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.     

The freshwater dissolved organic matter fluorescence–total organic carbon relationship

The fluorescent properties of dissolved organic matter (DOM) enable comparisons of humic‐like (H‐L) and fulvic‐like (F‐L) fluorescence intensities with dissolved organic carbon (DOC) in aquatic systems. The fluorescence‐DOC relationship differed in gradient, i.e. the fluorescence per gram of carbon, and in the strength of the correlation coefficient. We compare the fluorescence intensity of the F‐L and H‐L fractions and DOC of freshwater DOM in north Shropshire, England, featuring a river, wetland, spring, pond and sewage DOM sources. Correlations between fluorescence and DOC varied between sample sites. Wetland water samples for the F‐L peak gave the best correlation, r = 0·756; the lowest correlation was from final treated sewage effluent, r = 0·167. The relationship between fluorescence and DOC of commercially available International Humic Substances Society standards were also examined and they generally showed a lower fluorescence per gram of carbon for the F‐L peak than the natural samples, whereas peat wetland DOM gave a greater fluorescence per gram of carbon than river DOM. Here, we propose the strength of the fluorescence–DOC correlation to be a useful tool when discriminating sources of DOM in fresh water. Copyright © 2007 John Wiley & Sons, Ltd.     

Characteristics and role of groundwater dissolved organic matter on arsenic mobilization and poisoning in Bangladesh

The fluorescence and molecular weight characteristics of dissolved organic matter (DOM) in groundwater of Bangladesh were investigated to evaluate its multiple roles on arsenic (As) mobilization and poisoning. Fluorescence properties of DOM were measured in groundwater samples collected from two As contaminated areas of Bangladesh (Faridpur at the Ganges floodplain and Sonargaon at the Meghna floodplain) from different locations and depths. The three dimensional excitation–emission matrix (3DEEM) fluorescence spectra of groundwater samples showed two characteristic peaks around Ex/Em = 335–365 nm/435–480 nm for fulvic-like peaks and peak at around Ex/Em = 275–290 nm/310–335 nm for the protein-like materials. The similarity of fluorescence spectra of groundwater and surface water of both the study areas with high intensity of fluorescence and its strong correlation with DOC reflect the in situ generation of fluorescent DOM from sedimentary organic matter (SOM) and recent recharge of terrestrial labile organic carbon into shallow aquifer. High performance size-exclusion chromatography (HPSEC) analysis of DOM shows positive correlations between fluorescence intensities (FI) of small molecular fractions (0.65 kDa) and As concentrations, with the signatures of protein-like peaks of DOM in groundwater. This result provides new evidence that small molecular weight fraction of DOM in groundwater of Bangladesh can play an important role on As mobilization and toxicity. In addition, high concentration of fluorescence materials in DOM of As contaminated groundwater of Bangladesh may pose a threat to public health.     

River network travel time is correlated with dissolved organic matter composition in rivers of the contiguous United States

Most terrestrial allochthonous organic matter enters river networks through headwater streams during high flow events. In headwaters, allochthonous inputs are substantial and variable, but become less important in streams and rivers with larger watersheds. As allochthonous dissolved organic matter (DOM) moves downstream, the proportion of less aromatic organic matter with autochthonous characteristics increases. How environmental factors converge to control this transformation of DOM at a continental scale is less certain. We hypothesized that the amount of time water has spent travelling through surface waters of inland systems (streams, rivers, lakes, and reservoirs) is correlated to DOM composition. To test this hypothesis, we used established river network scaling relationships to predict relative river network flow-weighted travel time (FWTT) of water for 60 stream and river sites across the contiguous United States (3090 discrete samples over 10 water years). We estimated lentic contribution to travel times with upstream in-network lake and reservoir volume. DOM composition was quantified using ultraviolet and visible absorption and fluorescence spectroscopy. A combination of FWTT and lake and reservoir volume was the best overall predictor of DOM composition among models that also incorporated discharge, specific discharge, watershed area, and upstream channel length. DOM spectral slope ratio (R² = 0.77) and Freshness Index (R² = 0.78) increased and specific ultraviolet absorbance at 254 nm (R² = 0.68) and Humification Index (R² = 0.44) decreased across sites as a function of FWTT and upstream lake volume. This indicates autochthonous-like DOM becomes continually more dominant in waters with greater FWTT. We assert that river FWTT can be used as a metric of the continuum of DOM composition from headwaters to rivers. The nature of the changes to DOM composition detected suggest this continuum is driven by a combination of photo-oxidation, biological processes, hydrologically varying terrestrial subsidies, and aged groundwater inputs.     

