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.     

Influence of temperature and origin of dissolved organic matter on the partitioning behavior of polycyclic aromatic hydrocarbons

Background, aim, and scope  

The behavior of polycyclic aromatic hydrocarbons (PAHs) is affected by dissolved organic matter (DOM) present in pore water of soils and sediments. Since partitioning to DOM reduces the bioavailable or freely dissolved PAH concentration in pore water, it is important to assess the effect of environmental variables on the magnitude of dissolved organic matter to water partition coefficients (K _DOC). The objective of this study was to apply passive samplers to measure freely dissolved PAHs allowing depletion from the aqueous phase. The method was applied to determine K _DOC at different temperatures for a selection of PAHs with natural DOM of very different origin.     

The effects of dissolved organic matter and pH on sampling rates for polar organic chemical integrative samplers (POCIS)

The effect of solution pH and levels of dissolved organic matter (DOM) on the sampling rates for model pharmaceuticals and personal care products (PPCPs) and endocrine disrupting substance (EDS) by polar organic chemical integrative samplers (POCIS) was investigated in laboratory experiments. A commercially available POCIS configuration containing neutral Oasis HLB (hydrophilic-lipophilic balance) resin (i.e. pharmaceutical POCIS) and two POCIS configurations prepared in-house containing MAX and MCX anion and cation exchange resins, respectively were tested for uptake of 21 model PPCPs and EDS, including acidic, phenolic, basic and neutral compounds. Laboratory experiments were conducted with dechlorinated tap water over a pH range of 3, 7 and 9. The effects of DOM were studied using natural water from an oligotrophic lake in Ontario, Canada (i.e. Plastic Lake) spiked with different amounts of DOM (the concentration of dissolved organic carbon ranged from 3 to 5 mg L⁻¹ in uptake experiments). In experiments with the commercial (HLB) POCIS, the MCX-POCIS and the MAX-POCIS, the sampling rates generally increased with pH for basic compounds and declined with pH for acidic compounds. However, the sampling rates were relatively constant across the pH range for phenols with high pKa values (i.e. bisphenol A, estrone, estradiol, triclosan) and for the neutral pharmaceutical, carbamazepine. Thus, uptake was greatest when the amount of the neutral species in solution was maximized relative to the ionized species. Although the solution pH affected the uptake of some model ionic compounds, the effect was by less than a factor of 3. There was no significant effect of DOM on sampling rates from Plastic Lake. However, uptake rates in different aqueous matrixes declined in the order of deionized water > Plastic Lake water > dechlorinated tap water, so other parameters must affect uptake into POCIS, although this influence will be minor. MAX-POCIS and MCX-POCIS showed little advantage over the commercial POCIS configuration for monitoring in natural waters.     

硅藻土强化混凝去除微污染原水中的有机物

研究了联用硅藻土与聚合氯化铝（PAC）强化混凝对有机微污染原水中不同性质溶解性有机物的去除效果。采用超滤膜和XAD系列树脂对微污染原水中溶解性有机物进行分级表征,物理分级表明分子量〈4 kD的溶解性有机物占50%以上,化学分级表明原水中以憎水酸（HoA）和亲水物质（HiM）为主。硅藻土助凝去除溶解性有机物,实验结果表明,当PAC投加量30 mg/L,硅藻土投加量0.5 g/L时,溶解性有机碳去除率由22.5%提高到26.3%。     

Manipulation of precipitation in small headwater catchments at Storgama, Norway: effects on leaching of organic carbon and nitrogen species

Projected changes in climate in Southern Norway include increases in summer and autumn precipitation. This may affect leaching of dissolved organic matter (DOM) from soils. Effects of experimentally added extra precipitation (10 mm week) during the growing season of 3 years (2004-2006) to small headwater catchments at Storgama (59 degrees 0'N, 550-600 m a.s.l.) on leaching of total organic carbon (TOC) and total organic nitrogen (TON) were assessed. Extra precipitation did not have a significant effect on average TOC and TON concentrations in runoff. Thus, fluxes of TOC and TON increased nearly proportionally with water fluxes. This suggests that a store of adsorbed and potentially mobile TOC and TON in catchment soils buffers the concentration of DOM in runoff. The size and dynamics of the pool of TOC and TON depends on the balance between production and leaching rates. Infrequent short droughts had only small effects on TOC and TON fluxes in runoff from the reference catchments.     

