Revealing the Impact of Sample Enrichment Method on Concentration and Cytotoxicity of Volatile Disinfection Byproducts in Drinking Water: A Quantitative Study for Liquid-liquid Extraction

Abstract

Liquid-liquid extraction (LLE) combined with the N2 blow-down method is a promising tool for bioanalysis of drinking water. However, detailed information on which disinfection byproduct (DBP) classes are retained in LLE extracts is currently unavailable. In this study, the recovery of seven classes of volatile DBPs and total adsorbable organic halogens (TOX) during the LLE method, combined with three common N2 blow-down methods, for bioanalysis in real tap water was analyzed at a 2-L scale, along with their corresponding cytotoxicity. The total concentration of seven classes of volatile DBPs in drinking water in Suzhou ranged from 64.6 to 83.0 µg/L, with the majority contributed by trihalomethanes (THMs: 59.9 µg/L), haloaldehydes (HALs: 5.4 µg/L), haloacetamides (HAMs: 3.4 µg/L), and haloacetonitriles (HANs: 3.2 µg/L). During the LLE - N2 blow-down process for bioanalysis, about 69-85% of targeted volatile DBPs and 64-75% of TOX were lost, respectively. Seven classes of volatile DBPs accounted for 52.8-64.3% and 23.8-61.3% of TOX in tap water and LLE - N2 blow-down samples, respectively, suggesting that targeted aliphatic DBPs are the key contributors to TOX. Furthermore, although LLE - solvent exchange had a better recovery performance than other N2 blow-down methods, the recoveries of volatile DBPs using this method were still not ideal. For example, HALs and HAMs had a slightly better recovery (>50%), while most volatile DBPs had a poor recovery, including iodo-trihalomethanes (I-THMs, 0%), haloketones (28%), THMs (26%), halonitromethanes (33%), and HANs (38%). During LLE - solvent exchange, 31% and 36% of targeted DBPs and TOX, respectively, in real tap water can be retained, which shows better performance than non-ionic macroporous copolymers (XAD). More importantly, the water volume required in this method for cytotoxicity analysis is 2 L, which greatly reduces the burden of water sample collection, transport, and pre-treatment compared to XAD (which typically requires 5 or 10 L). In general, this paper reveals the fate of volatile DBPs during LLE - N2 blow-down and indicates that LLE - solvent exchange is a good substitute for the XAD method in bioanalysis.