Atmospheric concentration of Polychlorinated biphenyls (PCBs) were measured on diurnal basis by active air sampling during Dec 2006 to Feb 2007 in seven major cities from the northern (New Delhi and Agra), eastern (Kolkata), western (Mumbai and Goa) and southern (Chennai and Bangalore) parts of India. Average concentration of Σ25PCBs in the Indian atmosphere was 4460 (±2200) pg/m−3 with a dominance of congeners with 4–7 chlorine atoms. Model results (HYSPLIT, FLEXPART) indicate that the source areas are likely confined to local or regional proximity. Results from the FLEXPART model show that existing emission inventories cannot explain the high concentrations observed for PCB-28. Electronic waste, ship breaking activities and dumped solid waste are attributed as the possible sources of PCBs in India. Σ25PCB concentrations for each city showed significant linear correlation with Toxicity equivalence (TEQ) and Neurotoxic equivalence (NEQ) values.

Covalent coupling to natural humic constituents comprises an important transformation pathway for anilinic pollutants in the environment. We systematically investigated the reactions of chlorine substituted anilines with catechol and syringic acid in horseradish peroxidase (HRP) catalyzed systems. It was demonstrated that although nucleophilic addition was the mechanism of covalent bonding to both catechol and syringic acid, chloroanilines coupled to the 2 humic constituents via slightly different pathways. 1,4-addition and 1,2-addition are involved to catechol and syringic acid, respectively. 1,4-addition showed empirical 2nd order kinetics and this pathway seemed to be more permanent than 1,2-addition. Stability experiments demonstrated that cross-coupling products with syringic acid could be easily released in acidic conditions. However, cross-coupling with catechol was relatively stable at similar conditions. Thus, the environmental behavior and bioavailability of the coupling products should be carefully assessed.

Trace element concentrations on a dry ash basis in saline-irrigated biomass feedstock from the San Joaquin Valley are investigated using multi-element spectroscopic techniques. The results show high concentrations of both Na and K compared to local baseline soil. The content of Na is higher than observed for nonsaline-irrigated biomass reflecting the salinity of the drainage water. The alkali earth elements as well as other alkali trace elements are, however, not markedly affected by the salinity of the irrigation water. The transition elements Cu and Zn are enriched only in the herbaceous feedstock compared to nonsaline biomass. Sulfur, chlorine, and phosphorus are markedly enriched in the saline feedstock. The ash content of toxic elements invariably exceeds the concentrations in the baseline soil for Cu, As, Se, Cd, Sb, and Pb. Compared to nonsaline biomass ashes, Cu is relatively enriched in the herbaceous feedstock ashes, As only in eucalyptus wood, and Cd, Sb, and Pb in woody feedstock. Selenium is relatively enriched in all saline feedstock. Only the concentrations of Cd in woody saline-irrigated feedstock may potentially exceed environmental guideline concentrations and may, thus, warrant caution for using saline biomass for soil amendment.

The catalytic effect of Cu(II) on the formation of disinfection by-products (DBPs) and chlorine degradation during chlorination of humic acid (HA) solutions was comparatively investigated under different experimental conditions. The experimental results showed that the total organic halogen (TOX) and trihalomethane (THM) formation increased with increasing Cu(II) concentration during chlorination, while haloacetic acids (HAAs) increased insignificantly. Accelerated chlorine decay and increased TOX and HAA formation were observed at high pH in the presence of 1.0 mg/L Cu(II) compared with that observed at low pH but THM formation decrease. Furthermore, the Cu(II) effect catalyzed the formation of brominated DBPs as it did for chlorine analogues in the presence of bromide ion. The microcalorimetry analysis demonstrated that more DBPs were formed in the Cu(II)-catalyzed chlorination, in which second-order rate constants obtained from reaction of HA with chlorine under given experimental conditions were 0.00256 M⁻¹ s⁻¹ (without Cu(II)) and 0.00865 M⁻¹ s⁻¹ (with Cu(II)), respectively. To discriminately examine the role of Cu(II) in greater detail, nine model compounds, which approximately represent the chemical structural units of HA, were individually oxidized by chlorine. It was demonstrated that carboxylic acids significantly enhanced the formation of TOX, THMs, and HAAs in the presence of Cu(II). Based on the previously published information and our experimental results, the possible pathway for Cu(II)-catalyzed TOX, THM, and HAA formation from chlorination of carboxylic acids were tentatively proposed.

