Dissolved Organic Carbon Fluorescence Research Articles

Molecular weight-dependent differences in spectral properties and metal-binding behaviors of dissolved organic matter from different lakes

Dissolved organic matter (DOM) plays an important role in governing metal speciation and migration in aquatic systems. In this study, various DOM samples were collected from Lakes Erhai, Kokonor, and Chaka, and size-fractionated into high molecular weight (HMW, 1 kDa–0.7 μm) and low molecular weight (LMW, <1 kDa) fractions for measurements of dissolved organic carbon (DOC), spectral properties, and metal binding behaviors. Our results demonstrated that samples from Lake Chaka exhibited the highest DOC concentration and fluorescence indices but the lowest percentage of carbohydrates. Regardless of sampling locations, the HMW-DOM fractions contained higher abundances of aromatic DOM, carbohydrates and protein-like substances, but lower abundance of fulvic acid-like substances compared to those in the LMW fractions. Metal titration experiments coupled with the excitation-emission matrix (EEM)-parallel factor (PARAFAC) modeling revealed that the quenching of the PARAFAC-derived fluorescent components was more pronounced in the presence of Cu(II) compared to Pb(II). Humic-like components emerged as a superior model, exhibiting higher binding affinities for Cu(II) than protein-like substances, while the opposite trend was observed for Pb(II). In samples obtained from Lakes Erhai and Kokonor, the condition stability constants (Log KM) for the binding of both Cu(II) and Pb(II) with the HMW-DOM fraction were higher than those with the LMW-DOM fraction. Conversely, a contrasting trend was observed for Lake Chaka. This study highlighted the heterogeneity in spectral properties and metal-binding behaviors of natural DOMs, contributing to an improved understanding of the molecular interactions between DOM components and metal ions and their environmental fate in aquatic ecosystems.

Climate Impact on Dissolved Organic Carbon Composition in a North‐Temperate Peatland and Recipient Surface Water

AbstractClimate may regulate dissolved organic carbon (DOC) composition across the peat‐water interface, but experimental evidence is scarce. We manipulated the climate in peatland and recipient surface water mesocosms to reflect four different climate warming scenarios. In half of the mesocosms, the water level was managed to avoid drought, after which responses were recorded during two annual cycles. It was hypothesized that warming and drought increase the aromaticity and humic‐like fluorescence character of DOC, and that this change propagate to recipient waters. Pore water DOC concentrations increased with temperature and peaked in hydrologically unmanaged mesocosms. Aromaticity increased as expected after drought in the warmest scenario (+3.2°C), but the overall evidence for hypothesized changes in DOC aromaticity and fluorescence composition (%) was limited. In managed warming scenarios, one aromatic humic component expectedly increased together with microbially derived humic fluorescence, whereas two other humic‐like components decreased. In the unmanaged mesocosms which were exposed to drought, water level exerted an overriding control of humic DOC; for example, as the microbially derived humic fluorescence diminished after drought in all climate scenarios. In the surface water recipients, warming had nearly no impact on humic‐like fluorescence, but there were decreases in protein‐like fluorescence. Overall, this experiment revealed no conclusive support for the hypothesized aromatization and humification of peatland‐derived DOC in response to drought or warming. Nonetheless, both factors increase the quantity of DOC in peatland pore waters and affect composition in complex ways, calling for further investigation of chemical and functional traits of peatland DOC in a changing environment.