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.     

Sequential UV-biological degradation of polycyclic aromatic hydrocarbons in two-phases partitioning bioreactors

A method based on UV-irradiation in organic solvent followed by transfer of the remaining pollutants into silicone oil for subsequent biodegradation in a biphasic system inoculated with a phenanthrene degrading Pseudomonas sp. was tested for the treatment of various mixtures of PAHs. Acetone was first selected as the most suitable solvent compared to methanol, acetonitrile and silicone oil for the removal of pyrene and phenanthrene. The sequential treatment was then applied to the treatment of a mixture of fluorene, phenanthrene, anthracene, fluoranthrene, pyrene, benzo(a)anthracene and benzo(a)pyrene in acetone. These compounds were photodegraded in the following order of initial removal rates (mg l(-1) d(-1)): benzo(a)pyrene (7.8) > anthracene (5.0) > benzo(a)anthracene (2.5) > fluoranthrene (1.8) > pyrene (1.5) > phenanthrene (1.2) > fluorene (0.2). UV-treatment allowed complete removal of, anthracene, benzo(a)anthracene and benzo(a)pyrene and removals of 63% of pyrene and 37% of fluorene after 434 h or irradiation. The subsequent biological treatment removed the remaining phenanthrene and fluorene by 100% and 90%, respectively, after 790 h of cultivation. Although less efficient due to the presence of interfering compounds, the UV-biological treatment of a soil extract allowed a 63% removal of the seven PAHs named above. Microbial growth did not occur when the pollutants were directly supplied to the microorganism showing that biphasic systems reduced the toxicity effects cause by mixtures of PAHs at high concentrations. This study demonstrates the potential of selective UV treatment of high molecular weight PAHs followed by biological treatment of the low molecular weight species in biphasic systems.     

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.     

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。     

Evaluation of ion exchange resins for the removal of dissolved organic matter from biologically treated paper mill effluent

In this study, the efficiency of six ion exchange resins to reduce the dissolved organic matter (DOM) from a biologically treated newsprint mill effluent was evaluated and the dominant removal mechanism of residual organics was established using advanced organic characterisations techniques. Among the resins screened, TAN1 possessed favourable Freundlich parameters, high resin capacity and solute affinity, closely followed by Marathon MSA and Marathon WBA. The removal efficiency of colour and lignin residuals was generally good for the anion exchange resins, greater than 50% and 75% respectively. In terms of the DOM fractions removal measured through liquid chromatography–organic carbon and nitrogen detector (LC–OCND), the resins mainly targeted the removal of humic and fulvic acids of molecular weight ranging between 500 and 1000 g mol^?1, the portion expected to contribute the most to the aromaticity of the effluent. For the anion exchange resins, physical adsorption operated along with ion exchange mechanism assisting to remove neutral and transphilic acid fractions of DOM. The column studies confirmed TAN1 being the best of those screened, exhibited the longest mass transfer zone and maximum treatable volume of effluent. The treatable effluent volume with 50% reduction in dissolved organic carbon (DOC) was 4.8 L for TAN1 followed by Marathon MSA – 3.6 L, Marathon 11 – 2.0 L, 21K-XLT – 1.5 L and Marathon WBA – 1.2 L. The cation exchange resin G26 was not effective in DOM removal as the maximum DOC removal obtained was only 27%. The resin capacity could not be completely restored for any of the resins; however, a maximum restoration up to 74% and 93% was achieved for TAN1 and Marathon WBA resins. While this feasibility study indicates the potential option of using ion exchange resins for the reclamation of paper mill effluent, the need for improving the regeneration protocols to restore the resin efficiency is also identified. Similarly, care should be taken while employing LC–OCND for characterising resin-treated effluents, as the resin degradation is expected to contribute some organic carbon moieties misleading the actual performance of resin.     

