Occurrence and speciation of chlorination byproducts in marine waters and sediments of a semi-enclosed bay exposed to industrial chlorinated effluents

Abstract

Chlorination of seawater is one of the most effective technologies for industrial biofouling control. However, chlorination leads to the formation of halogenated chlorination byproducts (CBPs) associated with potential risks to environmental and human health. The present study investigated the occurrence and distribution of CBPs in the Gulf of Fos, a semi-enclosed bay where chlorinated effluents of multiple industrial plants are discharged. Seawater samples (surface and bottom) were collected at 24 sampling stations, with some near industrial outlets and others dispersed throughout the bay. Sediment samples were also collected at 10 sampling stations. Physicochemical parameters including water temperature, pH, salinity, bromide content, and free and total residual oxidant were determined. Several chemical classes of CBPs including trihalomethanes, haloacetic acids, haloacetonitriles, trihaloacetaldehydes, and halophenols were analyzed. Bromoform was the most abundant CBP in seawater, and it was detected at most of the sampling stations of the bay with highest concentrations occurring near the industrial effluent outlets. Dibromoacetic acid was the second most abundant CBP at most of the sites followed by dibromoacetonitrile. Other detected CBPs included tribromoacetic acid, bromochloroacetonitrile, and bromal hydrate. To our knowledge, the concentration of the latter CBP was reported here for the first time in the context of industrial seawater chlorination. In sediments, two bromine-containing halophenols (2-chloro-4-bromophenol and 2,4,6-tribromophenol) were detected at two sampling stations. Ecotoxicological assays and risk assessment studies based on the detected environmental concentrations are warranted to elucidate the impacts of marine CBP contamination.

Assessment of individual and mixed toxicity of bromoform, tribromoacetic-acid and 2,4,6 tribromophenol, on the embryo-larval development of Paracentrotus lividus sea urchin

“…These PS embryos were exposed to TBP, BMF and TBAA at their respective LOEC, EC50 and EC90, and to mix LOECs condition. They were found slighly less sensitive to TBP and TBAA than NPS embryos, while very resistant to BMF, which is the most prevalent molecule found in seawater where genitors were harvested ( Figure 2) (Manasfi et al 2018). Moreover, exposure to mix LOECs reduced the proportion of normal Pluteus by 40% instead of 80% for the NPS embryos.…”

“…Adult Paracentrotus lividus sea urchins were harvested by scuba diving, on the morning of each experiment, at a non-polluted site (NPS) near the Toulon (Var, France) embayment (Garonne Bay: 43.098503-6.018430)and at a polluted site (PS) where sweater is chronically chlorinated (Manasfi et al, 2018). P. lividus were induced to spawn by gentle shaking.…”

“…Hence, in some industrialized embayment areas, huge volumes of coastal seawater are continuously being pumped and chlorinated before being re-released into the original embayment (Allonier et al 1999;Boudjellaba et al 2016;Manasfi et al 2018). As chlorine is very reactive in the presence of natural organic matter, seawater chlorination generates a complex set of brominated and chloro-brominated disinfection-by-products (DBPs).…”

“…Although the diversity and occurrence of brominated DBPs in contaminated coastal seawater is relatively undocumented (Richardson et al 2007;Manasfi et al 2017), bromoform (halomethane), tribromoacetic acid (haloacetic acid) and tribromophenol (halophenol) are among the most prevalent molecules, often measured at relatively high concentrations (i.e. µg/L) (Manasfi et al 2018).…”

Development of an automated system for the analysis of inorganic chloramines in swimming pools via multi-syringe chromatography and photometric detection with ABTS

“…These chloramines are present in various types of waters where chlorine is used as disinfectant or for biofouling control (drinking waters, swimming pools waters, wastewaters, industrial chlorinated effluents) [1,[3][4][5][6]. In particular for swimming pools, respiratory issues, such as asthma, wheeze, cough and lower respiratory tract infections, have been correlated with swimming pool attendance, which is likely due to chlorinated volatile DBPs, such as chloramines and especially TCA [7][8][9].…”