Dissolved Organic Matter Loading Research Articles

DOM degradation by light and microbes along the Yukon River-coastal ocean continuum

The Arctic is experiencing rapid warming, resulting in fundamental shifts in hydrologic connectivity and carbon cycling. Dissolved organic matter (DOM) is a significant component of the Arctic and global carbon cycle, and significant perturbations to DOM cycling are expected with Arctic warming. The impact of photochemical and microbial degradation, and their interactive effects, on DOM composition and remineralization have been documented in Arctic soils and rivers. However, the role of microbes, sunlight and their interactions on Arctic DOM alteration and remineralization in the coastal ocean has not been considered, particularly during the spring freshet when DOM loads are high, photoexposure can be quite limited and residence time within river networks is low. Here, we collected DOM samples along a salinity gradient in the Yukon River delta, plume and coastal ocean during peak river discharge immediately after spring freshet and explored the role of UV exposure, microbial transformations and interactive effects on DOM quantity and composition. Our results show: (1) photochemical alteration of DOM significantly shifts processing pathways of terrestrial DOM, including increasing relative humification of DOM by microbes by > 10%; (2) microbes produce humic-like material that is not optically distinguishable from terrestrial humics; and (3) size-fractionation of the microbial community indicates a size-dependent role for DOM remineralization and humification of DOM observed through modeled PARAFAC components of fluorescent DOM, either through direct or community effects. Field observations indicate apparent conservative mixing along the salinity gradient; however, changing photochemical and microbial alteration of DOM with increasing salinity indicate changing DOM composition likely due to microbial activity. Finally, our findings show potential for rapid transformation of DOM in the coastal ocean from photochemical and microbial alteration, with microbes responsible for the majority of dissolved organic matter remineralization.

Potential effect of upstream sediment trap by a dam on dissolved organic matter transported into the Three Gorges Reservoir, China

This paper demonstrates how suspended sediment trapped by dam construction may impact the quantity of dissolved organic matter (DOM) exported discharge entering the Three Gorges Reservoir (TGR). Suspended sediment and water samples were collected along the upper Yangtze River and its major tributaries, and their water and sediment properties determined. The results provided evidence of the more organic polluted nature of the tributaries compared to the upper mainstream Yangtze River. However, the measured DOM concentration in the waters within the TGR downstream from the tributary confluence, was 14% — 25% lower than that estimated just from mixing runoff. In contrast, the measured contents of particulate organic matter (POM) along the main Yangtze River increased by around 20%, whilst the partitioning coefficient of organic matter between sediment and water peaked 2.99 × 103. The results indicated that the sediment from the upper Yangtze River possibly absorbed the DOM sourced from the tributaries with the organic contamination. The annual DOM load which equals the average concentration of DOM multiplied by exported runoff, entering the TGR has been predicted to increase by 15% — 23% during the operation period of an another dam named after Xiluodu constructed upstream from the TGR.

Dissolved organic matter regulates nutrient limitation and growth of benthic algae in northern lakes through interacting effects on nutrient and light availability

AbstractWidespread increases in dissolved organic matter (DOM) concentration across northern lakes can alter rates of primary production by increasing nutrient availability and decreasing light availability. These dual effects of DOM generate a unimodal relationship in pelagic primary production and primary producer biomass among lakes over a gradient of DOM concentration. However, the responses of benthic algae to variation in DOM loading are less clear because of their potential to access sediment nutrients. We tested algal production and nutrient limitation along a DOM gradient in northern Sweden. Without added nutrients, benthic algal production showed a unimodal relationship with DOM, similar to reported pelagic responses. Nutrient addition revealed widespread nitrogen limitation, with decreasing severity in lakes with higher DOM. Because the majority of northern Swedish lakes currently fall below the inflection point in this unimodal relationship, moderate increases in DOM have the potential to increase benthic primary production, particularly for epilithic algae.

High Anthropogenic Organic Matter Inputs during a Festival Increase River Heterotrophy and Refractory Carbon Load.

