Effects of photodegradation of dissolved organic matter on the binding of benzo(a)pyrene

Dissolved organic matter (DOM) in natural waters can bind various organic pollutants, and the affinity of this binding is strongly influenced by the chemical characteristics of the DOM and water pH. This study examined the effects of photochemically induced alteration of the DOM's chemical properties and water pH on the binding of benzo(a)pyrene (BaP). Time- and pH-series of solar-simulated irradiations were performed on a natural water sample and aqueous DOM solutions prepared from aquatic and soil humic substances. The binding affinity of BaP, expressed as a partition coefficient of a compound to DOM, decreased substantially after the DOM samples were irradiated over environmentally relevant radiation doses and pH ranges. The lowering of the pH due to the photoproduction of acidic products often partly offsets the reduction of the binding affinity caused by direct photoalteration of the DOM's chemical structure. The decrease of the binding affinity, after correction for the photoinduced pH change, was positively correlated with the decrease in the molecular weight and the aromaticity of the DOM in the course of irradiation. Increasing O(2) abundance accelerated the decrease of the binding affinity as a result of enhanced DOM photodegradation. Visible light played a more important role in reducing the molecular weight and aromaticity of the DOM than in reducing the content of dissolved organic carbon (DOC) via photoremineralization while the reverse was true for UV radiation, indicating that photochemical reduction of the binding affinity may occur in natural waters at depths greater than UV radiation can reach. A decrease of the affinity of DOM for binding BaP will increase the free dissolved fraction of BaP and thus its availability and toxicity to aquatic organisms. The results from this study may have similar implications for organic pollutants other than BaP.     

Photochemical alteration of the molecular weight of dissolved organic matter

Molecular weight (MW) is a key control on the physical, chemical, and biological characteristics of dissolved organic mater (DOM). This study investigated the effect of photooxidation on the average MW of DOM by exposing DOM of diverse origins to simulated solar radiation at varying levels of dissolved oxygen and under different incident light wavelength regimes. During irradiation, high-molecular-weight fractions were destroyed and low-molecular-weight constituents were formed. The average MW decreased with irradiation time in all treatments in a manner that can be described by a quasi-exponential function, which suggests that solar radiation is incapable of completely mineralizing DOM even after prolonged exposure. Increasing the oxygen concentration accelerated the MW reduction while the removal of oxygen strongly suppressed this process. The fractional contributions from UV-B, UV-A, and visible radiations to full-spectrum photoinduced MW reduction varied considerably among the DOM samples examined, ranging from 19% to 60%, 17% to 36%, and 15% to 46%, respectively. The MW changes in time-series irradiations were inversely correlated with the ratio of the absorbance at 250 nm to that at 365 nm (i.e., the E₂/E₃ quotient). Photoinduced MW reduction was accompanied by a decrease of polydispersity, which is indicative of a reduced DOM heterogeneity.     

Microbial degradation of dissolved organic matter (DOM) and its influence on phenanthrene-DOM interactions

Microbial degradation-induced changes in the characteristics of dissolved organic matter (DOM), and the subsequent effects on phenanthrene-DOM interactions were investigated based on the microbial incubation of DOM collected from four different sources for 28 d. Partially biodegraded DOM presented higher specific UV absorbance (SUVA), lower protein-like fluorescence, higher humic-like fluorescence, lower aliphatic carbon fraction, and higher hydrophobic neutral fractions compared to the original DOM. Microbial changes in DOM led to an increase in the isotherm nonlinearity as well as the extent of phenanthrene binding. A negative relationship between SUVA and the Freundlich n values was established for the original and the biodegraded DOM, suggesting that aromatic condensed structures may play important roles in providing nonlinear strong binding sites irrespective of microbial degradation. In contrast, there were two separate slopes of the correlations between the percentage of hydrophobic acid (HoA) fraction and the n values for the original and the biodegraded DOM with a higher slope exhibited for the latter, implying that the microbial utilization of oxygen-containing structures in the HoA fractions may contribute to enhancing the associated isotherm nonlinearity.     

