter (DOM) varies in soils is critical because DOM influences an array of biological, chemical, and physical processes. We used PARAFAC modeling of excitation–emission fluorescence spectroscopy, specific UV absorbance (SUVA₂₅₄) and biodegradable dissolved organic carbon (BDOC) incubations to investigate the chemical quality of DOM in soil water collected from 25 cm piezometers in four different wetland and forest soils: bog, forested wetland, fen and upland forest. There were significant differences in soil solution concentrations of dissolved organic C, N, and P, DOC:DON ratios, SUVA₂₅₄ and BDOC among the four soil types. Throughout the sampling period, average DOC concentrations in the four soil types ranged from 9–32 mg C l⁻¹ and between 23–42% of the DOC was biodegradable. Seasonal patterns in dissolved nutrient concentrations and BDOC were observed in the three wetland types suggesting strong biotic controls over DOM concentrations in wetland soils. PARAFAC modeling of excitation–emission fluorescence spectroscopy showed that protein-like fluorescence was positively correlated (r ² = 0.82; P < 0.001) with BDOC for all soil types taken together. This finding indicates that PARAFAC modeling may substantially improve the ability to predict BDOC in natural environments. Coincident measurements of DOM concentrations, BDOC and PARAFAC modeling confirmed that the four soil types contain DOM with distinct chemical properties and have unique fluorescent fingerprints. DOM inputs to streams from the four soil types therefore have the potential to alter stream biogeochemical processes differently by influencing temporal patterns in stream heterotrophic productivity.     

Characterization of Nanming River (southwestern China) sewerage-impacted pollution using an excitation-emission matrix and PARAFAC

Nanming River, the largest urban river in Guizhou Province, southwestern China plateau, has been severely polluted for decades. This study characterizes the organic materials and their sources in the upstream and downstream waters by dissolved organic carbon (DOC), excitation emission matrix (EEM) spectroscopy, parallel factor (PARAFAC) analysis and photo-microbial experiments. DOC concentrations were low (47–120 μM C) upstream and relatively high (146–462 μM C) downstream. The PARAFAC studies on the sample EEM spectra demonstrated that the upstream dissolved organic matter (DOM) was mostly composed of one component that had a fulvic acid-like substance; downstream DOM was composed of two components with mixtures of tryptophan-like and fulvic acid-like substances. From the results of the sewerage drainage samples collected along the bank of the river, it is evident that both household detergent-like and protein-like or tryptophan-like substances are predominantly present, indicating that untreated sewerage effluents are the major sources of organic matter pollution in Nanming River. The degradation experiments conducted on river, sewerage drainage and commercial detergent samples demonstrated that the detergent-like and tryptophan-like substances are both photochemically and microbiologically more decomposable than fulvic acid-like materials under sunlight and dark incubations. These results suggest that the input of the untreated sewerage effluents along the streams is the major pollution source in Nanming River, and the fluorescent DOM was efficiently affected by both photochemical and microbial processes.     

Stream dissolved organic matter bioavailability and composition in watersheds underlain with discontinuous permafrost

We examined the impact of permafrost on dissolved organic matter (DOM) composition in Caribou-Poker Creeks Research Watershed (CPCRW), a watershed underlain with discontinuous permafrost, in interior Alaska. We analyzed long term data from watersheds underlain with varying degrees of permafrost, sampled springs and thermokarsts, used fluorescence spectroscopy, and measured the bioavailabity of dissolved organic carbon (DOC). Permafrost driven patterns in hydrology and vegetation influenced DOM patterns in streams, with the stream draining the high permafrost watershed having higher DOC and dissolved organic nitrogen (DON) concentrations, higher DOC:DON and greater specific ultraviolet absorbance (SUVA) than the streams draining the low and medium permafrost watersheds. Streams, springs and thermokarsts exhibited a wide range of DOC and DON concentrations (1.5–37.5 mgC/L and 0.14–1.26 mgN/L, respectively), DOC:DON (7.1–42.8) and SUVA (1.5–4.7 L mgC⁻¹ m⁻¹). All sites had a high proportion of humic components, a low proportion of protein components, and a low fluorescence index value (1.3–1.4), generally consistent with terrestrially derived DOM. Principal component analysis revealed distinct groups in our fluorescence data determined by diagenetic processing and DOM source. The proportion of bioavailable DOC ranged from 2 to 35%, with the proportion of tyrosine- and tryptophan-like fluorophores in the DOM being a major predictor of DOC loss (p < 0.05, R ² = 0.99). Our results indicate that the degradation of permafrost in CPCRW will result in a decrease in DOC and DON concentrations, a decline in DOC:DON, and a reduction in SUVA, possibly accompanied by a change in the proportion of bioavailable DOC.     

