Changes in dissolved organic matter (DOM) amount and composition along nested headwater stream locations during baseflow and stormflow

Amount and composition of dissolved organic matter (DOM) were evaluated for multiple, nested stream locations in a forested watershed to investigate the role of hydrologic flow paths, wetlands and drainage scale. Sampling was performed over a 4‐year period (2008–2011) for five locations with drainage areas of 0.62, 3.5, 4.5, 12 and 79 ha. Hydrologic flow paths were characterized using an end‐member mixing model. DOM composition was determined using a suite of spectrofluorometric indices and a site‐specific parallel factor analysis model. Dissolved organic carbon (DOC), humic‐like DOM and fluorescence index were most sensitive to changes with drainage scale, whereas dissolved organic nitrogen, specific UV absorbance, Sr and protein‐like DOM were least sensitive. DOM concentrations and humic‐like DOM constituents were highest during both baseflow and stormflow for a 3.5‐ha catchment with a wetland near the catchment outlet. Whereas storm‐event concentrations of DOC and humic DOM constituents declined, the mass exports of DOC increased with increasing catchment scale. A pronounced dilution in storm‐event DOC concentration was observed at peak stream discharge for the 12‐ha drainage location, which was not as apparent at the 79‐ha scale, suggesting key differences in supply and transport of DOM. Our observations indicate that hydrologic flow paths, especially during storms, and the location and extent of wetlands in the catchment are key determinants of DOM concentration and composition. This study furthers our understanding of changes in DOM with drainage scale and the controls on DOM in headwater, forested catchments. Copyright © 2014 John Wiley & Sons, Ltd.     

三峡库区土地利用对河流溶解性有机质的多时空尺度影响

三峡库区拥有目前世界上规模最大的水利枢纽工程,自投入使用以来,为长江流域提供了丰富的水源及电力,促进了经济的发展,但同时也对该区域的生态环境造成了严重的冲击。澎溪河流域作为三峡库区长江流域干流的典型回水区和消落带,是众多学者研究三峡库区生态环境变化的重点区域。为探究不同时空尺度下土地利用对河流溶解性有机质（DOM）的影响,以澎溪河流域为研究对象,基于紫外-可见光谱分析和三维荧光光谱矩阵-平行因子分析,结合河段缓冲区、河岸带缓冲区及子流域3种空间尺度的二级土地利用类型,解析了旱雨季水体DOM的组成及来源特征,并采用相关分析和冗余分析方法探讨了3种空间尺度下土地利用方式对旱雨季水体DOM的多时空尺度影响。结果表明：（1）旱季水体DOM荧光组分以陆源类腐殖质所占比例更大,雨季水体DOM荧光组分以富里酸贡献为主。（2）流域内陆源输入和内源产生对水体DOM丰度均有贡献,雨季较旱季水体DOM的陆源性更强,自生源特征较弱。（3）土地利用在雨季和子流域尺度下对水体DOM的影响更显著,其中,雨季子流域尺度下,土地利用指数对水体DOM参数的解释率为90.35%。（4）不同土地利用方式对水体DOM产生的影响...     

Spectrophotometric properties of surface water dissolved organic matter in an afforested upland peat catchment

Many upland catchments in the UK have undergone afforestation; their characteristic waterlogged soils require extensive pre‐plantation ground drainage to allow tree establishment. In peatland areas this can result in very highly coloured runoff and enhanced dissolved organic matter (DOM) export in rivers of naturally high concentrations. In 1966, the Coalburn Experimental Catchment, northern England, was established to investigate the impact of afforestation on an upland peat catchment. Here we report the variations in DOM spectrophotometric properties of streamflow in the catchment at canopy closure, especially with respect to potential carbon sources within the artificial drainage ditches. Drainage ditches are characterized by water that has higher absorption coefficients and which is more highly coloured than in the catchment tributaries. Ditched, afforested areas produce more highly‐coloured runoff waters that are more fluorescent and absorbent normalized to carbon concentration compared to ditches in open moorland. Ditches that had been experimentally re‐excavated have organic matter of different spectrophotometric character, with higher dissolved organic carbon concentration and less aromatic or lower molecular weight material. It is hypothesized that this is due to the exposure of bare peat faces within and adjacent to the ditches that are more susceptible to drying compared to vegetated areas. The large extent of this drainage network acts as both a rapid transport network increasing hydrological connectivity and a pool for the storage of DOM, which is of different spectrophotometric character under low flow conditions, depending on management conditions. Copyright © 2007 John Wiley & Sons, Ltd.     