Streams and rivers metabolize dissolved organic matter (DOM). Although most DOM compounds originate from natural sources, recreational use of rivers increasingly introduces chemically distinct anthropogenic DOM. So far, the ecological impact of this DOM source is not well understood. Here, we show that a large music festival held adjacent to the Traisen River in Austria increased the river’s dissolved organic carbon (DOC) concentration from 1.6 to 2.1 mg L–1 and stream ecosystem respiration from −3.2 to −4.5 mg L–1. The DOC increase was not detected by sensors continuously logging absorbance spectra, thereby challenging their applicability for monitoring. However, the fluorescence intensity doubled during the festival. Using parallel factor analysis, we were able to assign the increase in fluorescence intensity to the chemically stable UV-B filter phenylbenzimidazole sulfonic acid, indicating organic compounds in sunscreen and other personal care products as sources of elevated DOC. This observation was confirmed by liquid chromatography coupled with mass spectrometry. The elevated respiration is probably fueled by anthropogenic DOM contained in beer and/or urine. We conclude that intense recreational use of running waters transiently increases the anthropogenic DOM load into stream ecosystems and alters the fluvial metabolism. We further propose that chemically distinct, manmade DOM extends the natural range of DOM decomposition rates in fluvial ecosystems.

Impacts of Hurricane Disturbance on Water Quality across the Aquatic Continuum of a Blackwater River to Estuary Complex

Hurricanes cause landscape-scale disturbances that affect biogeochemical cycling and water quality in coastal ecosystems. During Hurricane Irma’s passage through northern Florida, water movements driven by wind velocities up to 105 km h−1 caused a salinity peak in an estuary/blackwater river complex. Water quality was monitored across the 15 km site to detect the magnitude and duration of disturbance. Saline water intruded 15 km inland into a freshwater portion of the river that peaked at a salinity of 2 psu. Due to the volume of precipitation from the hurricane, significant runoff of freshwater and dissolved organic matter (DOM) caused a decrease in salinity, dissolved oxygen (DO), and Chlorophyll-a concentrations while increasing turbidity and fluorescent dissolved organic matter (fDOM). The disturbance caused rapid changes observed by in-situ water quality monitors over a 3-week period, but some effects persisted for longer periods as shown by 3-month weekly water sampling. This disturbance caused shifts in DOM loading, altered salinity dynamics, and reshaped landscapes due to wind and wave surge both in upland marsh and downstream estuary. Hurricane disturbance temporarily and abruptly alters the aquatic continuum, and observations of system response can help us understand the mechanisms associated with ecosystem resilience and recovery.

Selective Adsorption of Terrestrial Dissolved Organic Matter to Inorganic Surfaces Along a Boreal Inland Water Continuum

AbstractDifferent processes contribute to the loss or transformation of dissolved organic matter (DOM) and change DOM concentration and composition systematically along the inland water continuum. Substantial efforts have been made to estimate the importance of microbial and photochemical degradation for DOM concentration and composition and, to some extent, also DOM losses by flocculation, whereas the significance of DOM adsorption to inorganic surfaces has received less attention. Hence, knowledge on the possible extent of adsorption, its effect on DOM loads and composition and on where along the aquatic continuum it might be important, is currently limited or lacking altogether. Here we experimentally determine DOM adsorption onto mineral particles in freshwater ecosystems covering a water residence time gradient in boreal landscape Sweden. We hypothesized that adsorption would gradually decrease with increasing water residence time but actually found that DOM is highly susceptible to adsorption throughout the aquatic continuum. Mass spectrometry and fluorescence analysis on DOM suggest that freshly produced aquatic DOM is less susceptible to adsorption than more terrestrial material. Moreover, the percentage DOM adsorbed in the experiments greatly exceeds the actual adsorption taking place in boreal inland waters across all studied systems. These results illustrate the potential impact of mineral erosion, for example, as a result of agriculture, mining or forestry practices, on the availability, transport, and composition of organic carbon in inland waters.