Distribution of dissolved organic carbon and nitrogen in a coral reef

Dissolved organic matter (DOM) concentrations in a fringing coral reef were measured for both carbon and nitrogen with the analytical technique of high-temperature catalytic oxidation. Because of high precision of the analytical system, not only the concentrations of dissolved organic carbon and nitrogen (DOC and DON, respectively) but the C:N ratio was also determined from the distribution of DOC and DON concentrations. The observed concentrations of DOC and DON ranged 57–76 and 3.8–5.6 μmol l⁻¹, respectively. The C:N ratios of the DOM that was produced on the reef flat were very similar between seagrass- and coral-dominated areas; the C:N ratio was 10 on average. The C:N ratio of DOM was significantly higher than that of particulate organic matter (POM) that was produced on the reef flat. Production rates of DOC were measured on the reef flat during stagnant periods and accounted for 3–7% of the net primary production, depending on the sampling site. The production rate of DON was estimated to be 10–30% of the net uptake of dissolved inorganic N in the reef community. Considering that the DOM and POM concentrations were not correlated with each other, a major source of the reef-derived DOM may be the benthic community and not POM such as phytoplankton. It was concluded that a widely distributed benthic community in the coral reef released C-rich DOM to the overlying seawater, conserving N in the community.     

Chemical Characteristics and Origin of Dissolved Organic Matter in the Yukon River

Monthly (or bi-weekly) water samples were collected from the Yukon River, one of the largest rivers in North America, at a station near the US Geological Survey Stevens Village hydrological station, Alaska from May to September 2002, to examine the quantity and quality of dissolved organic matter (DOM) and its seasonal variations. DOM was further size fractionated into high molecular weight (HMW or colloidal, 1 kDa–0.45 μm) and low molecular weight (LMW, <1 kDa) fractions. Dissolved organic carbon (DOC), colored dissolved organic matter (C-DOM) and total dissolved carbohydrate (TCHO) species were measured in the size fractionated DOM samples. Concentrations of DOC were as high as 2830 μmol-C l⁻¹ during the spring breakup in May and decreased significantly to 508–558 μmol-C l⁻¹ during open-water season (June–September). Within the DOC pool, up to 85% was in the colloidal fraction (1 kDa–0.45 μm) in early May. As DOC concentration decreased, this colloidal portion remained high (70–85% of the bulk DOC) throughout the sampling season. Concentrations of TCHO, including monosaccharides (MCHO) and polysaccharides (PCHO), varied from 722 μmol-C l⁻¹ in May to 129 μmol-C l⁻¹ in September, which comprised a fairly constant portion of bulk DOC (24±2%). Within the TCHO pool, the MCHO/TCHO ratio consistently increased from May to September. The C-DOM/DOM ratio and the size fractionated DOM increased from May to September, indicating that DOM draining into the Yukon River contained increased amounts of humified materials, likely related to a greater soil leaching efficiency in summer. The average composition of DOM was 76% pedogenic humic matter and 24% aquagenic CHO. Characteristics of soil-derived humic substances and low chlorophyll-a concentrations support a dominance of terrestrial DOM in Yukon River waters.     