Sources and biodegradability of dissolved organic matter in two headwater peatland catchments at the Marcell Experimental Forest,northern Minnesota,USA

Where they are present in catchments, peatlands are a dominant source of dissolved organic matter (DOM) to surrounding waterways due, in part, to high production rates. Despite the preponderance of peatlands in northern latitudes and expected peatland vulnerability to climate change, little is known about peatland DOM degradation relative to a more comprehensive understanding of degradation when DOM is sourced from upland-dominated catchments. We compared DOM biodegradability of various sources of stream water in two catchments having peatlands (22%–33% of the area) surrounded by upland forests (70%–90% of the area, either deciduous or coniferous). We measured total organic carbon (TOC), and biodegradable dissolved organic carbon concentrations; bacterial respiration rates; streamflow; and upland runoff during and after snowmelt (March to June, 2009–2011). We also explored if DOM in upland runoff stimulated biodegradation of peatland-derived DOM (i.e., a priming effect), and if forest cover type affected DOM biodegradability. As expected, the peatlands were the largest sources of both water (72%–80%) and TOC (92%–96%) to the streams although more area in each catchment was in uplands (70%–90%). Several results were unexpected, yet revealing: (1) DOM from peatlands sometimes had the same biodegradability as DOM from uplands, (2) upland sources of DOM had negligible effects on biodegradability in the peatland and downstream, and (3) upland deciduous cover did not yield more degradable DOM than conifer cover. The most pronounced effect of upland runoff was dilution of downstream TOC concentrations when there was upland runoff. Overall, the effects of upland DOM may have been negligible due to the overriding effect of the large amount of biodegradable DOM that originated in bogs. This research highlights that peatland-sourced DOM has important effects on downstream DOM biodegradability even in catchments where upland area is substantially larger than peatland area.     

Continuous fluorescence assessment of organic matter variability on the Bournbrook River,Birmingham, UK

Continuous monitoring of dissolved organic matter (DOM) character and concentration at hourly resolution is rare, despite the importance of analysing organic matter variability at high‐temporal resolution to evaluate river carbon budgeting, river water health by detecting episodic pollution and to determine short‐term variations in chemical and ecological function. The authors report a 2‐week experiment performed on DOM sampled from Bournbrook, Birmingham, UK, an urban river for which spectrophotometric (fluorescence, absorbance), physiochemical (dissolved organic carbon [DOC], electrical conductivity, pH) and isotopic (D/H) parameters have been measured at hourly frequency. Our results show that the river had sub‐daily variations in both organic matter concentration and characteristics. In particular, after relatively high‐magnitude precipitation events, organic carbon concentration increased, with an associated increase in intensity of both humic‐like and tryptophan‐like fluorescence. D/H isotopic ratio demonstrates different hydrological responses to different rainfall events, and organic matter character reflects this difference. Events with precipitation < 2 mm typically yielded isotopically heavy water with relatively hydrophilic DOM and relatively low specific absorbance. Events with precipitation > 2 mm had isotopically lighter water with higher specific absorbance and a decrease in the proportion of microbially derived to humic‐like fluorescence. In our heavily urbanized catchment, we interpret these signals as one where riverine DOM is dominated by storm sewer‐derived ‘old’ organic matter at low‐rainfall amounts and a mixed signal at high‐precipitation amounts where ‘event’ surface runoff‐derived organic matter dominate during storm sewer and combined sewer overflow routed DOM. Copyright © 2009 John Wiley & Sons, Ltd.     

Determination of dissolved organic matter in streamwater using visible spectrophotometry

Absorbance at 360 nm was measured on 44 filtered streamwater samples of different dissolved organic matter (DOM) contents. A regression equation of DOM on absorbance predicted DOM with a standard error of estimate of 1.26 mgl^?1, Use of a published equation relating dissolved organic carbon (DOC) to absorbance gave DOC values for the samples which were consistent with measured DOM. The method offers considerable potential for rapid quantification of dissolved organic matter concentrations in streamwater.     

