Rapid determination of trace haloacetic acids in water and wastewater using non-suppressed ion chromatography with electrospray ionization-tandem mass spectrometry.

A simple and rapid method employing non-suppressed ion chromatography with electrospray ionization tandem mass spectrometry has been developed for the direct determination of trace-level haloacetic acids (HAAs) in water samples. Using 70/30 (v/v) acetonitrile/1 M aqueous methylamine as the mobile phase, three IC columns - AS16, AS18 and AS24 from Thermo-Scientific - were tested, respectively, with the AS16 column exhibiting the best overall performance with respect to resolution and retention time. To assess the effects of mobile phase composition on retention time of HAAs, the AS16 column was further tested using (i) different proportions of acetonitrile to aqueous methylamine, (ii) different proportions of acetonitrile to aqueous solution at fixed methylamine concentrations, and (iii) different concentrations of methylamine at fixed proportions of acetonitrile to aqueous solution. With a low proportion of aqueous solution, van der Waals and/or hydrogen-bonding interactions appeared to play an important role in governing HAA retention, i.e., HAAs with relatively higher apparent logKow* caused by elevated solvent sspKa exhibited longer retention times; whereas with a high proportion of aqueous solution, ionic interactions appeared to dominate retention of HAAs, with the more polarizable HAAs exhibiting longer retention times. Using 70/30 (v/v) acetonitrile/1 M aqueous methylamine, the method detection limits were in the range of 0.090-0.216 µg/L for the 11 selected chloro-, bromo- and iodoacetic acids. Finally, this method was applied to monitor HAAs yields in laboratory chlorination experiments and to determine concentrations of HAAs in tap water and wastewater effluent samples.

Developing a restricted chlorine-dosing strategy for UV/chlorine and post-chlorination under different pH and UV irradiation wavelength conditions.

UV/chlorine and chlorination processes have drawn great interests of water treatment utilities for oxidation and disinfection purposes. This work proposed a restricted chlorine-dosing strategy for UV/chlorine and post-chlorination under different pH and UV irradiation conditions by comprehensively assessing the oxidation of natural organic matter (NOM), formation of 9 haloacetic acids (HAA9) and bromate, and alteration of toxicity. During UV/chlorine with restricted chlorine doses, the oxidation of NOM chromophores (i.e., ΔUVA254) showed an apparent dependence on cumulative exposures of free available chlorine (CTFAC); Meanwhile, HAA9 formation was determined by CTFAC values and could be linearly correlated with ΔUVA254 irrespective of pH and UV irradiation wavelength. Irradiated by 254 nm LP-Hg lamp, the faster chlorine photolysis produced relatively higher steady-state concentrations of Cl• and HO• species but resulted in lower CTFAC. Reducing CTFAC values by operation parameters (pH, UV wavelength and irradiation fluence) could mitigate HAA9 formation during UV/chlorine at a specific chlorine dose. Additionally, high bromide concentration and acidic pH promoted more bromo-HAAs formation, and the presence of NOM significantly suppressed bromate formation. Analogous to ozonation, the UV/chlorine pre-oxidation could reduce the HAA9 formation potentials during post-chlorination at mildly alkaline pH. The photobacterium bioassay further demonstrated that although the UV/chlorine treatment might have increased the acute toxicity, the post-chlorination treatment could polish the acute toxicity to the level of chlorination alone. These results suggest that with the restricted chlorine-dosing strategy, the trade-off between oxidation/disinfection efficiency and DBPs formation can be controlled by monitoring CTFAC and ΔUVA254 values during UV/chlorine treatment.

Developing surrogate indicators for predicting suppression of halophenols formation potential and abatement of estrogenic activity during ozonation of water and wastewater.

This study focused on developing surrogate indicators for predicting oxidation of phenolic groups in dissolved organic matter (DOM), suppression of halophenols' formation potential and abatement of estrogenic activity during ozonation of water and wastewater. The evolution of pH-dependent differential absorbance spectra suggests that O3 preferentially reacts with the DOM phenolic moieties and less so with the aromatic carboxylic groups with increasing O3/DOC (dissolved organic carbon) ratios and changes of UV absorbance and fluorescence. When ozonation used as pretreatment, the formation of halophenols in subsequent chlorination decreased linearly with increasing O3 doses or changes of UV absorbance until it reached 85% suppression of the halophenols' formation from unaltered DOM. The thresholds of decreases of UVA254, UVA280 and humic-like fluorescence corresponding to 85% suppression of halophenols' formation were in the range of 25%-30%, 30%-35% and 30%-45%, respectively. Pre-ozonation also showed a moderate suppression of haloacetic acids (HAAs) formation potentials, ≤26.5% for reverse osmosis isolate of Suwannee River natural organic matter and ≤31.5% for Yangtze River at applied O3 doses. Measurement of changes of estrogenic activity during ozonation of water and wastewater showed that to attain a >90% abatement of estrogenic activity, the corresponding thresholds of decreases of UVA254, UVA280 and humic-like fluorescence were ∼30%, ∼40%, and ∼70%, respectively. Bromate formation was also suppressed to below 10 µg/L before these thresholds. This study suggests that optimal ozonation conditions and a balance between control of disinfection byproducts (halophenols, HAAs and bromate) and elimination of estrogenic activity can be reached based on online data.

[Determination of glyphosate in air of workplaces by ion chromatography].

OBJECTIVE: To establish a method for determining glyphosate in the air of workplaces by ion chromatography. METHODS: Ultra-fine glass fiber filter paper was used to collect glyphosate from the workplace air. After being ultrasonically eluted with deionized water, samples were determined by ion chromatography using a conductivity detector. RESULTS: Within the range of 0.05-1.00 mg/L, a linear relationship was found with a limit of detection of 0.003 mg/m(3). The minimum detectable concentration was 0.000 41 mg/m(3) (calculated by sampling 75 L of air). For three different concentrations of glyphosate, the intra-batch relative standard deviations (RSDs) were 1.8%, 1.6%, and 0.8%, respectively, and the inter-batch RSDs were 1.9%, 2.1%, and 2.2%, respectively. The recovery rate ranged from 94.8% to 97.4%. The elution efficiency ranged from 94.5% to 96.7%. The sampling efficiency was 100%. Samples could be stored at room temperature for at least 7 days. CONCLUSION: This presented method meets the requirements of Guide for establishing occupational health standards-Part 4: Determination methods of air chemicals in workplace and is feasible for determination of glyphosate in the air of workplaces.