Dissolved organic matter as P source for biofilms in two contrasting low-order streams

Forest streams receive large amounts of leaves whose leachates are an important source of dissolved organic matter (DOM), providing not only carbon but also organic nutrients to the microbial communities in streams. I carried out a field study to evaluate the effect of different DOM concentrations on the biofilm structure and functional traits in two similar forest streams belonging to the same catchment. I compared biofilm biomass and nutri- ent content throughout one year, algal species composition, and biofilm community-level physiological profiles in two streams with different DOM concentration and aromaticity. Dissolved nutrient concentrations were higher in the stream with higher DOM concentration, with a concomitant higher biofilm biomass, and there was also a temporal pattern, with higher values during the autumn. Phosphorus content in biofilms was also higher in the high DOM stream, coincidently with a higher capacity of the community to utilize organic P source (glucose-1-P) as a substrate. In contrast, the biofilms from the stream with lower DOM concentrations preferentially used N-organic substrates (amino acids and amines). These results reveal that the biofilms of forest streams make use of organic matter nutrients, so that streams with different DOM loads may differ in biofilm biomass due to changes in both bacterial and autotrophic biomass. In addition, biofilm dynamics may be related to forest phenology, as the highest OM input in this deciduous forest is represented by tree leaves, which supply DOM through leachates, and in particular, with P-rich leachates. In conclusion, different DOM concentrations in two nearby streams led to differences in the community-level physiological profile, as has been previously demonstrated at larger spatial scales in oceans, lakes and along larger rivers.

Improved resistance to organic matter load by compositing a cationic flocculant into the titanium xerogel coagulant

Titanium xerogel coagulant (TXC) has been proved as a promising coagulant in water treatment. However, the turbidity removal efficiency of TXC is unsatisfactory as there is a considerable amount of dissolved organic matter (DOM). To overcome this shortage, a cationic flocculant, poly(diallyl dimethyl ammonium chloride) (PDADMAC), was composited into the TXC. With the removal of Escherichia coli (E. coli) and the residual turbidity as evaluation index, the composition of PDADMAC to TXC was proved to result in an enhanced resistance to DOM load. The resultant PDADMAC-TXC (P-T) composites had a good pH-resistance. In the pH range of 4.0–10.3, the required dose of P-T composites kept at a low level, whereas much higher doses were needed for the TXC. At pH 8.7, the minimum dose required to achieve a 90% E. coli removal from a 10 mg/L DOM solution was reduced from 70 mg/L TXC to 15 mg/L P-T composites. The improvements could be attributed to the three effects of PDADMAC in the P-T composites: strengthened charge neutralization for negatively charged E. coli, enhanced adsorption bridging through the polymer chains, and weakened complexation between organic matter and titanium due to the hydrophobic interactions between the aliphatic chains of PDADMAC and the hydrophobic segments of TXC. The work here provides a useful strategy for the fabrication of DOM-resistant coagulants to meet the requirements for some special kinds of water.

Coupling biogeochemical process rates and metagenomic blueprints of coastal bacterial assemblages in the context of environmental change

Bacteria are major drivers of biogeochemical nutrient cycles and energy fluxes in marine environments, yet how bacterial communities respond to environmental change is not well known. Metagenomes allow examination of genetic responses of the entire microbial community to environmental change. However, it is challenging to link metagenomes directly to biogeochemical process rates. Here, we investigate metagenomic responses in natural bacterioplankton communities to simulated environmental stressors in the Baltic Sea, including increased river water input, increased nutrient concentration, and reduced oxygen level. This allowed us to identify informative prokaryotic gene markers, responding to environmental perturbation. Our results demonstrate that metagenomic and metabolic changes in bacterial communities in response to environmental stressors are influenced both by the initial community composition and by the biogeochemical factors shaping the functional response. Furthermore, the different sources of dissolved organic matter (DOM) had the largest impact on metagenomic blueprint. Most prominently, changes in DOM loads influenced specific transporter types reflecting the substrate availability and DOC assimilation and consumption pathways. The results provide new knowledge for developing models of ecosystem structure and biogeochemical cycling in future climate change scenarios and advance our exploration of the potential use of marine microorganisms as markers for environmental conditions.