Reverse quantitative structure-activity relationship for modelling the sorption of esfenvalerate to dissolved organic matter. A multivariate approach

The sorption of the pyrethroid, esfenvalerate, to the dissolved and/or dispersed fraction of eight different natural humic compounds has been investigated. The dissolved organic matters (DOMs) included in this study originate from ground water, soil pore water, and surface waters. Sorption was modelled at DOM concentration levels where equilibrium partitioning of esfenvalerate between DOM and the aqueous bulk phase prevails. The inherent characteristics of the eight different humic materials, quantified in the preceding paper by Thomsen et al. (2002, this issue (PII: S0045-6535(02)00335-1)), have been used as explanatory variables for modelling this equilibrium partitioning. Using a reverse QSAR approach based on by projection-into-latent-structure regression (PLS-R) inherent sorbent properties determining for the sorption affinity of esfenvalerate to DOM were analysed. For all humic substances a decrease in the DOM-normalised equilibrium-partitioning coefficient, K_DOM, with increasing concentration of DOM was observed. Significant variations in K_DOM values, as function of the inherent characteristics of the individual humic substances, were found at DOM concentrations of 75 and 100 ppm, respectively. The latter is a strong indication of variations in sorption mechanisms of esfenvalerate to DOM of varying inherent properties. Groupings in the principal property space quantifying DOMs may indicate that separate models are needed for quantifying the equilibrium partitioning to different classes of DOM.     

Copper complexation by dissolved organic matter and uncertainty assessment of their stability constants

The interaction of Cu with dissolved organic matter (DOM, extracted from an organic forest floor) was investigated and the resulting data was evaluated in terms of their uncertainty. The speciation of Cu over ‘free’ Cu (as analysed by diffusive gradients in thin films (DGT)), dissolved Cu–DOM complexes and precipitated Cu–DOM was determined as a function of pH (3.5, 4.0 and 4.5) and Cu/C ratio. The dissolved organically bound fraction was highest at pH 4.5, but this fraction decreased with increasing Cu/C ratio, which was observed for all pH levels. In the range of Cu/C=7×10⁻⁵–2.3×10⁻² (mol/mol) the precipitated fraction was very small. The speciation of both Al and Fe was not affected by increasing Cu concentrations. From a continuous distribution model using the Scatchard approach, we calculated the optimal fit and corresponding upper and lower 95% uncertainty bounds of the overall stability constants (K_o) with the shuffled complex evolution Metropolis (SCEM) algorithm. Although the optimal equation fitted the data very well, the uncertainty of the, according to literature, most reliable approach to establish stability constants, was still large. Accordingly, the usually reported intrinsic stability constants exhibited large uncertainty ranging from logK_i=6.0–7.1 (optimal 6.7) for pH 3.5, logK_i=6.5–7.1 (optimal 6.8) for pH 4.0, and logK_i=6.4–7.2 (optimal 6.8) for pH 4.5 and showed only little effect of pH.     

Microbial transformation of dissolved organic matter from different sources and its influence on disinfection byproduct formation potentials

Biodegradation-induced changes in the characteristics of dissolved organic matter (DOM) and the subsequent effects on disinfection byproduct formation potentials (DBPFPs) were investigated using six different sources of DOM (algae, leaf litter, reed, compost, paddy water, and treated municipal sewage effluent). Microbial incubation of the DOM samples increased the specific ultraviolet absorbance and humic-like fluorescence but decreased the protein/tannin-like fluorescence and relative distribution of smaller-sized DOM components. Comparison of the original versus biodegraded DOM samples using resin fractionation and pyrolysis–gas chromatography/mass spectrometry revealed that the biodegradation-induced changes were highly dependent on DOM sources and exhibited no consistent trends among the different sources. Changes in DBPFPs also differed with DOM source. Vascular plant-derived DOM (leaf litter and reed) demonstrated an enhancement in specific DBPFP after biodegradation, whereas little change or even a slight decrease was observed for the other DOM sources. Correlations that were significant between specific DBPFPs and the aromatic content or humic-like fluorescence for the original DOM samples were no longer significant after microbial degradation. The relative abundance of hydrophobic to hydrophilic structures in DOM is suggested to be a general indicator for the formation potential of trihalomethanes irrespective of DOM source and the state of biodegradation.     