Irrigation alters source-composition characteristics of groundwater dissolved organic matter in a large arid river basin, Northwestern China

It has been well documented that agricultural activities lead to significant alterations in surface water dissolved organic matter (DOM), yet their impacts on groundwater DOM remain poorly constrained. The quantity, source, and composition of DOM play a pivotal role in a range of groundwater ecosystem services that are of important ecological and societal values. We assessed the impact of irrigation on the source and compositional characteristics of groundwater DOM in a large river basin supporting intensive agriculture in arid northwestern China. We sampled five water types along a river reach of approximately 40 km, including groundwater, river water, irrigation canal water, hyporheic water, and soil leachates. The excitation-emission matrix (EEM) measurements coupled with parallel factor analysis (PARAFAC) identified two terrestrial-derived, humic-like fluorescent components (C1 and C2) and one protein-like autochthonous component (C3). DOM composition and dissolved organic carbon (DOC) concentration varied as a function of water type, with subsurface waters showing relatively lower DOC and terrestrial humic fluorescence than surface waters. Combining nitrate, electrical conductivity, dissolved inorganic carbon (DIC), and δ13C-DIC, irrigation-influenced samples were identified, and the influence of irrigation on groundwater DOM appeared only in shallow aquifers (<50 m). Irrigation-influenced groundwater exhibited higher DOC and terrestrial fluorescence than unimpacted groundwater, suggesting that irrigation return flows accelerated the downward movement of terrestrial humic compounds and led to their accumulation in aquifers. This effect was propagated via surface water-groundwater interactions to upwelling hyporheic water, which also showed enrichment in terrestrial fluorescence. Our findings demonstrate that irrigation can accelerate the biogeochemical cycling of organic compounds via a subsurface pathway of from the soil to aquifer to hyporheic zone. The enrichment of soil-derived compounds in subsurface waters may have important ecological consequences, such as altering the transport of nutrients and pollutants and changing carbon and energy flows across the surface-subsurface boundary.

The photochemical release of dissolved organic matter from resuspended sediments: Insights from fluorescence spectroscopy

Sediments exposed to sunlight can serve as an important source of dissolved organic carbon (DOC) and nutrients to overlying waters. However, the photochemical release processes of dissolved organic matter (DOM) from resuspended sediments and the characteristics of photoreleased DOM are not fully understood. In this study, excitation-emission matrix fluorescence combined with parallel factor analysis (EEMs-PARAFAC) was used to study the photochemical release of DOM qualitatively and quantitatively. The EEMs-PARAFAC demonstrated that the photoreleased DOM is dominated by humic-like substances, and the photorelease process could be consist of the photoproduction and photodegradation of DOM. The concurrent photodegradation may result in the underestimation of photoreleased DOM. Moreover, the significant increases in DOC content and fluorescence intensity of humic-like components along with increasing nitrate and ferric ion indicated that nitrate and ferric ion could facilitate the photoproduction of DOM through the photochemical produced hydroxyl radical. However, the decreases in DOC and fluorescence intensity were also observed at high concentration of nitrate and ferric ion, owing to the photodegradation of DOM by redundant hydroxyl radical. All of these results suggest that EEMs-PARAFAC is an effective and sensitive analytical technique for evaluating DOM photoreleased from suspended lake sediments and previous studies may underestimate photochemical release of DOM from sediments due to the overlook of the subsequently photodegradation of these released DOM. Thus, the photochemical release of DOM and its associated pollutants from suspended particles in shallow and eutrophic lakes should be more significant then should be paid more attention.

DOC fluorescence properties and degradation in the Changjiang River Network, China: implications for estimating in-stream DOC removal

Dissolved organic carbon (DOC) in large river networks is an important carbon pool in the global biogeochemical cycle. DOC compositions vary spatially at global and regional scales, which influences DOC degradation and subsequent in-stream removal in river networks. The Changjiang River Network (CRN) is the third largest river system worldwide and plays an important role in DOC transformation and transportation. However, the relationships between DOC composition and degradation, as well as the quantification of in-stream removal, remain poorly understood. In this study, we chose the CRN to study spatial patterns of DOC fluorescence, as proxies for chemical composition, and degradation. Laboratory degradation experiments were conducted to explore DOC degradability and mechanisms of photodegradation and microbial respiration. We found that DOC fluorescence properties and degradation showed significant spatial differences in the lower reaches of the CRN. DOC with higher proportions of humic acid-like materials showed higher photodegradability. In degradation experiments, the total DOC loss was 49.1–66.0% over about the first 6 to 7 days. Microbial respiration removed 33.0–47.3% of total DOC, while photodegradation removed 9.0–35.3%. The relative contributions of photodegradation and microbial respiration to DOC degradation varied with different DOC fluorescence properties. The experimental values of DOC decay rate constants were 0.217–0.250 d−1. Our study improves understanding of DOC degradability, linking to its composition and providing a reference for estimating DOC in-stream removal in large river networks.

