Characterization of the colloidal organic matter from the Amazonian basin by asymmetrical flow field-flow fractionation and size exclusion chromatography

Colloidal organic matter (COM) collected in small and large watercourse tributaries of the Negro River (Brazil) were fractionated and characterized by an asymmetrical flow field-flow fractionation (AFlFFF) coupled to UV and seven angle laser light scattering (LS) detectors, and by size exclusion chromatography (SEC) coupled with a UV detection. Number and weight average molar masses, weight average gyration radiuses R_Gw and polydispersity indexes were obtained for each sample in two separate runs under conditions optimized for lower and larger size fractions. The results demonstrate the existence of a decrease of size of the colloidal matter when passing from first order streams to higher order rivers. No significant changes were found in size distributions of samples collected during the low and high flow stages at the same site. The influence of selected pre-treatments such as filtration and reverse osmosis pre-concentration on the size and molar mass distributions was also studied.     

The influence of weathering and organic matter on heavy metals lability in silicatic, Alpine soils

We investigated the effect of organic matter and weathering on the lability and solid phase speciation of heavy metals (Cd, Cr, Cu, Ni, Pb, Zn) in two contrasting subalpine regions in the Italian Alps. Cr, Ni and Cu could be linked to weathering. This was not the case for Pb. Since organic matter (OM) influences the solid phase speciation of heavy metals, the total organic C and N content, the C and N content of different density fractions of OM and also of the labile (oxidised by H₂O₂) and stable (H₂O₂-resistant) fractions were determined. Soil OM stocks were high and soils on north-facing slopes had more OM than the south-facing sites to which they were paired. Density measurements and the H₂O₂ fractionation indicated that the higher OM content on north-facing sites was due to an accumulation of weakly degraded organic material. Due to higher weathering intensity on north-facing sites, the abundance of the EDTA-extractable heavy metals was higher than on south-facing sites. All EDTA-extractable heavy metals showed a good correlation to the water-soluble phenolic concentrations which indicates that the metals were probably translocated as metal-organic complexes. Pb and Cu correlate not only to the light (density < 1 g/cm³) and labile, organic fraction but also to the heavy (density > 2 g/cm³) and stable fraction. High-mountain ecosystems like the Alps are sensitive to changing environmental conditions such as global warming. A warmer climate and the more favourable conditions it brings for biological activity, especially at cooler sites, will probably lead in the short- to mid-term to an increased loss of accumulated, weakly degraded OM. As the Pb and Cu content is significantly related to the labile organic matter pools, the risk exists that an increase in OM mineralisation could affect the storage capacity and mobility of these metals in soils.     

Adsorption of dissolved natural organic matter by modified activated carbons

Adsorption of dissolved natural organic matter (DOM) by virgin and modified granular activated carbons (GACs) was studied. DOM samples were obtained from two water treatment plants before (i.e., raw water) and after coagulation/flocculation/sedimentation processes (i.e., treated water). A granular activated carbon (GAC) was modified by high temperature helium or ammonia treatment, or iron impregnation followed by high temperature ammonia treatment. Two activated carbon fibers (ACFs) were also used, with no modification, to examine the effect of carbon porosity on DOM adsorption. Size exclusion chromatography (SEC) and specific ultraviolet absorbance (SUVA(254)) were employed to characterize the DOMs before and after adsorption. Iron-impregnated (HDFe) and ammonia-treated (HDN) activated carbons showed significantly higher DOM uptakes than the virgin GAC. The enhanced DOM uptake by HDFe was due to the presence of iron species on the carbon surface. The higher uptake of HDN was attributed to the enlarged carbon pores and basic surface created during ammonia treatment. The SEC and SUVA(254) results showed no specific selectivity in the removal of different DOM components as a result of carbon modification. The removal of DOM from both raw and treated waters was negligible by ACF10, having 96% of its surface area in pores smaller than 1 nm. Small molecular weight (MW) DOM components were preferentially removed by ACF20H, having 33% of its surface area in 1--3 nm pores. DOM components with MWs larger than 1600, 2000, and 2700 Da of Charleston raw, Charleston-treated, and Spartanburg-treated waters, respectively, were excluded from the pores of ACF20H. In contrast to carbon fibers, DOM components from entire MW range were removed from waters by virgin and modified GACs.     

