Changes in the sorption and rate of 17β-estradiol biodegradation by dissolved organic matter collected from different water sources

The potential biodegradation and subsequent transformation of 17β-estradiol (E2) to estrone (E1) were examined in the presence of various dissolved organic matter (DOM) isolated from effluent, river and lake waters. In addition, estrogenicity was estimated in association with the removal of E2 via its sorption onto DOM and biodegradation. The more biodegradable lake-derived DOM promoted more extensive transformation of E2 into E1 than the effluent organic matter through a biodegradation process. Overall, under all conditions, biodegradation dominated the removal of E2 in water. The increased dissolved organic carbon (DOC) concentrations in river and lake-derived DOM (e.g. 6.5 mg C L(-1)) reduced the removal of E2 by decreasing its biodegradation due to the moderate sorption of E2 onto DOM. The effluent organic matter showed greater removal of E2 via biodegradation, as well as significantly high sorption. This was associated with a large amount of hydrophobic fulvic acid (FA)- and humic acid (HA)-like organic components, as shown by the small increase in the specific UV absorbance at 254 nm (SUVA(254)). An increase in the DOC concentration reduced the removal of E2, resulting in high estrogenicity. The present study suggests that both organic composition and DOC concentration influenced the removal of E2 and, therefore, should be fully considered when assessing estrogenicity and its impacts on the aquatic environment.     

Penetration of polar brominated DBPs through the activated carbon columns during total organic bromine analysis

Total organic bromine (TOBr) is a collective parameter representing all the brominated organic disinfection byproducts (DBPs) in water samples. TOBr can be measured using the adsorption-pyrolysis method according to Standard Method 5320B. This method involves that brominated organic DBPs are separated from inorganic halides and concentrated from aqueous solution by adsorption onto the activated carbon (AC). Previous studies have reported that some commonly known brominated DBPs can partially penetrate through the AC during this adsorption step. In this work, the penetration of polar brominated DBPs through AC and ozone-modified AC was explored with two simulated drinking water samples and one chlorinated wastewater effluent sample. Polar brominated DBPs were selectively detected with a novel precursor ion scan method using electrospray ionization-triple quadrupole mass spectrometry. The results show that 3.4% and 10.4% of polar brominated DBPs (in terms of total ion intensity) in the chlorinated Suwannee River fulvic acid and humic acid samples, respectively, penetrated through the AC, and 19.6% of polar brominated DBPs in the chlorinated secondary wastewater effluent sample penetrated through the AC. The ozone-modification of AC minimized the penetration of polar brominated DBPs during the TOBr analysis.     

BDE-47在土壤矿物质与有机质上的吸附解吸特征

以多溴联苯醚典型单体2,2′,4,4′?四溴联苯醚（BDE?47）为研究对象,阐明了其在土壤矿物质与有机质上的吸附解吸行为及特征。结果表明：土壤中无机矿物质对BDE?47的吸附贡献不大,而有机质是调控BDE?47在土壤中吸附行为的关键组分;有机质对BDE?47的吸附能力与其有机碳含量和物理化学特性相关;BDE?47在腐殖酸上的解吸存在显著的滞后现象。     

The simultaneous modelling of metal ion and humic substance transport in column experiments

Pulsed column experiments using Co, fulvic acid and porous sediment packing, along with up/down-flooding experiments using Eu, humic acid and intact sandstone blocks have been performed. The elution of metal and humic and their distribution along the sandstone columns have been measured. A mixed equilibrium and kinetic coupled chemical transport model has been used to simulate the results. In both cases, one exchangeable and one non-exchangeable component have been used to simulate the interaction of metal and humic substance. For the pulsed experiments, a simple equilibrium approach was used to model humic sorption, while a two component, kinetic model was required for the sandstone columns.     

