Organic micropollutants (OMPs) in natural waters: Oxidation by UV/H2O2 treatment and toxicity assessment

Abstract

Organic micropollutants (OMPs) are ubiquitous in natural waters even in places where the human activity is limited. The presence of OMPs in natural water sources for human consumption encourages the evaluation of different water purification technologies to ensure water quality. In this study, the Biobío river (Chile) was selected since the watershed includes urban settlements and economic activities (i.e. agriculture, forestry) that incorporate a variety of OMPs into the aquatic environment, such as pesticides, pharmaceuticals and personal care products. Atrazine (herbicide), caffeine (psychotropic), diclofenac (anti-inflammatory) and triclosan (antimicrobial) in Biobío river water and in different stages of a drinking and two wastewater treatment plants downstream Biobío river were determined using solid phase extraction (SPE) and liquid chromatography/tandem mass spectrometry (LC-MS/MS) and electrospray ionization (ESI). Quantification of these four compounds showed concentrations in the range of 8 ± 2 to 55 ± 10 ng L(-1) in Biobío river water, 11 ± 2 to 74 ± 21 ng L(-1) in the drinking water treatment plant, and 60 ± 10 to 15,000 ± 1300 ng L(-1) in the wastewater treatment plants. Caffeine was used as an indicator of wastewater discharges. Because conventional water treatment technologies are not designed to eliminate some emerging organic pollutants, alternative treatment processes, UV and UV/H2O2, were employed. The transformation of atrazine, carbamazepine (antiepileptic), diclofenac and triclosan was investigated at laboratory scale. Both processes were tested at different UV doses and the Biobío river water matrix effects were evaluated. Initial H2O2 concentration used was 10 mg L(-1). Results showed that, the transformation profile obtained using UV/H2O2 at UV doses up to 900 mJ cm(-2), followed the trend of diclofenac > triclosan > atrazine > carbamazepine. Furthermore acute toxicity tests with Daphnia magna were carried out after UV/H2O2 treatments of the OMPs mixture studied. At the lower UV doses tested (300 mJ cm(-2)) a higher toxicity was observed, suggesting the formation of toxic intermediates in the course of the reaction. As expected, at higher UV doses the toxicity declined. Considering the treatment of the mixture of ATZ, CBZ, DCL and TCS with a UV dose of 1200 mJ cm(-2) and 10 mg L(-1) of H2O2 the acute toxicity results exhibits values for Daphnia magna immobilization equal to 20 and 42% evaluated after 24 and 48 h, respectively.

Keywords: Advanced oxidation process; Biobío river; Daphnia magna; Emerging contaminant; SPE-LC-MS/MS; UV/H(2)O(2).