Impact of a severe rain event on C- and N-DBP precursor removal using IEX

Abstract During disinfection, dissolved organic matter (DOM) is the major precursor to form disinfection by-products (DBPs), which may be of potential human health concern. Previous research focused on waters of continental climates and less on subtropical environments. However, water sources in subtropical climates are regularly impacted by major rain events during the summer months. This study evaluated the C- and N-DBP precursor removal capacity of two conventional ion exchange (IEX) resins and one magnetic ion exchange (MIEX) resin with a raw water at normal conditions and impacted by a heavy rain event. The rain event introduced 3 mg C/L total organic carbon (TOC) comprised mainly of low to medium molecular weight organics. All three resins were able to remove TOC and DBP precursors (>66%) but being less efficient in reducing turbidity (3–48%) and colour (9–24%). The resin with the smallest bead size was affected the most by the increased medium MW DOM loading resulting in DOM and C-DBP precursor removal performance losses of 10% and 22%. When applied as a pre-treatment for coagulation, MIEX was more efficient in DBP precursor control than coagulation in addressing the additional organic and DBP precursor loading after a heavy rain event.

Hydrological changes of DOM composition and biodegradability of rivers in temperate monsoon climates

Summary The spatial and hydrological dynamics of dissolved organic matter (DOM) composition and biodegradability were investigated for the five largest rivers in the Republic of Korea (South Korea) during the years 2012–2013 using incubation experiments and spectroscopic measurements, which included parallel factor analysis (PARAFAC). The lower reaches of the five rivers were selected as windows showing the integrated effects of basin biogeochemistry of different land use under Asian monsoon climates, providing an insight on consistency of DOM dynamics across multiple sites which could be difficult to obtain from a study on an individual river. The mean dissolved organic carbon (DOC) concentrations of the five rivers were relatively low, ranging from 1.4 to 3.4 mg L −1 , due to the high slope and low percentage of wetland cover in the basin. Terrestrial humic- and fulvic-like components were dominant in all the rivers except for one, where protein-like compounds were up to ∼80%. However, terrestrial components became dominant in all five of the rivers after high precipitation during the summer monsoon season, indicating the strong role of hydrology on riverine DOM compositions for the basins under Asian monsoon climates. Considering that 64% of South Korea is forested, our results suggest that the forests could be a large source of riverine DOM, elevating the DOM loads during monsoon rainfall. Although more DOM was degraded when DOM input increased, regardless of its sources, the percent biodegradability was reduced with increased proportions of terrestrially derived aromatic compounds. The shift in DOM quality towards higher percentages of aromatic terrestrial compounds may alter the balance of the carbon cycle of coastal ecosystems by changing microbial metabolic processes if climate extremes such as heavy storms and typhoons become more frequent due to climate change.

Adsorption and desorption of dissolved organic matter by carbon nanotubes: Effects of solution chemistry

Increasing use of carbon nanotubes (CNTs) has led to their introduction into the environment where they can interact with dissolved organic matter (DOM). This study focuses on solution chemistry effects on DOM adsorption/desorption processes by single-walled CNTs (SWCNTs). Our data show that DOM adsorption is controlled by the attachment of DOM molecules to the SWCNTs, and that the initial adsorption rate is dependent on solution parameters. Adsorbed amount of DOM at high ionic strength was limited, possibly due to alterations in SWCNT bundling. Desorption of DOM performed at low pH resulted in additional DOM adsorption, whereas at high pH, adsorbed DOM amount decreased. The extent of desorption conducted at increased ionic strength was dependent on pre-adsorbed DOM concentration: low DOM loading stimulated additional adsorption of DOM, whereas high DOM loading facilitated release of adsorbed DOM. Elevated ionic strength and increased adsorbed amount of DOM reduced the oxidation temperature of the SWCNTs, suggesting that changes in the assembly of the SWCNTs had occurred. Moreover, DOM-coated SWCNTs at increased ionic strength provided fewer sites for atrazine adsorption. This study enhances our understanding of DOM–SWCNT interactions in aqueous systems influenced by rapid changes in salinity, and facilitates potential use of SWCNTs in water-purification technologies.

