Isolation and characterization of polymeric organic materials in a polluted river water

Organic matter was isolated from water samples from a river mainly polluted by domestic sewage by using Amberlite XAD-2 resin after being acidified to pH 2. The amount of the isolated organic matter comprises about 40% of the total dissolved organic matter. Measurements of elementary composition, molecular weight distribution, u.v. and i.r. spectra and GC/MS analysis of alkaline potassium permanganate oxidation products were performed for the isolated matter. The results indicate that more than a half of the isolated organic matter have apparent molecular weights higher than 5000. The chemical oxidation of the isolated organic matter produced (a) aliphatic monocarboxylic acids (C₆---C₂₄), (b) aliphatic dicarboxylic acids (C₃-C₁₂) and (c) benzene-mono-di-, tri- and tetracarboxylic acids: the latter two groups (b and c) are most abundant. The relative amounts of those three groups seem to be explained in terms of the nature and degree of pollution.     

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.     

Isolation of dissolved organic matter from the suwannee river using reverse osmosis

A portable reverse osmosis (RO) system was constructed and used to concentrate dissolved organic matter (DOM) from the Suwannee River in southeastern Georgia. Using this RO system, 150–180 1/h of river water could be processed with 90% recovery of DOM. After further cation exchange and lyophilization of the concentrated river water samples, large quantities of low-ash freeze-dried products were isolated. We highly recommend this RO method for concentration of DOM in fresh waters because (1) a very high percentage of DOM is recovered, which indicates minimal fractionation of the original sample; and (2) the process is quite rapid, which permits large quantities of DOM to be concentrated in a reasonable length of time.     

Analytical fractionation of dissolved organic matter in water using on-line carbon detection

A routine method is described for the analytical fractionation of dissolved organic matter (DOM) in natural freshwater and in used waters. The fractionation is based on the different adsorption behaviours of various constituents of the DOM on octadecyl-silica as a function of pH. The DOM is separated into a hydrophilic, an acid and a hydrophobic fraction. The detection is carried out by an on-line carbon detector. The method requires only small water samples (20 ml) with low dissolved organic carbon (DOC) concentrations (1–5 mg Cl⁻¹). The samples can be analysed rapidly with no preconcentration. Fractionation of model compounds and mixtures demonstrates the performance of the method. The application of the method is illustrated by an investigation of the changes of the DOC composition occurring in a longitudinal transect of a river and during the infiltration of river water to groundwater.     

颗粒活性炭吸附对预臭氧后微污染原水水质影响研究

在不同的预臭氧浓度条件下处理微污染原水,考察了颗粒活性灰（GAC）吸附对处理后水样水质的影响.选择化学需氧量（CODMn）、溶解性有机碳（DOC）、生物可降解溶解性有机碳（BDOC）、UV254和氨氮（NH;-N）含量及有机物分子量分布作为考察吸附效果的检测指标.结果表明,在静态吸附时间达到5天时,颗粒活性炭吸附曲线开始趋于平缓,吸附时间超过5天之后吸附趋于饱和;预臭氧含量为2.5 mg/L时,颗粒活性炭对有机物的吸附效果最佳,对CODMn、DOC、BDOC的去除率分别为53.2％,63.2％和36.2％;在不同预臭氧处理条件下,颗粒活性炭对NH;-N的吸附效果并未表现出较大的差异,吸附去除率约为5％;颗粒活性炭优先吸附水中分子量＞ 10kDa的有机物,其次为分子量＜1 kDa的有机物.     

Automatic photocatalytic method for the determination of dissolved organic carbon (DOC) in natural waters

An automatic method for the determination of dissolved organic carbon in natural waters is described. The method relies on the catalytic oxidation of dissolved organic matter to CO₂ by UV radiation and using a titanium dioxide semiconductor as a catalyst. Several compounds including urea and fulvic acid were mineralised completely. Compared with direct photolysis, the semiconductor catalytic photolysis gave consistently higher mineralisation yields for natural organic matter in seawater. The fraction resistant to direct UV photolysis (i.e. UV-refractory) was found to be in the range of 2%–5% of total DOC and it is suggested that this consists of organic macromolecules that fragment to non-UV absorbing species and escape further oxidation in direct UV photolysis. Organic macromolecules concentrated by molecular filtration contained 10%–50% such material, the higher proportion was found during the productive season in the sea, suggesting their primary biological origin (rather than degraded organic matter).The throughput of the method can be up to 30 samples per h and it is capable of online real-time analysis of DOC. The method gives linear calibration of up to 1000 μM C and blanks (instrument, reagent and distilled water blanks) can be readily and easily evaluated.Attempted validation of the method against CHN elemental analysis, highlighted several inherent basic problems. Initial validation showed that within the analytical errors, the two methods were in close agreement.     