活性炭纤维处理腐植酸废水

采用活性碳纤维处理腐植酸模拟废水,通过静态吸附和动态吸附的研究,测定吸附等温线和动态吸附曲线;研究不同温度、不同活性炭纤维、不同pH值和流速对处理效果的影响。     

Almond shell activated carbon: adsorbent and catalytic support in the phenol degradation

In this work, two technologies are studied for the removal of phenol from aqueous solution: dynamic adsorption onto activated carbon and photocatalysis. Almond shell activated carbon (ASAC) was used as adsorbent and catalytic support in the phenol degradation process. The prepared catalyst by deposition of anatase TiO₂ on the surface of activated carbon was characterized by scanning electron microscopy, sorption of nitrogen, X-ray diffraction, Fourier transform infrared (FT-IR) spectroscopy, and pH_ZPC point of zero charge. In the continuous adsorption experiments, the effects of flow rate, bed height, and solution temperature on the breakthrough curves have been studied. The breakthrough curves were favorably described by the Yoon–Nelson model. The photocatalytic degradation of phenol has been investigated at room temperature using TiO₂-coated activated carbon as photocatalyst (TiO₂/ASAC). The degradation reaction was optimized with respect to the phenol concentration and catalyst amount. The kinetics of disappearance of the organic pollutant followed an apparent first-order rate. The findings demonstrated the applicability of ASAC for the adsorptive and catalytic treatment of phenol.     

Effects of salinity and organic matter on the partitioning of perfluoroalkyl acid (PFAs) to clay particles

The influence of salinity and organic matter on the distribution coefficient (K(d)) for perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in a brackish water-clay system was studied. The distribution coefficients (K(d)) for PFAs onto inorganic clay surfaces increased with salinity, providing evidence for electrostatic interaction for the sorption of PFAs, whereas the relationship between K(d) and organic carbon content (f(oc)) suggested that hydrophobic interaction is the primary driving force for the sorption of PFAs onto organic matter. The organic carbon normalized adsorption coefficient (K(oc)) of PFAs can be slightly overestimated due to the electrostatic interaction within uncoated inorganic surfaces. In addition, the dissolved organic matter released from coated clay particles seemed to solvate PFA molecules in solution, which contributed to a decrease in K(d). A positive relationship between K(d) and salinity was apparent, but an empirical relationship for the 'salting-out' effect was not evident. The K(d) values of PFAs are relatively small compared with those reported for persistent organic pollutants. Thus, sorption may not be a significant route of mass transfer of PFAs from water columns in estuarine environments. However, enhancement of sorption of PFAs to particulate matter at high salinity values could evoke potential risks to benthic organisms in estuarine areas.     

Preferential sorption of some natural organic matter fractions to titanium dioxide nanoparticles: influence of pH and ionic strength

Natural organic matter (NOM) sorption to nanoparticles (NPs) can influence their transport and bioavailability in the aquatic environment. The sorption affinity of NOM to surfaces including NPs is size dependent, and depending on environmental conditions, NOM may enhance or mitigate NPs toxicity. The aim of this study was to investigate the preferential sorption of different-sized fractions of NOM to titanium dioxide (TiO₂) NPs. We specifically investigated the influence of pH, ionic strength, and NOM concentration on the extent of this preferential sorption using a constant sorbent concentration (400 mg/L TiO₂ NPs). Additionally, sorption of NOM to TiO₂ NPs at varying pH was investigated. The nonsorbed NOM was separated from the sorbed, by 50 nm polycarbonate membrane filters and ultracentrifugation. High-performance size exclusion chromatography (HPSEC) was used to determine the average molecular weights of NOM (MWw). Corroborative evidence of preferential sorption of different-sized molecular weight fractions of NOM was obtained from optical techniques such as absorbance and fluorescence spectrophotometry. The total organic carbon was measured by the Total Organic Carbon Analyzer—Shimadzu (TOC-VCPH). The results indicated that there is preferential sorption of larger sized fractions of NOM to TiO₂ NPs irrespective of NOM concentration. It was observed that the sorption of larger sized fractions of NOM was much enhanced at lower pH and at higher ionic strength. Both absorbance and fluorescence spectrophotometric techniques gave credible corroborative evidence on the extent of preferential sorption of lager sized fractions of NOM with respect to pH and ionic strength. The sorption results demonstrated higher sorption at lower pH than at higher pH. Overall, the results of this study suggest that the environmental conditions are key factors that can contribute to NOM’s fractional preferential sorption to NPs in the aquatic environment.     