Bacterial production and their role in the removal of dissolved organic matter from tributaries of drinking water reservoirs

Enhanced concentrations of dissolved organic matter (DOM) in freshwaters are an increasing problem in drinking water reservoirs. In this study we investigated bacterial DOM degradation rates in the tributaries of the reservoirs and tested the hypotheses that (1) DOM degradation is high enough to decrease DOM loads to reservoirs considerably, (2) DOM degradation is affected by stream hydrology, and (3) phosphorus addition may stimulate bacterial DOM degradation. Bacterial biomass production, which was used as a measure of DOM degradation, was highest in summer, and was usually lower at upstream than at downstream sites. An important proportion of bacterial production was realized in epilithic biofilms. Production of planktonic and biofilm bacteria was related to water temperature. Planktonic production weakly correlated to DOM quality and to total phosphorus concentration. Addition of soluble reactive phosphorus did not stimulate bacterial DOM degradation. Overall, DOM was considerably degraded in summer at low discharge levels, whereas degradation was negligible during flood events (when DOM load in reservoirs was high). The ratio of DOM degradation to total DOM release was negatively related to discharge. On annual average, only 0.6–12% of total DOM released by the catchments was degraded within the tributaries.

Reduced adsorption of propanil to black carbon: Effect of dissolved organic matter loading mode and molecule size

In the present study, the reduced adsorption of propanil on black carbon (BC) influenced by dissolved organic matter (DOM) was verified to be closely related to DOM molecule size and loading mode. Two congenetic carbons, a rice-residue-derived BC and the reduced product (RC), were characterized by similar specific surface area and different surface properties. Reduced product exhibits higher adsorption of propanil and DOM than BC. A series of model DOMs, including tannic acid (TA), pentagalloylglucose (PA), 3-O-galloylmucic acid (OA), and gallic acid (GA), characterized by different molecule sizes and molecular weights, were used to evaluate the different inhibitory effects. The DOM adsorption (mmol/g) on BC and RC follows the order of GA > PA > OA > TA, whereas the reduction of propanil adsorption influenced by the model DOM follows the order of PA ≈ TA > OA ≈ GA. The suppressive degree is connected to their molecule sizes rather than to molecular weights. Tannic acid and PA weakened propanil adsorption more effectively than OA and GA because the large DOM molecules may hinder propanil molecules into the micropore regions. Because of the similar molecule size, TA and PA present a similar suppressive effect on propanil adsorption. The influence of the DOMs was greater when preloaded than when in competition with propanil. The preloading of macromolecules (TA and PA) and OA on the carbons may lead to secondary and primary micropore blocks, respectively. The preloading of GA may cause partial GA molecule sequestration in the primary micropore, thus leading to strong attenuation of propanil adsorption on the carbons.

Comparative simulations of dissolved organic matter cycling in idealized oceanic, coastal, and estuarine surface waters

In this paper we used a steady-state ecosystem model that simulates both dissolved organic carbon (DOC) and nitrogen (DON) cycling to study how the planktonic community structure, nutrient availability, and dissolved organic matter (DOM) loading affect these cycles in idealized oceanic, coastal, and estuarine surface waters. The model was able to reproduce DOM and planktonic biomass distributions, uptake rates, and production rates (including DOM) that fell within ranges reported for oceanic, coastal, and estuarine systems. Using a sensitivity analysis we show that DOM cycling was intricately tied to the biomass concentration, distribution, and productivity of plankton. The efficiency of nutrient remineralization and the availability of inflowing nutrients and DON also played a large role in DOM cycling. In these simulations the largest autochthonous source of DOC was always phytoplankton exudation while important sources of DON varied considerably. In the oceanic simulations heterotrophic bacteria were particularly important for mediating DOM cycling because they were the primary agents that controlled nutrient recycling and supply (i.e., strong bottom-up control). In contrast, in the estuarine simulations mortality (mainly from grazing and viral lysis) had the most influence on DOM production. However, DOM cycling was generally less dependent on interactions between plankton in the estuarine case because of high nutrient and DOM loading. The coastal simulations were somewhere in between. In all simulations competition between different size classes of phytoplankton also played an important role in DOM cycling.

