Relationships between regulated DBPs and emerging DBPs of health concern in U.S. drinking water

A survey was conducted at eight U.S. drinking water plants, that spanned a wide range of water qualities and treatment/disinfection practices. Plants that treated heavily-wastewater-impacted source waters had lower trihalomethane to dihaloacetonitrile ratios due to the presence of more organic nitrogen and HAN precursors. As the bromide to total organic carbon ratio increased, there was more bromine incorporation into DBPs. This has been shown in other studies for THMs and selected emerging DBPs (HANs), whereas this study examined bromine incorporation for a wider group of emerging DBPs (haloacetaldehydes, halonitromethanes). Moreover, bromine incorporation into the emerging DBPs was, in general, similar to that of the THMs. Epidemiology studies that show an association between adverse health effects and brominated THMs may be due to the formation of brominated emerging DBPs of heath concern. Plants with higher free chlorine contact times before ammonia addition to form chloramines had less iodinated DBP formation in chloraminated distribution systems, where there was more oxidation of the iodide to iodate (a sink for the iodide) by the chlorine. This has been shown in many bench-scale studies (primarily for iodinated THMs), but seldom in full-scale studies (where this study also showed the impact on total organic iodine. Collectively, the THMs, haloacetic acids, and emerging DBPs accounted for a significant portion of the TOCl, TOBr, and TOI; however, ∼50% of the TOCl and TOBr is still unknown. The correlation of the sum of detected DBPs with the TOCl and TOBr suggests that they can be used as reliable surrogates.     

Penetration of polar brominated DBPs through the activated carbon columns during total organic bromine analysis

Total organic bromine (TOBr) is a collective parameter representing all the brominated organic disinfection byproducts (DBPs) in water samples. TOBr can be measured using the adsorption-pyrolysis method according to Standard Method 5320B. This method involves that brominated organic DBPs are separated from inorganic halides and concentrated from aqueous solution by adsorption onto the activated carbon (AC). Previous studies have reported that some commonly known brominated DBPs can partially penetrate through the AC during this adsorption step. In this work, the penetration of polar brominated DBPs through AC and ozone-modified AC was explored with two simulated drinking water samples and one chlorinated wastewater effluent sample. Polar brominated DBPs were selectively detected with a novel precursor ion scan method using electrospray ionization-triple quadrupole mass spectrometry. The results show that 3.4% and 10.4% of polar brominated DBPs (in terms of total ion intensity) in the chlorinated Suwannee River fulvic acid and humic acid samples, respectively, penetrated through the AC, and 19.6% of polar brominated DBPs in the chlorinated secondary wastewater effluent sample penetrated through the AC. The ozone-modification of AC minimized the penetration of polar brominated DBPs during the TOBr analysis.     

Occurrence of Primidone,Carbamazepine, Caffeine,and Precursors for N‐Nitrosodimethylamine in Drinking Water Sources Impacted by Wastewater1

Abstract: Wastewater impact on drinking water sources was assessed using several approaches, including analysis of three pharmaceuticals and personal care products (PPCPs) – primidone, carbamazepine, and caffeine – as indicators, and determination of precursor concentrations for the disinfection byproduct N‐nitrosodimethylamine (NDMA) using formation potential (FP) tests. Samples were collected in 2006 and 2007 in rivers impacted by wastewater treatment plant (WWTP) discharges, at drinking water treatment plant (DWTP) intakes upstream or downstream from these discharges, and from two WWTP effluents in two watersheds. The levels [10th percentile ? maximum (median)] of primidone, carbamazepine, caffeine, and NDMAFP were 2‐95 (7) ng/l, 2‐207 (18) ng/l, 7‐687 (78) ng/l, and 12‐321 (35) ng/l, respectively. The highest concentrations of primidone, carbamazepine, and NDMA precursors were from one of the WWTP effluents, whereas the highest concentration of caffeine was detected in a river heavily impacted by treated wastewater discharges. The lowest concentrations of the three PPCPs were from a DWTP influent upstream of a metropolitan urban area with minimum wastewater impact. Temporal variations in PPCP and NDMAFP concentrations and streamflows in two selected watersheds were also observed. Furthermore, correlation analysis between caffeine or carbamazepine and primidone was evaluated. The results show that measurement of the two pharmaceuticals and NDMAFP tests can be used to evaluate wastewater impact in different watersheds, whereas caffeine results were more variable.     

Case study approach to modeling historical disinfection by-product exposure in Iowa drinking waters

In the 1980 s, a case–control epidemiologic study was conducted in Iowa(USA) to analyze the association between exposure to disinfection by-products(DBPs) and bladder cancer risk. Trihalomethanes(THMs), the most commonly measured and dominant class of DBPs in drinking water, served as a primary metric and surrogate for the full DBP mixture.Average THM exposure was calculated, based on rough estimates of past levels in Iowa. To reduce misclassification, a follow-up study was undertaken to improve estimates of past THM levels and to re-evaluate their association with cancer risk. In addition, the risk associated with haloacetic acids, another class of DBPs, was examined. In the original analysis, surface water treatment plants were assigned one of two possible THM levels depending on the point of chlorination. The re-assessment considered each utility treating surface or groundwater on a case-by-case basis. Multiple treatment/disinfection scenarios and water quality parameters were considered with actual DBP measurements to develop estimates of past levels. The highest annual average THM level in the re-analysis was156 μg/L compared to 74 μg/L for the original analysis. This allowed the analysis of subjects exposed at higher levels( 96 μg/L). The re-analysis established a new approach, based on case studies and an understanding of the water quality and operational parameters that impact DBP formation, for determining historical exposure.