Seasonal and downstream alterations of dissolved organic matter and dissolved inorganic ions in a human-impacted mountainous tributary of the Yellow River, China.

Human activities impose important disturbances on both organic and inorganic chemistry in fluvial systems. In this study, we investigated the intra-annual and downstream variations of dissolved organic carbon (DOC), dissolved organic matter (DOM) excitation-emission matrix fluorescence (EEM) with parallel factor analysis (PARAFAC), major ions, and dissolved inorganic nitrogen (DIN) species in a mountainous tributary of the Yellow River, China. Both DOM quantity and quality, as represented by DOC and DOM fluorescence respectively, changed spatially and seasonally in the studied region. Fluorescence intensity of tryptophan-like components (C3) were found much higher at the populated downstream regions than in the undisturbed forested upstream regions. Seasonally, stronger fluorescence intensity of protein-like components (C3 and C4) was observed in the low-flow period (December) and in the medium-flow period (March) than in the high-flow period (May), particularly for the downstream reaches, reflecting the dominant impacts of wastewater pollution in the downstream regions. In contrast to the protein-like fluorescence, humic-like fluorescence components C1 and C2 exhibited distinctly higher intensity in the high-flow period with smaller spatial variation indicating strong flushing effect of increasing water discharge on terrestrial-sourced humic-like materials in the high-flow period. Pollution-affected dissolved inorganic ions, particularly Na+, Cl-, and NH4+-N, showed similar spatial and seasonal variations with protein-like fluorescence of DOM. The significant positive correlations between protein-like fluorescence of DOM and pollution-affected ions, particularly Na+, Cl-, and NH4+-N, suggested that there were similar pollution sources and transportation pathways of both inorganic and organic pollutants in the region. The combination of DOM fluorescence properties and inorganic ions could provide an important reference for the pollution source characterization and river basin management.

Temporal changes in photoreactivity of dissolved organic carbon and implications for aquatic carbon fluxes from peatlands

Abstract. Aquatic systems draining peatland catchments receive a high loading of dissolved organic carbon (DOC) from the surrounding terrestrial environment. Whilst photo-processing is known to be an important process in the transformation of aquatic DOC, the drivers of temporal variability in this pathway are less well understood. In this study, 8 h laboratory irradiation experiments were conducted on water samples collected from two contrasting peatland aquatic systems in Scotland: a peatland stream and a reservoir in a catchment with high percentage peat cover. Samples were collected monthly at both sites from May 2014 to May 2015 and from the stream system during two rainfall events. DOC concentrations, absorbance properties and fluorescence characteristics were measured to investigate characteristics of the photochemically labile fraction of DOC. CO2 and CO produced by irradiation were also measured to determine gaseous photoproduction and intrinsic sample photoreactivity. Significant variation was seen in the photoreactivity of DOC between the two systems, with total irradiation-induced changes typically 2 orders of magnitude greater at the high-DOC stream site. This is attributed to longer water residence times in the reservoir rendering a higher proportion of the DOC recalcitrant to photo-processing. During the experimental irradiation, 7 % of DOC in the stream water samples was photochemically reactive and direct conversion to CO2 accounted for 46 % of the measured DOC loss. Rainfall events were identified as important in replenishing photoreactive material in the stream, with lignin phenol data indicating mobilisation of fresh DOC derived from woody vegetation in the upper catchment. This study shows that peatland catchments produce significant volumes of aromatic DOC and that photoreactivity of this DOC is greatest in headwater streams; however, an improved understanding of water residence times and DOC input–output along the source to sea aquatic pathway is required to determine the fate of peatland carbon.