The effect of ozonation on natural organic matter removal by alum coagulation

Natural organic matter (NOM) was extracted from a moderately colored, eutrophic surface water source (Forge Pond, Granby, MA), and fractionated into quasi-homogeneous fractions. Fulvic acid (FA) and hydrophilic neutrals (HN) were the two most abundant NOM fractions that were isolated. Adsorption affinity of the isolated NOM fractions on preformed aluminum hydroxide flocs increased with increase in specific organic charge of the fractions, except for the two most highly charged fractions, FA and hydrophilic acids (HAA), which showed less adsorption affinity than expected based on their specific organic charge. Prior ozonation of FA and HN fractions resulted in a decline and an increase, respectively, in their adsorption affinity on aluminum hydroxide surface. Prior ozonation of Forge Pond raw water resulted in a progressive decline in dissolved organic carbon (DOC) removal by alum coagulation with increase in ozone dose. It appeared that ozone applied to raw water reacted preferentially with the humic fraction of NOM, resulting in the detrimental effects of ozonation on subsequent NOM removal by alum coagulation being magnified. Forge Pond raw water was pre-coagulated to remove humic substances. Ozonation of the pre-coagulated water demonstrated the beneficial effects of ozonation on the removal of non-humic NOM through alum coagulation. A strategy for staged coagulation with intermediate ozonation was proposed for waters containing both humic and non-humic NOM for maximum DOC and specific UV absorbance at 254nm (SUVA) removal.     

Thermal fluorescence quenching properties of dissolved organic matter

The fluorescence excitation-emission matrices of dissolved organic matter (DOM) are investigated between 10 and 45 degrees C for river and waste waters and organic matter standards. With increased temperature, fluorescence intensity is quenched. It is demonstrated that for a range of river and wastewater samples, that tryptophan-like fluorescence exhibits a greater range of quenching (between 20+/-4% and 35+/-5%) than fulvic-like fluorescence (19+/-4 to 26+/-3%) over this temperature range. Humic substance standards exhibit similar fulvic-like (23+/-4%) fluorescence thermal quenching properties to river water samples (23+/-3%); however none of the samples exhibit quenching of tryptophan-like fluorescence to the same extent as the tryptophan standards (approximately 50%). Thermal fluorescence quenching is related to the exposure of the fluorophores to the heat source; our findings suggest that the tryptophan-like groups within DOM is more exposed in untreated wastewaters than in treated wastewaters riverine DOM. Thermal fluorescence properties have the potential to be used to source DOM, to provide additional chemical structural information, to temperature correct laser-induced remotely sensed DOM fluorescence, and to characterise DOM through the wastewater treatment process.     

Ozonation effect on natural organic matter adsorption and biodegradation - Application to a membrane bioreactor containing activated carbon for drinking water production

More stringent legislation on dissolved organic matter (DOM) urges the drinking water industry to improve in DOM removal, especially when applied to water with high dissolved organic carbon (DOC) contents and low turbidity. To improve conventional processes currently used in drinking water treatment plants (DWTPs), the performances of a hybrid membrane bioreactor containing fluidised activated carbon were investigated at the DWTP of Rennes. Preliminary results showed that the residual DOC was the major part of the non-biodegradable fraction. In order to increase the global efficiency, an upstream oxidation step was added to the process. Ozone was chosen to break large molecules and increase their biodegradability. The first step consisted of carrying out lab-scale experiments in order to optimise the necessary ozone dose by measuring the process yield, in terms of biodegradable dissolved organic carbon (BDOC). Secondly, activated carbon adsorption of the DOC present in ozonated water was quantified. The whole process was tested in a pilot unit under field conditions at the DWTP of Rennes (France). Lab-scale experiments confirmed that ozonation increases the BDOC fraction, reduces the aromaticity of the DOC and produces small size organic compounds. Adsorption tests led to the conclusion that activated carbon unexpectedly removes BDOC first. Finally, the pilot unit results revealed an additional BDOC removal (from 0.10 to 0.15 mg L⁻¹) of dissolved organic carbon from the raw water considered.     