Optical signatures of dissolved organic matter in the watershed of a globally large river (Yangtze River,China)

Parallel factor analysis of fluorescence excitation emission matrices of surface water samples of a globally large river (Yangtze River, China) watershed identified three classes of fluorescent dissolved organic matter (FDOM) that had ex/em = 280/330 nm, 305/385 nm and 350/450 nm respectively, resembling “peak T”, “peak M” and “peak C” commonly identified in natural water, respectively. Peak T (a tyrosine/tryptophan-like FDOM) did not show correlations to peak M or C which were humic-like substances, while a positive correlation (r = 0.935, p < 0.001) was present between the natural log-transformed maximum fluorescence intensity (F_max) of peaks T and M indicating a tight link during their production and processing. F_max values (in Raman unit nm^?1) normalized to dissolved organic carbon (DOC) concentration were low, varying in ranges 15.93–85.95, 29.83–83.54 and 19.73–51.05 × 10^?5 nm^?1 (μmol/L)^?1 for peaks T, M and C, respectively, in line with the history of strong photobleaching of the water samples as indicated by fairly high absorption spectral slope ratios (0.75–1.53 with a mean 1.03). Intermediate fluorescence index (FI) (1.46–1.83 with a mean 1.61) and small specific absorption at 254 nm (0.64–1.93 with a mean 1.15 m^?1 mg^?1 L) of the water samples, indicated the presence of both aquatic microbial DOM (e.g. peak T) and soil DOM (e.g. peak C). Peak C could be substantially removed by UV-A (320–400 nm) irradiation, while peak M was slightly increased when a microbe-containing water was exposed to the same UV-A irradiation. Taken together, peak C was attributed to diffuse soil source while peak M was likely attributed to joint effects of microbial activities and solar irradiation on the chromophores in the sample.     

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.     

Nitrate content and potential microbial signature of rock glacier outflow,Colorado Front Range

Here we characterize the nutrient content in the outflow of the Green Lake 5 rock glacier, located in the Green Lakes Valley of the Colorado Front Range. Dissolved organic carbon (DOC) was present in all samples with a mean concentration of 0·85 mg L^?1 . A one‐way analysis of variance test shows no statistical difference in DOC amounts among surface waters (p = 0·42). Average nitrate concentrations were 69 µmoles L^?1 in the outflow of the rock glacier, compared to 7 µmoles L^?1 in snow and 25 µmoles L^?1 in rain. Nitrate concentrations from the rock glacier generally increased with time, with maximum concentrations of 135 µmoles L^?1 in October, among the highest nitrate concentrations reported for high‐elevation surface waters. These high nitrate concentrations appear to be characteristic of rock glacier outflow in the Rocky Mountains, as a paired‐difference t‐test shows that nitrate concentrations from the outflow of 7 additional rock glaciers were significantly greater compared to their reference streams (p = 0·003). End‐member mixing analysis suggest that snow was the dominant source of nitrate in June, ‘soil’ solution was the dominant nitrate source in July, and base flow was the dominant source in September. Fluoresence index values and PARAFAC analyses of dissolved organic matter (DOM) are also consistent with a switch from terrestrial DOM in the summer time period to an increasing aquatic‐like microbial source during the autumn months. Copyright © 2006 John Wiley & Sons, Ltd.     

