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Fractionation and characterization of dissolved organic matter in a shallow eutrophic lake, its inflowing rivers, and other organic matter sources.

Dissolved organic matter (DOM) in water from eutrophic Lake Kasumigaura, its inflowing rivers, and several other DOM sources in the lake catchment area was fractionated using resin adsorbents into five classes: aquatic humic substances (AHS), hydrophobic neutrals (HoN), hydrophilic acids (HiA), bases (BaS), and hydrophilic neutrals (HiN). The DOM-fraction distribution pattern and the ultraviolet absorbance to dissolved organic carbon ratio (UV/DOC ratio) were found remarkably effective for evaluating the characteristics of DOM in water. DOM-fraction distribution patterns were significantly different depending on the origin of the sample. AHS and HiA were found to be the dominant fractions in DOM in all samples studied. HiA prevailed over AHS in the lake water, whereas AHS were slightly more abundant than HiA in the river waters. AHS were in the great majority in forest streams and plowed-field percolates. HiA abounded in paddy-field outflow, domestic sewage, and sewage-treatment-plant effluent. Only domestic sewage contained a significant amount of HoN. The UV/DOC ratio also varied depending on the origin of the sample: the ratios in total DOM, AHS, and HiA were greater in river waters than in the lake water. The greatest ratio of AHS was found in paddy-field outflow and the lowest in domestic sewage. The UV/DOC ratios in the sewage-treatment-plant effluent were very similar to those in the lake water.

Absorption↗

Characterization of dissolved organic matter in effluents from wastewater treatment plants.

Dissolved organic matter (DOM) in effluents from sewage and human-wastes treatment plants (STPEs and HWTPEs) was fractionated using resin adsorbents into six classes: aquatic humic substances (AHS), hydrophobic bases (HoB), hydrophobic neutrals (HoN), hydrophilic acids (HiA), hydrophilic bases (HiB), and hydrophilic neutrals (HiN). DOM-fraction distribution varied substantially depending on the kind of wastewater and the type of treatment process. AHS and HiA dominated in all effluents, collectively accounting for more than 55% of the DOM measured as dissolved organic carbon (DOC). In particular, HiA were the most abundant fraction in the effluents, constituting 32-74% of the DOM. AHS appeared to be the second most dominant fraction and varied considerably, accounting for 3-28% of the DOM. The HoN fraction also varied from 0-21%. AHS, HoN, and HiA were the fractions that changed substantially and differed characteristically among the samples studied. The ratios of ultraviolet absorbance to DOC (UV: DOC ratio) in all effluents exhibited a common relationship: AHS> total DOM > HiA. Nevertheless, the ratios were substantially different between STPEs and HWTPEs and among HWTPEs. For HWTPEs, the effluent from the chemical coagulation process had the highest UV: DOC ratios. On the other hand, the effluent from the ultrafiltration and activated carbon adsorption processes had the lowest ratios. Molecular size distribution of the effluents was determined by size exclusion chromatography and found to exhibit a relatively narrow size range and low weight-averaged molecular weights ranging from 380 to 830 g mol(-1). The weight-averaged molecular weight of DOM increased as the UV: DOC ratio of total DOM increased.

Chromatography↗

The role of colloidal particles in the speciation and analysis of "dissolved" phosphorus.

Colloidal-sized particles (1-1,000 nm) and high molecular mass material play an important, yet poorly understood role in the aqueous speciation of P. This study assessed the size distribution of P in 0.45-microm filtered soil solutions and soil-water extracts from three sandy soils (grassland, arable field and forest) using gel filtration chromatography (GFC) and membrane filtration (0.22- and 0.025-microm pore-size) and evaluated the impact of P speciation on colorimetric and ion-chromatographic methods for orthophosphate analysis. Between 40% and 58% of molybdate reactive P (MRP) and > 85% of molybdate unreactive P in the soil solution from the agricultural soils (pH 5.9-6.3) were associated with high molecular mass material (apparent size > 0.025 microm, or > 600 kDa on Superdex). In solutions from the forest soil (pH 3.2), high molecular mass P (HMMP) compounds were of minor importance (<8% of TP). The GFC elution profiles, composition and spectral characteristics of HMMP-containing solutions as well as the small relevance of HMMP at low pH were all indicative for associations between humic substances, Fe and/or Al, and P. Both MRP and ion chromatographic P measurements overestimated the free orthophosphate concentration (up to 2.3- and 1.4-fold, respectively) in 0.45-microm filtered HMMP-containing solutions. In 0.025-microm filtrates, free orthophosphate was the only MRP species present.