Dissolved organic carbon transformations and microbial community response to variations in recharge waters in a shallow carbonate aquifer

In carbonate aquifers, dissolved organic carbon from the surface drives heterotrophic metabolism, generating CO2 in the subsurface. Although this has been a proposed mechanism for enhanced dissolution at the water table, respiration rates and their controlling factors have not been widely evaluated. This study investigates the composition and concentration of dissolved organic carbon (DOC) reaching the water table from different recharge pathways on a subtropical carbonate island using a combination of DOC concentration measurements, fluorescence and absorption characterisation. In addition, direct measurements of the microbial response to the differing water types were made. Interactions of rainfall with the vegetation, via throughfall and stemflow, increase the concentration of DOC. The highest DOC concentrations are associated with stemflow, overland recharge and dissolution hole waters which interact with bark lignin and exhibit strong terrestrial-derived characteristics. The groundwater samples exhibit the lowest concentrations of DOC and are comprised of refractory humic-like organic matter. The heterotrophic response seems to be controlled by the concentration of DOC in the sample. The terrestrially sourced humic-like matter in the stemflow and dissolution hole samples was highly labile, thus increasing the amount of biologically produced CO2 to drive dissolution. Based on the calculated respiration rates, microbial activity could enhance carbonate dissolution, increasing porosity generation by a maximum of 1 % kyr−1 at the top of the freshwater lens.

Homogenization of detrital leachate in an old-growth coniferous forest, OR: DOC fluorescence signatures in soils undergoing long-term litter manipulations

Characterizing the relationship between plant detrital inputs and the resulting dissolved organic carbon (DOC) leachate is vital to understanding the ultimate fate of root carbon, fallen wood and needles in forested watersheds. Similarly, elucidating chemical differences in the soil DOC pool may help to explain which DOC fractions are sorbed to mineral surfaces and contribute to accumulation of soil organic carbon, are respired as CO2, or are exported to nearby catchments. In order to test the hypothesis that soils with different detrital inputs impart a detectable signal on DOC in mineral soil, soil solution DOC was sampled from the Detrital Input and Removal Treatment (DIRT) plots located in the H.J. Andrews Experimental Forest, OR. Multiple types of fresh litter extracts, along with lysimeter and soil extracts from DIRT treatment plots were characterized using UV-Vis and fluorescence spectroscopy coupled with the Cory and McKnight (Environ Sci Technol 39:8142–8149, 2005) parallel factor analysis (PARAFAC) model. Principal component analysis of 13 unique fluorophores distinguished using PARAFAC show that litter and soil extracts (Douglas-fir needles, wood of decomposition Class 2, Class 3 and Class 5, O-horizon, and 0–5 cm A-horizon) each have distinct fluorescence signatures. However, while litter-leached DOC chemistry varies by litter type, neither lysimeter-collected DOC or soil extracts in the DIRT plots show statistically significant differences in fluorescence signatures among treatments, even after 17 years of litter manipulations. The lack of observed differences among DIRT treatments suggests that both abiotic interactions and microbial activity effectively homogenize organic carbon constituents within the dissolved pool. Minor but observable changes in PARAFAC components and optical indices during a 1-month biodegradation incubation of litter and soil extracts indicate that while biodegradation significantly alters DOC chemistry, abiotic mechanisms are also critical to DOC transformation in these soils with high sorption capacity. Although leachates from different plant detrital sources have distinct carbon chemical signatures, these DOC signatures are effectively homogenized after passage through mineral soil. These results highlight the dominant role of both biotic and abiotic interactions in controlling the chemistry of DOC in shallow soils.

Mercury proxies and mercury dynamics in a forested watershed of the US Northeast.