Combined effect of nonionic surfactant Tween 80 and DOM on the behaviors of PAHs in soil--water system

Batch experiments were performed to examine the desorption behavior of phenanthrene and pyrene in soil–water system in the presence of nonionic surfactant Tween 80 and dissolved organic matter (DOM) derived from pig manure or pig manure compost. Addition of 150 mg l⁻¹ Tween 80 desorbed 5.8% and 2.1% of phenanthrene and pyrene from soil into aqueous phase, respectively, while the addition of both Tween 80 and DOM derived from pig manure compost and pig manure could further enhance the desorption of phenanthrene to 15.8% and 16.2%, respectively, and 6.4% and 10.9%, respectively, for pyrene. In addition, our finding also suggested that subsequent addition of Tween 80 into the soil–water system could further enhance PAHs desorption. The enhancement effect of the co-existence of Tween 80 and DOM was more than the additive effect of the Tween 80 and DOM individually. It is likely that the formation of DOM–surfactant complex in the soil–water system may be a possible reason to explain such desorption enhancement phenomenon. Therefore, it is anticipated that the coexistence of both Tween 80 and DOM derived from pig manure or pig manure compost in soil environment will enhance the bioavailability of PAHs as well as other hydrophobic organic contaminants (HOCs) by enhancing the desorption during remediation process.     

Aniline and 2,4,6-trinitrotoluene associate preferentially to low molecular weight fractions of dissolved soil organic matter

Aniline and 2,4,6-trinitrotoluene (TNT) were equilibrated with particulate (POM) and dissolved organic matter (DOM) from an organic soil at different compositions of adsorbed major cations (Na, Al) and pH (aniline: 3.7–5.1, TNT: 4.8–5.0). After separation of POM, concentrations of ¹⁴C-labelled aniline and TNT* (including TNT degradation products) were determined in DOM size fractions using size-exclusion chromatography (SEC) and UV-detection. Concentrations in the <3.5 kDa size fraction were 2.8–6.0 and 8.5–9.5 times higher for aniline and TNT*, respectively, as compared to the >40 kDa fraction. Thus, both aniline and TNT* were preferentially associated to the smallest DOM size fraction. The significant binding to DOM (similar extent as to POM) and the fact that the <3.5 kDa DOM fraction was less susceptible to flocculation by major metals suggests that the mobility of aniline and TNT is highly affected by the solubility of soil organic matter.     

Rising trends of dissolved organic matter in drinking-water reservoirs as a result of recovery from acidification in the Ore Mts., Czech Republic

The concentration of chemical oxygen demand (COD), a common proxy for dissolved organic matter (DOM), was measured at seven drinking-water reservoirs and four streams between 1969 and 2006. Nine of them showed significant DOM increases (median COD change +0.08 mg L⁻¹ yr⁻¹). Several potential drivers of these trends were considered, including air temperature, rainfall, land-use and water sulfate concentration. Temperature and precipitation influenced inter-annual variations, but not long-term trends. The long-term DOM increase was significantly associated with declines of acidic deposition, especially sulfur deposition. Surface water sulfate concentrations decreased from a median of 62 mg L⁻¹-27 mg L⁻¹ since 1980. The magnitude of DOM increase was positively correlated with average DOM concentration (R² = 0.79, p < 0.001). Simultaneously, DOM concentration was positively correlated with the proportion of Histosols within the catchments (R² = 0.79, p < 0.001). A focus on the direct removal of DOM by water treatment procedures rather than catchment remediation is needed.     