Chromatography, Gel↗

Characterization and comparison of hydrophobic neutral and hydrophobic acid dissolved organic carbon isolated from three municipal landfill leachates.

The acid-precipitated (AP) and acid-soluble (AS) fractions of the combined hydrophobic neutral and hydrophobic acid dissolved organic carbon (DOC) were isolated from leachate collected from three municipal landfills of different age and redox conditions. The AP and the AS combined hydrophobic neutral and hydrophobic acid DOC comprised 6-15% and 51-66%, respectively, of the leachate nonpurgable organic carbon. Elemental analysis, infra-red spectroscopy, 13C CP-MAS nuclear magnetic resonance spectroscopy and dipolar dephasing experiments, and thermochemolysis gas chromatography/mass spectrometry results showed that the AP and AS fractions of hydrophobic neutral and hydrophobic acid DOC are highly aliphatic, with linear and branching moieties, and less oxidized than most terrestrial and aquatic humic substances. Very little, if any, polysaccharide or cellulose, lignin, or cutin components comprise these fractions. It is hypothesized that a majority of the organic carbon in these fractions originates highly branched, cyclic aliphatic organic compounds.

Acids↗

Chlorination of model drinking water biofilm: implications for growth and organic carbon removal.

The influence of chlorine on biofilm in low organic carbon environments typical of drinking water or industrial process water was examined by comparing biomass and kinetic parameters for biofilm growth in a chlorinated reactor to those in a non-chlorinated control. Mixed-population heterotrophic biofilms were developed in rotating annular reactors under low concentration, carbon-limited conditions (< 2 mg/L as carbon) using three substrate groups (amino acids, carbohydrates and humic substances). Reactors were operated in parallel under identical conditions with the exception that chlorine was added to one reactor at a dose sufficient to maintain a free chlorine residual of 0.09-0.15 mg/L in the effluent. The presence of free chlorine resulted in development of less biofilm biomass compared to the control for all substrates investigated. However, specific growth and organic carbon removal rates were on the average five times greater for chlorinated biofilm compared to the control. Observed yield values were less for chlorinated biofilm. Although chlorinated biofilm's specific organic carbon removal rate was high, the low observed yield indicated organic carbon was being utilized for purposes other than creating new cell biomass. The impacts of free chlorine on mixed-population biofilms in low-nutrient environments were different depending upon the available substrate. Biofilms grown using amino acids exhibited the least difference between control and chlorinated kinetic parameters; biofilm grown using carbohydrates had the greatest differences. These findings are particularly relevant to the fundamental kinetic parameters used in models of biofilm growth in piping systems that distribute chlorinated, low-carbon-concentration water.

Biofilms↗

Removal of natural organic matter by ion exchange.

Ion exchange is an effective method for removing humic substances from drinking water supplies. We have explored a range of anion exchangers for removal of natural organic matter (NOM), both as isolated from surface waters and after fractionation into four fractions based on hydrophobic and hydrophilic properties. Resins of open structure and high water content are confirmed as the better performers, being very efficient at removal of any charged material, especially that of smaller molecular size. Quaternary ammonium resins containing polar groups are especially effective. The presence of a neighbouring OH group close to the quaternary nitrogen, heteroatoms in the bridge between the exchange site and the polymer backbone, a secondary amino group as the exchange site, or a low ratio of carbon to quaternary nitrogen is beneficial. A suitable balance of polar and non-polar regions in the resin structure appears to be required. Weakly basic amino groups may have a greater affinity for hydrophilic counter ions than quaternary ammonium groups, but generally there are fewer charged sites in the resin at neutral pH. Nevertheless, weak base resins have NOM uptakes nearly as high as strong base resins of similar water content. Water content was found to be the most important parameter, though the effect was less pronounced for strong base resins. For weak base resins of low charge density a non-electrostatic mechanism involving hydrogen bonding of the undissociated acidic species in the NOM to the unprotonated amino groups on the resins is proposed.