Hydroclimatic controls on dissolved organic matter (DOM) characteristics and implications for trace metal transport in Hwangryong River Watershed,Korea, during a summer monsoon period

Frequent heavy rainfalls during the East Asian summer monsoon drastically increase water flow and chemical loadings to surface waters. A solid understanding of hydroclimatic controls on watershed biogeochemical processes is crucial for water quality control during the monsoon period. We investigated spatio‐temporal variations in the concentrations and spectroscopic properties of dissolved organic matter (DOM) and the concentrations of trace metals in Hwangryong River, Korea, during a summer period from the relatively dry month of June through the following months with heavy rainfall. DOM and its spectroscopic properties differed spatially along the river, and also depended on storm and flow characteristics around each sampling time. At a headwater stream draining a forested watershed, the concentrations (measured as dissolved organic carbon (DOC)), aromaticity (measured as specific UV absorbance at 254 nm), and fulvic acid‐ and protein‐like fluorescence of DOM were higher in stormflow than in baseflow waters. DOC concentrations and fluorescence intensities increased along the downstream rural and urban sites, in which DOC and fluorescence were not higher in stormflow waters, except for the ‘first flush’ at the urban site. The response of DOM in reservoir waters to monsoon rainfalls differed from that of stream and river waters, as illustrated by storm‐induced increases in DOM aromaticity and fulvic‐like fluorescence, and no significant changes in protein‐like fluorescence. The results suggest that surface water DOM and its spectroscopic properties differentially respond to changes in hydroclimatic conditions, depending on watershed characteristics and the influence of anthropogenic organic matter loadings. DOC concentrations and intensities of spectroscopic parameters were positively correlated with some of the measured trace metals (As, Co, and Fe). Further research will be needed to obtain a better understanding of climate effects on the interaction between DOM and trace metals. Copyright © 2006 John Wiley & Sons, Ltd.     

Variation in the photochemical lability of dissolved organic matter in a large boreal watershed

Boreal watersheds contain a vast quantity of terrestrially derived dissolved organic matter (DOM) originating from wetland and forest soils, yet variation in the potential for photochemical transformation of boreal aquatic DOM sources remains poorly understood. Laboratory solar radiation exposure experiments were conducted on DOM samples collected in three seasons, across nine sites, representing contrasting catchment composition and watershed position to assess variation in the photochemical lability of boreal DOM source and stable carbon isotopic signature (δ¹³C) of photomineralized DOM. Dissolved organic carbon (DOC) loss rates during laboratory exposure were lowest in summer, suggesting that DOM may have been more photo-degraded during summer. DOM from upstream portions of forested stream sites and wetland-influenced sites was more photolabile relative to downstream portions and the river DOM, suggesting potential losses in photolabile DOM downstream and in the lower reaches of the watershed. Increased a₂₅₄:a₃₅₀ and spectral slope following sample exposure suggest photoproduction of low molecular weight (LMW) CDOM and/or a higher photoreactivity of high molecular weight versus LMW compounds. Photomineralization of nitrogen was regulated by organic nitrogen concentration and resulted in NH₄ ⁺-photoproduction rates between 0.01 and 0.3?μM N?h^?1 and ecologically significant increases in NH₄ ⁺ for these waters. The δ¹³C of the photomineralized DOM was positively correlated to initial DOC concentration and generally lower when initial DOC concentrations were lower, suggesting variation in photomineralized DOM δ¹³C may be a result of kinetic isotope fractionation. Results from this study demonstrate significant variation in the photochemical lability of boreal watershed sources of DOM. Such variation suggests landscape and environmental change has the potential to alter the biogeochemical role photochemical transformations play in downstream portions of boreal watersheds.     

Relationships among dissolved organic matter,iron, and discharge in a moorland stream

Dissolved organic matter (DOM) and iron in a moorland stream were determined at 8-hour intervals over a 6-month period to examine relationships with streamflow. Regression of both solutes on discharge were positive and explained 50–70 per cent of the variance in the solute data, but better predictions were obtained in both cases when a covariate reflecting temporal variation in the relationships was introduced (explained variance 80–90 per cent). Variations in the regression of Fe on DOM were also identified, indicating differences in the complexing power of DOM for Fe and possible variations in the chemical composition of the DOM.     

Seasonal changes in iron transport and nature of dissolved organic matter in a humic river in northern Finland

Changes in the concentration of iron and dissolved organic matter (DOM), and in the colour and fluorescence properties in the River Kiiminkijoki were investigated as functions of the seasonal flow regime over a two-year period. The iron concentration in filtrates and the ratio of Fe to DOC in the river increased under low flow conditions and decreased during the flood periods. The colour of the dissolved organic matter increased with increasing iron content, the effect being more pronounced during the warm period of the year than in winter. The ratio of fluorescence to DOC increased during the warm period of the year but not in winter, and decreased rapidly with discharge at the beginning of the flood period in autumn. The results give indications of the origin, formation, nature, and fate of the DOM in the river water. Temperature-dependent microbiological processes in the formation and sedimentation of iron-organic colloids seem to be important. Estimates are given for the amounts and transport rates of iron discharged into the Gulf of Bothnia by the river.     