Organic Carbon Composition and Oxygen Metabolism across a Gradient of Seasonally Inundated Limesink and Riparian Wetlands in the Southeast Coastal Plain,USA

A set of three relatively pristine seasonally inundated limesink wetlands and one riparian wetland was studied over a 4–6 month long inundation period in 2001. Patterns in organic matter properties and oxygen consumption in the water column followed a previously documented ecological gradient based on soil composition, vegetation type, and canopy cover. The full canopy, cypress-gum swamp had the highest mean concentrations of dissolved organic carbon (DOC; 26.2 mg/l) and dissolved lignin (sum 6; 299 μg/l) with lower concentrations observed in the partial canopy, cypress savanna (22.0 mg/l DOC; 252 μg/l sum 6) and the open marsh savanna (20.6 mg/l DOC; 135 μg/l sum 6), respectively. During the inundation period, DOC increased in concentration, dissolved lignin decreased, and δ¹³C shifted to more positive values which collectively indicate a large reduction in the percentage of aromatic carbon during the inundation period. All wetlands had very high concentrations of organic matter, yet microbial oxygen consumption was almost always stimulated by the addition of glucose rather than inorganic nutrients. Stimulation by glucose suggests that there were very small pools of highly bioavailable forms of DOC in the wetlands. A larger pool of moderately bioavailable organic matter had the capacity to sustain microbial oxygen consumption rates under dark conditions for at least 15 d. During the inundation period, the cypress-gum swamp had the lowest average rates of whole water oxygen consumption (1.0 μM/h) with increasing rates observed in the cypress savanna (1.3 μM/h), marsh savanna (1.6 μM/h), and riparian wetland (1.9 μM/h), respectively. The lignin compositional fingerprint varied across the gradient of limesink wetlands, and was useful for identifying different sources of vascular plant-derived DOM. Vascular plant production, algal production, microbial respiration, and UV degradation are all important drivers of DOM cycling, and the consistencies observed in this initial assessment of seasonally inundated limesink wetlands suggest they vary in predictable ways across the ecological gradient.     

Dissolved Organic Matter Characteristics Across a Subtropical Wetland’s Landscape: Application of Optical Properties in the Assessment of Environmental Dynamics

Wetlands are known to be important sources of dissolved organic matter (DOM) to rivers and coastal environments. However, the environmental dynamics of DOM within wetlands have not been well documented on large spatial scales. To better assess DOM dynamics within large wetlands, we determined high resolution spatial distributions of dissolved organic carbon (DOC) concentrations and DOM quality by excitation–emission matrix spectroscopy combined with parallel factor analysis (EEM–PARAFAC) in a subtropical freshwater wetland, the Everglades, Florida, USA. DOC concentrations decreased from north to south along the general water flow path and were linearly correlated with chloride concentration, a tracer of water derived from the Everglades Agricultural Area (EAA), suggesting that agricultural activities are directly or indirectly a major source of DOM in the Everglades. The optical properties of DOM, however, also changed successively along the water flow path from high molecular weight, peat-soil and highly oxidized agricultural soil-derived DOM to the north, to lower molecular weight, biologically produced DOM to the south. These results suggest that even though DOC concentration seems to be distributed conservatively, DOM sources and diagenetic processing can be dynamic throughout wetland landscapes. As such, EEM–PARAFAC clearly revealed that humic-enriched DOM from the EAA is gradually replaced by microbial- and plant-derived DOM along the general water flow path, while additional humic-like contributions are added from marsh soils. Results presented here indicate that both hydrology and primary productivity are important drivers controlling DOM dynamics in large wetlands. The biogeochemical processes controlling the DOM composition are complex and merit further investigation.     

Impact of deforestation on solid and dissolved organic matter characteristics of tropical peat forests: implications for carbon release

This study compares the organic chemistry of peat beneath one of last remaining pristine tropical peat forests in Southeast Asia with a neighbouring peat dome that has been deforested, but not intentionally drained, in the Belait district of Brunei Darussalam, Borneo. We characterized the solid and dissolved organic matter collected from the two domes, through a combination of methods including elemental analysis, phenolic content and Fourier transform infrared spectroscopy (FTIR) investigation of solid peat, as well as optical characterisation (absorbance, fluorescence) of dissolved organic matter (DOM). The peat had a high content of lignin, consistent with its origin from the Shorea albida trees on the domes. Dissolved organic carbon (DOC) concentration in the pore water was significantly greater in the deforested site (79.9 ± 5.5 mg l^?1) than the pristine site (62.2 ± 2.2 mg l^?1). The dissolved organic matter was richer in nitrogen and phenolics in the deforested site. The optical properties (Fluorescence Index) indicated a modification of DOM cycling in the deforested site (enhanced decomposition of the peat and fresh litter). Comparison of the solid peat composition between the two sites also suggests effects of deforestation: sulphur, nitrogen and phenolic contents were higher in the deforested site. Taken together, these observations are consistent with peat enhanced decomposition in the deforested site, even without engineered drainage.     