Although many studies focus on mercury (Hg) and methylmercury (MeHg) dynamics in streams, challenges remain in identifying the relative importance of land cover and seasonality at regulating Hg and MeHg dynamics at the watershed scale. Developing robust proxies for Hg and/or MeHg determination also remains a challenge. Our study used Hg, MeHg, and dissolved organic carbon (DOC) concentration measurements and various DOC fluorescence indices to characterize Hg and DOC dynamics in a forested watershed of the US Northeast. Principal component analysis indicated that land cover/landscape position (i.e., headwater vs. wetland-influenced area vs. lake-influenced area) explained 44% of the variance in Hg, MeHg, DOC concentrations, and DOC quality during the snow-free season, while seasonality (i.e., air temperature and discharge) explained only 21% of the variance in the results. Furthermore, finding a good proxy for Hg that is valid across a range of landscape positions remains a challenge; however, regression analysis indicated that the fluorescence peak Humic C (excitation = 350nm; emission = max (420-480)), which corresponds to the presence of melanoidins in water, explained 21% of the variability in MeHg concentrations across both space and time (p = 0.001), and thus appears to be a possible proxy for MeHg determination in our study watershed. From a management perspective, land cover modifications (lake, reservoir, and wetland) are likely to play more important roles at regulating Hg, MeHg, and DOC exports at the watershed scale than long-term changes in the climate of this region.

Spatial and temporal variability in stream dissolved organic carbon quantity and quality in an Adirondack forested catchment

The dissolved organic carbon (DOC) quantity and quality in streams regulate many ecosystem processes at the watershed scale. There is, however, a dearth of information on the spatial variability of in-stream DOC quality in small catchments. Our study used direct DOC concentration measurements and fluorescence spectroscopy indices to determine how stream DOC quantity and quality changed over space and time in a forested catchment of the US Northeast, and provided insight into how these systems might respond to changes in land use and/or climate in the coming years. Land cover (e.g., wetlands, lakes) exerted a dominant role over changes in flow and/or air temperature at regulating DOC concentrations in the watershed. Wetland areas acted as large sources of humic-rich DOC, while lakes were DOC sinks, especially for humic-rich DOC. DOC quality indices were generally significantly (p<0.05) correlated to DOC concentrations regardless of location and time of year, with high DOC concentrations (>7mgCL−1) primarily tied to the mobilization of terrestrial highly degraded humic rich DOC, likely to be less bioavailable (and less fresh) than the DOC exported at times when DOC concentrations are low (<7mgCL−1). Overall, results pointed to a two-phase DOC export whereby mobile and bioavailable fractions of DOC in surface water (protein-like DOC) are produced throughout the watershed (including the wetland), while recalcitrant humic-like DOC fractions are predominantly generated by the wetland, before preferentially sedimenting out in the lake. As the climate continues to change, we will likely find not only an increase in the amount of DOC exported at the watershed scale, but also a shift in the quality of this DOC toward less bioavailable DOC fractions rich in humic substances.

Higher reactivity of allochthonous vs. autochthonous DOC sources in a shallow lake

Dissolved organic carbon (DOC) reactivity in aquatic systems is essentially dependent on DOC precursor material and on the processes regulating its bioavailability, especially photodegradation and microbial activity. We investigated temporal changes (from hours to weeks) in the reactivity of allochthonous and autochthonous DOC sources in a macrophyte-dominated shallow lake using a set of incubation experiments. Changes in DOC fluorescence and absorbance properties due to biodegradation (BD) and to the combined effect of photo- and biodegradation (UV + BD) were traced. Allochthonous DOC was more reactive than autochthonous DOC (AutoDOC), showing higher DOC losses (between 22 and 36 %) and faster changes in DOC properties than AutoDOC. The effect of UV + BD was larger than BD alone for both sources of DOC. The rates of change of DOC properties were stronger during the first days of incubation and showed no regular pattern for any of the treatments or DOC sources. Our findings highlight the relevance of the timescale when assessing changes in DOC quality under different degradation pathways, as well as the need of discussing the labile character usually attributed to autochthonous DOC in systems dominated by submerged vegetation, as many shallow lakes or lagoons.

