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Sorption of phenols onto sandy aquifer material: the effect of dissolved organic matter (DOM).

The influence of dissolved organic matter (DOM) on the sorption of four phenols, 2,4,6-trichlorophenol (2,4,6-TCP), pentachlorophenol (PCP), 2,4-dinitrophenol (2,4-DNP) and 2-methyl-4,6-dinitrophenol (2-M-4,6-DNP), onto sandy aquifer material at different pH values was investigated using flow through column experiments. The pH-dependent sorption of the chlorinated phenols 2,4,6-TCP and PCP was not significantly affected by DOM (measured as dissolved organic carbon, DOC), whereas in the case of nitrophenols a significant lower retardation was found, depending on the DOC concentration and pH value of the aqueous solution. Sorption decreases with increasing DOC concentration, which indicates a binding of these compounds by DOM. The degree of sorption reduction depends on the pH value and increases with increasing fraction of neutral species. The different behaviour of nitrophenols in comparison to the chlorophenols is assumed to be a result of specific charge-transfer interactions. A combined sorption and complex formation model was used to describe the effect of pH and DOC concentration on the sorption of nitrophenols onto aquifer material and to estimate binding coefficients of neutral nitrophenols on DOM.

Adsorption↗

[Influence of dissolved organic matter (DOM) on environmental behaviors of organic pollutants in soils].

Dissolved organic matter (DOM) is an important component of solutions in terrestrial and aquatic ecosystems through its influence on acidity, nutrient availability, and toxicity. DOM could enhance the apparent solubility of organic pollutants and alter adsorption-desorption equilibrium of organic pollutants on soil. The enhancement of organic pollutants desorption in the presence of DOM could facilitate the mobility of organic pollutants in soil. On the other hand, the sorption of DOM by solid sorbents in soil could also enhance the retention of DOM-associated organic pollutants in soil. Furthermore, as a photosensitizer, DOM could promote the photogradation of organic pollutants in soil. And under certain condition, DOM also affected the hydrolysis of organic pollutants in soil solution. The effects of DOM on environmental behaviors of organic pollutants in soils were related to the physico-chemical characteristics of organic pollutants, DOM, and soil.

Adsorption↗

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.

Disinfection↗

The ability of dissolved organic matter (DOM) to influence benzo[a]pyrene bioavailability increases with DOM biodegradation.

The biodegradation of two substrates and the ability of dissolved organic matter (DOM) to influence benzo[a]pyrene bioavailability as DOM biodegradation progressed were monitored in reactors. Substrates were composed of algae extracts and an artificial substrate that mimics raw wastewater, which were considered to be autochthonous and anthropogenic allochthonous models for DOM, respectively. The soluble microbial products formed during biomass activity were also studied. The aromaticity of DOM was investigated with specific ultraviolet absorbance. Partitioning coefficients between DOM and benzo[a]pyrene, K(DOC)(biol), were biologically determined by means of 4-h bioaccumulation experiments on Daphnia magna. Parent and degraded substrates always significantly reduced the bioaccumulation of benzo[a]pyrene at environmental DOM concentrations. Soluble microbial products also significantly affected the benzo[a]pyrene bioaccumulation. K(DOC)(biol) ranged between 2 x 10(4) and 4 x 10(5) L/kg. As the artificial wastewater biodegraded, DOM aromaticity increased, as did K(DOC)(biol). During the biodegradation of algae extract DOM, K(DOC)(biol) increased, whereas their aromaticity slightly decreased.

Algorithms↗

Characterization of copper complexation with natural dissolved organic matter (DOM)--link to acidic moieties of DOM and competition by Ca and Mg.