Tracing the sources of nitrate in the Han River watershed in Korea, using delta15N-NO3- and delta18O-NO3- values

The dissolved nitrate concentrations and their nitrogen and oxygen isotopic ratios were analyzed in seasonal samples from Korea's Han River to ascertain the seasonal and spatial variations of dissolved nitrate and its possible sources. Nitrate concentrations in the South Han River (SHR) were much higher than those in the North Han River (NHR), probably because of the more extensive distribution of agricultural fields, residential areas and animal farms in the SHR drainage basin. The nitrogen isotopic composition of dissolved nitrate indicates that nitrate-nitrogen (NO(3)(-)-N) is derived mainly from atmospheric deposition and/or soil organic matter in the NHR but comes principally from manure or sewage, with only a minor contribution from atmospheric deposition or soil organic matter, in the SHR. The oxygen isotopic compositions of dissolved nitrate suggest that most atmospheric nitrate undergoes microbial nitrification before entering the river.     

Binding of organic solutes to dissolved humic substances and its effects on adsorption and transport in the aquatic environment

Humic substances constitute a major fraction of dissolved organic matter in natural water and effluents. Their effect on the adsorption of organic contaminants to aquifer material was elucidated, and a model was proposed for the adsorption of organic solutes to aquifer solids in the presence of dissolved humic substances. The model is based on the assumption that organic solute binds to dissolved humic substances in a reversible manner to form a solute-humate complex. Following binding, both free and bound fractions of the organic solute are independently adsorbed onto the solid phase. In order to evaluate the validity of the model, the following parameters were determined: (1) the adsorption coefficient of the organic solute to clay; (2) the binding constant of the solute-humate complex; and (3) the adsorption of humic acid (HA) to clay, assuming that the solute-humate complex is adsorbed similarly to humic acid itself. Using these parameters in the model enabled the effect of dissolved humic substances on adsorption to be evaluated. Experimental results obtained for the adsorption of fluoranthene (a model compound of the PAH group) to clay in the presence of dissolved HA were compared with calculated values derived from the model described above. The sensitivity of the model to various parameters was evaluated and a prediction was made with respect to the effect of dissolved humic substances on the adsorption of a variety of organic solutes. It appears that dissolved humic substances solubilize organic solutes which have higher adsorption coefficients to clay than humic substances, but increase the adsorption of solutes having lower adsorption coefficients relative to humic substances.     

The impact of combined sewer overflows on the dissolved oxygen concentration of a river

As described in the preceding paper by Harremoës (Harremoës, Water Res.16, 1093–1098, 1982) it is important to distinguish between removal and degradation of organic matter for non-steady-state discharges to rivers. These effects were investigated to determine the impact of combined sewer overflows on the dissolved oxygen concentration of a small river. Two different effects on the DO-concentration in the receiving river were observed during and after the passage of the bulk of combined sewage discharged at an existing outlet:

1. 1. An immediate effect caused mainly by degradation of the soluble BOD-fraction in the water body and by direct absorption and degradation of organic matter at the bottom.

2. 2. A delayed effect caused by degradation of adsorbed soluble, colloidal and fine particulate organic matter. After the passage of the bulk discharge a delayed effect on the DO-concentration in the river would be observed. This delayed effect lasted 12–24 hours after the discharge event.

Only 4% of the discharged organic matter was degraded during passage of the investigated stretch of the river, approx. 4 km. On the other hand about 35% of the discharged organic matter was removed by transfer to the bottom sediments. The rest was carried past the stretch of river investigated. This results in a rate of adsorption from the water phase of k = 9 m day⁻¹. The deposited organic matter was degraded with a first order reaction rate of K₄ = 0.75 day⁻¹.     

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.     

Adsorptive ozonation of 2-methylisoborneol in natural water with preventing bromate formation

This paper presents an application of our newly developed adsorptive ozonation process using a high silica zeolite adsorbent (USY) for drinking water treatment. First, the adsorption of 2-methylisoborneol (2-MIB) on USY in a river water/pure water mixture was clarified by a batch-type adsorption experiment. The results showed that 2-MIB was adsorbed on USY; however, almost all of the adsorbed 2-MIB was desorbed over time. The desorption rate was increased with the ratio of river water to pure water, indicating that compounds dissolved in the river water, such as natural organic matter (NOM), prevent the adsorption of 2-MIB on USY. Second, the ability of the river water to consume ozone was confirmed in an experiment using a USY-packed column reactor. The ozone consumption was obviously increased by the presence of USY, indicating that USY-adsorbing compounds dissolved in the river water (probably small size NOM) consumed the ozone. However, the rapid ozone consumption was occurred by 6-8 s in the retention times when 3.14-4.38 mgL(-1) of water dissolved ozone was fed, this rapid ozone consumption lasted no more than these times. This result revealed that the rapid consumption of ozone by the adsorptive compounds in our process could be avoided within a certain retention time (6-8 s; especially for the river water used in this study) when enough concentration of ozone (3.14 mgL(-1) or more; same above) was supplied. We therefore performed a trial in which 2-MIB dissolved in river water was continuously decomposed using a USY-packed column with various ozone concentrations. In the process, the adsorptive compound dissolved in the river water adsorbed and reacted with ozone in the parts of the apparatus upstream of the column, while the adsorption and decomposition of 2-MIB took place in the parts of the apparatus downstream of the column. This resulted in a sufficient 2-MIB decomposition with minimizing bromate ion formation.     