Distribution of surface imperviousness in small urban catchments predicts runoff peak flows and stream flashiness

Urban growth is a global phenomenon, and the associated impacts on hydrology from land development are expected to increase, especially in peri‐urban catchments. It is well understood that greater peak flows and higher stream flashiness are associated with increased surface imperviousness and storm location. However, the effect of the distribution of impervious areas on runoff peak flow response and stream flashiness of peri‐urban catchments has not been well studied. In this study, a new geometric index, Relative Nearness of Imperviousness to the Catchment Outlet (RNICO), is defined to correlate imperviousness distribution of peri‐urban catchments with runoff peak flows and stream flashiness. Study sites include 21 suburban catchments in New York representing a range of drainage area from 5 to 189 km² and average imperviousness from 10% to 48%. On the basis of RNICO, all development patterns are divided into 3 classes: upstream, centralized, and downstream. Results showed an obvious increase in runoff peak flows and decrease in time to peak when moving from upstream to centralized and downstream urbanization classes. This indicates that RNICO is an effective tool for classifying urban development patterns and for macroscale understanding of the hydrologic behavior of small peri‐urban catchments, despite the complexity of urban drainage systems. We also found that the impact of impervious distribution on runoff peak flows and stream flashiness decreases with catchment scale. For small catchments (A < 40 km²), RNICO was strongly correlated with the average (R² = .95) and maximum (R² = .91) gaged peak flows due to the relatively efficient subsurface routing through stormwater and sewer networks. Furthermore, the Richards–Baker stream flashiness index in small catchments was positively correlated with fractional impervious area (R² = .84) and RNICO (R² = .87). For large catchments (A > 40 km²), the impact of impervious surface distribution on peak flows and stream flashiness was negligible due to the complex drainage network and great variability in travel times. This study emphasizes the need for greater monitoring of discharge in small peri‐urban catchments to support flood prediction at the local scale.     

Comparison of five snow water equivalent estimation methods across categories

Snow water equivalent (SWE) is an important indicator used in hydrology, water resources, and climate change impact. There are various methods of estimating SWE (falling in 3 categories: indirect sensors, empirical models, and process‐based models), but few studies that provide comparison across these different categories to help users make decisions on monitoring site design or method selection. Five SWE estimation methods were compared against manual snow course data collected over 2 years (2015–2016) from the Dorset Environmental Science Centre, including the gamma‐radiation‐based CS725 sensor, 3 empirical estimation models (Sexstone snow density model, McCreight & Small snow density model, and a meteorology‐based model), and the University of British Columbia Watershed Model snow energy‐balance model. Snow depth, density, and SWE were measured at the Dorset Environmental Science Centre weather station in south‐central Ontario, on a daily basis over 6 winters from 2011 to 2016. The 2 snow density‐based models, requiring daily snow depth as input, gave the best performance (R² of .92 and .92 for McCreight & Small and Sexstone models, respectively). The CS725 sensor that receives radiation coming from soil penetrating the snowpack provided the same performance (R² = .92), proving that the sensor is an applicable method, although it is expensive. The meteorology‐based empirical model, requiring daily climate data including temperature, precipitation and solar radiation, gave the poorest performance (R² = .77). The energy‐balance‐based University of British Columbia Watershed Model snow module, only requiring climate data, worked better than the empirical meteorology‐based model (R² = .9) but performed worse than the density models or CS725 sensor. Given differences in application objectives, site conditions, and budget, this comparison across SWE estimation methods may help users choose a suitable method. For ongoing and new monitoring sites, installation of a CS725 sensor coupled with intermittent manual snow course measurements (e.g., weekly) is recommended for further SWE method estimation testing and development of a snow density model.     

Prediction of river temperature surges is dependent on precipitation method

Urban river systems are particularly sensitive to precipitation‐driven water temperature surges and fluctuations. These result from rapid heat transfer from low‐specific heat capacity surfaces to precipitation, which can cause thermally polluted surface run‐off to enter urban streams. This can lead to additional ecological stress on these already precarious ecosystems. Although precipitation is a first‐order driver of hydrological response, water temperature studies rarely characterize rain event dynamics and typically rely on single gauge data that yield only partial estimates of catchment precipitation. This paper examines three precipitation measuring methods (a statutory automatic weather station, citizen science gauges, and radar estimates) and investigates relationships between estimated rainfall inputs and subhourly surges and diurnal fluctuations in urban river water temperature. Water temperatures were monitored at 12 sites in summer 2016 in the River Rea, in Birmingham, UK. Generalized additive models were used to model the relationship between subhourly water temperature surges and precipitation intensity and subsequently the relationship between daily precipitation totals and standardized mean water temperature. The different precipitation measurement sources give highly variable precipitation estimates that relate differently to water temperature fluctuations. The radar catchment‐averaged method produced the best model fit (generalized cross‐validation score [GCV] = 0.30) and was the only model to show a significant relationship between water temperature surges and precipitation intensity (P < 0.001, R² = 0.69). With respect to daily metrics, catchment‐averaged precipitation estimates from citizen science data yielded the best model fit (GCV score = 0.20). All precipitation measurement and calculation methods successfully modelled the relationship between standardized mean water temperature and daily precipitation (P < 0.001). This research highlights the potential for the use of alternative precipitation datasets to enhance understanding of event‐based variability in water quality studies. We conclude by recommending the use of spatially distributed precipitation data operating at high spatial (<1 km²) and temporal (<15 min) resolutions to improve the analysis of event‐based water temperature and water quality studies.     