Hydrogen-Ion Concentration↗

Effect of fulvic acid on the sorption of Cu and Pb onto gamma-Al2O3.

This work investigated the adsorption of Cu and Pb at the surface of gamma-Al(2)O(3) in the presence of fulvic acid to address the significance of dissolved organic matters on metal partitioning. Fulvic acid, obtained from International Humic Substance Society, represented dissolved organic matter. Fulvic acid concentrations employed herein were 1, 5, and 10 mg C/L, which simulated the relevant environmental conditions. Ion selective electrodes were employed to ascertain free Cu and Pb measurements. The maximum adsorption of 10mg C/L fulvic acid on gamma-Al(2)O(3) was 5 x 10(-2)mgC/mg gamma-Al(2)O(3). Fulvic acid promoted Cu adsorption in low pH conditions. The effects of fulvic acid on Pb adsorption were similar to those of Cu. The conditional stability constants of sorbed fulvic acids with Cu and Pb were determined to be in the order of 4 to 6 (log K). Cu and Pb species were modeled in heterogeneous systems using triple-layer model. Simulation results indicated that metal species are dominantly in complexation with fulvic acid, both in solution and at the gamma-Al(2)O(3) surface.

Adsorption↗

Copper catalysis in chloroform formation during water chlorination.

The seminal work of Rook initiated a considerable body of research regarding the formation of trihalomethanes (THMs) and other by-products of chlorine-based disinfection. Since that time, a broad spectrum of compounds has been identified as precursors to THM formation. More recently, it has been demonstrated that the presence of copper in solution enhances THM formation. Copper is known to catalyze a number of reactions that are similar to the conventional haloform reaction. A study was therefore initiated to investigate the specific role played by copper in the formation of chloroform during chlorination of water supplies. Aqueous solutions containing a number of known THM precursors were chlorinated in the presence and absence of copper, and subjected to time-course monitoring of chloroform concentration. The results of experiments with humic acid demonstrated an apparent catalytic effect on the part of copper in chloroform formation. To examine the role of copper in greater detail, a series of experiments involving aqueous solutions of pure compounds of humic substance structural units was conducted. Of the pure compounds investigated as THM precursors, only citric acid demonstrated enhanced chloroform formation in the presence of copper. A detailed matrix of experiments conducted with citric acid as a precursor demonstrated that copper, at environmentally relevant concentrations, can have a profound effect on chloroform formation. Based on previously published information regarding the mechanism of chloroform formation from citric acid and the results of these experiments, it is hypothesized that copper promotes chloroform formation from chlorination of citric acid through catalysis of oxidative decarboxylation, and the subsequent chlorination of beta-ketoglutaric acid.

Catalysis↗

Leaching behaviour of wood treated with creosote.

The results of a laboratory investigation on the leaching behaviour of wood treated with creosote and of untreated wood are reported. A special leaching test derived from the German standard method DEV S4 test (DIN 38414) has been developed. Samples were leached in deionized water, in a solution buffered at pH 4.7 and in a solution of humic substances. The organic fraction of the leachate was extracted using liquid-liquid extraction. The extracts were analysed qualitatively with GC/MSD and quantified with GC/FID. The results were compared with those of Soxhlet-extracts from creosote-treated wood.

Chromatography, Gas↗

Influence of heavy organic pollutants of anthropic origin on PAH retention by kaolinite.