Isolation of Humic and Non-Humic NOM Fractions: Structural Characterization

The combination of RO concentration and XAD-8/XAD-4 resin adsorption techniques was used to isolate the different constituents of the Natural Organic Matter (NOM) from inorganic salts. NOM fractions i.e. colloids, hydrophobic NOM (HPO humic substances), transphilic NOM (TPI) and hydrophilic NOM (HPI) fractions isolated from different surface waters were characterized using 13C NMR and FT-IR spectroscopy and HPLC/Size Exclusion Chromatography coupled with UV and DOC detection. Results showed that the isolation procedure was suitable to quantitatively isolate the different fractions of NOM.     

Investigation of 15-year-old municipal solid waste deposit profiles by means of FTIR spectroscopy and thermal analysis

Five profiles of a 15-year-old bank containing over three weeks composted municipal solid waste were characterized by means of different parameters habitually applied in waste management (loss on ignition, total organic carbon, total nitrogen, NH(4)-N, pH), and in addition by humic acid determination, FTIR spectroscopy and thermal analysis. Stabilization processes are revealed by humic acid contents. Over the 15 year period organic matter had developed in various ways. Highest humic acid contents were found at 0.5 m below the surface. Below 1.0-1.5 m anaerobic conditions dominated causing a strong decline of humic acid concentrations. Despite similar contents of organic matter at 0.5 m and at 3.0 m organic matter quality differed. These differences were verified by infrared spectroscopic investigations and thermal analyses (differential scanning calorimetry DSC). The spectral pattern of 15-year-old profile samples (municipal solid waste including the biogenic fraction) was compared to current municipal solid waste and abandoned landfill materials. Current municipal solid waste samples comprised different degradation stages from fresh materials to stabilized waste, suitable for landfilling according to Austrian standards. Municipal solid waste originating from abandoned landfills closed in the seventies represented stable material. Principal component analysis was performed to detect similarities and differences. It is evident that the profile samples constitute a particular group in between municipal solid waste and abandoned landfill material. Some differences can be attributed to the divergent composition of municipal solid waste in the eighties when the organic fraction was not separated. Otherwise, landfill materials from the seventies with the same composition regarding the organic fraction were deposited together with construction waste. Heat flow curves (DSC profiles) of municipal solid waste, representing different decomposition stages, illustrate the development of enthalpies and reveal the status of the profile samples. It is evident that mechanical-biological pretreatment leads to a faster stabilization of waste organic matter.     

Soil Aquifer Treatment (SAT) as a Natural and Sustainable Wastewater Reclamation/Reuse Technology: Fate of Wastewater Effluent Organic Matter (EfOM) and Trace Organic Compounds

Through the use of innovative analytical tools, the removal/transformation of wastewater effluent organic matter (EfOM) have been tracked through soil aquifer treatment (SAT). While the total amount of EfOM is significantly reduced by SAT, there are trends of shorter term versus longer term removals of specific EfOM fractions. The preferential removal of non-humic components (e.g., proteins, polysaccharides) of EfOM occurs over shorter travel times/distances while humic components (i.e., humic substances) are removed over longer travel times/distances, with the removal of both by sustainable biodegradation. Dissolved organic nitrogen (DON), a surrogate for protein-like EfOM, is also effectively removed over shorter term SAT. There is some background humic-like natural organic matter (NOM), associated with the drinking water source within the watershed, that persists through SAT. While most effluent-derived trace organic compounds are removed to varying degrees as a function of travel time and redox conditions, a few persist even through longer term SAT.     

Monochloramine loss in the presence of humic acid

Free chlorine has been used extensively as a primary and secondary disinfectant for potable water. Where it is difficult to maintain a free chlorine residual or when disinfection by-products (DBPs) are of concern, monochloramine has been used to provide a stable disinfectant residual in distributions systems. Reactions of disinfectants, free chlorine or monochloramine, with natural organic matter (NOM) consequently result in the formation of DBPs such as trihalomethanes and haloacetic acids. However, few studies have focused on the fate and kinetics of monochloramine loss in the presence of reactive constituents such as NOM. Monochloramine is inherently unstable and decays even without reactive constituents present via a mechanism known as autodecomposition. Therefore, to predict monochloramine concentrations in the presence of NOM is clearly associated with the ability to adequately model autodecomposition. This study presents the results of a semi-mechanisiic model capable of predicting the loss of monochloramine in the presence of humic material in the pH range of 6.55-8.33. The model accounts for both fast and a slow monochloramine demand to explain the loss of monochloramine over the pH range of this study. The formation of dichloroacetic acid was also predicted due to the ability of the model to differentiate monochloramine reaction pathways in the presence NOM. The results shown here demonstrate the ability of a semi-mechanistic model to predict monochloramine residuals and DBP formation in the presence of humic material.     