We investigated Cu complexation by three dissolved organic matters (DOMs) collected by reverse osmosis (RO). Alkalimetric titration, pH-stat Cu and Ca titrations, pH edges of Cu-DOM complexation, and Ca/Mg-Cu exchange experiments were investigated at 1 = 109-2)M for DOM samples of 10mg C/L. The proton and Cu binding characteristics indicated similarity for all three DOMs. All Cu titrations employed ion selective electrode measurement and indicated the presence of relatively small amounts of strong Cu-binding sites. Four distinct classes of Cu binding sites are required for FITEQL 4.0 to provide good fits to the entire curves. The estimated total Cu binding site density is 4.55 mmol/g C, much less than the total acidity but very close to the phenolic site content. Cu-DOM complexation increases approximately 10-fold per pH unit, even at relatively high pH (> 8). We suggest that sites characterized as phenolic based on alkalimetric titration, not carboxyl sites, account for the majority of Cu complexation under natural water conditions, and Cu-DOM complexation is principally through the replacement of H + by Cu2+ at the phenolic binding sites. The Cu-H exchange ratio is 1:1 for the first three sites and about 1:2 for the 4th site. This 4-site model describes well the pH dependency of Cu-DOM complexation and provides good estimates of free Cu concentrations throughout wide total copper (Cu(T)) and pH ranges. Comparison between Ca-DOM and Cu-DOM complexation demonstrated that (i) Ca-DOM complexation increases much less than an order of magnitude per pH unit and decreases at higher Ca concentration, different from that of Cu-DOM complexation; and (ii) Cu-DOM complexation is highly non-linear, in contrast to the much reduced extent of non-linearity of Ca-DOM complexation. Ca/Mg-Cu exchange experiments showed small competition effect, less than expected by a simple competition model, and the competition tended to reduce with increasing Ca or Mg concentrations. The extent of the competition by Mg and Ca are essentially comparable. Put all together, it suggests that Ca and Mg are preferably bound by carboxyl sites, especially at relatively high concentrations, resulting in a weakened apparent competition effect.

Calcium↗

Molecular weight fractionation of dissolved organic matter (DOM) released by phytoplankton.

The application of an ultrafiltration procedure for fractionation of molecular weight of dissolved organic matter (DOM) extracellularly released by phytoplankton is described. Seven ultrafiltration membranes Diaflo (Amicon Corp. USA), with range 500--300,000 molecular weight (MW), were used for separation of different molecular weight compounds released by phytoplankton in Rhode River estuary of Chesapeake Bay, and their composition was determined. Percentage of extracellular release of DOM by phytoplankton varied from 3.92--68.07% of total carbon fixed in photosynthesis. The composition of algal extracellular products varied with different phytoplankton populations. However, two fractions of molecular weight compounds dominated in the composition of DOM released, i.e. a low molecular weight fraction of less than 1,000 MW and the fraction between 10,000--30,000 MW. The ultrafiltration procedure is effective for studying the composition of DOM released by phytoplankton in natural waters.

Biological Products↗

Effects of dissolved organic matter (DOM) on the bioconcentration of organic chemicals in aquatic organisms--a review.

Current knowledge on the effects of dissolved organic matter (DOM) on the bioconcentration of organic chemicals in aquatic animals (water fleas, mussels, amphipods and fish) is summarized. A graphical representation of the available data gives an overview of the magnitude of the observed effects. Most of the studies have shown decreases in bioconcentration in the presence of DOM (2 to 98% relative to DOM-free controls). However, at low DOM levels, up to 10 mg/L, also enhancements of bioconcentration due to DOM, ranging from 2 to 303% have been reported. Generally, the change in BCFW (Bioconcentration factor on a wet weight basis) per mg/L DOC was most pronounced at low levels of DOC. The data also show that DOM from different sources with different characteristics and quality can lead to substantial variations in the bioconcentration of organic compounds at comparable levels of DOC. While decreases in bioconcentration have generally been attributed to a lack of bioavailability of DOM-bound chemical, no mechanisms have been proposed to explain increased uptake of xenobiotics caused by DOM.

Animals↗

Transformation of dissolved organic matter (DOM) and 14C-labelled organic contaminants during composting of municipal biowaste.

