Iodinated Disinfection Byproducts Research Articles

A comparative study on the degradation of iohexol and diatrizoate during UV/persulfate process: kinetics, degradation pathways and iodinated disinfection by-products

Iodinated X-ray contrast media (ICM) are widely used in medical imaging due to their stable properties, but they cannot be effectively removed in wastewater treatment plants (especially hospital wastewater).

Low Parts Per Trillion Detection of Iodinated Disinfection Byproducts in Drinking Water and Urine using Vacuum-Assisted Sorbent Extraction and GC-MS/MS.

Disinfection byproducts (DBPs) are ubiquitous environmental contaminants, which are present in virtually all drinking water and linked to detrimental health effects. Iodinated-DBPs are more cytotoxic and genotoxic than chloro- and bromo-DBPs and are formed during disinfection of iodide-containing source water. Liquid-liquid extraction (LLE) paired with gas chromatography (GC)-mass spectrometry (MS) has been the method of choice in the study of low molecular weight iodinated-DBPs; however, this method is laborious and time-consuming and struggles with complex matrices. We developed an environmentally friendly method utilizing headspace solid phase extraction with the application of vacuum to measure six iodinated-trihalomethanes (I-THMs) in drinking water and urine. Vacuum-assisted sorbent extraction (VASE) has the ability to exhaustively and rapidly extract volatile and semivolatile compounds from liquid matrices without the use of solvent. Using VASE with GC-MS/MS provides improved analyte recovery and reduced matrix interference compared to LLE. Additionally, VASE enables extraction of 30 samples simultaneously with minimal sample handling and improved method reproducibility. Using VASE with GC-MS/MS, we achieved quantification limits of 3-4 ng/L. This technique was demonstrated on drinking water from four cities, where five I-THMs were quantified at levels 10-33 times below comparable LLE methods with 10 times lower volumes of sample (10 mL vs 100 mL).

High efficiency removal of organic and inorganic iodine with ferrate[Fe(VI)] through oxidation and adsorption

I− is a halogen species existing in natural waters, and the transformation of organic and inorganic iodine in natural and artificial processes would impact the quality of drinking water. Herein, it was found that Fe(VI) could oxidize organic and inorganic iodine to IO3−and simultaneously remove the resulted IO3− through Fe(III) particles. For the river water, wastewater treatment plant (WWTP) effluent, and shale gas wastewater treated by 5 mg/L of Fe(VI) (as Fe), around 63 %, 55 % and 71 % of total iodine (total-I) had been removed within 10 min, respectively. Fe(VI) was superior to coagulants in removing organic and inorganic iodine from the source water. Adsorption kinetic analysis suggested that the equilibrium adsorption amount of I− and IO3− were 11 and 10.1 μg/mg, respectively, and the maximum adsorption capacity of IO3− by Fe(VI) resulted Fe(III) particles was as high as 514.7 μg/mg. The heterogeneous transformation of Fe(VI) into Fe(III) effectively improved the interaction probability of IO3− with iron species. Density functional theory (DFT) calculation suggested that the IO3− was mainly adsorbed in the cavity (between the γ-FeOOH shell and γ-Fe2O3 core) of Fe(III) particles through electrostatic adsorption, van der Waals force and hydrogen bond. Fe(VI) treatment is effective for inhibiting the formation of iodinated disinfection by-products in chlor(am)inated source water.

Evaluation of the DBP formation potential of biocides and identification of knowledge gaps in environmental risk assessment