Dissolved organic matter variations in coastal plain wetland watersheds: The integrated role of hydrological connectivity,land use,and seasonality

Dissolved organic matter (DOM) is integral to fluvial biogeochemical functions, and wetlands are broadly recognized as substantial sources of aromatic DOM to fluvial networks. Yet how land use change alters biogeochemical connectivity of upland wetlands to streams remains unclear. We studied depressional geographically isolated wetlands on the Delmarva Peninsula (USA) that are seasonally connected to downstream perennial waters via temporary channels. Composition and quantity of DOM from 4 forested, 4 agricultural, and 4 restored wetlands were assessed. Twenty perennial streams with watersheds containing wetlands were also sampled for DOM during times when surface connections were present versus absent. Perennial watersheds had varying amounts of forested wetland (0.4–82%) and agricultural (1–89%) cover. DOM was analysed with ultraviolet–visible spectroscopy, fluorescence spectroscopy, dissolved organic carbon (DOC) concentration, and bioassays. Forested wetlands exported more DOM that was more aromatic‐rich compared with agricultural and restored wetlands. DOM from the latter two could not be distinguished suggesting limited recovery of restored wetlands; DOM from both was more protein‐like than forested wetland DOM. Perennial streams with the highest wetland watershed cover had the highest DOC levels during all seasons; however, in fall and winter when temporary streams connect forested wetlands to perennial channels, perennial DOC concentrations peaked, and composition was linked to forested wetlands. In summer, when temporary stream connections were dry, perennial DOC concentrations were the lowest and protein‐like DOM levels the highest. Overall, DOC levels in perennial streams were linked to total wetland land cover, but the timing of peak fluxes of DOM was driven by wetland connectivity to perennial streams. Bioassays showed that DOM linked to wetlands was less available for microbial use than protein‐like DOM linked to agricultural land use. Together, this evidence indicates that geographically isolated wetlands have a significant impact on downstream water quality and ecosystem function mediated by temporary stream surface connections.     

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.     

Landscape influences on aluminium and dissolved organic carbon in streams draining the Hubbard Brook valley,New Hampshire,USA

Concentrations of both aluminium (Al) and dissolved organic carbon (DOC) in stream waters are likely to be regulated by factors that influence water flowpaths and residence times, and by the nature of the soil horizons through which waters flow. In order to investigate landscape‐scale spatial patterns in streamwater Al and DOC, we sampled seven streams draining the Hubbard Brook valley in central New Hampshire. We observed considerable variation in stream chemistry both within and between headwater watersheds. Across the valley, concentrations of total monomeric aluminium (Al_m) ranged from below detection limits (<0·7 µmol l⁻¹) to 22·3 µmol l⁻¹. In general, concentrations of Al_m decreased as pH increased downslope. There was a strong relationship between organic monomeric aluminium (Al_o) and DOC concentrations (R² = 0·92). We observed the highest Al_m concentrations in: (i) a watershed characterized by a steep narrow drainage basin and shallow soils and (ii) a watershed characterized by exceptionally deep forest floor soils and high concentrations of DOC. Forest floor depth and drainage area together explained much of the variation in ln Al_m (R² = 0·79; N = 45) and ln DOC (R² = 0·87; N = 45). Linear regression models were moderately successful in predicting ln Al_m and ln DOC in streams that were not included in model building. However, when back‐transformed, predicted DOC concentrations were as much as 72% adrift from observed DOC concentrations and Al_m concentrations were up to 51% off. This geographic approach to modelling Al and DOC is useful for general prediction, but for more detailed predictions, process‐level biogeochemical models are required. Copyright © 2005 John Wiley & Sons, Ltd.     

