Comparison of UV-based advanced oxidation processes for the removal of different fractions of NOM from drinking water

This study examined the effectiveness for degradation of hydrophobic (HPO), transphilic (TPI) and hydrophilic (HPI) fractions of natural organic matter (NOM) during UV/H₂O₂, UV/TiO₂ and UV/K₂S₂O₈ (UV/PS) advanced oxidation processes (AOPs). The changing characteristics of NOM were evaluated by dissolved organic carbon (DOC), the specific UV absorbance (SUVA), trihalomethanes formation potential (THMFP), organic halogen adsorbable on activated carbon formation potential (AOXFP) and parallel factor analysis of excitation–emission matrices (PARAFAC-EEMs). In the three UV-based AOPs, HPI fraction with low molecular weight and aromaticity was more likely to degradate than HPO and TPI, and the removal efficiency of SUVA for HPO was much higher than TPI and HPI fraction. In terms of the specific THMFP of HPO, TPI and HPI, a reduction was achieved in the UV/H₂O₂ process, and the higest removal rate even reached to 83%. UV/TiO₂ and UV/PS processes can only decrease the specific THMFP of HPI. The specific AOXFP of HPO, TPI and HPI fractions were all able to be degraded by the three UV-based AOPs, and HPO content is more susceptible to decompose than TPI and HPI content. UV/H₂O₂ was found to be the most effective treatment for the removal of THMFP and AOXFP under given conditions. C1 (microbial or marine derived humic-like substances), C2 (terrestrially derived humic-like substances) and C3 (tryptophan-like proteins) fluorescent components of HPO fraction were fairly labile across the UV-based AOPs treatment. C3 of each fraction of NOM was the most resistant to degrade upon the UV-based AOPs. Results from this study may provide the prediction about the consequence of UV-based AOPs for the degradation of different fractions of NOM with varied characteristics.     

Monitoring the formation of trihalomethanes in the effluents from a shrimp hatchery

Formation of trihalomethanes (THM) was monitored at the Laboratório de Camarões Marinhos (LCM) from the Universidade Federal de Santa Catarina. THM could be present because chlorinated effluents from disinfection are discharged from the different hatchery rooms. THM quantification was done through an analytical methodology using Purge&;Trap coupled with a gas chromatograph equipped with an electron capture detector. Relative standard deviation (RSD), limit of detection (LOD) and limit of quantification (LOQ) for the methodology corresponded to the ranges of 8–17%; 0.01–0.03 μg L^?1 and 0.03–0.08 μg L^?1, respectively. Linear working range was of 0.1–8.0 μg L^?1 for all compounds. Enrichment and recovery method was applied to evaluate possible matrix effects and the results varied from 71.2% to 107.9%. LCM was monitored between August and December, 2004. This study showed that THM did not increase with the increase in postlarvae production and also that the aquatic life and the surrounding environment were not affected.     

Exposure to inhaled THM: Comparison of continuous and event-specific exposure assessment for epidemiologic purposes

Trihalomethanes (THMs) (chloroform, bromoform, dibromochloromethane, and bromodichloromethane) are the most abundant by-products of chlorination. People are exposed to THMs through ingestion, dermal contact and inhalation. The objective of this study was to compare two methods for assessing THM inhalation: a direct method with personal monitors assessing continuous exposure and an indirect one with microenvironmental sampling and collection of time–activity data during the main event exposures: bathing, showering and swimming. This comparison was conducted to help plan a future epidemiologic study of the effects of THMs on the upper airways of children. 30 children aged from 4 to 10 years were included. They wore a 3M^™ 3520 organic vapor monitor for 7 days. We sampled air in their bathrooms (during baths or showers) and in the indoor swimming pools they visited and recorded their time–activity patterns. We used stainless steel tubes full of Tenax^® to collect air samples. All analyses were performed with Gas Chromatography and Mass Spectrometry (GC-MS). Chloroform was the THM with the highest concentrations in the air of both bathrooms and indoor swimming pools. Its continuous and event exposure measurements were significantly correlated (r_s = 0.69 p < 0.001). Continuous exposures were higher than event exposures, suggesting that the event exposure method does not take into account some influential microenvironments. In an epidemiologic study, this might lead to random exposure misclassification, thus underestimation of the risk, and reduced statistical power. The continuous exposure method was difficult to implement because of its poor acceptability and the fragility of the personal monitors. These two points may also reduce the statistical power of an epidemiologic study. It would be useful to test the advantages and disadvantages of a second sample in the home or of modeling the baseline concentration of THM in the home to improve the event exposure method.     