Transformation of organic matter and bank filtration from a polluted stream

A case study of the examination of the changes of organic matter in a small, highly polluted stream and the adjacent alluvial aquifer is presented. The investigated stream was actually a collector of effluents from baker's yeast and pharmaceutical industries. The stream was characterized by a COD of several thousands of mg O₂ l⁻¹, most of which was biodegradable organic matter. Biodegradation processes took place in the surface water, with consequent oxygen depletion in the stream. The organic matter content of the river sediment was more than 10% of its dry weight. Bank filtration of organic substances was investigated in a number of observation wells at distances of 5–150 m from the river (under different hydrological conditions). The infiltration of organic matter from the polluted stream into the aquifer was found to be significant only at hydrological conditions where the water level exceeds the altitude of the stream bed. The organic matter present in groundwater samples was mainly a humic/fulvic type, and was not degraded during the 64 days of the laboratory biodegradation experiment.     

Discriminatory classification of natural and anthropogenic waters in two U.K. estuaries

The ability to distinguish water inputs from both natural and anthropogenic sources was investigated in the complex environment of an urban estuary (Tyne) and a relatively pristine estuary (Tweed). We used a data set from a total of 11 estuarine transects, comprising measurements of bulk dissolved organic matter (dissolved organic carbon and nitrogen), dissolved nitrogen (total dissolved nitrogen, ammonium, nitrate+nitrite and dissolved organic nitrogen), optical absorbance measurements (a350, S290-350) and fluorescence excitation emission matrix measurements (fluorophores A, H, B and T intensity and A and H emission wavelength maxima). In order to investigate trends within the numerous parameters measured, multivariate statistics were employed. Principal components analyses showed 63.4% of the variability in the total data set can be explained by two sets of components and 74.9% of the variability by the spectrophotometric measurements alone. In both analyses the first component correlated to the mixing of terrestrial and marine waters and the second component was correlated to sources of pollution such as domestic sewage. Within the data set, river flow and terrestrially derived DOM were significantly correlated, and situations with high river input showed an increase in terrestrial signature in the estuary. Discriminant analyses were also carried out and indicated that 59.8% (total data set) and 53.3% (solely spectrophotometric data) of the samples can be correctly classified into their respective groups (water categories) assigned on the basis of salinity and sampling location. Overall the results clearly show the potential of spectrophotometric techniques to discriminate distinct water categories with different DOM characteristics. In particular, measurement of the fluorophore H emission maxima, the spectral slope parameter, S290-350, and fluorophores T and B intensity enabled discrimination of DOM from riverine, estuarine, marine, and sewage affected water categories. The results presented here indicate the ability of spectrophotometric data alone to distinguish between marine, anthropogenic and terrestrial DOM and distinguish terrestrial DOM from different catchments (Tyne vs. Tweed). With current advances in the in-situ deployment of absorbance and fluorescence spectroscopy it is anticipated that multivariate statistics will gain importance as a cost effective, powerful and diagnostic approach to assessing the distributions of water types and their associated DOM characteristics and fluxes at the land-ocean interface.     

Relationship between coliform culturability and organic matter in low nutritive waters