An independent prediction of the effect of dissolved organic matter on the transport of polycyclic aromatic hydrocarbons

The transport of polycyclic aromatic hydrocarbons (PAH) in porous media in the presence of dissolved organic matter (DOM) was predicted with a transport bicontinuum model using independently obtained relationships to derive transport parameters for describing the effect of PAH binding to the DOM. The sorption constants of PAHs to soil and their binding constants to DOM were derived from basic correlations with K(ow) (indicator of hydrophobicity). The kinetic (rate) constants were derived from previously published correlations with K(p) (sorption constant). The independently obtained sorption and rate constants were corrected for binding to DOM and were used to predict the breakthrough curves (BTC) of contaminants in the presence and the absence of DOM. Column results confirmed the independently predicted BTC of PAHs in the presence of DOM that did not sorb to the solid phase, as well as the effect of DOM on the rate of the sorption and desorption processes. These findings confirm the ability to quantitatively describe how DOM facilitates transport of contaminants in the subsurface using independently derived parameters.     

Characterization of binding site heterogeneity for copper within dissolved organic matter fractions using two-dimensional correlation fluorescence spectroscopy

The heterogeneity of copper binding characteristics for dissolved organic matter (DOM) fractions was investigated based on the fluorescence quenching of the synchronous fluorescence spectra upon the addition of copper and two-dimensional correlation spectroscopy (2D-COS). Hydrophobic acid (HoA) and hydrophilic (Hi) fractions of two different DOM (algal and leaf litter DOM) were used for this study. For both DOM, fluorescence quenching occurred at a wider range of wavelengths for the HoA fractions compared to the Hi fractions. The combined information of the synchronous and asynchronous maps derived from 2D-COS provided a clear picture of the heterogeneous distribution of the copper binding sites within each DOM fraction, which was not readily recognized by a simple comparison of the changes in the synchronous fluorescence spectra upon the addition of copper. For the algal DOM, higher stability constants were exhibited for the HoA versus the Hi fractions. The logarithms of the stability constants ranged from 4.8 to 6.1 and from 4.5 to 5.0 for the HoA and the Hi fractions of the algal DOM, respectively, depending on the associated wavelength and the fitted models. In contrast, no distinctive difference in the binding characteristics was found between the two fractions of the leaf litter DOM. This suggests that influences of the structural and chemical properties of DOM on copper binding may differ for DOM from different sources. The relative difference of the calculated stability constants within the DOM fractions were consistent with the sequential orders interpreted from the asynchronous 2D-COS. It is expected that 2D-COS will be widely applied to other DOM studies requiring detailed information on the heterogeneous nature and subsequent effects under a range of environmental conditions.     

Structural and optical characterization of dissolved organic matter from the lower Athabasca River, Canada

Dissolved organic matter (DOM) is a ubiquitous constituent of natural waters and is comprised of a variety of chemically heterogeneous molecular structures and functional groups. DOM is often considered to be a major ligand for metals in most natural waters and its reactivity is thought to be strongly dependent on its chemical composition and structure. In this study, a combination of UV/visible, emission excitation matrix fluorescence (EEM) and ¹H NMR spectroscopies were used to characterize DOM from the Athabasca River (Alberta, Canada). The chemical characterization of river DOM showed that the most upstream samples located in agricultural areas were blue-shifted and less aromatic and contained more hydrogens connected with oxygen functional groups than those in the wetland dominated area in the Athabasca oil sand deposit region. The presence of paramagnetic ions (Fe and Al) was not found to significantly affect the structural composition of DOM as revealed by ¹H NMR. Such change in the quality of DOM may have a profound impact on metal binding in the Athabasca River watershed.     

