Effect of bromide ion on isolated fractions of dissolved organic matter in secondary effluent during chlorination

The role of bromide ion in the trihalomethane (THM) formation and structure of dissolved organic matter (DOM) during chlorination of the secondary effluent taken from the Wenchang Wastewater Treatment Plant (Harbin, China) was investigated. DOM was fractionated using XAD resins into five fractions: hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N) and hydrophilic fraction (HPI). The patterns of individual THM species with increased bromide concentrations were similar for all DOM fractions. The THM speciation as well as halogen fraction for these five fractions followed similar trends with the Br(-)/Cl(2) ratio. Chlorination resulted in decreased ultraviolet (UV) absorbance across wavelengths from 250 to 280 nm for DOM fractions whether bromide ions existed or not, and bromide addition led to lower differential UV absorbance values. Fourier-transform infrared (FT-IR) results indicated that chlorination, whether bromide ions existed or not, resulted in the near elimination of aromatic CH and amide peaks, increased CO absorption intensity and occurrence of CO and CCl peaks for HPO-A, HPO-N, TPI-A and TPI-N. Furthermore, bromide addition in chlorination led to the occurrence of CBr peak for all four fractions.     

Investigation of bromide ion effects on disinfection by-products formation and speciation in an Istanbul water supply

Recent epidemiological studies reported that brominated DBPs may be more carcinogenic than their chlorinated analogs. Thus, this research was designed to investigate the role of bromide ion in the formation and speciation of disinfection by-products (DBPs) during chlorination of Buyukcekmece Lake Water (BLW) in Istanbul. Chlorination of BLW samples was carried out at pH 7.0 with 5 and 12 mg/l chlorine dosages. For each chlorine dosage, six bromide concentrations ranging from 0.05 to 4.0mg/l were added to form a 2 x 6 experimental matrix. In general, increasing bromide concentration gradually shifted trihalomethanes (THMs) and haloacetic acids (HAAs) speciation from chlorinated species to the mixed bromochloro species during chlorination. The halogen substitution ability of HOBr and HOCl during the formation of THMs and HAAs can be estimated through the use of probability theory. It was concluded that, in both halogen substitution for THM and dihalogenated HAA formation, HOBr was found to be 20 times more reactive than HOCl.     

Characterization of isolated fractions of dissolved organic matter from sewage treatment plant and the related disinfection by-products formation potential

Dissolved organic matter (DOM) in effluent from a conventional sewage treatment plant was isolated using resin adsorbents into six classes: hydrophobic bases (HoB), hydrophobic acids (HoA) and hydrophobic neutrals (HoN); hydrophilic bases (HiB), hydrophilic acids (HiA) and hydrophilic neutrals (HiN). Organic acids were the most abundant fractions of DOM. Hydrophobic organics especially hydrophobic acids were found to have higher overall disinfection by-products formation potential (DBPFP). Moreover, the potential decreased as the sequence of acids, neutrals and bases. Ultraviolet spectrophotometry at 254nm (UV(254)), fluorescence spectroscopy, size exclusion chromatography and Fourier transform infrared spectroscopy (FTIR) were employed to characterize DOM fractions. And the relationship between the characteristics of DOM fractions and the related DBPFP was discussed in detail. It was found that UV(254) to DOC ratio (SUVA) exhibited a positive correlation with haloacetic acids (HAAs) formation potential whereas distinctive linear correlation was not observed between SUVA and trihalomethanes (THMs) formation potential. Of the fluorescence organics contained in DOM, humic acids exhibited higher chlorine reactivity than fulvic acids. Smaller molecules of humic acids produced more DBPs. Furthermore, a combination of aromatic moieties and aliphatic structures with nu(C_O) groups contributed largely to the formation of DBPs.     