The objective of this work was to investigate the behaviour of coliform bacteria in specific low nutritive waters conveying organic fractions from different origin of which an unknown part is likely to pass through the treatment barrier. For this purpose, we studied the growth (microscopic counting) and the culturability (count on nutritive medium) of ten coliform bacteria species as a function of the amount of organic matter in a river water collected after a period of heavy rain and in an algal bloom water. Assays were carried out in the presence of autochthonous heterotrophic bacteria from the Nancy (France) drinking water, with variable concentrations of dissolved organic carbon (DOC) representative of drinking waters (0.5-1.5 mg l(-1) for diluted river water samples and 1.3-2.5 mg l(-1) for diluted algal bloom water samples). Bacterial growth was measured in the two types of water, regardless of the initial concentration of DOC. We found that coliform bacteria lost their culturability in both sample series, and that the lower the initial DOC concentration the more rapidly the culturability was lost. The quantity of DOC consumed by the bacteria in the two water types (0.03-0.13 mg l(-1) in river water and 0.77-1.29 mg l(-1) in algal bloom water) and the resulting consequences on bacterial behaviour suggested that bloom water contains algal organic compounds that are antagonistic to the growth and/or the culturability of coliform bacteria. Organic matter thresholds, beyond which coliform bacteria are unlikely to keep their culturability, have not been determined experimentally. Indeed, at the end of the assays some culturable coliform bacteria were systematically detected in both types of water. Enterobacter cloacae was the predominant species. Thus, during these adverse events the probability of coliform occurrence can be considered as high in treated water.     

Adsorption and desorption of trace organic contaminants from granular activated carbon adsorbers after intermittent loading and throughout backwash cycles

A granular activated carbon (GAC) adsorption simulation methodology using the observed trace organic contaminant mid-point breakthrough and the pore diffusion model is presented, validated, and used to model adsorption and concentration gradient driven desorption. Trace organic contaminant adsorption was well-simulated by this approach; however, desorption from GAC adsorbers was found to occur at lower concentrations than predicted by either pore or surface diffusion model calculations. The observed concentration profiles during desorption yielded a lower peak concentration and more elongated attenuation of contaminants after intermittent loading conditions than predicted by the models. Hindered back diffusion caused by irreversibly adsorbed dissolved organic matter on the GAC surface is hypothesized to be responsible for slowing the desorption kinetics. In addition, laboratory test results indicate a negligible impact of simulated backwashing the GAC media on trace organic contaminant breakthrough.     

Isolation of dissolved organic matter (DOM) from surface waters using reverse osmosis and its impact on the reactivity of DOM to formation and speciation of disinfection by-products

Dissolved organic matter (DOM) from three low-hardness surface waters was isolated and concentrated using a reverse osmosis (RO) membrane system. The efficacy of the RO isolation method and its impact on the subsequent reactivity between DOM and chlorine were examined. DOM mass balances (quantified as dissolved organic carbon) ranged from 96.1 to 102.1% for the three waters tested, and DOM mass recoveries of 93.9 to 98.2% indicated successful isolation, minimal fractionation. and negligible loss of organic matter. RO isolates were diluted using distilled and deionized water in the laboratory to reconstitute the source waters. Both source water (collected at the time of isolation) and reconstituted source water samples were chlorinated. Formation of several disinfection by-products (DBPs: e.g., THMs, HAA9, HANs, and HKs) were measured. For all waters tested, DBP formation of source and corresponding reconstituted source water agreed within 95% confidence intervals. Therefore, RO isolation had no impact on the DOM reactivity of the three low-hardness surface waters tested in this study. In addition, the degree of bromine substitution, as expressed by the bromine incorporation factor, was calculated. Comparison of bromine incorporation factors for source and reconstituted source waters further indicated that, as with the total DBP formations, bromine speciation and the relative occurrence of individual species in THMs and HAA9 did not change as a result of the isolation. Overall, in terms of DBP formation, RO isolation appears to maintain the integrity and reactivity of DOM.     

Mutagenic activity in the rivers Rhine and Meuse in The Netherlands

Several water samples of the rivers Rhine and Meuse have been tested for mutagenic activity in the Ames Salmonella/microsome assay and a fluctuation assay. Samples were taken at places where the rivers enter The Netherlands and at several downstream locations relevant to drinking water supplies. For the Rhine this included samples of each of the river-branches Waal, Lek and IJssel. Before testing, all water samples were concentrated by adsorption on XAD-resins and subsequent elution with dimethylsulfoxide.The results obtained clearly show that all water samples derived from the river Rhine and its branches contain mutagenic activity. Positive Ames test results showing dose—response relations were observed primarily with strain TA 98 after metabolic activation (rat liver microsomal enzymes). In contrast to this, little or no mutagenic activity was detected in samples from the river Meuse. This indicated that, with the methods used, the overall mutagenic activity of the river Meuse was at least 10 times below that of the river Rhine. In the fluctuation assay, using the same bacterial strains, the river water concentrates could not be tested as such. However, after appropriate dilution of the dimethylsulfoxide with distilled water, this assay proved to be about 10–15 times more sensitive than the Ames test. The significance of these results with respect to human health is briefly discussed.