Do parafluvial zones have an impact in regulating river pollution? Spatial and temporal dynamics of nutrients,carbon, and bacteria in a large gravel bar of the Doubs River (France)

The changes in both physical and chemical properties of interstitial water were investigated within a large gravel bar to determine if the parafluvial zone was a hotspot for nutrient transformations in a lowland eutrophic river, the Doubs (Eastern France). Interstitial water was sampled in 30 piezometers along five transects across the gravel bar, surface water was sampled in main and chute channels. Five campaigns of sampling were performed among summer and winter. In both interstitial and surface samples, water chemistry (electrical conductivity, pH, chloride, dissolved oxygen concentrations—DO) and nutrient concentrations (nitrate—NO₃ ⁻, ammonium—NH₄ ⁺, soluble reactive phosphorus—SRP, dissolved organic carbon—DOC) were measured. Moreover, temperature, water level, sediment grain size distribution and total bacterial abundance were assessed along a flowpath through a lateral gravel bar of the Doubs River. Measurements of water table elevation in the bar, main and chute channels indicated that the parafluvial flowpath was perpendicular to the main channel. Very low changes in chloride concentration and electrical conductivity showed minor groundwater input along the flowpath. The parafluvial zone was 0.9 m thick under the mean piezometric level, hydraulic gradients along the flowpath were 0.3%, and the discharge of interstitial water through the bar calculated at low flow was 40.6 m³ day⁻¹. Most changes in interstitial nutrients occurred during the warm season, suggesting that biotic mechanisms occurred. Along the flowpath, DO, DOC, and bacterial abundance declined, while phosphate increased. Temporal trends of nitrate were less clear, exhibiting a slight increase during spring (organic matter biodegradation) and a decrease during summer (denitrification). Using the parafluvial discharge and nutrient concentrations of water infiltrating into and seeping from the gravel bar, the retention capacity of the bar was 171 gC day⁻¹ for DOC and 48.3 gN day⁻¹ for nitrate. Phosphate production ranged from 0.65 to 2.3 gP day⁻¹. These values were low compared to the nutrient fluxes in the river Doubs, suggesting a minimal local impact of the parafluvial zone in regulating of river pollution. Handling editor: J. Padisak     

Uncoupling of Bacterial and Terrigenous Dissolved Organic Matter Dynamics in Decomposition Experiments

The biodegradability of terrigenous dissolved organic matter (tDOM) exported to the sea has a major impact on the global carbon cycle, but our understanding of tDOM bioavailability is fragmentary. In this study, the effects of preparative tDOM isolation on microbial decomposition were investigated in incubation experiments consisting of mesocosms containing mesohaline water from the Baltic Sea. Dissolved organic carbon (DOC) consumption, molecular DOM composition, bacterial activities, and shifts in bacterial community structure were compared between mesocosms supplemented with riverine tDOM, either as filtered, particle-free river water or as a concentrate obtained by lyophilization/tangential ultrafiltration, and those containing only Baltic Sea water or river water. As shown using ultra-high-resolution mass spectrometry (15 Tesla Fourier-transform ion cyclotron resonance mass spectrometry, FT-ICR-MS) covering approximately 4600 different DOM compounds, the three DOM preparation protocols resulted in distinct patterns of molecular DOM composition. However, despite DOC losses of 4–16% and considerable bacterial production, there was no significant change in DOM composition during the 28-day experiment. Moreover, tDOM addition affected neither DOC degradation nor bacterial dynamics significantly, regardless of the tDOM preparation. This result suggested that the introduced tDOM was largely not bioavailable, at least on the temporal scale of our experiment, and that the observed bacterial activity and DOC decomposition mainly reflected the degradation of unknown, labile, colloidal and low-molecular weight DOM, both of which escape the analytical window of FT-ICR-MS. In contrast to the different tDOM preparations, the initial bacterial inoculum and batch culture conditions determined bacterial community succession and superseded the effects of tDOM addition. The uncoupling of tDOM and bacterial dynamics suggests that mesohaline bacterial communities cannot efficiently utilize tDOM and that in subarctic estuaries other factors are responsible for the removal of imported tDOM.     