Composting of municipal biowaste in the presence of 14C-labelled organic contaminants was studied in an attempt to characterize the mobilization potential of dissolved organic matter (DOM) for hydrophobic contaminants. The properties and transformation of DOM extracted from municipal biowaste compost with 10 mM KCl at six stages during 370 days of composting were investigated. DOM was fractionated into molecular weight fractions by ultrafiltration, and DOM structure was studied using CPMAS 13C-NMR- and UV-spectroscopy. The distribution of 14C-labelled model substances (DEHP, pyrene, simazine) upon molecular weight fractions was investigated by ultrafiltration, and association to DOM was studied performing flocculation experiments. The binding capacity of DOM for the model substances was of secondary influence for the mobilization because the intense biochemical reactions during composting pre-dominated the fate of the substances. Composting favoured the degradation of model substances to polar metabolites and supported their binding to the DOM matrix. DEHP and simazine were mainly found in the low- to medium-molecular DOM fraction and showed a small amount of DOM-associated radioactivity (approx. 10%). Pyrene and its metabolites had high affinities to high-molecular DOM. However, a direct relationship between DOM-quality and enhancement of pyrene solubility was not visible. After 120 days of composting DOM showed the highest binding capacity for hydrophobic contaminants.

Biodegradation, Environmental↗

Dissolved organic matter (DOM) in recycled leachate of bioreactor landfill.

Landfill leachate needs sufficient treatment before safe disposal. Bioreactor landfill technology could effectively degrade the organic matters in recirculated leachate, hence leaving a leachate stream of low biodegradability. This study characterized the dissolved organic matter (DOM) in the leachate from simulated bioreactor landfill columns with or without presence of trace oxygen. The removal efficiencies of this DOM using coagulation-sedimentation or electrolysis processes were demonstrated. Recirculated leachates were sampled from the simulated landfill columns applying conventional mode, intermittent-aeration mode, and natural aeration mode, whose DOM was fractionated into humic acids (HA), fulvic acids (FA) and hydrophilic fractions (HyI) by the XAD-8 resin combined with the cation exchange resin method. The recirculated leachate had low BOD/COD ratio, high humic substances contents, and high aromatic content. Their HA fraction comprised mainly large molecules (>10 k Da), while the FA and HyI were composed of smaller molecules (<50 k and <4 k Da, respectively). With the presence of oxygen, the TOC contents and the contents of HA, FA and HyI in leachate reduced, with FA and HyI fractions of molecular weight (MW) lower than 4 k Da more readily degraded. The organic matters left in leachates from intermittent-aeration mode and natural aeration mode were of low biodegradability. It was tested in the following sections the effects of coagulation-sedimentation process and of electrolysis process on the removal of residual DOM in recirculated leachate. Coagulation-sedimentation tests revealed that poly ferric sulphate (PFS) could remove more COD (58.1%) from leachate than polyaluminum chloride (PACl) (22.9%), particularly on the HA fraction with MW>10 k Da. Coagulation-sedimentation could not remove most of HyI in leachate. Furthermore, the corresponding BOD/COD ratio was not improved through coagulation. Electrolysis test could also effectively removed HA of MW>10 k Da. However, the biodegradability of treated effluent considerably was improved. The electrolysis could decompose high MW substances and increase biodegradability of recirculated leachate from bioreactor landfill.

Aerobiosis↗

Sensitivity analysis of calculated exposure concentrations and dissipation of DEHP in a topsoil compartment: the influence of the third phase effect and dissolved organic matter (DOM).