Characterization of natural organic matter adsorption in granular activated carbon adsorbers

The removal of natural organic matter (NOM) from lake water was studied in two pilot-scale adsorbers containing granular activated carbon (GAC) with different physical properties. To study the adsorption behavior of individual NOM fractions as a function of time and adsorber depth, NOM was fractionated by size exclusion chromatography (SEC) into biopolymers, humics, building blocks, and low molecular weight (LMW) organics, and NOM fractions were quantified by both ultraviolet and organic carbon detectors. High molecular weight biopolymers were not retained in the two adsorbers. In contrast, humic substances, building blocks and LMW organics were initially well and irreversibly removed, and their effluent concentrations increased gradually in the outlet of the adsorbers until a pseudo-steady state concentration was reached. Poor removal of biopolymers was likely a result of their comparatively large size that prevented access to the internal pore structure of the GACs. In both GAC adsorbers, adsorbability of the remaining NOM fractions, compared on the basis of partition coefficients, increased with decreasing molecular size, suggesting that increasingly larger portions of the internal GAC surface area could be accessed as the size of NOM decreased. Overall DOC uptake at pseudo-steady state differed between the two tested GACs (18.9 and 28.6 g-C/kg GAC), and the percent difference in DOC uptake closely matched the percent difference in the volume of pores with widths in the 1-50 nm range that was measured for the two fresh GACs. Despite the differences in NOM uptake capacity, individual NOM fractions were removed in similar proportions by the two GACs.     

Effects of reverse osmosis isolation on reactivity of naturally occurring dissolved organic matter in physicochemical processes

A field reverse osmosis system was used to isolate dissolved organic matter (DOM) from two lacustrine and two riverine surface water sources. The rejection of DOM was on the order of 99% and did not vary significantly with pressure. A simple mass balance model using a single measured value of rejection predicted the concentration within the closed-loop isolation system. The effect of operating pressure and solution flux on mass recovery of DOM was evaluated in laboratory and field trials. Under controlled laboratory conditions, >99% of a lacustrine DOM could be accounted for. A fraction of the isolated DOM was not recoverable using hydrodynamic cleaning; however, this fraction was recovered by using a pH 10 NaOH wash solution. The mass recovered in the NaOH solution increased from <1% to >6% with increasing transmembrane pressures from 414 kPa (60 psi) to1000 kPa (145 psi), respectively. This is consistent with fouling that results from an increase in solution flux, and a decrease in tangential crossflow velocity. Under field conditions, mass balances were generally >95% and mass recovery was >90% in all cases. The effects of temperature on solution flux were consistent with changes in fluid viscosity; effects of temperature on membrane diffusivity or morphological properties were small. RO isolation under low pressure conditions designed to maximize DOM recovery had little effect on DOM reactivity evaluated in terms of nanofiltration membrane fouling, XAD-8 resin adsorption, activated carbon adsorption, competition with trichloroethylene for adsorption sites on activated carbon, and molecular weight distribution measured using size exclusion chromatography.     