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.     

Formation control of bromate and trihalomethanes during ozonation of bromide-containing water with chemical addition: Hydrogen peroxide or ammonia?

To ensure the safety of drinking water, ozone (O₃) has been extensively applied in drinking water treatment plants to further remove natural organic matter (NOM). However, the surface water and groundwater near the coastal areas often contain high concentrations of bromide ion (Br^?). Considering the risk of bromate (BrO₃^?) formation in ozonation of the sand-filtered water, the inhibitory efficiencies of hydrogen peroxide (H₂O₂) and ammonia (NH₃) on BrO₃^? formation during ozonation process were compared. The addition of H₂O₂ effectively inhibited BrO₃^? formation at an initial Br^? concentration amended to 350 µg/L. The inhibition efficiencies reached 59.6 and 100% when the mass ratio of H₂O₂/O₃ was 0.25 and > 0.5, respectively. The UV₂₅₄ and total organic carbon (TOC) also decreased after adding H₂O₂, while the formation potential of trihalomethanes (THMsFP) increased especially in subsequent chlorination process at a low dose of H₂O₂. To control the formation of both BrO₃^? and THMs, a relatively large dose of O₃ and a high ratio of H₂O₂/O₃were generally needed. NH₃ addition inhibited BrO₃^? formation when the background ammonia nitrogen (NH₃N) concentration was low. There was no significant correlation between BrO₃^? inhibition efficiency and NH₃ dose, and a small amount of NH₃N (0.2 mg/L) could obviously inhibit BrO₃^? formation. The oxidation of NOM seemed unaffected by NH₃ addition, and the structure of NOM reflected by synchronous fluorescence (SF) scanning remained almost unchanged before and after adding NH₃. Considering the formation of BrO₃^? and THMs, the optimal dose of NH₃ was suggested to be 0.5 mg/L.     

The occurrence of disinfection by-products in the drinking water of Athens,Greece

Application of chlorination for the disinfection of drinking water results in the formation of a wide range of organic compounds, called disinfection by-products (DBPs), which occur due to the reaction of chlorine with natural organic materials. The occurrence of DBPs was studied in samples from four drinking-water treatment plants (WTPs) and from the distribution network of Athens, Greece. Twenty-four compounds, which belong to different categories of DBPs, were monitored, including trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs), haloketones (HAKs), chloral hydrate (CH) and chloropicrin (CP). Sampling was performed monthly for a period of two years, from three different points at each WTP and from eight points atthe distribution network. Samples were analyzed by GC-ECD methods, which included pretreatment with liquid-liquid extraction for volatile DBPs and acidic methanol esterification for HAAs. The results of the analyses have shown the presence of disinfection by-products belonging to all categories studied in all water samples collected after prechlorination. The major categories of DBPs detected were THMs and HAAs, while the other volatile DBPs occurred at lower concentrations. The concentrations of DBPs did not in any case exceed the maximum contaminant levels (MCL) set by USEPA and WHO. However, monitoring these compounds needs to be continued, because their levels could increase due to changes in the quality of water entering the water treatment plants. Reduction of the concentrations of DBPs could be achieved by optimization of the chlorination conditions, taking into account the effect of time. Moreover, research on alternative disinfection methods (e.g. ozone, chlorine dioxide, chloramines) and their by-products should be conducted to evaluate their applicability in the case of the drinking water of Greece.     