The fate and risk assessment of hydrophobic substances in the terrestrial environment can be associated with large errors. These can be attributed to the partitioning and process coefficients derived in experimental studies and to the model set-up that is designed to calculate the exposure concentrations. In many cases, the concentration of xenobiotics are low in the environment, which gives the aqueous phase the characteristics of a true solution, which are in accordance with the thermodynamic description of dilute solutions. Under these circumstances, the conventional equilibrium coefficients, such as Kd, Henry's Law constant H and the bioconcentration factor, BCF, are independent of the activity coefficient of the partitioning compound in the respective phases. However, for hydrophobic substances, these coefficients are often measured in laboratory experiments, where the nominal concentration levels are above the substance saturation point within the bulk water phase. In the case of the phthalates, the hydrophobic effect induces the formation of microdroplets (third phase) in the bulk water phase, by which the system is characterised as a heterogeneous mixture. Consequently, the linearity between dissolved and sorbed concentration is no longer true. Furthermore, in the terrestrial and aquatic environment, the presence of natural Dissolved Organic Matter (DOM) will have an influence on the fate and effects of hydrophobic substances. Hydrophobic compounds show large affinity for sorption to DOM, and contrary to Fixed Organic Matter (FOM), DOM is mobile and can be transported through the soil pores with the advective flow. It is therefore crucial that dispersed or emulsified phases within the continuous aqueous phase, e.g. DOM and microemulsions of phthalates, are distinguished from true solutions in the experimental measurements of partitioning coefficients, e.g. in order not to underestimate the mobility of sorbed substance. These aspects are treated in this study, where the exposure concentration, vertical transport and microbial degradation of Di-(2-ethylhexyl)-phthalate (DEHP) is modelled in an organic rich topsoil compartment, using experimental partitioning coefficients and degradation rates from the literature. Two model set-ups are derived for the topsoil compartment, i.e. (1) a system with dilute solution of substance and (2) a system with the presence of a third phase of microdroplets. In both models, the presence of DOM is incorporated. The first model shows that the error in the calculated exposure concentration, by using partitioning coefficients derived under unfavourable experimental conditions, compared to realistic conditions, amounts to 1400%. A comparison between the two models shows that when emulsion formation is not incorporated in the model, the calculated flux will be overestimated by a factor of 60.

Adsorption↗

Cadmium accumulation in zebrafish (Danio rerio) eggs is modulated by dissolved organic matter (DOM).

Experiments were conducted to investigate factors influencing the accumulation of cadmium (Cd(2+)) into zebrafish (Danio rerio) eggs. The accumulation of (109)Cd was affected by: (1) concentration, (2) time, (3) presence of dissolved organic material (DOM), (4) different origin of DOM and (5) different parts of fish eggs. Over a 5-h exposure, zebrafish eggs showed a steady increase in Cd-accumulation. DOM-concentrations over 15ppm carbon (C) decreased Cd-uptake significantly. Both samples of DOM, brown water marsh (LM) and a eutrophic pond (SP), at 16.9ppmC, reduced the Cd-accumulation in the chorion, perivitelline liquid and the embryo. Cd was mainly accumulated in the egg's outer shell chorion (61%) and only small amounts passed through the chorion into the perivitelline liquid (38%) and embryo (1%). In the presence of LM-DOM, the accumulation of Cd into the egg components was decreased by 43% (chorion), 52% (perivitelline liquid) and 52% (embryo), respectively, compared with the control group. Similarly, the presence of SP-DOM reduced the Cd-accumulation by 29% (chorion), 61% (perivitelline liquid) and 60% (embryo), respectively, compared with the controls. DOM-concentration should be taken into consideration when determining ecotoxicological effects of Cd on fish populations.

Animals↗

Quantification of dissolved natural organic matter (DOM) mediated phototransformation of phenylurea herbicides in lakes.