The adsorption of heavy fuel oil No. 2 (F2) on a reference kaolinite (Arvor kaolin, France), and the influence of this anthropic organic matter on the phenanthrene (PHEN) retention capacity of a kaolinite were investigated in the laboratory. The heaviest and most polar compounds of F2 are adsorbed on kaolinite preferentially to the other compounds and also partly irreversibly. The precoating of kaolinite by F2 significantly increases the sorption of PHEN in the range of concentrations studied (10-500 microg l(-1)). The partition coefficients normalized to organic carbon content (Koc) of kaolin precoated with fuel oil (5.2 < log Koc < 5.5) are one order of magnitude higher than those of the original kaolin (4.2 < logKoc < 4.5), and show very good agreement with the literature for polluted industrial soils. The Koc measured on the uncoated kaolin are in close agreement with the values determined for natural soils in which humic substances represent the organic component. This demonstrates that the composition of organic matter is the primary factor in PHEN retention by the soils. Therefore, in predicting the transport of PHEN, and other Polycyclic aromatic hydrocarbons (PAHs) in general, in soils of industrial sites containing heavy hydrocarbons or tars requires that the specific nature of the organic matter contained in these soils be taken into consideration.

Adsorption↗

Long-term tillage effects on soil metolachlor sorption and desorption behavior.

Sorption and desorption are two important processes that influence the amount of pesticides retained by soils. However, the detailed sorption mechanisms as influenced by soil tillage management are unclear. This study examined the sorption and desorption characteristics of metolachlor [2-chloro-N-(2-ethyl-6-methyphenyl)-N-(2-methoxy-1-methylethyl)-acetamide] using the soil samples collected from the long-term conservation tillage (CnT) and conventional tillage (CT) research plots established in 1979 in Darlinton, SC. Humic acid (HA) and humin were extracted from the soils and used in the sorption experiments along with the whole soil samples. The sorption experiments were conducted using a batch-equilibration method. Three sequential desorption rinses were carried out following the sorption experiments. By comparing metolachlor sorption and desorption results we observed hysteresis for all soil samples and their organic matter fractions. Sorption nonlinearity (N) and hysteresis were dependent on the structure and composition of soil organic matter (SOM), e.g., Freundlich isotherm exponents (N) of HA and humin from CnT were higher than those of CT treatment, which may be related to high aromaticity of SOM fractions in CT treatment. Sorption capacity (K'f) was positively correlated with soil organic carbon (SOC) content. These results show that long-term tillage management can greatly affect metolachlor sorption and desorption behavior probably by qualitative differences in the structural characteristics of the humic substances.

Acetamides↗

Silica reduces the toxicity of aluminium to a tropical freshwater fish (Mogurnda mogurnda).

The toxicity of aluminium (Al) to fish in acidic waters has been well documented. It was therefore expected that Al toxicity would be significant in fish communities in Gadjarrigamarndah (Gadji) Creek, a seasonally flowing stream in tropical northern Australia. This creek receives acidic groundwater containing elevated concentrations of Al from earlier land irrigation of treated mine tailings water from the former Nabarlek uranium mine. It was hypothesised that Al toxicity was reduced by high levels of silica (Si) in the water, and the subsequent formation of Al-silicate complexes. This prompted a laboratory assessment of the toxicity of Gadji Creek water to sac-fry of the native fish, Mogurnda mogurnda, followed by more detailed investigation of the toxicity of Al and the influence of Si in reducing Al toxicity. No mortality of M. mogurnda sac-fry was observed in two toxicity tests using Gadji Creek water collected in August 1997 and September 1998. The majority of Al (80-95%) was calculated to be complexed with humic substances and sulfate, with < 1% being complexed with silicate. Assessment of the influence of silica on the acute toxicity of Al in the absence of natural organic complexants (i.e. in reconstituted freshwater, pH 5) revealed that Si reduced Al toxicity. As the molar ratio of Si:Al was increased, the percent survival of M. mogurnda sac-fry increased until there was no significant (P > 0.05) difference from the controls. However, speciation modelling again predicted that little (< 3%) Al complexed with silicate, with the speciation and bioavailability of Al remaining constant as the molar ratio of Si:Al increased. Therefore, the original hypothesis that Al-silicate complexes in solution reduced the toxicity of Al to M. mogurnda could not be supported. This potential mechanism, and an alternative hypothesis, that Si competes with Al for binding sites at the fish gill surface, requires further investigation.