Rainfall partitioning through a mixed cedar swamp and associated C and N fluxes in Southern Ontario,Canada

Partitioning of rainfall through a forest canopy into throughfall, stemflow, and canopy interception is a critical process in the water cycle, and the contact of precipitation with vegetated surfaces leads to increased delivery of solutes to the forest floor. This study investigates the rainfall partitioning over a growing season through a temperate, riparian, mixed coniferous‐deciduous cedar swamp, an ecosystem not well studied with respect to this process. Seasonal throughfall, stemflow, and interception were 69.2%, 1.5%, and 29.3% of recorded above‐canopy precipitation, respectively. Event throughfall ranged from a low of 31.5 ± 6.8% for a small 0.8‐mm event to a high of 82.9 ± 2.4% for a large 42.7‐mm event. Rain fluxes of at least 8 mm were needed to generate stemflow from all instrumented trees. Most trees had funnelling ratios <1.0, with an exponential decrease in funnelling ratio with increasing tree size. Despite this, stand‐scale funnelling ratios averaged 2.81 ± 1.73, indicating equivalent depth of water delivered across the swamp floor by stemflow was greater than incident precipitation. Throughfall dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) averaged 26.60 ± 2.96 and 2.02 ± 0.16 mg L^?1, respectively, which were ~11 and three times above‐canopy rain levels. Stemflow DOC averaged 73.33 ± 7.43 mg L^?1, 35 times higher than precipitation, and TDN was 4.45 ± 0.56 mg L^?1, 7.5 times higher than rain. Stemflow DOC concentration was highest from Populus balsamifera and TDN greatest from Thuja occidentalis trees. Although total below‐canopy flux of TDN increased with increasing event size, DOC flux was greatest for events 20–30 mm, suggesting a canopy storage threshold of DOC was readily diluted. In addition to documenting rainfall partitioning in a novel ecosystem, this study demonstrates the excess carbon and nitrogen delivered to riparian swamps, suggesting the assimilative capacity of these zones may be underestimated.     

Dynamic stream network intermittence explains emergent dissolved organic carbon chemostasis in headwaters

Dissolved organic carbon (DOC) concentrations vary among headwaters, with variation typically decreasing with watershed area. We hypothesized that streamflow intermittence could be an important source of variation in DOC concentrations across a small watershed, through (a) temporal legacies of drying on organic matter accumulation and biotic communities and (b) spatial patterns of connectivity with DOC sources. To test these hypotheses, we conducted three synoptic water chemistry sampling campaigns across a 25.5‐km² watershed in south‐eastern Idaho during early spring, late summer, and late fall. Using changepoint analysis, we found that DOC variability collapsed at a consistent location (watershed areas ~1.3 to ~1.8 km²) across seasons, which coincided with the watershed area where variability in streamflow intermittence collapsed (~1.5 km²). To test hypothesized mechanisms through which intermittence may affect DOC, we developed temporal, spatial, and spatio‐temporal metrics of streamflow intermittence and related these to DOC concentrations. Streamflow intermittence was a strong predictor of DOC across seasons, but different metrics predicted DOC depending on season. Seasonal changes in the effects of intermittence on DOC reflected seasonal changes from instream to flowpath controls. A metric that captured spatial connectivity to sources significantly predicted DOC during high flows, when DOC is typically controlled by transport. In contrast, a reach‐scale temporal metric of intermittence predicted DOC during the late growing season, when DOC is typically controlled by instream processes and when legacy effects of drying (e.g., diminished biological communities) would likely affect DOC. The effects of intermittence on DOC extend beyond temporal legacies at a point. Our results suggest that legacy effects of intermittence do not propagate downstream in this system. Instead, snapshots of spatial patterns of intermittence upstream of a reach are critical for understanding spatial patterns of DOC through connectivity to DOC sources, and these processes drive patterns of DOC even in perennial reaches.     

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.