Interaction of bisphenol A with dissolved organic matter in extractive and adsorptive removal processes

The fate of endocrine disrupting chemicals (EDCs) in natural and engineered systems is complicated due to their interactions with various water constituents. This study investigated the interaction of bisphenol A (BPA) with dissolved organic matter (DOM) and colloids present in surface water and secondary effluent as well as its adsorptive removal by powdered activated carbons. The solid phase micro-extraction (SPME) method followed by thermal desorption and gas chromatography-mass spectrometry (GC-MS) was utilized for determining the distribution of BPA molecules in water. The BPA removal by SPME decreased with the increased DOM content, where the formation of BPA-DOM complexes in an aqueous matrix was responsible for the reduced extraction of BPA. Colloidal particles in water samples sorbed BPA leading to the marked reduction of liquid phase BPA. BPA-DOM complexes had a negative impact on the adsorptive removal of BPA by powered activated carbons. The complex formation was characterized based on Fourier transform infrared (FTIR) and ultraviolet-visible (UV-Vis) spectroscopy, along with the calculation of molecular interactions between BPA and functional groups in DOM. It was found that the hydrogen bonding between DOM and BPA would be preferred over aromatic interactions. A pseudo-equilibrium molecular coordination model for the complexation between a BPA molecule and a hydroxyl group of the DOM was developed, which enabled estimation of the maximum sorption site and complex formation constant as well as prediction of organic complexes at various DOM levels.     

The role of humic substances in chromium sorption onto natural organic matter (peat)

To elucidate mechanisms of Cr³⁺ sorption onto the unaltered solid natural organic matter, the comparative studies of this ion binding from a solution at pH 4.0 onto three selected particle size fractions: 2000–1000 μm, 630–200 μm and 63–20 μm of markedly different HS content and structure, separated by a wet sieving from an overall sample of peat (Brushwood Peat Humus) were carried out. Comparable patterns of COOH groups and CEC_t confirmed that for cation exchange capacity were responsible mainly cations connected with COO⁻ functional groups. It was though found that aliphatic acids in the solid state did not take part in Cr³⁺ binding, thus the finest studied fraction 63–20 μm of the highest contents of functional groups showed the lowest sorption capacity for Cr³⁺, while similar patterns of sorbed Cr³⁺, soluble HS content and base CEC₀ indicated that these parameters were directly interrelated. The base ion exchange processes determined by CEC₀ (with Ca²⁺ as a predominant exchangeable cation) appeared to be not the major mechanisms responsible for Cr³⁺ sorption. For this metal, strong binding to insoluble large molecular weight organic pool two- to threefold prevailed over the ion exchange processes. Very low acid desorption indicated generally low mobility of Cr³⁺-organic compounds.     

乌梁素海沉积物孔隙水中溶解有机质的荧光及紫外光谱研究

运用紫外可见光吸收光谱与荧光光谱研究乌梁素海沉积物孔隙水中溶解有机质的来源、结构及腐殖化程度。r_(A，C)、HIX、SUVA₂₈₀和SUVA₂₅₄等被用于表征DOM的腐殖化程度和芳香构化程度及结构，f_450/500用于指示DOM的来源。研究结果表明：腐殖化程度最高的点为湖泊东部的W4样点，腐殖化程度最低的为总排干影响区域的W1样点。E_253/203表明湖泊入口处沉积物孔隙水中有机质主要为不可取代的芳香环结构。荧光指数f_450/500为1.57～1.82之间。总体而言，f_450/500的值更接近于1.6，处于2个端源中间，说明乌梁素海DOM中的腐殖质主要来源于陆源输入。相关分析的结果表明， DOM的不同来源对其腐殖化程度产生影响。随着腐殖化值的增大，DOM的来源由生物源向陆源过渡。     

Distribution of DDT and benzo[a]pyrene between water and dissolved organic matter in natural humic water