Adsorption characteristics of a phenoxy acetic acid herbicide on activated carbon

The adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) by two powdered coal activated carbons was studied in aqueous solution. The modelling of the adsorption equilibrium showed that the adsorption of 2,4-D fitted a Langmuir isotherm. Adsorption was influenced by the activated carbon type, adsorbent concentration and solution characteristics. The adsorption was found to decrease with an increase in pH over the range 1.5-9. Maximum adsorption occurred at pH approximately 2.5, which corresponds to the 2,4-D pKa value. The amount of 2,4-D adsorbed was also found to depend on the NaCl concentration.     

焦化废水生化处理过程中溶解性有机物及毒性变化规律

焦化废水中的溶解性有机物(DOM)作为废水污染物和毒性的主要来源受到广泛关注。厌氧-缺氧-好氧(A-A-O)生物法联合混凝沉淀工艺在焦化废水处理中被广泛应用。于2018年4,7和11月分别采集4座焦化废水处理厂废水,采用光谱学分析手段和水生生物急性毒性试验对A-A-O联合混凝沉淀处理过程中焦化废水的DOM和毒性变化进行分析。结果表明,焦化废水中含有大量不饱和芳香性物质,其中类色氨酸、络氨酸物质占主导,其次为类溶解性微生物代谢产物、类富里酸物质和类腐殖酸类物质;未经处理的焦化废水对藻类和大型溞的急性毒性等级为中毒至高毒。A-A-O联合混凝沉淀处理可去除90%以上的类色氨酸、络氨酸和类富里酸物质,但对类腐殖酸类物质去除率相对较低,仅为约80%,关键去除段为缺氧段和好氧段;该工艺对焦化废水急性毒性削减率为80.51%~94.30%,关键削减段为厌氧段。Pearson相关性分析结果显示,焦化废水溶解性总有机碳(TOC)、类腐殖酸类物质荧光组分C1和类富里酸类物质荧光组分C4与废水急性毒性存在显著正相关关系,可利用其作为水样急性毒性初筛的指示性指标。可为焦化废水生化处理的效能优化和废水毒性控制及安全评估提供科学支撑。     

Monitoring dissolved organic carbon in surface and drinking waters

The presence of natural organic matter (NOM) strongly impacts drinking water treatment, water quality, and water behavior during distribution. Dissolved organic carbon (DOC) concentrations were determined daily over a 22 month period in river water before and after conventional drinking water treatment using an on-line total organic carbon (TOC) analyzer. Quantitative and qualitative variations in organic matter were related to precipitation and runoff, seasons and operating conditions. Following a rainfall event, DOC levels could increase by 3.5 fold over baseflow concentrations, while color, UV absorbance values and turbidity increased by a factor of 8, 12 and 300, respectively. Treated water DOC levels were closely related to the source water quality, with an average organic matter removal of 42% after treatment.     

Effects of natural organic matter type and concentration on the aggregation of citrate-stabilized gold nanoparticles

The aggregation of 12 nm citrate-stabilized gold nanoparticles (cit-AuNPs) in the presence of four different natural organic matter (NOM) isolates and a monovalent electrolyte (KCl) was evaluated using time-resolved dynamic light scattering. All four NOM isolates stabilized the cit-AuNPs with respect to aggregation. However, specific effects varied among the different NOM isolates. At pH = 6 in 80 mM KCl, low concentrations (<0.25 mg C per L) of large molecular weight Suwannee River Humic Acid (SRHA) was required to stabilize cit-AuNPs, while larger concentrations (>2 mg C per L) of smaller Suwannee River Fulvic Acid (SRFA) were necessary at the same ionic strength. Suwannee River NOM (SRNOM) which contains both SRHA and SRFA behaved in a manner intermediate between the two. Pony Lake Fulvic Acid (PLFA), an autochthonous NOM isolate, provided substantial stability at low concentrations, yet aggregation was induced at NOM concentrations > 2 mg C per L, a trend that is hypothesized to be the result of favourable hydrophobic interactions between coated particles induced at increased surface coverage. For all NOM isolates, it appears that NOM adsorption or conformational changes at the AuNP surfaces result in significant increases in the hydrodynamic diameter that aren't attributable to NP-NP aggregation.     

