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.     

Quantification and characterization of dissolved organic carbon and iron in sedimentary porewater from Green Bay,WI, USA

Both dissolved organic carbon (DOC) and iron play an important role in biogeochemical processes in lacustrine benthic environments. Moreover, recent evidence has shown that both substances can act as active reductants in the redox transformation of organic pollutants. This paper examines the nature and abundance of DOC and dissolved ferrous iron (Fe^II) in porewaters from a sediment core collected in Green Bay, WI, USA. The concentration of dissolved Fe^II and the abundance, absorbance at 280 nm (A _{280 nm}), molar absorptivities (_{280 nm}), molecular weights, and polydispersities of DOC were measured as a function of depth in porewaters. Dissolved Fe^II concentrations increased from 3.6 M near the sediment–water interface to 163 M at a depth of 11 cm, then gradually declined. The DOC distribution varied with sediment depth, with the greatest variation in porewater DOC content and properties occurring in the transitional zone between oxic and suboxic conditions. The down-core porewater DOC profile was characterized by an increase in DOC concentration with depth from 0.64 mM OC at 1 cm to 1.23 mM OC at 13 cm, below which it remained relatively constant. A strong correlation was observed between Fe^II and DOC concentrations, suggesting that these constituents co-accumulate in these porewaters. The correlation between the DOC concentration of the porewaters and A _{280 nm} was significant, making this parameter a good predictor for DOC concentrations in these waters. The molecular weight distributions of the porewater DOC were primarily monomodal, with relatively low polydispersivities. Weight-average molecular weights ranged from 1505 to 1949 Da. This data set is unique in that it is the first detailed study of a relatively highly resolved DOC profile of benthic porewater in surficial sediment from the Laurentian Great Lakes.     

Redox Changes of Iron Caused by Erosion,Resuspension and Sedimentation in Littoral Sediment of a Freshwater Lake

Depth profiles of oxygen concentration and the redox status of acid-extractable iron were measured in littoral sediment cores of Lake Constance after mechanical removal of surface sediment, mixing, and re-deposition. In undisturbed sediment cores, oxygen penetrated down to 2.9±0.4 mm or 4.6±0.4 mm depth, respectively, after 12 h of incubation in the dark or light; causing a net diffusive flux of 108±20 nmol cm⁻² h⁻¹ oxygen into or 152±35 nmol cm⁻² h⁻¹ out of the sediment. The uppermost 20 mm layer of the undisturbed sediment cores contained 10.2± 0.7 μmol cm⁻³ ferrous and 3.8±1.1 μmol cm⁻³ ferric iron. After erosion, the oxic–anoxic interface in the newly exposed sediment was shifted to about 2 mm depth within 30 min, causing an oxygen flow into the sediment. During the following 12 h, oxygen penetrated deeper into the sediment, and in the light oxygen was produced photosynthetically. Ferrous iron was largely oxidized within two days after erosion. The oxidation rates were higher in oxic than in anoxic sediment layers, and decreased with time. This oxidation process took the longer and was confined closer to the surface the more reduced the exposed sediment had been before. Resuspension of eroded sediment in aerated lake water did not cause a significant oxidation or reduction of iron. After re-deposition, the oxic–anoxic interface in the re-sedimented material shifted to about 2 mm depth within 30 min, causing an oxygen flow into the sediment. During the following 12 h, the oxygen penetration depth and the oxygen flow rate into the re-deposited sediment did not change any further, and no oxygen was produced in the light. Ferric iron was reduced during the first day after re-deposition, and partly re-oxidized during the second day. The extent of reduction was stronger and the extent of oxidation weaker the more reduced the resuspended sediment was before. Oxic conditions in the sediment surface were established faster and ferrous iron was oxidized to a larger extent after erosion of sediment than after resuspension and sedimentation.     