Aluminum↗

Horizontal and vertical variabilities of mercury concentration and speciation in sediments of the Gdansk Basin, Southern Baltic Sea.

The mercury compounds introduced to the environment because of anthropogenic activity are accumulated, mainly, in marine sediments. Both distribution of mercury in the Baltic Sea and factors affecting it are remain largely unknown. Due to its complex chemistry and variable conditions in the Baltic Sea bottom sediments, mercury may be reemitted to the overlaying water, and thus to the environment. The aim of this study was twofold. Total mercury contents were measured in sediments of the Gdansk Basin along a Vistula mouth (main source)--Gdansk Deep (deposition area) transect in order to assess spatial distribution of the element. Soft and sandy bottom sediment cores were collected and cut into slices. The mercury measurements consisted of acid digestion followed by CV-AAS determination. A five-step sequential extraction procedure involving measurements of mercury species water soluble, bound to humic substances and insoluble, was employed in order to investigate mercury speciation. On the basis of speciation results stability and remobilisation potential was assessed. The second aim was demonstrating that mercury gradients in vertical profiles of the investigated sediment cores exist. Total mercury contents varied in range from 28 ng/g x dw to 844 ng/g. Mercury associated with organic matter and sulphides, (respectively 39% and 49%) were the dominant species of the element. The results indicated that the river run-off is a source of mercury in the area. Vertical gradients of both total content and speciation of mercury in the soft sediments were attributed to both remobilisation from sediments, and decreasing trend in the anthropogenic load of the element deposited to sediments.

Baltic States↗

Relation between extracellular polymers' composition and its ability to complex Cd, Cu and Pb.

Activated sludges originated from wastewater treatment plants (WWTPs) play an important role in heavy metal removal from effluents. Extracellular polymers (ECP) form a major part of the activated sludge and are heavily involved in biosorption of heavy metals. The complexation of three heavy metals (Cd, Cu and Pb) with ECP extracted from six activated sludges, originated from different WWTPs, was investigated at pH 7. ECP in the study were shown to be mainly composed of proteins, humic acids, uronic acids and polysaccharides along with smaller amounts of lipids and nucleic acids. IR spectra confirmed the presence of the functional groups usually found in the ECP and the content in each fraction was determined using colorimetric methods. The determination of surface charge was carried out on each ECP sample and allowed two pK(a) values characteristic of two distinctive functional groups to be determined. At the pH used in the study, the value of these constants indicates that only one functional group is under protonated form. A polarographic method was used to determine the complexation parameters (number of binding sites and complexation constant) of ECP solutions towards metals. The following orders were established for the number of binding sites: Cu > Pb > or = Cd and for the stability of the ECP-metal complex: Cd > Pb approximately = Cu. A matrix of correlation between the composition of the polymers and the complexation parameters showed that the number of binding sites and the complexation constant were strongly linked to proteins, polysaccharides and humic substances content.

Binding Sites↗

Influence of eutrophication on the coagulation efficiency in reservoir water.

Water from the three reservoirs, Min-ter, Li-yu-ten and Yun-ho-shen, was examined for concentration of chlorophyll a, ultraviolet absorption (UV(254)), fluorescence intensity (FI), concentration of dissolved organic carbon (DOC), and fractionation of dissolved molecules by molecular weight. The water samples were collected over the change from spring to summer (May to July but before the typhoon season) when the water temperature and extent of eutrophication increase. Analytical results indicate that the concentration of DOC is proportional to the concentration of chlorophyll a, but not to the values of UV(254) and FI. Therefore, eutrophication, extraneous contaminants of small molecules, and the extracellular products of algae cause an increase in DOC, but a decrease in the proportion of large organic molecules such as of humic substances. The fraction of DOC with a molecular weight of less than 5000 Da increases with the concentration of chlorophyll a. All these data suggest that changes in the quality of water after eutrophication make the treatment of drinking water more difficult. The method of enhanced coagulation was recently developed for removing DOC. However, the results of this paper demonstrate that the efficiency of DOC removal falls as the degree of eutrophication increases. When the percentage of DOC with small molecules excreted by algae increased by 1%, the efficiency of DOC removal decreased by approximately 1%, implying that enhanced coagulation are not able to remove the DOC excreted by the algae during eutrophication, and resulting an increased concentration of trihalomethanes formation in water disinfections process.