Removal of natural organic matter and THM formation potential by ultra- and nanofiltration of surface water

Natural organic matter (NOM) and trihalomethane formation potential (THMFP) removal were evaluated by ultrafiltration (UF) and nanofiltration (NF). Ten different raw water sources in Alicante province (SE Spain) were analysed. Five types of membranes of different materials were tested with a dead-end-type stirred UF cell. Additional measurements, such as dissolved organic carbon, ultraviolet absorbance (254nm), THMFP, ion concentration, pH, conductivity, etc. were made on raw water, permeates and concentrates. The SUVA value was used to determine the hydrophobicity of the water analysed. The elimination of NOM and THMFP is correlated with the molecular weight (MW) of NOM determined by size exclusion chromatography (SEC). The flux decline trends were correlated with cation concentration. NOM removal by UF is low, which correlates with the average MW determined by SEC with an average value of 922g/mol (between 833 and 1031g/mol). However, the NOM removal obtained with the NF90 and NF270 NF membranes for all water sources is almost complete (90%). THMFP removal is related to hydrophobicity and permeability of membrane. The NFT50 membrane removes almost 100% of the THMFP of more hydrophobic waters.     

Reconsidering the quantitative analysis of organic carbon concentrations in size exclusion chromatography

The evaluation of the molecular size distribution of natural organic matter (NOM) in aquatic environments via size exclusion chromatography (SEC) is important for the understanding of environmental processes such as nutrient cycling and pollutant transport as well as of technical water treatment processes. The use of organic carbon (OC) detectors has become popular in recent studies due to improved availability and quantification possibilities, which supposedly are superior to those of ultraviolet (UV) detectors. A set of 12 NOM samples was used to demonstrate the limitations of online OC detection (OCD) when analyzing complex aquatic organic matter. A novel evaluation approach for SEC data is introduced by combining the information from UV absorbance (UVA) and OCD chromatograms as well as offline total OC (t-OC) and dissolved OC-specific UVA (SUVA) measurements. It could be shown that about 70% of certain OC components were not detected with the OCD system used in this study. For the investigated samples, these types of carbon accounted for up to 72% of the t-OC, i.e. for such NOM samples quantification by OCD is not possible or at least highly questionable. The addition of an oxidant improved the overall oxidation efficiency only slightly. Most likely NOM that predominantly consists of polysaccharides and features a nominal molecular weight of 150 kg/mol or more was responsible for low OCD yields. For future applications, a further improvement of the OCD system would be worthwhile so that quantitative analytical data on the molecular size distribution of NOM and its structural characteristics such as the SUVA distribution can be obtained.     

Composition of a protein-like fluorophore of dissolved organic matter in coastal wetland and estuarine ecosystems

This study demonstrates the compositional heterogeneity of a protein-like fluorescence emission signal (T-peak; excitation/emission maximum at 280/325 nm) of dissolved organic matter (DOM) samples collected from subtropical river and estuarine environments. Natural water samples were collected from the Florida Coastal Everglades ecosystem. The samples were ultrafiltered and excitation-emission fluorescence matrices were obtained. The T-peak intensity correlated positively with N concentration of the ultrafiltered DOM solution (UDON), although, the low correlation coefficient (r(2)=0.140, p<0.05) suggested the coexistence of proteins with other classes of compounds in the T-peak. As such, the T-peak was unbundled on size exclusion chromatography. The elution curves showed that the T-peak was composed of two compounds with distinct molecular weights (MW) with nominal MWs of about >5 x 10(4) (T(1)) and approximately 7.6 x 10(3) (T(2)) and with varying relative abundance among samples. The T(1)-peak intensity correlated strongly with [UDON] (r(2)=0.516, p<0.001), while T(2)-peak did not, which suggested that the T-peak is composed of a mixture of compounds with different chemical structures and ecological roles, namely proteinaceous materials and presumably phenolic moieties in humic-like substances. Natural source of the latter may include polyphenols leached from senescent plant materials, which are important precursors of humic substances. This idea is supported by the fact that polyphenols, such as gallic acid, an important constituent of hydrolysable tannins, and condensed tannins extracted from red mangrove (Rhizophora mangle) leaves exhibited the fluorescence peak in the close vicinity of the T-peak (260/346 and 275/313 nm, respectively). Based on this study the application of the T-peak as a proxy for [DON] in natural waters may have limitations in coastal zones with significant terrestrial DOM input.     