Responses of kinetics and capacity of phenanthrene sorption on sediments to soil organic matter releasing

Soil organic matter (SOM) releasing with dissolved organic matter (DOM) formed in solution was confirmed in a sediment/water system, and the effects of SOM releasing on the sorption of phenanthrene on sediments were investigated. Inorganic salt (0–0.1 mol L^?1 NaCl) was used to adjust SOM releasing, and two sediments were prepared, the raw sediment (S1) from Weihe River, Shann’xi, China, and the eluted sediments with and without DOM supernatant remained, termed as S2a and S2b, respectively. The FTIR and ¹H NMR analysis indicate that the low molecular weight hydrophilic SOM fraction released prior to the high molecular weight hydrophobic fraction. As a response, phenanthrene sorption kinetics on S1 showed atypical and expressed as three stages: rapid sorption, pseudo sorption with partial desorption, and slow sorption, thus a defined “sorption valley” occurred in kinetic curve. In all cases, partition dominates the sorption, and sorption capacity (K_d) ranked as S2b > S1 > S2a. Compared with the alterations of sediment characters, DOM solubilization produced by SOM releasing exhibited a greater inhibitory effect on sorption with a relative contribution of 0.67. Distribution coefficients (K_doc) of PHE into DOM clusters were 2.10?×?10⁴–4.18?×?10⁴ L kg^?1, however a threshold concentration of 6.83 mg L^?1 existed in DOM solubilization. The study results will help to clarify PAHs transport and their biological fate in a sediment/water system.     

Occurrence and assessment of polycyclic aromatic hydrocarbons in soils from vegetable fields of the Pearl River Delta, South China

Surface soil (0-20 cm) samples from nine representative vegetable fields located in Guangzhou, Shenzhen, Zengcheng and Huadu within the Pearl River Delta, South China were collected and analyzed for 16 USEPA priority polycyclic aromatic hydrocarbons (PAHs) using gas chromatography coupled to mass spectrometry (GC-MS). Total concentrations of 16 PAHs (Sigma(PAHs)) ranged from 160 to 3700 microg kg(-1). Large variations were observed also between concentrations of individual PAHs from different vegetable fields and within the site as well. Acenapthylene, benzo[b]fluoranthene, fluoranthene, benzo[a]pyrene and benzo[k]fluoranthene were consistently the most prevalent individual PAHs. The values of PAH isomer ratios [anthracene/(anthracene+phenanthrene) and fluoranthene/(fluoranthene+pyrene)] indicate that combustion processes are the major sources of PAHs. Concentrations of PAHs were poorly correlated with organic carbon concentrations of soils, suggesting different sources and also indicating that the PAH pollution of this area is recent. The same outcome is confirmed by the predominance of PAHs with fewer rings (相似文献   

Occurrence of priority organic pollutants in Strymon river catchment, Greece: inland, transitional, and coastal waters

Twenty-five sampling stations were selected in order to monitor persistent organic pollutants (polycyclic aromatic hydrocarbons (PAHs), organochlorine (OC) pesticides and total polychlorinated biphenyls (PCBs)) in surface water from Kerkini Lake, the Strymon River, its main tributaries and estuary in N. Aegean Sea during January to July, 2008, according to recent European Union (EU) guidelines. The data were divided among the high (January to April) and the low flow season (May to July). Generally, the values for organic pollutants were within the range reported worldwide for surface water. Elevated PAHs concentrations were observed compared with other places in Greece. Anthracene and benzo(a)pyrene exceeded maximum allowable concentration (MAC) of the relative EU guideline. Also, concentrations above MAC were observed for OCs, γ-HCH, and a-endosulfan. Despite the fact that it is banned since 1972, Aldrin was detected during the monitoring season (from limit of detection (LOD) to 15 ng L(-1)). Total PCB concentrations ranged from LOD to 162 ng L(-1). In addition, the load of organic pollutants was estimated in April (high flow) and June (low flow) in selected sampling stations. According to this estimation, napthalene, anthracene, and fluoranthene (PAHs), total dichlorodiphenyltrichloroethane (DDT), aldrin, and total PCBs had the highest load. Taking into account the relative EU guidelines concerning the pollutants studied, the water quality in the Strymon River catchment could be characterized as poor, which can lead to negative impacts to its biota.     