Absorption↗

Thermodynamic properties of several soil- and sediment-derived natural organic materials.

Improved understanding of the structure of soil- and sediment-derived organic matter is critical to elucidating the mechanisms that control the reactivity and transport of contaminants in the environment. This work focuses on an experimental investigation of thermodynamic properties that are a function of the macromolecular structure of natural organic matter (NOM). A suite of thermal analysis instruments were employed to quantify glass transition temperatures (Tg), constant-pressure specific heat capacities (Cp), and thermal expansion coefficients (alpha) of several International Humic Substances Society (IHSS) soil-, sediment-, and aquatic-derived NOMs. Thermal mechanical analysis (TMA) of selected NOMs identified Tgs between 36 and 72 degrees C, and alphas ranging from 11 mum/m degrees C below the Tg to 242 mum/m degrees C above the Tg. Standard differential scanning calorimetry (DSC) and temperature-modulated differential scanning calorimetry (TMDSC) measurements provided additional evidence of glass transition behavior, including identification of multiple transition behavior in two aquatic samples. TMDSC also provided quantitative measures of Cp at 0 and 25 degrees C, ranging from 1.27 to 1.44 J/g degrees C. Results from TMA, DSC, and TMDSC analyses are consistent with glass transition theories for organic macromolecules, and the glass transition behavior of other NOM materials reported in previous studies. Discussion of the importance of quantifying these thermodynamic properties is presented in terms of improved physical and chemical characterization of NOM structures, and in terms of providing constraints to molecular simulation models of NOM structures.

Differential Thermal Analysis↗

The role of aqueous iron(II) and manganese(II) in sub-aqueous active barrier systems containing natural clinoptilolite.

Increasing attention is being placed on capping as a relatively new option in managing both contaminated sediments and dredged materials, due to its economic and environmental benefits. Capping denotes the placement of a cover onto potentially hazardous sediments or dredged material dumps to inhibit the transfer of contaminants into the water column. Retention of divalent iron and manganese cations using sandy capping layers containing natural zeolites as a reactive additive (active barrier systems, ABS) is evaluated in this study. Three different natural zeolite (clinoptilolite) rocks, two from deposits in Australia and one from a North-American deposit, were investigated and compared with respect to their mineralogical, physical and chemical properties. In particular, results from batch and column experiments show that ABS based on these materials can efficiently demobilise iron and manganese from percolating, anoxic pore water by cation exchange under favourable conditions. The retention, however, may be reduced strongly where competitive exchange with divalent cations such as calcium prevails or where mobile colloidal pore water constituents such as clay minerals or humic substances bind fractions of the dissolved iron or manganese. Therefore, the potential of ABS as a means for in situ remediation has to be evaluated diligently with particular regard to the pore water composition of the sediment to be capped.

Cations, Divalent↗

The use of 13C-labelled polycyclic aromatic hydrocarbons for the analysis of their transformation in soil.

The formation of non-extractable residues during biodegradation and humification processes in soils and sediments represents a major sink for organic contaminants. The mode of incorporation of polycyclic aromatic hydrocarbons (PAH) and their metabolites into macromolecular organic matter during microbial degradation was studied applying 13C-labelled compounds. Mineralisation rates were determined by measuring the 13CO2 production. An incorporation of 13C-PAH-fragments into humic material could be traced by isotopic analysis of the bulk organic matter. Furthermore, selective chemical degradation reactions were performed to analyse the precise chemical structure of covalently bound 13C-labelled PAH fragments in soil humic substances. Structural assignments by GC-MS combined with isotope measurements on the bulk organic carbon and at the molecular level (Isotope Ratio Monitoring-GC-MS) provided useful information on the fate of xenobiotics within the soil.

Anthracenes↗