Measurement and modeling of mercury complexation by dissolved organic matter isolates from freshwater and effluents of a major wastewater treatment plant

Dissolved organic matter (DOM) samples were obtained from a low-density urbanized area located upstream of Paris (along the Marne River, France) and from the treated effluents at the Paris main wastewater treatment plant. These samples were then fractionated according to their hydrophobicity. DOM fractions consisted of nanomolar to sub-micromolar fresh organic substances with extremely strong Hg-complexing ligands. The conditional stability constants (i.e. K(HgL)'; pH similar to 6.8, I(NaCl) = 0.5 M, T = 25 degrees C) of the Hg-DOM complexes formed were greater than 10(24) M (1), for the reaction Hg(2+) + L = HgL (with L as ligand). For upstream of Paris, thermodynamic calculations indicated that the vast majority of Hg-DOM was associated with hydrophobic DOM. In contrast, in the Paris main wastewater treatment plant effluents, Hg-DOM was mainly bound to hydrophilic DOM. Simple dilution calculations highlighted that due to the large DOM loading of urban discharges, the hydrophilic urban DOM ligands may commonly dominate Hg-DOM speciation in the downstream Seine River, except under extreme dilution (i.e. high water episodes or floods). (C) 2011 Elsevier Ltd. All rights reserved.

Dissolved organic matter (DOM) export to a temperate estuary: seasonal variations and implications of land use

Inputs of dissolved carbon, nitrogen, and phosphorus were assessed for an estuary and its catchment (Horsens, Denmark). Seasonal patterns in the concentrations of DOM in the freshwater supply to the estuary differed depending on the soil and drainage characteristics of the area. In streams draining more natural areas the, patterns observed were largely driven by seasonal temperature fluctuations. The material exported from agricultural areas was more variable and largely controlled by precipitation events. Positive exponential relationships were found between the nitrogen and phosphorus loading, and the percentage of catchment area used for agriculture. Colored DOM (CDOM) loading measurements were found to be a good predictor of dissolved organic carbon (DOC) loading across the different subcatchments, offering a rapid and inexpensive alternative of operationally monitoring DOC export. For all the dissolved nutrient inputs to the estuary, dissolved inorganic nitrogen (DIN) and dissolved organic phosphorus dominated the loadings. Although 81% of the nitrogen annually supplied to the estuary was DIN, 83% of the nitrogen exported from the estuary was dissolved organic nitrogen (DON). Results show that increasing the area of the catchment covered by forest and natural pastures would have a positive effect on the trophic status of the estuary, leading to a considerable decrease in the phosphorus loading and a shift in the nitrogen loading from DIN to DON. Such a change in land use would also increase the export of DOC and CDOM to the estuary having the potential to increase oxygen consumption and reduce the photic depth.

COUPLED CYCLING OF DISSOLVED ORGANIC NITROGEN AND CARBON IN A FOREST STREAM

Dissolved organic nitrogen (DON) is an abundant but poorly understood pool of N in many ecosystems. We assessed DON cycling in a N-limited headwater forest stream via whole-ecosystem additions of dissolved inorganic nitrogen (DIN) and labile dissolved organic matter (DOM), hydrologic transport and biogeochemical modeling, and laboratory experiments with native sediments. We sampled surface and subsurface waters to understand how interaction among hydrologic exchange, DIN, DON, and dissolved organic carbon (DOC) influence stream N losses at summer baseflow. Added DON was taken up rapidly from the water column at rates exceeding DOC and DIN. A significant fraction of this DON was mineralized and nitrified. Combined DON and NO 3-N uptake lengths resulted in spiraling lengths of ;210 m, suggesting the potential for multiple transformations of labile N loads within catchment boundaries. Simultaneous addition of DIN increased DOM uptake, but more so for C, resulting in an upward shift in the C:N ratio of uptake. Sediment incubations also showed a strong biotic influence on DOC and DON dynamics. Despite efficient uptake of added DOM, background DON and high mo- lecular mass DOC concentrations increased downstream, resulting in higher DOM loads than could be accounted for by groundwater discharge and suggesting net release of less bioavailable forms from the channel/hyporheic zone. At the same time, subsurface DOM was characterized by very low C:N ratios and a disproportionately large DON pool despite rapid hydrologic mixing with dilute and high C:N ratio surface waters. Analysis of expected DON loads from conservative hyporheic fluxes indicated that watershed losses of DON would have been seven times greater in the absence of apparent benthic demand, suggesting tight internal cycling of subsurface DON. Our study further demonstrates the potential for significant transformation of N in headwater streams before export to downstream ecosys-