DOC-dynamics in a small headwater catchment as driven by redox fluctuations and hydrological flow paths – are DOC exports mediated by iron reduction/oxidation cycles?

Abstract. Dissolved organic carbon (DOC) exports from many catchments in Europe and North-America are steadily increasing. Several studies have sought to explain this observation. As possible causes, a decrease in acid rain or sulfate deposition, concomitant reductions in ionic strength and increasing temperatures were identified. DOC often originates from riparian wetlands; but here, despite higher DOC concentrations, ionic strength in pore waters usually exceeds that in surface waters. In the catchment under study, DOC concentrations were synchronous with dissolved iron concentrations in pore and stream water. This study aims at testing the hypothesis that DOC exports are mediated by iron reduction/oxidation cycles. Following the observed hydrographs, δ18O of water and DOC fluorescence, the wetlands were identified as the main source of DOC. Antecedent biogeochemical conditions, i.e., water table levels in the wetlands, influenced the discharge patterns of nitrate, iron and DOC during an event. The correlation of DOC with pH was positive in pore waters, but negative in surface waters; it was negative for DOC with sulfate in pore waters, but only weak in surface waters. Though, the positive correlation of DOC with iron was universal for pore and surface water. The decline of DOC and iron concentrations in transition from anoxic wetland pore water to oxic stream water suggests a flocculation of DOC with oxidising iron, leading to a drop in pH in the stream during high DOC fluxes. The pore water did not per se differ in pH. There is, thus, a need to consider processes more thoroughly of DOC mobilisation in wetlands when interpreting DOC exports from catchments. The coupling of DOC with iron fluxes suggested that increased DOC exports could at least, in part, be caused by increasing activities in iron reduction, possibly due to increases in temperature, increasing wetness of riparian wetlands, or by a shift from sulfate dominated to iron reduction dominated biogeochemical regimes.

Temporal and spatial changes in dissolved organic carbon concentration and fluorescence intensity of fulvic acid like materials in mountainous headwater catchments

Dissolved organic carbon (DOC) such as humic substances are key to understanding the aquatic environment in catchments, because they, containing a large number of phenolic and carboxylic acid groups, adsorb many kinds of inorganic materials and also affect nutrition and carbon transport in catchments. To understand the detailed DOC dynamics, we conducted hydrological observations at mountainous headwater catchments dominated by different vegetation types (planted evergreen coniferous forest of 1.29 ha and natural deciduous broadleaf forest of 1.28 ha). The relationship between DOC concentrations and fluorescence intensity of fulvic acid-like materials (F-FAM) were positively correlated in both catchments but different between soil extracts, baseflow, and near surface flow represented by biomat flow. The ratios of change in F-FAM to that in DOC concentration (F-FAM/DOC) were higher in the baseflow (about 6 in both catchments) and lower in the soil extracts (about 4.5 in both catchments, respectively). However, the relationship in stormflow was distributed between the trends of baseflow and soil extracts. The higher F-FAM/DOC in baseflow may thus indicate that DOC (and FAM) in groundwater discharge mainly contributed to the stream flow, and the stormflow mainly reflect subsurface flow through soil during most rainstorms. In contrast, a high F-FAM/DOC ratio (>6) appeared in the stormflow of both catchments especially during large storms of short duration and high intensity following a dry antecedent period. The F-FAM/DOC in biomat flow developing distinctly in the coniferous catchment was high (about 6.5). Thus, rapid shallow subsurface flow through the biomat or near-surface of slopes might explain the unique transport dynamics of DOC and FAM in stormflows with the high F-FAM/DOC ratio. These results imply that the DOC and FAM relationship responds variably depending on both the distribution of soil organic matter and rainwater flow paths in steep slopes as well as on storm size and characteristics.