Degradation of sulfonamides and formation of trihalomethanes by chlorination after pre-oxidation with Fe(VI)

Sulfonamides are used in human therapy, animal husbandry and agriculture but are not easily biodegradable, and are often detected in surface water. Sulfamethazine (SMZ) and sulfadiazine (SDZ) are two widely used sulfonamide antibiotics that are used heavily in agriculture. In this study, they were degraded in an aqueous system by chlorination after pre-oxidation with ferrate(VI) (Fe^VIO₄^2 ?, Fe(VI)), an environmentally friendly oxidation technique that has been shown to be effective in degrading various organics. The kinetics of the degradation were determined as a function of Fe(VI) (0–1.5 mg/L), free chlorine (0–1.8 mg/L) and temperature (15–35°C). According to the experimental results, SMZ chlorination followed second-order kinetics with increasing Fe(VI) dosage, and the effect of the initial free chlorine concentration on the reaction kinetics with pre-oxidation by Fe(VI) fitted a pseudo-first order model. The rate constants of SDZ and SMZ chlorination at different temperatures were related to the Arrhenius equation. Fe(VI) could reduce the levels of THMs formed and the toxicity of the sulfonamide degradation systems with Fe(VI) doses of 0.5–1.5 mg/L, which provides a reference for ensuring water quality in drinking water systems.     

Monitoring trihalomethanes in water by differential ultraviolet spectroscopy

Ultraviolet (UV) spectroscopy is a valid surrogate for monitoring the formation of disinfection by-products (DBPs). Sodium thiosulphate is commonly used to remove disinfectant residual. However, it produces interferences with absorbance in the UV region. Relationship between trihalomethane (THM) formation and differential UV absorbance (−ΔA _λ ) was explored in the presence of sodium thiosulphate. Chlorination of two synthetic and five natural waters was carried out. Sodium thiosulphate showed high UV absorption at 254 nm. This effect can be overcome selecting a higher wavelength. Optimum wavelength varied being about 290 nm for fulvic acid and 300 nm for humic acid type natural organic matter. Correlation between THMs formation and −ΔA _λ was linear for all the analysed samples. Regression curves do not pass through zero indicating the existence of a threshold absorbance decreasment. Once it is surpassed THM release begins. Chlorination of surface waters showed that the presence of bromide significantly increases THMs vs. −ΔA _λ slope. Furthermore, slope decreased with the aromaticity–hydrophobicity of organic matter.     

A teratological assessment of four trihalomethanes in the rat

Abstract

Four trihalomethanes were administered by gavage to Sprague‐Dawley rats from day 6 to day 15 of gestation. Chloroform (Ch) was administered at levels of 100, 200 and 400 mg/kg and bromoform (Br), bromodichloromethane (BDCM) and chlorodibromomethane (CDBM) were administered at levels of 50, 100 or 200 mg/kg/day. A separate control was used for each compound. Maternal weight gain was depressed in all groups receiving Ch and at the highest dose levels of BDCM and CDBM. Ch administration caused decreased maternal hemoglobin and hematocrit values at all dose levels and also produced increased serum inorganic phosphorus and cholesterol at the highest dose. Liver enlagement was observed at all dose levels of Ch but in no other treatment groups. Evidence of a fetotoxic response was observed with Ch, CDBM and Br but not BDCM. No dose‐related histopathological changes were observed in either mothers or fetuses as a result of treatment. None of the chemicals tested produced any teratogenic effects.     

Effects of bromide on the formation of THMs and HAAs

The role of bromide in the formation and speciation of disinfection by-products (DBPs) during chlorination was investigated. The molar ratio of applied chlorine to bromide is an important factor in the formation and speciation of trihalomethanes (THMs) and halogenacetic acids (HAAs). A good relationship exists between the molar fractions of THMs and the bromide incorporation factor. The halogen substitution ability of HOBr and HOCl during the formation of THMs and HAAs can be determined based on probability theory. The formation of HAAs, and their respective concentrations, can also be estimated through use of the developed model.