Advances in environmental behaviors and effects of dissolved organic matter in aquatic ecosystems

Dissolved organic matter (DOM) is a group of compounds that have complex chemical structures and multiple interactions with their surrounding materials. More than one trillion tons of DOM are stocked in the world’s aquatic ecosystems. DOM is a very important part of aquatic ecosystem productivity and plays a crucial role in global carbon cycling. DOM has rich environmental behaviors and effects such as influencing the bioavailability of contaminants, serving as an important inducer of reactive oxygen species (ROS), and protecting aquatic organisms from the harm of dangerous ultraviolet radiation. There have been many systematic studies on the composition, structure, and sources of DOM because such studies are much easier to conduct than studies on the environmental behaviors and effects of DOM. Due to many factors, the research systems of DOM’s environmental behaviors and effects are still being developed and have become a hotspot of environmental science. This review paper focuses on some critical progress, problems, and trends of DOM’s environmental behaviors and effects in aquatic ecosystems, including mutual exchange mechanisms between DOM and particulate organic matter (POM) with influencing factors, photochemical behaviors of DOM especially inducing ROS, binding interactions between DOM and anthropogenic organic contaminants (AOC), interactions between DOM and microorganisms, effects of DOM on pollutants’ bioavailability, ecotoxicity, and ecological risks. Hopefully, this paper will contribute to a more systematic understanding of the DOM environmental behaviors and effects and to promoting further relevant studies.     

Organic matter characteristics in a Mediterranean stream through amino acid composition: changes driven by intermittency

Amino acid composition (quality) and abundance (quantity) of organic matter (OM) in an intermittent Mediterranean stream were followed during transitions from wet to dry and dry to wet conditions. Amino acids were analyzed in benthic material (epilithic biofilms, sand sediments, leaf material) as well as in the flowing water (dissolved organic matter, DOM). A principal component analysis and the estimation of the amino acid degradation index (DI) elucidated differences in amino acid composition and quality among the wet–drought–wet cycle. Amino acid content and composition were dependent on the source of OM as well as on its diagenetic state. The highest-quality OM (high DI and high N content) occurred on epilithic biofilms and the most degraded and lowest-quality OM occurred in sandy sediments. Differences between the pre- and post-drought periods were evident in DOM quality; autochthonous-derived material was predominant during the pre-drought (wet period preceding drying), while allochthonous inputs dominated during the post-drought period (wet period following drying). In contrast, benthic OM compartments were more stable, but benthic OM quality decreased continuously throughout the drought period. This study revealed that wet–drought–wet cycles resulted in subtle changes in benthic OM quality, and degradation of DOM was related to flow intermittency.     

Dissolved organic matter in surface runoff in the Loess Plateau of China: The role of rainfall events and land-use

Exploring the chemical characterization of dissolved organic matter (DOM) is important for understanding the fate of laterally transported organic matter in watersheds. We hypothesized that differences in water-extractable organic matter (WEOM) in soils of varying land uses and rainfall events may significantly affect the quality and the quantity of stream DOM. To test our hypotheses, characteristics of rainfall-runoff DOM and WEOM of source materials (topsoil from different land uses and gullies, as well as typical vegetation) were investigated at two adjacent catchments in the Loess Plateau of China, using ultraviolet–visible absorbance and excitation emission matrix fluorescence with parallel factor analysis (PARAFAC). Results indicated that land-use types may significantly affect the chemical composition of soil WEOM, including its aromaticity, molecular weight, and degree of humification. The PARAFAC analysis demonstrated that the soils and stream water were dominated by terrestrial/allochthonous humic-like substances and microbial transformable humic-like fluorophores. Shifts in the fluorescence properties of stream DOM suggested a pronounced change in the relative proportion of allochthonous versus autochthonous material under different rainfall patterns and land uses. For example, high proportions of forestland could provide more allochthonous DOM input. This study highlights the relevance of soils and hydrological dynamics on the composition and fluxes of DOM issuing from watersheds. The composition of DOM in soils was influenced by land-use type. Precipitation patterns influenced the proportion of terrestrial versus microbial origins of DOM in surface runoff. Contributions of allochthonous, terrestrially derived DOM inputs were highest from forested landscapes.     