Sources and ages of dissolved organic matter in peatland streams: evidence from chemistry mixture modelling and radiocarbon data

Monitoring data over the period 1994–2007 were analysed for three streams (Cottage Hill Sike, CHS; Rough Sike, RS; Trout Beck, TB) draining blanket peat underlain by glacial clay and limestone-rich sub-strata at Moor House (Northern England). Dissolved organic carbon concentration, [DOC], showed complex relationships with both discharge and calcium concentration, [Ca]. A model based on [Ca] was constructed to simulate stream [DOC] by mixing dissolved organic matter (DOM) from shallow peat, quantified by measured [DOC] (15–30 mg l^?1) in peat porewater, with DOM assumed to be present at a constant concentration (c. 5 mg l^?1) in groundwater. A temperature-based adjustment to the measured porewater [DOC] was required to account for relatively low streamwater [DOC] during winter and spring. The fitted model reproduced short-term variation in streamwater [DOC] satisfactorily, in particular variability in RS and TB due to groundwater contributions. Streamwater DOM is largely derived from surface peat, which accounts for more than 96% of the total DOC flux in both RS and TB, and 100% in CHS. Model outputs were combined with streamwater and porewater DO¹⁴C data to estimate the ¹⁴C contents, and thereby the ages, of DOM from peat and groundwater. The peat-derived DOM is 5 years old on average, with most of it very recently formed. The derived age of groundwater DOM (8,500 years) is comparable to the 4,000–7,000 years estimated from the DO¹⁴C of water extracts of clay underlying the peat, suggesting that the clay is the source of groundwater DOM.     

华南典型树种凋落叶的野外分解和溶解性有机质溶出动态

选用华南亚热带地区常见阔叶树种木荷和针叶树种湿地松的新近凋落叶,在野外分解0、30、60、90、150、210、240、365 d,分析溶出的溶解性有机质(DOM)浓度、组成和性质的变化,以及对土壤可溶性有机碳(DOC)的影响.结果表明: 随着分解的进行,尽管木荷叶片的DOM浓度高于松针,但是2种凋落叶DOM浓度、性质和物质组成变化规律一致;2种凋落叶的DOM浓度均呈下降趋势,芳香化程度和分子量增大,富里酸、腐殖酸类物质逐渐增多,可降解的简单芳烃蛋白(如酪氨酸)逐渐减少.在分解初期,DOM主要由亲水中性和酸性部分组成,易分解、易迁移,对表层土壤DOC影响不显著;在分解后期,DOM主要为腐殖酸和富里酸类物质,吸附性强,表层土壤DOC浓度显著下降.     

Three-dimensional fluorescence as a tool for investigating the dynamics of dissolved organic matter in the Lake Biwa watershed

Quantitative and qualitative characterizations of dissolved organic matter (DOM) were carried out at the watershed level in central Japan by measuring dissolved organic carbon (DOC) concentration and the three-dimensional excitation–emission matrix (3-D EEM). DOC concentration was low (mean 37 ± 19 µM C) in the upstream waters, whereas, in general, it increased toward the downstream areas (mean 92 ± 47 µM C). Significant variations in DOC concentration were detected among rivers and channels. DOC concentration in the epilimnion of Lake Biwa increased during the summer period and decreased during the winter period. The lake hypolimnion has lower DOC concentration (mean 87 ± 7 µM C) compared with the epilimnion (107 ± 15 µM C). Fulvic acid (FA)-like substances in the DOM were directly characterized by 3-D EEM. The fluorescence peak for upstream DOM was found in regions with longer wavelengths (excitation/emission 386 ± 6/476 ± 5 nm) compared with downstream and lake DOM (351 ± 12/446 ± 15 nm and 341 ± 6/434 ± 6 nm, respectively). The DOC concentration is correlated with fluorescence peak intensity of FA-like substances in DOM in river waters. Such a relationship was not found in lake DOM. A blueshift of the fluorescence peak from upstream to lake DOM was observed. A decrease in fluorescence intensities was also detected during the summer period. These results may suggest that the degradation of FA-like substances in DOM occurs from natural solar irradiation. Protein-like fluorescence was significantly detected in the lake epilimnion during the summer period. A linear relationship between DOC concentration and protein-like fluorescence indicated that an autochthonous input of DOM gave rise to the increase in DOC concentration in the lake epilimnion during the summer. These results may suggest that the 3-D EEM can be used as a tool for the investigation of DOM dynamics at the watershed level with concurrent measurement of DOC concentration and the fluorescence properties of fulvic acid-like and protein-like substances.     