Distribution and Characteristics of Dissolved Organic Matter in Mangrove Sediment Pore Waters along the Coastline of French Guiana

Mangroves represent a major environment of tropical coasts. They are highly productive, and act both as a source and a sink of organic carbon. Concentrations and characteristics (fluorescence and hydrophobic–hydrophilic fractions) of dissolved organic matter (DOM) were investigated in relation to the organic content of sediments and to the chemistry of pore waters along the coastline of French Guiana. The pore waters studied were extracted (centrifugation, soil moisture sampler) from sediments cored beneath A. germinans mangrove stands representative of development stages: pioneer, mature and senescent. In order to asses the effects of seasonal changes, two cores were performed in each location, just after dry and wet seasons, respectively. Dissolved organic carbon (DOC) concentrations in pore waters of the upper sediment were found to increase, from 0.7 mmol l⁻¹ under the pioneers to 9 under senescent mangroves. The evolution of sedimentary organic carbon (SedOC) in the same sediment paralleled that of DOC, increasing from 0.7 to 28%. On the contrary, in the lower parts of sediment cores SedOC and DOC displayed contrasting vertical trends: SedOC decreased sharply with depth while DOC increased, reaching concentrations up to 30 mmol l⁻¹ at 50 cm in the older, senescent mangroves. In addition, the Fluorescence/DOC ratios and the hydrophobic contents of DOC were higher at greater depths in most cores, expressing changes in the DOC composition. These results suggest that the DOC of the upper layers originated directly from the SedOC of the enclosing sediment, while the hydrophobic and fluorescent DOC accumulated in the anoxic bottom layer. The mechanisms responsible for this accumulation at depth requires additional research to be fully understood. However, the anoxic conditions and high pH values prevailing in the lower sediment, by lessening DOM sorption and enhancing SedOC dissolution, may be partly responsible for the high DOC concentrations and fluorescences at depth. In addition, seasonal variation may be involved. During the rainy season, water sources were mixed resulting in lower DOC concentrations in the upper sediment, whereas during the dry season, increased evapotranspiration concentrate salts and DOC, which are transported vertically with percolating water.     

Dynamics of Redox Changes of Iron Caused by Light–dark Variations in Littoral Sediment of a Freshwater Lake

Depth profiles of oxygen concentration and the redox status of acid-extractable iron were measured in littoral sediment cores of Lake Constance incubated under a light–dark regimen of 12 h. While oxygen penetrated to 3.4±0.2 mm depth in the dark, photosynthetic oxygen production shifted the oxic–anoxic interface down to 4.0±0.2 mm or 5.9±1.6 mm depth, at low or high light intensity, respectively, and caused a net oxygen efflux into the water column. After a light–dark or dark–light transition, the oxygen concentration at the sediment surface reached a new steady state within about 20 min. The redox state of the bioavailable iron was determined in 1-mm slices of sediment subcores. After a dark period of 12 h, 85% of the acid-extractable iron (10.5 μmol cm⁻³ total) in the uppermost 8 mm was in the reduced state. Within 12 h at low or high light intensity, the proportion of ferrous iron decreased to 82 or 75%, respectively, corresponding to net rates of iron oxidation in the range of 244 and 732 nmol cm⁻³ h⁻¹, respectively. About 55 or 82% of the iron oxidation at low or high light intensity occurred in the respective oxic zone of the sediment; the remaining part was oxidized in the anoxic zone, probably coupled to nitrate reduction. The areal rates of iron oxidation in the respective oxic layer (21 or 123 nmol cm⁻² h⁻¹ at low or high light intensity, respectively) would account for 4 and 23% of the total electron flow to oxygen, respectively. Light changes caused a rapid migration of the oxic–anoxic interface in the sediment, followed by a slow redox reaction of biologically available iron, thus providing temporal niches for aerobic iron oxidizers and anaerobic iron reducers.     

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.     

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.     