Atmospheric deposition as a source of carbon and nutrients to an alpine catchment of the Colorado Rocky Mountains

Abstract. Many alpine areas are experiencing deglaciation, biogeochemical changes driven by temperature rise, and changes in atmospheric deposition. There is mounting evidence that the water quality of alpine streams may be related to these changes, including rising atmospheric deposition of carbon (C) and nutrients. Given that barren alpine soils can be severely C limited, atmospheric deposition sources may be an important source of C and nutrients for these environments. We evaluated the magnitude of atmospheric deposition of C and nutrients to an alpine site, the Green Lake 4 catchment in the Colorado Rocky Mountains. Using a long-term dataset (2002–2010) of weekly atmospheric wet deposition and snowpack chemistry, we found that volume weighted mean dissolved organic carbon (DOC) concentrations were 1.12 ± 0.19 mg l−1, and weekly concentrations reached peaks as high at 6–10 mg l−1 every summer. Total dissolved nitrogen concentration also peaked in the summer, whereas total dissolved phosphorus and calcium concentrations were highest in the spring. To investigate potential sources of C in atmospheric deposition, we evaluated the chemical quality of dissolved organic matter (DOM) and relationships between DOM and other solutes in wet deposition. Relationships between DOC concentration, fluorescence, and nitrate and sulfate concentrations suggest that pollutants from nearby urban and agricultural sources and organic aerosols derived from sub-alpine vegetation may influence high summer DOC wet deposition concentrations. Interestingly, high DOC concentrations were also recorded during "dust-in-snow" events in the spring, which may reflect an association of DOM with dust. Detailed chemical and spectroscopic analyses conducted for samples collected in 2010 revealed that the DOM in many late spring and summer samples was less aromatic and polydisperse and of lower molecular weight than that of winter and fall samples. Our C budget estimates for the Green Lake 4 catchment illustrated that wet deposition (9.9 kg C ha−1 yr−1) and dry deposition (6.9 kg C ha−1 yr−1) were a combined input of approximately 17 kg C ha−1 yr−1, which could be as high as 24 kg C ha−1 yr−1 in high dust years. This atmospheric C input approached the C input from microbial autotrophic production in barren soils. Atmospheric wet and dry deposition also contributed 4.3 kg N ha−1 yr−1, 0.15 kg P ha−1 yr−1, and 2.7 kg Ca2+ ha−1 yr−1 to this alpine catchment.

Using fluorescence spectroscopy EEM to evaluate the efficiency of organic matter removal during coagulation–flocculation of a tropical surface water (Agbo reservoir)

This study evaluate the use of fluorophores A, C and T fluorescence intensities to access the coagulation efficiency for removing dissolved organic carbon (DOC) in the raw water from Agbo reservoir in Ivory Coast. A coagulation–flocculation was conducted with aluminium sulphate as coagulant and DOC residual and fluorescence intensities were acquired. The consistency of fluorescence data was evaluated to ensure that no inner-effect, quenching or enhanced intensities affect the data. Fluorescence-inferred DOC removal was then calculated in percentage terms from the decrease in organic matter fluorescence intensity for each peak between raw and clarified water and correlated with measured DOC removal. The results indicate a high significant correlation between measured DOC removal and fluorescence-inferred DOC removal calculated for peak A ( R 2 = 0.91), peak C ( R 2 = 0.89), peak T ( R 2 = 0.92) indicating a strong linear relationship between DOC removal and fluorescence intensities. Furthermore, tryptophan-like (peak T) was found to be the least eliminated and thus, may be considered as an indicator of DOC residual after coagulation–flocculation process. This result shows that fluorescence spectroscopy offers a robust analytical technique to be used to evaluate DOM removal efficiency in water treatment.