Effects of varying estuarine conditions on the sorption of phenanthrene to sediment particles of Yangtze Estuary

The sorption of phenanthrene on the Yangtze Estuary sediment was studied under varying conditions of particle size, sediment organic contents, salinity, and dissolved organic matter (DOM) concentrations. Small sediment particles showed higher trapping capacity for phenanthrene due to the higher organic contents associated. The organic carbon-based partition coefficient of phenanthrene to the Yangtze Estuary sediment was obtained as 7120 L/kg, lower than the values for other soils or sediments reported in previous studies. The magnitude and direction of the salt effect were complicated by the specific DOM studied. The sediment sorption capacity was greatly increased in saline water in the absence of DOM but decreased in the presence of DOM. Given the conditions in the Yangtze Estuary, the equilibrium sorption of phenanthrene would be decreased with increasing salinity. Overall, the nature and content of both sediment-bound and dissolved organic matter dominate the sorption of hydrophobic organic contaminants in the estuary.     

Diurnal variability in riverine dissolved organic matter composition determined by in situ optical measurement in the San Joaquin River (California,USA)

Dissolved organic matter (DOM) concentration and composition in riverine and stream systems are known to vary with hydrological and productivity cycles over the annual and interannual time scales. Rivers are commonly perceived as homogeneous with respect to DOM concentration and composition, particularly under steady flow conditions over short time periods. However, few studies have evaluated the impact of short term variability (<1 day) on DOM dynamics. This study examined whether diurnal processes measurably altered DOM concentration and composition in the hypereutrophic San Joaquin River (California) during a relatively quiescent period. We evaluated the efficacy of using optical in situ measurements to reveal changes in DOM which may not be evident from bulk dissolved organic carbon (DOC) measurement alone. The in situ optical measurements described in this study clearly showed for the first time diurnal variations in DOM measurements, which have previously been related to both composition and concentration, even though diurnal changes were not well reflected in bulk DOC concentrations. An apparent asynchronous trend of DOM absorbance and chlorophyll‐a in comparison to chromophoric dissolved organic matter (CDOM) fluorescence and spectral slope S_290–350 suggests that no one specific CDOM spectrophotometric measurement explains absolutely DOM diurnal variation in this system; the measurement of multiple optical parameters is therefore recommended. The observed diurnal changes in DOM composition, measured by in situ optical instrumentation likely reflect both photochemical and biologically‐mediated processes. The results of this study highlight that short‐term variability in DOM composition may complicate trends for studies aiming to distinguish different DOM sources in riverine systems and emphasizes the importance of sampling specific study sites to be compared at the same time of day. The utilization of in situ optical technology allows short‐term variability in DOM dynamics to be monitored and serves to increase our understanding of its processing and fundamental role in the aquatic environment. Copyright © 2007 John Wiley & Sons, Ltd.     

Spectrophotometric discrimination of river dissolved organic matter

There is a need to be able to differentiate the dissolved organic matter (DOM) fraction in river waters. Research in the 1970s and 1980s has attempted to utilize both absorbance and fluorescence to distinguish between DOM fractions in river waters, but both were limited by the available technology. Total organic carbon content has, therefore, been widely used as a standard method of measuring DOM concentration, although it has little power to differentiate DOM fractions. Recent advances in fluorescence spectrophotometry enable rapid and optically precise analysis of DOM. Here, we show how a combination of both fluorescence and absorbance can be used to discriminate statistically between spatial variations of DOM in tributaries in a small catchment of the Ouseburn, NE England. The results of the discriminant analysis suggest that about 70% of the samples can be correctly classified to its tributary. Discriminant function 1 explains 60·8% of the variance in the data and the fulvic‐like fluorescence intensity has the largest absolute correlation within this function; discriminant function 2 explains a further 21·5% of the variance and the fulvic‐like fluorescence emission wavelength has the largest absolute correlation within this function. The discriminant analysis does not correctly classify all tributaries every time, and successfully discriminates between the different tributaries 70% of the time. Occasions when the tributary waters are less well discriminated are due to either episodic pollution events (at two sites) or due to tributaries that have strong seasonal trends in spectrophotometric parameters, which allows the sites to be misclassified. Results suggest that spectrophotometric techniques have considerable potential in the discrimination of DOM in rivers. Copyright © 2002 John Wiley & Sons, Ltd.