DDT and benzo[a]pyrene (BaP) were added both separately and as a mixture to filtered (0.22 μm) humic surface water samples. Following a contact time of 1 d, the fraction bound to dissolved organic matter and the freely dissolved part were separated by using reversed-phase octadecyl silica cartridges. The enriched solutes were analysed by gas chromatography-mass spectrometry in the selective ion monitoring (GC-MS/SIM) mode. Partition coefficients to dissolved organic matter, calculated on the basis of the recovery data, varied between 2.0 × 10⁴ and 6.6 × 10⁴ mL/g for BaP depending on the experimental conditions, whereas the corresponding values for DDT (0.6 × 10⁴ mL/g) showed no significant variation.     

Transformation of dissolved organic matter in a novel groundwater recharge system with reclaimed water

A novel process, enhanced direct injection-well recharge system (EnDir), can overcome the technical difficulties during the application of conventional surface spreading and has been developed to recharge groundwater with reclaimed water. In this study, removal and transformation of dissolved organic matter (DOM) in the system were investigated in laboratory-scale experiments. Results demonstrated that dissolved organic carbon and trihalomethane formation potential values could be reduced from 6.54 +/- 1.30 mg/L and 267.9 +/- 24.3 microg/L to 1.59 +/- 0.64 mg/L and 104.5 +/- 10.2 microg/L, respectively, as a result of DOM biodegradation in the aerobic short-term vadose soil treatment. Fluorescence spectra showed that aromatic protein-like substances and soluble microbial byproducts could be removed, to a great extent, in the soil system. Despite different removal efficiencies of DOM in different molecular weight fractions, the residual DOM was composed mainly of fulvic acid-like and humic acid-like substances, with molecular weights of 500 Da to 1 kDa.     

Dissolved organic matter with multi-peak fluorophores in landfill leachate

Dissolved organic matter (DOM) sampled from municipal landfill leachate of different ages with/without anoxic or aerobic treatment, was intensively fractionated via size exclusion chromatography (SEC) and hydrophobic resins, and was studied with fluorescence excitation and emission matrix (EEM). Six fluorophores with multiple EEM peaks (fluorophore A-F) were identified based on the collected EEM spectra and validated by bi-variate analysis, principal component analysis, and parallel factor analysis, as follows (excitation wavelength Ex and emission wavelength Em): (Ex 240, 310, 360 nm, Em 460 nm), (Ex 220, 280 nm, Em 340 nm), (Ex 220, 270 nm, Em 300 nm), (Ex 220, 280 nm, Em 360 nm), (Ex 230, 320 nm, Em 420 nm) and (Ex 220, 310 nm, Em 400 nm). The spectral characteristics of these fluorophores were discussed using fractional EEM and apparent molecular weight (AMW) data obtained via SEC analysis. The triple peak flurophore A was pointed at a hydrophobic acid or hydrophobic neutral compound with a pyrenyl functional group of AMW 2500-3500 Da, which displayed an excitation wavelength at 360 nm and a fluorescence intensity ratio of 6.70(+/-1.79):1.70(+/-0.41):1 (fluorescent intensities of Ex 240:Ex 310:Ex 360 nm at Ex 460 nm). This compound is observed to be refractory in landfilling or in anoxic/aerobic treatments, and is specific to this leachate contamination. This paper revealed that the coupling of SEC and EEM can be useful to track the fluorescent DOM fraction in landfill leachate.     