Effects of Fenton treatment on the properties of effluent organic matter and their relationships with the degradation of pharmaceuticals and personal care products

This study examined effects of Fenton oxidation on trace level pharmaceuticals and personal care products (PPCPs) commonly occurring in wastewater. The tested PPCPs included acetaminophen, atenolol, atrazine, carbamazepine, metoprolol, dilantin, DEET, diclofenac, pentoxifylline, oxybenzone, caffeine, fluoxetine, gemfibrozil, ibuprofen, iopromide, naproxen, propranolol, sulfamethoxazole, bisphenol-A and trimethoprim. Transformations of effluent organic matter (EfOM) caused by Fenton oxidation were also quantified. All tested PPCPs, except atrazine and iopromide, were completely removed by Fenton treatment carried out using a 20 mg/L Fe (II) concentration and a 2.5 H₂O₂/Fe (II) molar ratio. Up to 30% on the total carbon concentration was removed during Fenton treatment which was accompanied by the oxidation of EfOM molecules and formation of oxidation products such as oxalic, formic and acetic acids and, less prominently, formaldehyde, acetaldehyde, propionaldehyde and glycolaldehyde. The absorbance of EfOM treated with Fenton reagent at varying Fe (II) concentration and contact time underwent a consistent decrease. The relative decrease of EfOM absorbance was strongly and unambiguously correlated with the removal of all tested PPCPs.     

Comparison of advanced oxidation processes for the removal of natural organic matter

This study examined the impact of UV, ozone (O₃), advanced oxidation processes (AOPs) including O₃/UV, H₂O₂/UV H₂O₂/O₃ in the change of molecular weight distribution (MWD) and disinfection by-product formation potential (DBPFP). Bench-scale experiments were conducted with surface river water and changes in the UV absorbance at 254 nm (UV₂₅₄), total organic carbon (TOC), trihalomethane and haloacetic acid formation potential (THMFP, HAAFP) and MWD of the raw and oxidized water were analyzed to evaluate treatment performance. Combination of O₃ and UV with H₂O₂ was found to result in more TOC and UV₂₅₄ reduction than the individual processes. The O₃/UV process was found to be the most effective AOP for NOM reduction, with TOC and UV₂₅₄ reduced by 31 and 88%, respectively. Application of O₃/UV and H₂O₂/UV treatments to the source waters organics with 190-1500 Da molecular weight resulted in the near complete alteration of the molecular weight of NOM from >900 Da to <300 Da H₂O₂/UV was found to be the most effective treatment for the reduction of THM and HAA formation under uniform formation conditions. These results could hold particular significance for drinking water utilities with low alkalinity source waters that are investigating AOPs, as there are limited published studies that have evaluated the treatment efficacy of five different oxidation processes in parallel.     

Effects of activated carbon characteristics on the simultaneous adsorption of aqueous organic micropollutants and natural organic matter

The overall objective of this research was to determine the effects of physical and chemical activated carbon characteristics on the simultaneous adsorption of trace organic contaminants and natural organic matter (NOM). A matrix of 12 activated carbon fibers (ACFs) with three activation levels and four surface chemistry levels (acid-washed, oxidized, hydrogen-treated, and ammonia-treated) was studied to systematically evaluate pore structure and surface chemistry phenomena. Also, three commercially available granular activated carbons (GACs) were tested. The relatively hydrophilic fuel additive methyl tertiary-butyl ether (MTBE) and the relatively hydrophobic solvent trichloroethene (TCE) served as micropollutant probes. A comparison of adsorption isotherm data collected in the presence and absence of NOM showed that percent reductions of single-solute TCE and MTBE adsorption capacities that resulted from the presence of co-adsorbing NOM were not strongly affected by the chemical characteristics of activated carbons. However, hydrophobic carbons were more effective adsorbents for both TCE and MTBE than hydrophilic carbons because enhanced water adsorption on the latter interfered with the adsorption of micropollutants from solutions containing NOM. With respect to pore structure, activated carbons should exhibit a large volume of micropores with widths that are about 1.5 times the kinetic diameter of the target adsorbate. Furthermore, an effective adsorbent should possess a micropore size distribution that extends to widths that are approximately twice the kinetic diameter of the target adsorbate to prevent pore blockage/constriction as a result of NOM adsorption.     