Sources of dissolved organic matter (DOM) in a Rocky Mountain stream using chemical fractionation and stable isotopes

Dissolved organic matter (DOM) is an important vehicle for the movement of nutrients from terrestrial to aquatic systems. To investigate how the source and composition of aquatic DOM change in both space and time, we used chemical, spectroscopic, and isotopic analyses to characterize DOM in a headwater catchment in the Colorado Front Range. Streamwater samples for DOM analyses were collected from 2 sites, a lightly vegetated alpine site and a forested, subalpine site, in the North Boulder Creek catchment during the snowmelt runoff season (May–September). Concentrations of dissolved organic carbon (DOC) peaked on the ascending limb of the snowmelt hydrograph at both the alpine (2.6 mg C l−1) and the subalpine sites (7.0 mg C l−1) and decreased sharply on the descending limb of the hydrograph. Fractionation of DOM into operationally defined humic and non-humic components showed that the fulvic acid content of DOC decreased through the season at both sites and that spectroscopic (fluorescence and ultraviolet) properties of the humic DOM fraction shifted in a manner consistent with an increase in the proportion of humic DOM derived from instream sources as compared to terrestrial catchment sources. Humic and non-humic fractions of DOM isolated near peak flow in June and during low flows in September showed a seasonal enrichment in 15N and 13C as well as a seasonal decrease in the ratio of aromatic to aliphatic carbon, both of which were correlated with a decrease in the C:N ratio of the DOM fractions. These results suggest that seasonal shifts in the isotopic and chemical characteristics of DOM are a result of changes in catchment sources of DOM. In particular, it appears that DOM production in alpine lakes is an important contributor to the streamwater DOM load during late season low flows, especially in the alpine reach of the catchment. Our results further suggest that stable isotopes of C and N are useful tools, particularly when combined with ancillary data such as elemental analyses and catchment discharge, for evaluating sources and transformations of DOM at the catchment scale.

Modeling Trichloroethylene Adsorption by Activated Carbon Preloaded with Natural Dissolved Organic Matter Using a Modified IAST Approach

A model was developed, using an approach based on the Ideal Adsorbed Solution Theory (IAST), to predict trichloroethylene (TCE) adsorption by granular activated carbon (GAC) preloaded with natural dissolved organic matter (DOM) isolated from three surface water sources. The IAST model was formulated for a bi-solute system in which TCE and DOM single-solute uptakes were described by the Langmuir-Freundlich and Freundlich isotherms, respectively. The effect of DOM molecular size and polarity (as measured by XAD 8 resin fractionation) on TCE uptake by preloaded GAC was assessed to identify a reactive fraction of natural water DOM for the purpose of modeling competitive adsorption. Consistent with previous work that identified low molecular weight species as the most reactive with regard to preloading effects (i.e., reducing target compound uptake), the low molecular weight components of the polar (hydrophilic) and nonpolar (hydrophobic) DOM fractions, isolated using ultrafiltration (1 kDa molecular weight cutoff membrane), exhibited significant competitive effects. Furthermore, the effects of these fractions on TCE uptake were similar; therefore, theywere considered together to represent a single "reactive fraction" of DOM. On the basis of this finding, isotherms for the <1 kDa low molecular weight DOM fraction of the whole water were measured, and molar concentrations were computed based on an average molecular weight determined using size-exclusion chromatography. The IAST model was modified to incorporate surface area reduction due to pore blockage by DOM and to reflectthe hypothesis thatTCE molecules can access adsorption sites which humic molecules cannot, thus preventing competition on these sites. The model was calibrated with data for TCE uptake by carbon preloaded with the <1 kDa low molecular weight DOM fraction and was verified by predicting TCE uptake by carbon preloaded with whole natural waters for both constant GAC dose (hence constant DOM loading) and variable GAC dose (hence variable DOM loading) TCE isotherms. Preloading by DOM reduced volume in GAC pores having widths smaller than 1.25 nm (likely accessible only to TCE) to a greater extent than total pore volume, suggesting preferential blockage of micropores. Such preferential pore blockage may explain, in part, why increased DOM loading decreases the fraction of the total surface area on which no competition between TCE and DOM occurs.