The formation and distribution of haloacetic acids in copper pipe during chlorination

The formation and distribution of HAAs in copper pipe during chlorination was investigated. To determine the material influence of copper pipe, parallel experiments were performed in glass pipe. Results showed that there was no obvious difference between the sum of haloacetic acids (HAAs) and trihalomethanes (THMs) produced in copper pipe compared to that produced in glass pipe over a 12h period. However, significant differences were observed about the distribution of five haloacetic acids in copper pipe and in glass pipe. Relatively less trichloroacetic acid (TCAA) and more monochloroacetic acid (MCAA), dichloroacetic acid (DCAA), dibromoacetic acid (DBAA) and trihalomethanes (THMs) were produced in copper pipe than those in glass pipe. Corrosion scale on the wall of copper pipe was analyzed using X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS). The results showed the scales on the pipe surface mainly consisted of Cu2O, CuO and Cu (OH)2 or CuCO3. During 24h stagnation, copper released gradually from copper pipe. The influences of copper (II) and copper oxides on the distribution of HAAs were investigated in designed experiments. Results showed that less amount of TCAA, more amounts of DCAA and MCAA were formed with increasing concentration of copper (II). It was because the accelerative effect of copper (II) on the depletion of chlorination restricted the formation of TCAA precursor and the further formation of TCAA. Owing to the transformation of DCAA precursor to TCAA precursor was limited, more DCAA precursor could yield DCAA. The influences of Cu2O and CuO on the distribution of TCAA and DCAA were the result of copper released at higher content.     

The variation of mass and disinfection by-product formation potential of dissolved organic matter fractions along a conventional surface water treatment plant

Dissolved organic matter (DOM) influences many aspects of water treatment, including the formation of potentially harmful disinfection by-products (DBPs) when disinfectants are applied. DOM from a conventional surface water treatment plant (WTP) in Northern New Jersey was isolated and fractionated using resin adsorption chromatography into six different fractions. These fractions are operationally categorized as hydrophobic acid, hydrophobic neutral, hydrophobic base, hydrophilic acid, hydrophilic neutral and hydrophilic base. The hydrophilic acid fraction was found to be the most abundant fraction in the source water. The hydrophilic neutral, hydrophilic acid and hydrophobic acid fractions had the highest removal efficiency through the WTP (about 65%). The variation and removal effectiveness of each fraction along the WTP was studied. Seven-day chlorine DBP formation potential (FP) tests were performed on all DOM fractions through the WTP. For the source water studied, the hydrophilic acid fraction was found to be the most reactive precursor to the trihalomethane (THM) formation. The hydrophobic neutral fraction was found to be the fraction of concern with respect to the FP of haloacetic acids (HAAs) class of DBPs. The FP of each fraction's class of DBPs was found to be amenable for reduction along the treatment train, specifically by coagulation/sedimentation. The fractionated approach concept showed to be very beneficial in the study of DBP precursors and their effective removal by physical and chemical treatment.     

Seasonal variations of chemical and physical characteristics of dissolved organic matter and trihalomethane precursors in a reservoir: a case study

Dissolved organic matter (DOM) and its potential to form disinfection by-products (DBPs) during water treatment are of great public health concern. Understanding the seasonal changes in DOM composition and their reactivity in DBP formation could lead to a better treatment of drinking water and a more consistent water quality. DOM from the East-Lake, a reservoir in the south-China, was fractionated and characterized by XAD resin adsorption (RA) and ultrafiltration (UF) techniques during different seasons within a year. The properties of chemical fractions (isolated by RA) appeared more stable than those of physical fractions (separated by UF) throughout the sampling period. The relative contribution of each chemical fraction to the total dissolved organic carbon (DOC), UV(254) absorbance and trihalomethane formation potential (THMFP) remained relatively constant across the sampling period. However, the physical (molecular weight) fractions of the DOM exhibited large seasonal changes in UV(254) and THMFP. Compared to the parameter of DOC, the THMFP and specific THMFP (STHMFP) of either chemical or physical fractions were more variable. In terms of DOC concentration, the hydrophobic acids (HoA) and hydrophilic matter (HiM) dominated in the DOM in most of the seasons; while the components with molecular weight of 10-30 kDa and less than 1 kDa were the predominant physical fractions.     

Effects of dissolved organic matter from the rhizosphere of the hyperaccumulator Sedum alfredii on sorption of zinc and cadmium by different soils

Pot experiments were conducted to investigate the changes of the dissolved organic matter (DOM) in the rhizosphere of hyperaccumulating ecotype (HE) and non-hyperaccumulating ecotype (NHE) of Sedum alfredii and its effects on Zn and Cd sorption by soils. After planted with HE, soil pH in the rhizosphere reduced by 0.5-0.6 units which is consistent with the increase of DOM. The hydrophilic fractions (51%) in DOM from the rhizosphere of HE (HE-DOM) was much greater than NHE-DOM (35%). In the presence of HE-DOM, Zn and Cd sorption capacity decreased markedly in the following order: calcareous clay loam > neutral clay loam > acidic silty clay. The sorption isotherms could be well described by the Freundlich equation (R² > 0.95), and the partition coefficient (K) in the presence of HE-DOM was decreased by 30.7-68.8% for Zn and 20.3-59.2% for Cd, as compared to NHE-DOM. An increase in HE-DOM concentration significantly reduced the sorption and increased the desorption of Zn and Cd by three soils. DOM derived from the rhizosphere of the hyperaccumulating ecotype of S. alfredii could significantly reduce metal sorption and increase its mobility through the formation of soluble DOM-metal complexes.     