Mineralization and biodegradability enhancement of natural organic matter by ozone-VUV in comparison with ozone, VUV, ozone-UV, and UV: Effects of pH and ozone dose

The increase in mineralization and biodegradability of natural organic matter (NOM) by ozone-vacuum ultraviolet (VUV) in comparison with ozone, VUV, ozone-ultraviolet (UV), and UV were investigated. The effects of operating parameters including pH and ozone dose were evaluated. Results showed that the mineralization rate of dissolved organic carbon (DOC) provided by the processes tested was in the following order: ozone-VUV > VUV > ozone-UV > ozone > UV. Among three pH studied (7, 9, and 11), pH 7 provided the highest DOC mineralization rate and biodegradability increase. A synergistic effect was observed when combining ozone with UV or VUV at pH 7 and 9 but not at pH 11. The oxidized NOM samples were separated into six fractions based on polarity (hydrophobic/hydrophilic) and charge (acid/neutral/base) to reveal NOM characteristic changes. Ozone-VUV was effective in mineralizing hydrophobic neutral and acid fractions. The hydrophilic neutral fraction was a major NOM fraction after oxidation (39-87%) and was contributed to by the biodegradable DOC produced during oxidation. High performance size exclusion chromatography results revealed that the combination of UV or VUV with ozone was more effective in the decomposition of high molecular weight compounds than ozone alone.     

Characterisation of organic matter in IX and PACl treated wastewater in relation to the fouling of a hydrophobic polypropylene membrane

Extensive organic characterisation of a wastewater using liquid chromatography with a photodiode array and fluorescence spectroscopy (Method A), and UV₂₅₄ and organic carbon detector (Method B) was undertaken, as well as with fluorescence excitation emission spectroscopy (EEM). Characterisation was performed on the wastewater before and after ion exchange (IX) treatment and polyaluminium chlorohydrate (PACl) coagulation, and following microfiltration of the wastewater and pre-treated wastewaters. Characterisation by EEM was unable to detect biopolymers within the humic rich wastewaters and was not subsequently used to characterise the MF permeates. IX treatment preferentially removed low molecular weight (MW) organic acids and neutrals, and moderate amounts of biopolymers in contrast to a previous report of no biopolymer removal with IX. PACl preferentially removed moderate MW humic and fulvic acids, and large amounts of biopolymers. PACl showed a great preference for removal of proteins from the biopolymer component in comparison to IX. An increase in the fluorescence response of tryptophan-like compounds in the biopolymer fraction following IX treatment suggests that low MW neutrals may influence the structure and/or inhibit aggregation of organic compounds. Fouling rates for IX and PACl treated wastewaters had high initial fouling rates that reduced to lower fouling rates with time, while the untreated Eastern Treatment Plant (ETP) wastewater displayed a consistent, high rate of fouling. The results for the IX and PACl treated wastewaters were consistent with the long-term fouling rate being determined by cake filtration while both pore constriction and cake filtration contributed to the higher initial fouling rates. Higher rejection of biopolymers was observed for PACl and IX waters compared to the untreated ETP water, suggesting increased adhesion of biopolymers to the membrane or cake layer may lead to the higher rejection.     

Oxidized sterols as a significant component of dissolved organic matter: evidence from 2D HPLC in combination with 2D and 3D NMR spectroscopy

The elucidation of molecular structures present in dissolved organic matter (DOM) has the potential to unlock many of the queries associated with organic precursors, diagenetic processes and reactivity of this highly complex material. Suwannee River DOM was extensively fractionated by two dimensional hydrophilic interaction chromatography (HILIC)/HILIC and fractions were analyzed via a suite of two and three-dimensional NMR experiments. HILIC provided more greatly resolved fractions with a second dimension and enabled extensive and in-depth NMR analyses. The composite NMR experiments provide strong evidence for highly oxidized sterols as major structural components present in one of the most simplified and subsequently resolved fractions. Further interpretation of data on other fractions across the polarity gradient likewise supports the presence of alicyclic structures present with considerable hydroxyl groups, carboxylic acids and methyl groups associated with quaternary carbon suggesting that further sterol- and hopanoid-type structures are potentially dominant throughout DOM.     