For many important classes of pesticides including phenylurea herbicides (PUHs) and triazines, photosensitized transformation may be the only relevant elimination process in surface waters. In this study, the dissolved organic matter (DOM) mediated phototransformation of PUHs has been investigated in laboratory and field experiments. The results indicate that, in surface waters, the photosensitized transformation of PUHs may be significant and occurs primarily by an initial one-electron oxidation most likely involving excited triplet states of DOM (3DOM*) constituents. Using isoproturon and diuron as model compounds, it is shown that for a given DOM, quantum yield factors determined in the laboratory at a few selected wavelengths can be used to quantify the overall DOM- mediated phototransformation of a given PUH under sunlight irradiation. Furthermore, it is demonstrated that this process can be modeled for a given surface water, by applying the program GCSOLAR and a simple algorithm for cloud cover for quantification of average daily light intensities. Finally, the model has been successfully applied to predict vertical concentration profiles of isoproturon and diuron in a small lake in Switzerland. To our knowledge, this is the first study in which DOM-mediated phototransformation of organic pollutants has been quantitatively validated in the field.

Environmental Monitoring↗

Sorption of very hydrophobic organic compounds (VHOCs) on dissolved humic organic matter (DOM). 2. Measurement of sorption and application of a Flory-Huggins concept to interpret the data.

Sorption phenomena of very hydrophobic compounds (VHOCs, log K(OW) > 5) on dissolved humic organic matter (DOM) are overwhelmingly based on partitioning processes. In this respect, DOM is very similar to "rubbery" soil/sediment OM. To exclude system adsorption effects, the DOM sorption coefficients (K(DOM)) of VHOCs were determined using a dynamic approach based on the VHOCs' aqueous solubility enhancement in the presence of DOM. Partition coefficients are strongly correlated to the analytes' Kow across the alkane, PAH, and PCB groups under study. These three "families" are regarded to be good models of hydrophobic partitioning. On the basis of a uniform one-parameter concept characterizing sorption on amorphous polymers, Hildebrand solubility parameters of amorphous polymeric sorbents, including DOM, and of sorbates can be calculated on the basis of partition coefficients. Likewise, partition coefficients can be estimated using Hildebrand solubility parameters. Literature-based partition coefficients on DOM fit very well in this universal one-parameter concept. On using our own sorption data of PAHs, PCBs, and alkanes on DOM, an almost identical solubility parameter for the DOM polymer under study is obtained. The concept is also very useful in understanding both waterborne and airborne bioconcentration processes, which are considered to be partitioning phenomena.

Adsorption↗

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

It is well known that dissolved organic matter (DOM) increases in lakes associated with forestry activity but characterization of the DOM structure is incomplete. Twenty-three lakes with a wide range of forestry activities located in central Quebec, Canada were sampled and analyzed for dissolved organic carbon (DOC) concentration, DOC fluorescence, and ultra violet-visible (UV-VIS) absorption spectra. The results show that DOC increases (as does the associated DOC fluorescence) with increased logging (slope=0.122, r2=0.581, p<0.001; and slope=0.283, r2=0.308, p<0.01, respectively) in the 23 lakes sampled however, the aromaticity of the DOM does not change with changes in logging (as found by UV-VIS ratios, absorbance slope in the UV region, and DOC normalized fluorescence (slope=1.42x10(-2), r2=0.331, p<0.01). The DOM from four of these lakes was concentrated using reverse osmosis (RO) followed by freeze-drying. The structures of the concentrated dissolved organic matter (DOM) samples were analyzed using X-ray analysis of near edge structures (XANES), X-ray diffraction (XRD), and 13C solid-state nuclear magnetic resonance (13C NMR) analysis. XANES analysis of functional groups in the four concentrated samples shows that there are significant differences in reduced sulphur between the samples, however there was no clear relationship with forestry activity in the associated catchment. XRD data showed the presence of amorphous sulphide minerals associated with the DOM concentrate that may be important sites for mercury binding. The 13C NMR spectra of these samples show that the percentage of carbon present in carboxylic functional groups increases with increasing logging. Such structures are important for binding photo-reducible mercury and their presence may limit mercury photo-reduction and volatilization. We propose a mechanism by which increased logging leads to increased carboxylic groups in DOM and thereby increased weak binding of photo-reducible mercury. These results, in part, explain the decrease in dissolved gaseous mercury (DGM) production rates with increased logging found in our previous work.