Uranium speciation in moorland river water samples: a comparison of experimental results and computer model predictions

An on-line method has been developed for separating inorganic and organic bound uranium species present in river water samples. The method utilised a small chelating resin (Hyphan) column incorporated into the sample introduction manifold of an ICP-MS instrument. The method was evaluated for samples from rivers on Dartmoor (Devon, UK), an area of granite overlain with peat bogs. The results indicate that organic-uranium species form a major proportion (80%) of the total dissolved uranium present. Further work with synthetic water samples indicated that the level of dissolved organic carbon played a greater role in determining the level of organic-uranium species than did sample pH. Computer models for the water samples were constructed using the WHAM program (incorporating uranium data from the Nuclear Energy Agency Thermochemical Database project) in order to predict the levels of organic-uranium species that would form. By varying the proportion of humic and fulvic acids used in the humic component, predictions within 10% of the experimental results were obtained. The program did exhibit a low bias at higher pH values (7.5) and low organic carbon concentrations (0.5 microg ml(-1)), but under the natural conditions prevalent in the Dartmoor water samples, the model predictions were successful.     

Adsorption of antimony(V) by floodplain soils, amorphous iron(III) hydroxide and humic acid

Antimony (Sb) emissions to the environment are increasing, and there is a dearth of knowledge regarding Sb fate and behaviour in natural systems. In particular, there is a lack of understanding of sorption of the oxidised Sb(V) species onto soils and soil phases. In this study sorption of Sb(V) by two organic rich soils with high levels of oxalate extractable Fe was examined over the pH range of 2.5-7. Furthermore, the sorption behaviour of Sb(V) was examined in two phases mimicking those dominant in the experimental soils, namely a solid humic acid and an amorphous Fe(OH)3, across the same pH range. Sorption of Sb by the soils and the humic acid fitted a Freundlich type isotherm, with the equation parameters reflecting changes in bonding affinity corresponding to pH changes. The soils sorbed >75% of the added Sb in all trials, and 80-100% at pH values less than approximately 6.5. The Fe(OH)3 retained >95% of the added Sb in all experiments. The humic acid sorbed up to 60% of the added Sb at acidic pH values, but sorption decreased to zero at higher pH values. Further adsorption studies are recommended, such as examining the effects of ion competition and changes in ionic strength.     

Soil adsorption studies of a rice herbicide,cyhalofop-butyl,in two texturally different soils of India

The ability of herbicides to be adsorbed by the soil and sediment and their tendency to be desorbed are some of the most important factors affecting soil and water contamination. Therefore, a sorption study was conducted to evaluate the adsorption of cyhalofop-butyl, butyl (2R)-2-[4-(4-cyano-2-fluorophenoxy) phenoxy] propanoate, in the sandy clay loam and clayey soils using a batch equilibrium method. The adsorption of cyhalofop-butyl was found positively related with the clay and organic carbon content. Freundlich constants (K _f) of cyhalofop-butyl in the clayey and sandy clay loam were found to be 13.39 and 2.21, respectively. Sorption coefficients (K _oc) and distribution coefficients (K _d) were found to be 265.38 and 2,092.79, and 1.38 and 11.48, for sandy clay loam and clayey soils, respectively. The adsorption isotherm suggested a relatively higher affinity of cyhalofop-butyl to the adsorption sites at low equilibrium concentrations. The low value of the soil organic carbon partition coefficient (K _oc) of cyhalofop-butyl in the sandy loam soil suggested its weaker adsorption in soil and thus increased its risk of mobility into water sources; hence, it should be used judiciously to prevent groundwater contamination