Effects of benthic filamentous algae on the sediment–water interface in an acidic mining lake

Natural alkalinity generation by microbial sulphate reduction in acidic lakes is usually inhibited by the low pH and a low primary production which results in a lack of suitable organic carbon sources. In some acidic mining lakes mass developments of filamentous benthic algae occur. The effects of this periphyton layer on the biogeochemistry of the sediment–water interface were investigated by in situ microsensor measurements and laboratory incubations in Mining Lake Grünewalder Lauch (Germany). Microsensor measurements showed that the oxic–anoxic boundary was located in the periphyton layer and was moving up and down depending on light triggered photosynthesis. The sediment itself was permanently anoxic. The diurnal redox shift and the maintenance of neutral conditions in the periphyton layer lead to an effective precipitation of iron and phosphorus. Under the periphyton layer very high sulphate reduction rates up to 265 nmol cm⁻³ d⁻¹ were measured in the sediment. These are the highest rates reported for mining lakes so far. The microbial activity was high enough to keep the pH in the surface sediment neutral and contributed to natural alkalinity production. Handling editor: L. Naselli-Flores     

Distribution and characteristics of molecular size fractions of freshwater-dissolved organic matter in watershed environments: its implication to degradation

Distributions of molecular size and fluorescence properties of dissolved organic matter (DOM) in the Lake Biwa and Lake Baikal watersheds were investigated using the cross-flow ultrafiltration technique and three-dimensional fluorescence measurements. From the fluorescence properties, protein-like substances were usually found in the 0.1 μm-GF/F fraction (the Durapore membrane retentate of the GF/F filtrate) of the lake DOM. The results indicated autochthonous production of protein-like organic-matters in the lake environment. Fulvic acid (FA)-like components were composed of two fractions with respect to fluorescence properties and molecular size. Two FA-like fluorescence peaks, which showed different fluorescence peak positions in the excitation-emission matrix (EEM), were partly fractionated by the molecular size of 5000 daltons (5 kDa). The FA-like fluorescence peak position of the <5-kDa fraction was observed at the shorter wavelength region compared with that of the fraction between 5 kDa and 0.1 μm (5 kDa20.1 μm fraction). A blue shift of the FA-like fluorescence peak position as well as a decrease in the molecular size of the DOM was observed in lake samples. The relative contribution of the <5 kDa fraction to the DOC concentration was high in lake waters (68%–79%) compared with river waters (44%–68%), suggesting characteristic changes in molecular size between riverine and lacustrine DOM. DOM of the 5 kDa–0.1 μm fraction was relatively higher in river waters than in lake waters. These findings coincided with in situ distributions of the fluorescence properties and molecular size of DOM found in both stream and lake environments. These results indicate that FA-like substances from forested watersheds are decomposed qualitatively and quantitatively in the river-lake environment by photochemical and biological processes.     

The Effects of a Developing Biofilm on Chemical Changes across the Sediment-Water Interface in a Freshwater Environment

The development of a diatom biofilm on a river sediment was studied using a fluvarium channel with intensive investigations over a total duration of 16 days. The overlying solution was monitored for dissolved calcium, silicon and soluble reactive phosphorus, pH, dissolved oxygen and temperature. The surface of the sediment was sampled for chlorophyll a, algal cell density and porewater profile measurements of calcium concentration, pH and dissolved oxygen were made using microelectrodes. At the end of the experiment the sediment was longitudinally sectioned and porewaters isolated and analysed. A diatom biofilm developed within approximately 5 days leading to a decrease in the concentrations of dissolved silicon and phosphorus in the overlying solution. After approximately 270 hours, the dissolved silicon concentration remained low (average of 6.7 μM). As the diatom numbers increased, photosynthetic activity was evident from increases in dissolved oxygen and pH at the interface. By the end of the experiment diurnal changes in the overlying solution of dissolved calcium, alkalinity and soluble reactive phosphorus were evident. Vertical concentration gradients in dissolved calcium, phosphorus and silicon in the sediment porewater were found at the end of the experiment. The results are consistent with the development of a photosynthetically active diatom biofilm that acted as a barrier to the diffusion of silicon from the porewater. It also induced precipitation and dissolution of calcite and co-precipitation of phosphate with calcite. Chemical fluxes of silicon, calcium and phosphorus were estimated from concentration gradients in the sediment and found to be much smaller than fluxes measured from changes in the bulk solution indicating that processes at the sediment-water interface and biofilm mainly control the flux to the overlying solution.     