Dissolved organic carbon concentrations in runoff from shallow heathland catchments: effects of frequent excessive leaching in summer and autumn

Transport and turnover of dissolved organic carbon (DOC) is important in the C cycle of organic soils. The concentration of DOC in soil water is buffered by adsorption to the soil matrix, and has been hypothesized to depend on the pool size of adsorbed DOC. We have studied the effect of frequent artificial excessive leaching events on concentration and flux of DOC in shallow, organic rich mountain soils. Assuming a constant Kd value for DOC adsorption to the soil matrix, we used these data to assess the change in the pool of adsorbed (or potential) DOC in the soil. The study involved manipulation of precipitation amount and frequency in summer and autumn in small, heathland catchments at Storgama, southern Norway. The shallow soils (16–34 cm deep on average) limit the possibility for changes in water flow paths during events. The mini-catchments range in size from 75 to 98 m². Our data show that after leaching of about 1.2 g DOC m⁻² the DOC concentration in runoff declines by approximately 50%. From this we conclude that the pool size of adsorbed potential DOC in the shallow soils at any time is of the order 2–3 g m⁻². Frequent episodes suggest that the replenishment rate, which depends on the decomposition rate of soil organic matter, is fast and the potential DOC pool could be fully restored probably within days during summer, but with some more time required in autumn, due to lower temperatures. Both pool size of potential DOC and replenishment rate are seasonally dependent. The pool of potential DOC, and thus the DOC concentration in discharge, is at their maximum in the growing season. However, under non-leaching conditions, the concentration of DOC in soil water and thus the pool size of potential DOC seems to level off, possibly due to conversion of DOC to less reversibly bound forms, or to further decomposition to CO₂.     

Potential capacity of coprecipitation of dissolved organic carbon (DOC) with iron(III) precipitates

Hypolimnetic anoxic water of Lake Onogawa was subjected to aeration experiments. When the samples were agitated by magnetic stirrers for 24 h, dissolved oxygen increased from 0 to more than 7.6 mg l⁻¹, dissolved iron decreased from 98% to about 5% of the initial total iron, and from 32% to 48% of the dissolved organic carbon (DOC) disappeared. On the other hand, when the anoxic waters were left unstirred, dissolved oxygen increased from 0 to 2.2 mg l⁻¹, dissolved iron decreased from 98% to 31%, and 20% of the DOC disappeared within 48 h. Further 24-h incubation had little effect on the DOC loss, although dissolved oxygen increased to 3.9 mg l⁻¹ and dissolved iron decreased to 5%. These rates of DOC disappearance are too large to be explained by bacterial decomposition. It is quite conceivable that a part of the DOC is coprecipitated with iron(III) precipitates. When Fe(II) in the anoxic hypolimnion is oxidized by autumnal water mixing, probably anoxic water is mixed with aerobic water. The anoxic water must receive oxygen from the aerobic water during this mixing and be simultaneously diluted with the aerobic water. Because the present experimental conditions, especially the stirred one, significantly differ from in situ conditions, the present results are thought to be a potential capacity of DOC coprecipitation.     