Magnetic ion exchange treatment of stabilized landfill leachate

Stabilized landfill leachate is characterized by a high concentration of non-biodegradable organic matter, which is similar in chemistry to dissolved organic matter (DOM) in the natural aquatic environment. Magnetic ion exchange (MIEX) resin treatment is well-studied in drinking water for removal of DOM from natural waters. There are fewer studies evaluating MIEX treatment of waste waters, and there is no previous work evaluating MIEX treatment of landfill leachate. This work systematically evaluated MIEX treatment of stabilized landfill leachate and evaluated the results in the context of previous studies of MIEX treatment of natural and waste waters. Five leachates from four landfills were evaluated as a function of MIEX resin dose, mixing time, and regeneration efficiency. MIEX resin removed DOM from landfill leachate, even in the presence of a reported high background concentration of inorganic ions. MIEX resin that was exhausted with leachate DOM was effectively regenerated with a concentrated NaCl solution, and regenerated MIEX resin performed similarly to virgin resin. For a majority of the leachates, the removal trend for MIEX resin was color > UV-absorbing substances > dissolved organic carbon ≈ COD > total nitrogen. Finally, MIEX resin removed a wider range of DOM from leachate than coagulation. The most important contribution of this work is that MIEX treatment of leachate followed very similar trends as MIEX treatment of natural waters, which will allow previous MIEX data to be used to estimate the treatment efficiency of other waste waters.     

Oxidative biodegradation of dissolved organic matter during composting

Dissolved organic matter (DOM) plays an important role in the microbial degradation of compost since it represents the most active organic fraction, both biologically and chemically. The detailed evaluation of the changes in the chemical and biochemical characteristics of DOM induced by oxidative biodegradation, presented in this work highlights the mechanisms involved in the degradation of soluble organic matter during composting. In fact, the results show that during the initial stages of composting, DOM is highly degradable under aerobic conditions, particularly due to the predominance of labile, hydrophilic compounds such as carbohydrates, amino acids and proteins. As such compounds are degraded more resistant aromatic moieties accumulate in solution resulting in a reduction in the degradability of DOM with composting time. This decrease in degradability was found to be highly correlated with microbial oxygen demand, and could have important implications in the evaluation of the composting process.     

Appropriate combination of physico-chemical methods (coagulation/flocculation and ozonation) for the efficient treatment of landfill leachates

An integrated technique consisted of ozonation and coagulation/flocculation processes was studied, aiming to provide an efficient method for the treatment of stabilized/biologically pre-treated leachates, in order to reduce the organic pollutants' content to concentration values lower than the corresponding limits, imposed by the legislation. Leachates were collected from a municipal landfill site; samples containing around 1000 mg l(-1) COD and BOD(5)/COD ratio about 0.17 were treated by using two different processes or combinations between them, i.e. ozonation, coagulation-flocculation, ozonation followed by coagulation/flocculation and coagulation/flocculation followed by ozonation. The application of single ozonation resulted to the efficient removal of color and organic loading, due to the respective oxidation, induced by ozonation; however, COD values lower than 200 mg l(-1) could be only achieved after prolonged reaction times and for high ozone production rates. The coagulation of leachate samples was studied by the addition of ferric chloride or poly-aluminum chloride agents at various dosages. Maximum COD removal rates (up to 72%) were achieved by the addition of 7 mM Fe, or of 11 mM Al respectively. However, final COD values higher than 200 mg l(-1) were obtained indicating the requirement of an additional treatment step. Pre-ozonation followed by coagulation/flocculation was not found to be an efficient treatment approach for this aim, but coagulation/flocculation followed by ozonation, was proved to be an efficient process for the reduction of COD to lower than 180 mg l(-1).     

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.