Chlorine is the most commonly used chemical for water and wastewater disinfection worldwide, and it reacts with both ammonia and dissolved organic nitrogen. Using the salicylate spectrophotometric method, effects of glycine on the classic breakpoint chlorination are studied using glycine as a surrogate for dissolved organic nitrogen. The results show that the shape of the breakpoint chlorination curve with glycine was analogous to that of water without glycine. Increasing the glycine concentration moves the chlorination breakpoint curve to the right, demonstrating that more chlorine must be added to replace the chlorine consumed by glycine and yield the desired residual active chlorine concentration. At the peak of the chlorination breakpoint curve, both NH₂Cl and mono-chlorinated organic chloramine reach their maximum. The Cl₂/N ratio of the peak is linearly related to the glycine concentration, and our calculations indicate that the maximum of mono-chlorinated organic chloramine formation by glycine chlorination occurs at a stoichiometric ratio of 1:1; the same as that for chlorinating ammonia to NH₂Cl. The distribution of NH₂Cl and organic chloramines is controlled by [Gly]/[NH₃-N]. At the breakpoint, ammonia and glycine are completely oxidized by chlorine, which leads to chlorine depletion. The stoichiometric ratio for the complete oxidation of glycine was 3:1, larger than that for complete oxidation of ammonia (2:1). For the different stoichiometric ratio in reaction of oxidation of ammonia and glycine, the sum of ammonia and glycine cannot be used as a chlorine dosage control parameter. The chlorine control method involving ammonia and glycine for chlorine and chloramination process is established.

The electrochemical degradation of the Reactive Red 141 azo dye was done using a one-compartment filter-press flow cell with a boron-doped diamond anode. The response surface methodology (with a central composite design) was used to investigate the effect of current density (10–50 mA cm⁻²), pH (3–11), NaCl concentration ([NaCl]) (0–2.34 g L–¹), and temperature (15–55 °C) on the system’s performance. The charge required for 90 % decolorization (Q ⁹⁰), the fraction of chemical oxygen demand removal after 6 min of electrolysis (COD⁶), and the fraction of total organic carbon removal after 90 min of electrolysis (TOC⁹⁰) were used to model the obtained results. The lowest values of Q ⁹⁰ were attained at pH <4 in the presence of higher values of [NaCl] (>1.5 g L⁻¹), due to the electrogeneration of active chlorine, present mainly as HClO. The value of COD⁶ was not affected by the solution pH, but increased with [NaCl] up to 1.5 g L⁻¹. Higher temperatures (>40 °C) led to a decrease in COD⁶, as a consequence of side reactions. Higher values of TOC⁹⁰, which can be reached only with strong oxidants (such as ·OH and Cl·), were efficiently attained at low [NaCl] values (<0.7 g L⁻¹) in acidic solutions that inhibit the formation of ClO₃ ⁻ and ClO₄ ⁻. Finally, the obtained results allow inferring that most probably the mineralization of the dye starts with an attack on the chromophore group, followed by the degradation of intermediate species.

The ubiquitous presence of chlorophenols (CPs) continues to be a cause of concern, owing to their recalcitrant nature. In this context, the present work investigated the degradation of model compounds, 4-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol, by an organic oxidant, methyl ethyl ketone peroxide (MEKP) coupled with ultraviolet irradiation in basic media. Chemical analysis was followed by high-performance liquid chromatography and gas chromatography–mass spectrometry. Despite exhibiting varied patterns of decline, chemical oxygen demand was eventually noted to decrease to the extent of up to 70 %. Simultaneous increase/decrease in the release of chloride ions and decrease in pH indicated that parallel reactions were occurring, which led to the formation of acidic reaction products. First-order dynamics was approximated for all CP congener degradation. The degraded compounds showed absolutely no presence of chlorine atoms, which was a noteworthy feature testifying to the fact that MEKP action was capable of detoxification of CP congeners.