Formation of disinfection by-products in indoor swimming pool water: the contribution from filling water natural organic matter and swimmer body fluids

The contribution and role of different precursors in the formation of three class of disinfection by-products (DBPs) [trihalomethanes (THMs), haloacetic acids (HAAs), and halonitromethanes (HNMs)] in swimming pool waters were examined using filling waters obtained from five drinking water treatment plant (WTP) effluents and three body fluid analogs (BFAs). BFAs exerted higher chlorine demands as compared to natural organic matter (NOM) in filling waters. BFAs exhibited higher HAA formation potentials than THM formation potentials, while the opposite was observed for the filling water NOM. There was no appreciable difference in the HNM formation potentials of BFAs and filling water NOM. Different components in the BFAs tested exhibited different degree and type of DBP formation. Citric acid had significantly higher THM and HAA yields than other BFA components. The effect of temperature was greater on THM formation, whereas the effect of contact time had more impact on HAA formation. Experiments with filling waters collected from WTP effluents at three different times showed more variability in HAA than THM formation at the WTPs studied.     

Quantification of fossil organic matter in contaminated sediments from an industrial watershed: Validation of the quantitative multimolecular approach by radiocarbon analysis

The quantitative multimolecular approach (QMA) based on an exhaustive identification and quantification of molecules from the extractable organic matter (EOM) has been recently developed in order to investigate organic contamination in sediments by a more complete method than the restrictive quantification of target contaminants. Such an approach allows (i) the comparison between natural and anthropogenic inputs, (ii) between modern and fossil organic matter and (iii) the differentiation between several anthropogenic sources. However QMA is based on the quantification of molecules recovered by organic solvent and then analyzed by gas chromatography-mass spectrometry, which represent a small fraction of sedimentary organic matter (SOM). In order to extend the conclusions of QMA to SOM, radiocarbon analyses have been performed on organic extracts and decarbonated sediments. This analysis allows (i) the differentiation between modern biomass (contemporary ¹⁴C) and fossil organic matter (¹⁴C-free) and (ii) the calculation of the modern carbon percentage (PMC). At the confluence between Fensch and Moselle Rivers, a catchment highly contaminated by both industrial activities and urbanization, PMC values in decarbonated sediments are well correlated with the percentage of natural molecular markers determined by QMA. It highlights that, for this type of contamination by fossil organic matter inputs, the conclusions of QMA can be scaled up to SOM. QMA is an efficient environmental diagnostic tool that leads to a more realistic quantification of fossil organic matter in sediments.     

Insight into the heavy metal binding potential of dissolved organic matter in MSW leachate using EEM quenching combined with PARAFAC analysis

Dissolved organic matter (DOM) plays an important role in heavy metal migration from municipal solid waste (MSW) to aquatic environments via the leachate pathway. In this study, fluorescence excitation-emission matrix (EEM) quenching combined with parallel factor (PARAFAC) analysis was adopted to characterize the binding properties of four heavy metals (Cu, Pb, Zn and Cd) and DOM in MSW leachate. Nine leachate samples were collected from various stages of MSW management, including collection, transportation, incineration, landfill and subsequent leachate treatment. Three humic-like components and one protein-like component were identified in the MSW-derived DOM by PARAFAC. Significant differences in quenching effects were observed between components and metal ions, and a relatively consistent trend in metal quenching curves was observed among various leachate samples. Among the four heavy metals, Cu(II) titration led to fluorescence quenching of all four PARAFAC-derived components. Additionally, strong quenching effects were only observed in protein-like and fulvic acid (FA)-like components with the addition of Pb(II), which suggested that these fractions are mainly responsible for Pb(II) binding in MSW-derived DOM. Moreover, the significant quenching effects of the FA-like component by the four heavy metals revealed that the FA-like fraction in MSW-derived DOM plays an important role in heavy metal speciation; therefore, it may be useful as an indicator to assess the potential ability of heavy metal binding and migration.     