Complexation-flocculation of organic contaminants by the application of oxyhumolite-based humic organic matter

Control of hazardous organic micropollutants is a challenging water quality issue. Dissolved humic organic matter (DOM) isolated from oxyhumolite coal mined in Bohemia was investigated as a complexation agent to remove polycyclic aromatic hydrocarbons (PAHs) and functionalized phenols from water by a two-stage process involving complexation and flocculation. After the formation of humic-contaminant complexes, ferric salts were added resulting in the precipitation and flocculation of the DOM and the associated pollutants. Flocculation experiments with ferric ion coagulants indicated that precipitation of oxyhumolite DOM together with the complexed contaminants occurred at lower ferric ion concentrations than with the reference DOM in acidic environments (pH approximately 3.5). The complexation-flocculation removal rates for non-reactive PAHs characterized by small localization energies of pi-electrons correlated well with the complexation constants. On the other hand, the combined complexation-flocculation removal rates for activated PAHs including trans-stilbene, anthracene and 9-methyl anthracene, as well as functionalized polar phenols, were higher than predicted from the complexation coefficients. Methodological studies revealed for the first time that the ferric ion coagulant contributed to enhanced removal rates, most probably due to ferric ion-catalyzed pollutant degradation resulting in oxidized products.     

Degradation of aquatic humic material by ultraviolet light

Natural humic water was treated with ultraviolet (UV) light and UV + hydrogen peroxide (UV/H₂O₂. The effects on the dissolved organic carbon content (DOC), the UV-absorbance at 254 nm (UV-abs.), the molecular size distribution, pH, and mutagenic activity were monitored, and the identity and concentrations of the most abundant gas chromatographable organic degradation products were determined.

The DOC content and the UV-abs. of the water decreased substantially during treatment with UV/H₂O₂. The decreases were dependent on the time of irradiation (UV dose) as well as on the H₂O₂ dose applied. The humus macromolecules were degraded to smaller fragments during irradiation. At higher UV doses, however, part of the dissolved organic matter (DOM) was found to precipitate, probably as a result of polymerization. Oxalic acid, acetic acid, malonic acid, and n-butanoic acid were the most abundant degradation products detected. These acids were found to account for up to 20% and 80% of the DOM in UV- and UV/H₂O₂-treated waters, respectively. No mutagenic activity was generated by the UV irradiation or the UV/H₂O₂ treatment. It is further concluded that the substantial mutagenic activity formed during chlorination of humic waters cannot be decreased by using UV irradiation as a pretreatment step.     

The binding of three PCB congeners to dissolved organic carbon in freshwaters

The binding of three polychlorinated biphenyl (PCB) congeners to natural levels of dissolved organic carbon (DOC) was measured in 12 lakes and streams using Sep-Pak C₁₈ columns. The association coefficients calculated on the basis of DOC (i.e. K_DOC mL/g C), varied by over an order of magnitude among the different freshwaters and ranged between 2.05 × 10² and 8.86 × 10³ mL/g C for PCB 52 and 1.03 × 10⁴ and 1.70 × 10⁵ mL/g C for PCB 153. In general, there were no significant correlations (p > 0.05) between the K_DOC values and various chemical parameters in the study lakes and streams.

A relationship was derived between the fraction of bound PCB and the octanol-water partition coefficient. While this relationship explained almost 50% of the variation in the observed data, it is apparent that other factors influence K_DOC values and that in natural freshwaters, only a small fraction of the DOC is involved in the binding of PCBs and other hydrophobic pollutants.     

光催化氧化降解垃圾渗滤液中溶解性有机物

研究了UV-TiO2光催化氧化降解垃圾渗滤液过程中溶解性有机物(DOM)的变化特征。结果表明:在适宜条件下,UV-TiO2光催化氧化降解垃圾渗滤液的色度、COD和DOC的去除率分别可达97%、72%和60%;紫外光谱分析说明渗滤液DOM中包括多种含有共轭双键、羰基的大分子有机物及多环芳香类化合物,不同光催化处理液中DOM具有基本一致的结构单元和官能团;红外光谱分析说明渗滤液DOM中含有大量包括羟基、羧基、氨基和苯环的芳香族化合物,在光催化处理液中这几种官能团都能被有效降解;GC/MS分析结果表明,渗滤液DOM中含有72种有机污染物,醇类、羧酸和酮类分别为25、14和12种;在光催化72 h处理液中,有机物减少为44种;酯类和醇类较多,分别为12种和16种;酮类8种,羧酸没有检出。