Domestic water is abstracted from its sources in raw form with a high content of dissolved and suspended material. Polydiallyldimethylammonium chloride (polyDADMAC) is a cationic polyelectrolyte used in the initial water clarification process. However, its residues in treated water pose a health risk as they react with chlorine to produce a carcinogenic compound. There is a need to determine the concentration of the polyelectrolyte cations that pass through the flocculation stage before the chlorine disinfection process in water treatment plants to ascertain the safety of water to consumers. The cationic polymer is UV inactive, and previously available methods for determining the concentrations of polyelectrolytes are unsatisfactory due to poor detection limits. This paper describes a UV-Visible (UV-vis) spectrophotometry method for the determination of residual polyDADMAC as an epoxide. The novelty method lies on the epoxidation of polyDADMAC using 20 % sodium hydroxide dissolved in 30 % hydrogen peroxide to produce a UV-Vis active compound. The epoxidation was confirmed by UV-Vis, FTIR and 1H NMR techniques. Dilute solutions of varying concentrations of polyDADMAC (0.2-1.0 mg L-1) were treated with a basic solution of hydrogen peroxide then analysed by UV-Vis spectrophotometry. The wavelength at maximum absorption (λmax) was found to be 313 nm, and a linear calibration curve with a correlation coefficient (R 2) of 0.993 was used for quantification purposes. The detection limit measured as three times the signal of the blank and was found to be 2.1 × 10-4 mg L-1. The method was applied to determine the concentration of polyDADMAC spiked in water samples collected from a pool as a model for environmental matrix. The results obtained agreed with the quantities spiked in the solution, thus qualified the method to be suitable for the determination of polyDADMAC in treated waters at trace levels. The method was also used to investigate the adsorption capacity of polyDADMAC on sand filters. The adsorption method was found to be in accordance with Langmuir with an adsorption capacity of 2.068 mg g-1. © 2013 The Author(s).

The photocatalytic degradations of 4-chlorophenol (CP), 4-chloro-2-methylphenol (CMP), 4-chloro-3,5-dimethylphenol (CDMP) and 4-chloro-2-isopropyl-5-methylphenol (CIMP) were investigated in water and in simulated soil washing wastes containing Brij 35 (polyoxyethylene(23)dodecyl ether) in the presence of TiO₂ dispersions. A neat inhibition of substrate decomposition proportional to their growing hydrophobicity was observed in the washing wastes for CP, CMP and CDMP, whereas CIMP showed a different behaviour. The mineralization of the organic chlorine of CP and CIMP was relatively fast and complete, whereas it was much slower for CMP and CDMP. Micellar solubilization and substrate adsorption onto the semiconductor play opposite roles on the degradation kinetics, and a breakpoint between the corresponding induced effects was evidenced when the pollutants become completely bound to the micellar aggregates.

Both nitrate and pentachlorophenol (PCP) are familiar pollutants in aqueous environment. This research is focused on the simultaneous removal of nitrate and PCP from simulated contaminated groundwater using a laboratory-scale denitrification reactor packed with corncob as both carbon source and biofilm support. The reactor could be started up readily, and the removal efficiencies of nitrate and PCP reached up to approximately 98 % and 40–45 % when their initial concentrations were 50 mg N/L and 5 mg/L, respectively, after 15-day continuous operation at 10 h of hydraulic retention time (HRT) and 25 °C. Approximately 91 % of PCP removal efficiency was achieved, with 2.47 mg/L of chloride ion release at 24 h of HRT. Eighty-two percent of chlorine in PCP removed was ionized. The productions of 3-chlorophenol and phenol and chloride ion release indicate that the reductive dechlorination reaction is a major degradation pathway of PCP under the experimental conditions.