Characterization of dissolved organic matter in a submerged membrane bioreactor by using three-dimensional excitation and emission matrix fluorescence spectroscopy

Three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy was employed to characterize dissolved organic matter (DOM) in a submerged membrane bioreactor (MBR). Three fluorescence peaks could be identified from the EEM fluorescence spectra of the DOM samples in the MBR. Two peaks were associated with the protein-like fluorophores, and the third was related to the visible humic acid-like fluorophores. Only two main peaks were observed in the EEM fluorescence spectra of the extracellular polymeric substance (EPS) samples, which were due to the fluorescence of protein-like and humic acid-like matters, respectively. However, the EEM fluorescence spectra of membrane foulants were observed to have three peaks. It was also found that the dominant fluorescence substances in membrane foulants were protein-like substances, which might be due to the retention of proteins in the DOM and/or EPS in the MBR by the fine pores of the membrane. Quantitative analysis of the fluorescence spectra including peak locations, fluorescence intensity, and different peak intensity ratios and the fluorescence regional integration (FRI) analysis were also carried out in order to better understand the similarities and differences among the EEM spectra of the DOM, EPS, and membrane foulant samples and to further provide an insight into membrane fouling caused by the fluorescence substances in the DOM in submerged MBRs.     

高演化黑色岩系原始有机质恢复——以滇东会泽地区下寒武统筇竹寺组为例

残余有机质含量用于高成熟或过成熟烃源岩评价或油气资源量预测时可能会导致错误的结论,因此,恢复其原始有机质至关重要.静水缺氧沉积环境中的原始有机质含量与Mo/A1比值具有很好的相关性,据此提出的Mo-TOC相关性估算法是一种新的原始有机碳丰度恢复方法,简便易行,适合大量样品分析.该文以滇东会泽地区下寒武统筇竹寺组黑色岩系...     

Identifying the sources and fate of anthropogenically impacted dissolved organic matter (DOM) in urbanized rivers

Anthropogenic activities have dramatically changed the loads and compositions of dissolved organic matter (DOM) in urbanized streams. In this study, the spatial and temporal variations of DOM in the anthropogenically impacted Zhujiang River were investigated by analyzing the water samples in an upstream, urbanized area and downstream of the rivers on different days of one year. The results indicated that the levels of dissolved organic carbon (DOC) and total phosphorus (TP) were unaffected by seasonal changes, but the specific UV₂₅₄ absorbance (SUVA) values and the total nitrogen (TN) content were greater in the winter than those in the summer. Parallel factor (PARAFAC) analysis of the excitation emission matrices (EEM) revealed the presence of three anthropogenically derived components [tryptophan-like (C1) and tyrosine-like proteins (C3) and anthropogenic humic substances (C5)] in the urbanized rivers, and they had greater seasonal and spatial variability than the terrestrial and microbial humic substances (C2 and C4). Cluster analysis revealed that treated wastewater was an important source of DOM in the urbanized streams. Photodegradation experiments indicated that the DOM in the populous area of the rivers had greater photodegradation potentials than that in the downstream region or in the natural waters. Interestingly, that the anthropogenic humic substances (C5) were considerably more photoreactive than the other four PARAFAC components, which exhibited a decrease of 80% after exposure to sunlight for 0.5 d. This study suggests that the treated wastewater could be an important input to the DOM in the urbanized rivers and the naturally occurring photodegradation could help in eliminating the anthropogenic DOM during their transport.