Trichloramine and Hydroxyl Radical Contributions to Dichloroacetonitrile Formation Following Breakpoint Chlorination.

Breakpoint chlorination is applied to remove ammonia in water treatment. Trichloramine (NCl3) and transient reactive species can be present, but how they affect the formation of nitrogenous disinfection byproducts is unknown. In this study, the dichloroacetonitrile (DCAN) formation mechanisms and pathways involved during breakpoint chlorination (i.e., free chlorine to ammonia molar ratio ≥2.0) were investigated. DCAN formation during breakpoint chlorination of natural organic matter (NOM) isolates was 14.3-20.3 µg/L, which was 2-10 times that in chlorination without ammonia at similar free chlorine residual conditions (2.1-2.9 mg/L as Cl2). The probe tests and electron paramagnetic resonance spectra supported the presence of •OH, •NO, and NCl3 besides free chlorine in breakpoint chlorination. 15N-labeled ammonium-N tests indicated the incorporation of ammonium-N in DCAN formation though ammonia was eliminated during breakpoint chlorination. Aromatic non-nitrogenous moieties, such as phenols (i.e., none DCAN precursors in the free-chlorine-only system), became DCAN precursors during breakpoint chlorination. The reactions involved in reactive nitrogen species, such as •NO/•NO2 and NCl3, led to additional nitrogen sources in DCAN formation, accounting for 36-84% of total nitrogen sources in DCAN formation from NOM isolates and real water samples. Scavenging •OH by tert-butanol reduced DCAN formation by 40-56%, indicating an important role of •OH in transforming DCAN precursors. This study improves the understanding of breakpoint chlorination chemistry.

Urinary metabolites of organophosphate flame retardants in China: Health risk from tris(2-chloroethyl) phosphate (TCEP) exposure.

Organophosphate esters (OPs) are substitutes for polybrominated diphenyl ether (PBDE) flame retardants. China is the largest producer of OPs globally, with the production rate increasing at 15% annually. Since some OPs are neurodevelopmental and/or carcinogenic toxicants, human exposure is a concern. In this study, concentrations of eight OP metabolites (mOPs) were measured in human urine samples collected from 13 cities located in Northern, Eastern, Southern, and Southwestern China. All target mOPs were frequently detected with detection rates of 50% to 100%, indicating widespread human exposure to OPs. Bis(2-chloroethyl) phosphate (BCEP; median: 0.68 ng/mL), bis(1-chloro-2-propyl) phosphate (BCIPP; 0.30 ng/mL), diphenyl phosphate (DPHP; 0.30 ng/mL), and dibutyl phosphate (DBP; 0.29 ng/mL) were the dominant mOPs across all participants. Regional differences in concentrations (ΣmOPs varied from 0.86 to 3.7 ng/mL) and composition profiles (contribution of chlorinated mOPs to ΣmOPs varied from 35% to 95%) of mOPs were observed within China. In comparison to the concentrations reported worldwide, urinary DPHP and bis(1,3-dichloro-2-propyl) phosphate (BDCIPP) levels in China were lower, whereas BCEP and DBP levels were comparable or higher. The total daily intake (TDI) of tris(2-chloroethyl) phosphate (TCEP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and triphenyl phosphate (TPHP) were estimated from daily urine excretion rate and the fraction of OP metabolized in human liver microsomes (TDIHLM) or S9 fraction (TDIS9). The intake estimates showed that Chinese residents were exposed to TCEP from 96.9 to 46,700 (or 52.2 to 25,200) ng/kg bw/day. Depending on the reference dose, we found that approximately 5% of the individuals exceeded the limit (i.e., 2200 ng/kg bw/day) for TCEP intake. To our knowledge, this is the first nationwide baseline survey to determine urinary levels of mOPs in Chinese residents.

Urinary metabolites of organophosphate flame retardants in 0-5-year-old children: Potential exposure risk for inpatients and home-stay infants.

Organophosphate flame retardants (OPFRs) have been commonly observed in indoor dust, food, and drinking water in China, but little is known about their exposure levels or factors leading to exposure in Chinese children. In this study, we measured eight metabolites of OPFRs (mOPFRs) in 227 urine samples collected from 0- to 5-year-old children in China. The high detection rates of mOPFRs (60%-100%) in the collected urine samples demonstrated the widespread exposure of this population to OPFRs. The median concentrations indicated that bis(2-chloroethyl)phosphate (BCEP, 0.85 ng/mL) and diphenyl phosphate (DPHP, 0.27 ng/mL) were the dominant chlorinated mOPFRs and nonchlorinated mOPFRs, respectively. Interestingly, the median urinary levels of bis(1-chloro-2-propyl)phosphate (BCIPP, 6.48 ng/mL) and bis(2-butoxyethyl)phosphate (BBOEP, 0.31 ng/mL) in inpatient infants were one order of magnitude higher (p < 0.01) than those observed in outpatient infants. For home-stay participants, furthermore, infants (0-1 year) had the highest median levels of BCIPP (0.72 ng/mL) and dibutyl phosphate (DBP, 0.14 ng/mL) among the three age groups (i.e., 0-1, >1-3, and >3-5 years), and significantly (p < 0.05) negative age-related relationships were found for both urinary mOPFRs. Two set of data on estimated daily intakes (EDIs) were calculated based on the fraction of OPFR excreted as the corresponding mOPFR (FUE) in human liver microsomes (EDIHLM) and S9 fraction (EDIS9) system, respectively. In general, children have relatively high EDIs of tris(2-chloroethyl)phosphate (TCEP: EDIHLM = 485 ng/kg bw/day, EDIS9 = 261 ng/kg bw/day). Furthermore, 17% or 21% of inpatient infants had EDIs that exceeded the reference dose, whereas this value was reduced to 13% in outpatient infants; and this value decreased with age among all home-stay children (0-5 years). Our results indicated that inpatient and home-stay infants had a higher potential risk of OPFR exposure. To our knowledge, this is the first study to identify the elevated urinary levels of mOPFRs in inpatients.