Metal sorption on soils as affected by the dissolved organic matter in sewage sludge and the relative calculation of sewage sludge application

To evaluate the influences of sewage sludge-derived organic matters on metal sorption and on the resultant sludge loading estimates, a batch experiment was conducted to compare the sorption of Ni, Cu and Pb in sewage sludge filtrates (1:20 sewage sludge to water) on eight soils and the adsorption of metals in a reference solution which had the same matrix as the sewage sludge filtrate except dissolved organic material (henceforth referred to as reference solution). Metal sorption could be well fitted by linear isotherm and the dissolved organic matter in sludge significantly depressed the sorption (p<0.01). The main factor controlling sorption of Ni on different soils was dominated by soil cation exchange capacity (CEC) and sorption of Cu and Pb was by soil organic matter (SOM). The parameters obtained from the sorption isotherm equations were then used to estimate sludge loadings into the soils. When the sorption parameters derived from the reference solution were used for calculation, that is the effect of dissolved organic matter was not considered, the calculated safe application rates are approximately 47.8, 51.4, 34.2, 31.3, 21.7, 46.3, 187.1 and 27.6 t-sludge/ha for the Beijing, Jiangxi, Xiamen, Jilin, Guangdong, Wuhan, Gansu and Xinjiang soils, respectively. However, when the sorption parameters derived from the dissolved organo-metallic complexes are used for calculation, the corresponding application rates are reduced to approximately 6.0, 3.4, 1.9, 10.0, 6.3, 3.6, 7.3 and 3.5 t-sludge/ha, respectively. By this study we can get a conclusion that the effect of sewage sludge derived dissolved organic matter on heavy metal sorption and soil properties should be considered in the course of regulating the safe application rates of sewage sludge to soil.     

Characterisation of natural organic matter from the Nordic typing project water samples by chemometric analysis of their near infrared spectral profiles

Natural organic matter (NOM) from nine different water sources located in the southern part of Norway selected for the “NOM typing project” was characterised by using near infrared spectroscopy and multivariate data analysis.

The near infrared profiles of these NOM samples were corrected for multiple scattering effect and differentiated twice before subjecting them for multivariate data analysis. The preprocessed profiles were first subjected to multivariate calibration using partial least squares (PLS) technique against earlier determined values of four different biopolymer input (carbohydrates, N-acetyl amino sugars, proteins and polyhydroxy aromatics) of the NOM as dependent variables. The profiles were then classified using principal component analysis (PCA).

The PLS calibration models obtained demonstrate that the biopolymer input of the NOM samples can be predicted with acceptable precision.

The PCA reveals that the samples fall into three different groups. This classification agrees with earlier classifications carried out by using variables that were determined by alternative expensive and time-consuming analytical techniques.     

Isotherms,kinetics and thermodynamic studies of adsorption of Ni and Cu by modification of Al2O3 nanoparticles with natural organic matter

In this study, removal of Ni and Cu ions from aqueous media was assessed by the adsorption of Al₂O₃ nanoparticles (ANPs), with surface modification by natural organic matter (NOM). The obtained materials (NOM–ANPs) were characterized by Fourier transform infrared spectroscopy. Then, batch adsorption methods were carried out as a function of contact time, adsorbate concentration, pH and temperature. Kinetic experiments revealed that the pseudo-second-order model exhibited the best correlation with the adsorption data, the estimated maximum adsorption capacity of Ni and Cu could reach 15.38 and 62.50 mg g^?1 respectively at 303 K, displaying higher efficiency for Ni and Cu removal than previously reported adsorbent materials reported in the literature. Thermodynamic studies exposed the feasibility and endothermic nature of the system. The experimental results show the technical feasibility of NOM–ANPs, its easy synthesis, economic and a promising advanced adsorbent in environmental pollution cleanup.