Some generalizations based on stratification and vertical mixing in meromictic Lake Shira,Russia, in the period 2002–2009

In a brackish, temperate, 24-m-deep Lake Shira, the profiles of salinity, temperature, oxygen and sulfide concentrations were measured on a seasonal basis from 2002 to 2009. The lake was shown to be meromictic with autumnal overturn restricted to mixolimnion. The depth of mixolimnion and position of oxic–anoxic interface varied annually. The spring mixing processes contribute to the formation of mixolimnion in autumn. The exceptionally windy spring of 2007 caused the deepening of mixolimnion in the winter of 2008. The winter position of oxic–anoxic interface was affected by the position of lower boundary of mixolimnion in all winters. The salinity in the winter mixolimnion increased compared with the autumn because of freezing out of salts from the upper water layers meters during ice formation and their dissolution in water below. The profiles of salinity and temperature were simulated by the mathematical 1-D model of temperature and salinity conditions taking into account ice formation. The simulated profiles generally coincided with the measured ones. The coincidence implies that simplified one-dimensional model can be applied to roughly describe salinity and density profiles and mixing behavior of Lake Shira.     

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.     

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.     

Impact of sampling methods on sulfate reduction rates and dissolved organic carbon (DOC) concentrations in vegetated salt marsh sediments

The impact of sediment coring on measured rates of sulfate reduction(SRR) by the whole core ³⁵S-injection technique was assessed inmarshsediment vegetated by Spartina anglica. Simultaneously,therole of extraction method (centrifugation vs. sippers) for determination ofporewater DOC in vegetated sediment was evaluated. SRR was measuredinsitu with radiotracer injected directly into the sediment and in atime series from 1 to 24 h after coring. SRR incubations carriedout within 6 h (June) or 12 h (August) of coringyielded up to an order of magnitude higher rates than measured insitu. The enhancement of SRR was instantaneous but temporary andcorrelated with measured porewater DOC concentrations. Cores sampled fromrootedsediments should therefore not be used for sulfate reduction incubations withinthe first 12 h due to the effect of DOC leaching from roots cutduring the coring procedure. The labile fraction of leached DOC appears to beexhausted after a pre-incubation period of at least 12 h.Measurement of porewater DOC is also problematic in vegetated sediment.Porewater extraction by centrifugation of sediment may result in up to oneorderof magnitude higher DOC concentrations than in porewater obtained by anondestructive sipper technique. DOC is probably forced out of roots duringcentrifugation resulting in erroneously high porewater DOC concentrations.     

Sources and seasonal patterns of dissolved organic matter (DOM) in the hyporheic zone

The hyporheic zone is a region underneath streambeds that integrates surface and groundwater. Although its location is central to biogeochemical linkages between the riparian zone, dissolved nutrients, and benthic biota, the seasonal quality and likely sources of dissolved organic matter (DOM) in the hyporheic zone are not well understood. To investigate DOM characteristics in the hyporheic zone, water from the surface and subsurface (at depths 20, 60, and 100 cm below the streambed) was sampled every 4 weeks from 2007 to 2008 in a third-order stream in southern Ontario. Using UV spectroscopy, measures of spectral slopes, aromaticity, and A ₂₅₄/A ₃₆₅ ratios (molecular weight) were obtained. Temporal changes in these measures were consistent with watershed processes such as shedding of leaf litter in the fall, and photochemical and biofilm influence in the spring and summer. The fluorescence index (a measure of relative DOM source) suggested that at the surface and in the downwelling zone, DOM microbial sources increased with depth in the sediment, regardless of the season. Excitation–emission matrices (EEMs) showed seasonally distinct, protein-like DOM components of bacterial origin that were stronger in the fall. Leachates from specific allochthonous DOM sources—leaf litter from Betula papyrifera (white birch) and Thuja occidentalis (white cedar)—and an autochthonous source, biofilm, were isolated and incubated with unfiltered surface water. EEMs from these leachates indicated that these sources could indeed help explain observed patterns of DOM in surface and subsurface waters. These results suggest that although DOM sources were relatively constant, biogeochemical processing within the hyporheic zone resulted a DOM pool that was temporally dynamic and altered the nature of organic matter transported downstream into lakes and rivers.     