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

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

Colored dissolved organic matter in Tampa Bay, Florida

Absorption and fluorescence of colored dissolved organic matter (CDOM) and concentrations of dissolved organic carbon (DOC), chlorophyll and total suspended solids in Tampa Bay and its adjacent rivers were examined in June and October of 2004. Except in Old Tampa Bay (OTB), the spatial distribution of CDOM showed a conservative relationship with salinity in June, 2004 ( a CDOM(400) = − 0.19 × salinity + 6.78, R 2 = 0.98, n = 17, salinity range = 1.1–32.5) with little variations in absorption spectral slope and fluorescence efficiency. This indicates that CDOM distribution was dominated by mixing. In October, 2004, CDOM distribution was nonconservative with an average absorption coefficient ( a CDOM(400), ∼ 7.76 m − 1 ) about seven times higher than that in June (∼ 1.11 m − 1 ). The nonconservative behavior was caused largely by CDOM removal at intermediate salinities (e.g., a CDOM(400) removal > 15% at salinity ∼ 13.0), which likely resulted from photobleaching due to stronger stratification. The spatial and seasonal distributions of CDOM in Tampa Bay showed that the two largest rivers, the Alafia River (AR) and Hillsborough River (HR) were dominant CDOM sources to most of the bay. In OTB, however, CDOM showed distinctive differences: lower absorption coefficient, higher absorption spectral slopes, and lower ratios of CDOM absorption to DOC and higher fluorescence efficiency. These differences may have stemmed from (1) changes in CDOM composition by more intensive photobleaching due to the longer residence time of water mass in OTB; (2) other sources of CDOM than the HR/AR inputs, such as local creeks, streams, groundwater, and/or bottom re-suspension. Average CDOM absorption in Tampa Bay at 443 nm, a CDOM(443), was about five times higher in June and about ten times higher in October than phytoplankton pigment absorption, a ph(443), indicating that blue light attenuation in the water column was dominated by CDOM rather than by phytoplankton absorption throughout the year.

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

AbstractFrequent 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 &amp; Sons, Ltd.

The influence of forestry activity on the structure of dissolved organic matter in lakes: Implications for mercury photoreactions

It is well known that dissolved organic matter (DOM) increases in lakes associated with forestry activity but characterization of the DOM structure is incomplete. Twenty-three lakes with a wide range of forestry activities located in central Quebec, Canada were sampled and analyzed for dissolved organic carbon (DOC) concentration, DOC fluorescence, and ultra violet–visible (UV–VIS) absorption spectra. The results show that DOC increases (as does the associated DOC fluorescence) with increased logging (slope = 0.122, r 2 = 0.581, p < 0.001; and slope = 0.283, r 2 = 0.308, p < 0.01, respectively) in the 23 lakes sampled however, the aromaticity of the DOM does not change with changes in logging (as found by UV–VIS ratios, absorbance slope in the UV region, and DOC normalized fluorescence (slope = 1.42 × 10 − 2 , r 2 = 0.331, p < 0.01). The DOM from four of these lakes was concentrated using reverse osmosis (RO) followed by freeze-drying. The structures of the concentrated dissolved organic matter (DOM) samples were analyzed using X-ray analysis of near edge structures (XANES), X-ray diffraction (XRD), and 13C solid-state nuclear magnetic resonance ( 13C NMR) analysis. XANES analysis of functional groups in the four concentrated samples shows that there are significant differences in reduced sulphur between the samples, however there was no clear relationship with forestry activity in the associated catchment. XRD data showed the presence of amorphous sulphide minerals associated with the DOM concentrate that may be important sites for mercury binding. The 13C NMR spectra of these samples show that the percentage of carbon present in carboxylic functional groups increases with increasing logging. Such structures are important for binding photo-reducible mercury and their presence may limit mercury photo-reduction and volatilization. We propose a mechanism by which increased logging leads to increased carboxylic groups in DOM and thereby increased weak binding of photo-reducible mercury. These results, in part, explain the decrease in dissolved gaseous mercury (DGM) production rates with increased logging found in our previous work.