Autochthonous origin of semi-labile dissolved organic carbon in a large monomictic lake (Lake Biwa): carbon stable isotopic evidence

Semi-labile dissolved organic carbon (DOC) plays an important role in the transport and hypolimnetic remineralization of carbon in large freshwater lakes. However, sources of semi-labile DOC in lakes remain unclear. This study used a carbon stable isotope approach to examine relative contributions of autochthonous and allochthonous sources to semi-labile DOC. Vertical and seasonal variations in the concentration and carbon stable isotope ratio (δ¹³C) of DOC were determined in large (surface area 674 km²; maximum depth 104 m), monomictic Lake Biwa. A sharp vertical gradient of δ¹³C of DOC (δ¹³C-DOC) during the stratification period [mean ± standard error (SE) −25.5 ± 0.1 and −26.0 ± 0.0‰ in the epi- and hypolimnion, respectively] indicated the accumulation of ¹³C-rich DOC in the epilimnion. Vertical mixing explained the intermediate values of δ¹³C-DOC (−25.7 ± 0.0‰) measured throughout the water column during the overturn period. Both DOC concentration and δ¹³C-DOC decreased in the hypolimnion during stratification, indicating selective remineralization of ¹³C-rich DOC. Using a two-component mixing model, we estimated the δ¹³C value of semi-labile DOC to be −22.2 ± 0.3‰, which was close to the δ¹³C of particulate organic carbon collected in the epilimnion during productive seasons (−22.7 ± 0.7‰) but much higher than the δ¹³C-DOC in river waters (−26.5 ± 0.1‰). Semi-labile DOC appeared to be mainly autochthonous in origin, produced by planktonic communities during productive seasons. The spatiotemporal uncoupling between production and remineralization of semi-labile DOC implies that hypolimnetic oxygen consumption may be affected by pelagic primary production during productive seasons of the preceding year.     

Soil frost enhances stream dissolved organic carbon concentrations during episodic spring snow melt from boreal mires

Changes in winter time conditions at high‐latitude ecosystems could severely affect the carbon exchange processes. Using a 15 year stream record combined with winter field measurements and laboratory experiment, we studied the regulation of dissolved organic carbon (DOC) concentration in stream water draining boreal mire during snow melt. The most unanticipated finding was that cold soils with deep soil frost resulted in increased snow melt DOC concentrations in the stream runoff. Wintertime field measurements of DOC concentrations below the mire soil frost showed that this phenomenon could be explained by freeze‐out of DOC giving higher levels of DOC in the soil water below the ice as the soil frost developed downwards in the mire. Experimental freezing of water with a certain DOC concentration in the laboratory further corroborated the freeze‐out of DOC. In this experiment, as much as 96% of the DOC was excluded from the ice, whereas the freeze‐out in the mire was less effective (60%). The difference between the proportion of DOC retained in pure water relative to the proportion retained in peat water during freezing is probably due to trapped DOC in the solid peat soil matrix. A simple mass‐balance model showed that to explain the higher stream DOC concentrations during a winter with deep soil frost, approximately 0.5% of the mire area needed to be hydrologically connected to the stream discharge. In the stream records, we also found that the DOC concentrations during snow melt episodic runoff were negatively related to increasing intensity of the snow melt episodes (dilution by low DOC snow melt water) and higher previous export of DOC.     

Dissolved Organic Matter concentration and composition in the forests and streams of Olympic National Park, WA

Dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) character were investigated in soil water (15 and 40 cm) and streams at eleven sites in Olympic National Park. In addition, the effect of added nitrogen on soil water DOM concentration and composition was tested. Forested plots covering a gradient of precipitation, climate, slope, and aspect in Olympic National Park were fertilized with the addition of 20, 10 and zero (control) kg urea-N ha^–1 y^–1. Seven sites had the two different fertilizer treatments and control plots, while the additional four sites had no fertilizer treatments. Soil water DOC concentrations ranged from 0.5 mg C/L to 54.1 mg C/L, with an average value of 14.1 mg C/L. Streams had low DOC concentrations ranging from 0.2 mg C/L to 4.4 mg C/L, with an average value of 1.2 mg C/L. DOM composition was examined with regard to molar ratios, H:C, O:C and N:C, index of unsaturation, average carbon oxidation state, and specific absorbance. Fertilizer had no consistent effect on either DOM concentration or composition across the study sites. Soil depth influenced both DOM concentration and composition. Shallow soil water DOM had greater concentrations, higher specific absorbance, a higher degree of unsaturation, and had lower molar ratios compared to deep soil water samples. Overall, changes in DOM stoichiometry and specific absorbance as a function of soil depth were consistent despite the diversity of the forested study sites sampled.