The Role of Iron and Dissolved Organic Carbon in the Absorption of Ultraviolet Radiation in Humic Lake Water

Absorption of solar ultraviolet radiation (UVR) in aquatic ecosystems is primarily controlled by dissolved organic carbon (DOC). The role of iron (Fe) has also been suggested to contribute to UVR attenuation either directly or by interactions with DOC. Here we present findings from three laboratory manipulations of Fe and DOC on changes to the dissolved UVR absorption (a_d,320) in a mid-latitude, dimictic, humic lake. In a laboratory simulation of lake turnover where anoxic, hypolimnetic water was oxygenated a_d,320 significantly increased from 23.3 to 81.7 m⁻¹ (p<0.0001). In a second laboratory experiment, addition of ferrous Fe to deoxygenated lake water increased a_d,320 upon reoxygenation up to a concentration of 1.0 mg l⁻¹ Fe, where a solubility saturation threshold may have been reached. In situ lake experiments were designed to simulate release of UV absorbing substances from anoxic sediments by placing 20-l carboys (open at the bottom, sealed at the top) onto the lake bottom. UV absorption at 320 nm increased over time for samples from within the experimental carboys. Finally, samples from several lake profiles and sediment experiments were analyzed for a_d,320, total Fe, and DOC. UV absorption of dissolved substances at 320 nm and total Fe concentration both increased with depth, however DOC remained relatively constant over depth. Furthermore, total Fe and spectral slope showed tight coupling up to 1 mg l⁻¹ total Fe in our survey analysis. Our results provide evidence for the importance of anoxic sediments as a source of ferrous iron and UV absorbing substances and suggest a role for ferric iron in increasing UVR and PAR absorption in lake water. We suggest that as this ferrous Fe oxidizes, its absorptive properties increase, and it may bind with dissolved organic matter, enabling it to remain in solution and thus increasing the dissolved absorption of lake water for extended periods of time.     

Uptake of Allochthonous Dissolved Organic Matter from Soil and Salmon in Coastal Temperate Rainforest Streams

Dissolved organic matter (DOM) is an important component of aquatic food webs. We compare the uptake kinetics for NH₄–N and different fractions of DOM during soil and salmon leachate additions by evaluating the uptake of organic forms of carbon (DOC) and nitrogen (DON), and proteinaceous DOM, as measured by parallel factor (PARAFAC) modeling of DOM fluorescence. Seasonal DOM slug additions were conducted in three headwater streams draining a bog, forested wetland, and upland forest using DOM collected by leaching watershed soils. We also used DOM collected from bog soil and salmon carcasses to perform additions in the upland forest stream. DOC uptake velocity ranged from 0.010 to 0.063 mm s⁻¹ and DON uptake velocity ranged from 0.015 to 0.086 mm s⁻¹, which provides evidence for the whole-stream uptake of allochthonous DOM. These findings imply that wetlands could potentially be an important source of DOM to support stream heterotrophic production. There was no significant difference in the uptake of DOC and DON across the soil leachate additions (P > 0.05), although differential uptake of DOM fractions was observed as protein-like fluorescence was removed from the water column more efficiently than bulk DOC and DON (P < 0.05). Moreover, PARAFAC analysis of DOM fluorescence showed that protein-like fluorescence decreased downstream during all DOM additions, whereas humic-like fluorescence did not change. This differential processing in added DOM suggests slow and fast turnover pools exist for aquatic DOM. Taken together, our findings argue that DON could potentially fill a larger role in satisfying biotic N demand in oligotrophic headwater streams than previously thought. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. Author contributions  J.B.F. conceived of or designed study, performed research, analyzed data, contributed new methods or models, and wrote the paper. E.H. conceived of or designed study and analyzed data. R.T.E. conceived of or designed study and analyzed data. J.B.J. contributed new methods or models and analyzed data.     