Air Pollutants↗

Influence of organic complexation on the adsorption kinetics of nickel in river waters.

The kinetics of Ni adsorption in rivers of widely different chemical characteristics have been studied by monitoring the uptake of 63Ni by suspended sediment particles. The rate and extent of adsorption was critically dependent on the presence and concentration of dissolved organic matter (DOM), defined analytically as the concentration of dissolved organic carbon (DOC). Thus, adsorption was greatest in experiments in which the DOM was decomposed by UV-oxidation and least in experiments in which Ni was preequilibrated with filtered river water before addition of particles. The extent of adsorption arising from the latter approach displayed a clear, inverse dependency on the concentration of DOC in the sample. These observations were interpreted and modeled in terms of the competing effects of DOM and particle sorption sites for dissolved Ni. Adsorption onto suspended particles in the absence of dissolved complexing ligands was adequately described by a reversible, two-stage reaction and a single set of adsorption rate constants. Forward and reverse rate constants defining Ni complexation with DOM of about 8 x 10(4) h(-1) M(-1) and 10 h(-1), respectively, were derived from data-fitting. The experimental and model results indicate that the toxicity, availability, and transport of Ni in freshwater environments are largely dictated by the concentration of DOM and the speciation of Ni entering the watercourse.

Adsorption↗

[Effects of dissolved organic matter in landfill leachate on soil Cd- and Pb bioavailability].

A pot experiment was conducted to study the effects of dissolved organic matter (DOM) in landfill leachate on ryegrass growth and its uptake of soil Cd and Pb. Fresh sample and Shuige leachate were collected from the municipal waste landfills established 0 and 12 years, respectively. The results showed that after the landfill leachate added, the average concentration of DOM remained in soil was 1.39 (fresh sample) and 1.47 (Shuige) times higher than the control (CK). The bioavailability of Cd and Pb in the soils treated with the two leachates was fluctuated in early period, and then raised. Compared with CK, the bioavailability of soil Cd was increased by 4.81% (fresh sample) and 48.97% (Shuige), and that of soil Pb was enhanced by 7.22% (fresh sample) and 18.99% (Shuige). The total concentrations of plant Cd and Pb in the treatments of fresh sample and Shuige were 19.59% and 104.4%, and 36.03% and 44. 66% higher than CK, respectively, while the total biomass of ryegrass was decreased by 14.03% to approximately 52.24%, in compared with CK. It could be inferred that the dissolved organic matter (DOM) in landfill leachate, especially in that from the landfills established for a longer time, could enhance the bioavailability of soil heavy metals and their accumulation in plant, and thus, suppress the growth of plants.

Cadmium↗

Comparison of the effects of sonolysis and gamma-radiolysis on dissolved organic matter.

The effects of 640 kHz sonolysis and 60Co gamma-radiolysis on dissolved organic matter (DOM) were compared through UV/ vis absorption spectrometric, dissolved organic carbon concentration ([DOC]), and potentiometric titration analyses. A reverse-phase chromatographic technique was used to compare changes in the DOM hydrophobicity distribution, and a size exclusion chromatographic technique with inline UV-A absorbance, fluorescence, and [DOC] detectors was used to compare changes in the DOM molecular weight distribution. Whereas upon radiolysis major decreases in absorbance and [DOC] were induced and near-total DOC removal was achieved, upon sonolysis there were major decreases in UV/vis absorbance but only minor decreases in [DOC], and a substantial quantity of hydrophilic nonchromophoric material remained in solution. In radiolysis, hydrophilic and hydrophobic DOM solution components were exposed to equal hydroxyl radical (*OH) concentrations. However, in sonolysis, hydrophobic DOM components were exposed to more elevated *OH concentrations than the hydrophilic components and consequently had enhanced rates of degradation. Sonolysis may be of interest in the design of advanced oxidation processes in which the selective elimination of hydrophobic solution components, such as hydrophobic organic contaminants and hydrophobic DOM domains into which they partition, is desired.

Carbon↗