Revealing Sources and Distribution Changes of Dissolved Organic Matter (DOM) in Pore Water of Sediment from the Yangtze Estuary

Dissolved organic matter (DOM) in sediment pore waters from Yangtze estuary of China based on abundance, UV absorbance, molecular weight distribution and fluorescence were investigated using a combination of various parameters of DOM as well as 3D fluorescence excitation emission matrix spectra (F-EEMS) with the parallel factor and principal component analysis (PARAFAC-PCA). The results indicated that DOM in pore water of Yangtze estuary was very variable which mainly composed of low aromaticity and molecular weight materials. Three humic-like substances (C1, C2, C4) and one protein-like substance (C3) were identified by PARAFAC model. C1, C2 and C4 exhibited same trends and were very similar. The separation of samples on both axes of the PCA showed the difference in DOM properties. C1, C2 and C4 concurrently showed higher positive factor 1 loadings, while C3 showed highly positive factor 2 loadings. The PCA analysis showed a combination contribution of microbial DOM signal and terrestrial DOM signal in the Yangtze estuary. Higher and more variable DOM abundance, aromaticity and molecular weight of surface sediment pore water DOM can be found in the southern nearshore than the other regions primarily due to the influence of frequent and intensive human activities and tributaries inflow in this area. The DOM abundance, aromaticity, molecular weight and fluorescence intensity in core of different depth were relative constant and increased gradually with depth. DOM in core was mainly composed of humic-like material, which was due to higher release of the sedimentary organic material into the porewater during early diagenesis.     

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.     

Photooxidation of wetland and riverine dissolved organic matter: altered copper complexation and organic composition

In natural waters, the uptake of transition metals such as copper (Cu) by aquatic biota depends on the activity of the free cupric ion ({Cu²⁺}) rather than on total Cu concentration. Thus, an important ecological function of dissolved organic matter (DOM) in aquatic ecosystems is Cu–DOM complexation, which greatly decreases the {Cu²⁺}. However, Cu bioavailability is greatly modified by source and environmental history of DOM because DOM affinity for Cu varies by orders of magnitude among DOM sources; moreover, DOM is photochemically unstable. During 72-h irradiation experiments at intensities approximating sunlight with DOM from a palustrine wetland and a third-order river, we investigated photooxidative effects on DOM complexation of Cu as well as spectral and chemical changes in DOM that might explain altered Cu complexation. Irradiation decreased Cu complexation by riverine DOM, but unexpectedly increased Cu complexation by wetland DOM, resulting in 150% greater {Cu²⁺} in riverine DOM at the same dissolved organic carbon concentrations. The specific ultraviolet absorption (SUVa) and humic substances tracked photochemical changes in the conditional stability constants of Cu–DOM complexes, suggesting that the aromaticity of DOM influences its affinity for Cu. Carbonyl concentration in ¹³C nuclear magnetic resonance spectra (¹³C-NMR) covaried directly with Cu binding-site densities in DOM. However, no aspect of Cu–DOM complexation consistently covaried with fluorophores (i.e., the fluorescence index) or low molecular weight organic acids. Our results suggest that global increases in UV radiation will affect Cu–DOM complexation and subsequent Cu toxicity depending on light regime as well as DOM source. Handling editor: K. Martens