Disinfectants and preservatives used as biocides may contain or release active substances (a.s.) that can form by-products with the surrounding matrices during their application which may be released into the environment. Over the past 40 years, several hundred of these so-called disinfection by-products (DBPs) have been detected after applications of biocides used for disinfection. Due to intensive research and further development of analytical capabilities, many new DBP classes, such as iodinated DBPs (I-DBPs), halonitromethanes (HNMs), haloacetamides (HaAms), or halomethanesulfonic acids were detected worldwide in various matrices and applications. Due to the possible hazards and risks for humans and the environment, frequently occurring DBP classes, such as trihalomethanes (THM), haloacetic acids (HAA) and nitrosamines (NDMA), have already been included in many legislations and given limit values. In the European Union, biocides are assessed under the Biocidal Products Regulation 528/2012 (BPR) regarding their efficacy, potential hazards, and risks to human health and the environment. However, the available guidance for the environmental risk assessment (ERA) of DBPs remains vague. To identify knowledge gaps and to further develop the assessment scheme for the ERA of DBPs, a literature search on the multiple uses of biocides and their formation potential of DBPs was performed and the existing process for ERA was evaluated. The results show knowledge gaps on the formation of DBP in non-aqueous systems and DBP formation by non-halogen-based biocidal active substances. Based on the literature research on biocides, a possible proposal of grouping a.s. to consider their DBP formation potential is presented to simplify future ERAs. However, this also requires further research. Until then, a pragmatic approach considering the DBPs formation potential of the active substances and the identified knowledge gaps need to be established for the environmental risk assessment of DBPs in the EU.Graphical

Leaching of organic matter and iodine, formation of iodinated disinfection by-products and toxic risk from Laminaria japonica during simulated household cooking

Iodinated disinfection by-products (I-DBPs) exhibited potential health risk owing to the high toxicity. Our recent study demonstrated that I-DBPs from Laminaria japonica (Haidai), the commonly edible seaweed, upon simulated household cooking condition were several hundred times more than the concentration of drinking water. Here, the characterization of Haidai and its leachate tandem with the formation, identification and toxicity of I-DBPs from the cooking of Haidai were systemically investigated. The dominant organic matter in Haidai leachate were polysaccharides, while the highest iodine specie was iodide (∼90% of total iodine). Several unknown I-DBPs generated from the cooking of Haidai were tentatively proposed, of which 3,5-diiodo-4-hydroxybenzaldehyde was dominant specie. Following a simulated household cooking with real chloraminated tap water, the presence of Haidai sharply increased aggregate iodinated trihalomethanes, iodinated haloacetic acids, and total organic iodine concentrations to 97.4 ± 7.6 μg/L,16.4 ± 2.1 μg/L, and 0.53 ± 0.06 mg/L, respectively. Moreover, the acute toxicity of Haidai soup to Vibrio qinghaiensis sp.-Q67 was around 7.3 times higher than that of tap water in terms of EC50. These results demonstrated that the yield of I-DBPs from the cooking of Haidai and other seaweed should be carefully considered.

In-depth insights into Fe(III)-doped g-C3N4 activated peracetic acid: Intrinsic reactive species, catalytic mechanism and environmental application

In this study, we demonstrate that Fe(III)-doped g-C3N4 can efficiently activate peracetic acid (PAA) to degrade electron-rich pollutants (e.g., sulfamethoxazole, SMX) over a wide pH range (3−7). Almost ∼100% high-valent iron-oxo species (Fe(V)) was generated and acted as the dominant reactive species responsible for the micropollutants oxidation based on the analysis result of quenching experiments, 18O isotope-labeling examination and methyl phenyl sulfoxide (PMSO) probe method. Electrochemical testing (e.g., amperometric i−t and linear sweep voltammetry (LSV)) and density functional theory (DFT) calculations illustrated that the main active site Fe atom and PAA underwent electron transfer to form Fe(V) for attacking SMX. Linear free energy relationship (LFER) between the pseudo-first-order rates of different substituted phenols (SPs) and the Hammett constant σ+ depicted the electrophilic oxidation properties. The selective oxidation of Fe(V) endows the established system remarkable anti-interference capacity against water matrices, while the Fe(V) lead to the formation of iodinated disinfection by-products (I-DBPs) in the presence of I−. Fe(III)-doped g-C3N4/PAA system showed excellent degradation efficiency of aquaculture antibiotics. This study enriches the knowledge and research of high-valent iron-oxo species and provides a novel perspective for the activation of PAA via heterogeneous iron-based catalysts and practical environmental applications.

Electrochemical activation of periodate with graphite electrodes for water decontamination: Excellent applicability and selective oxidation mechanism

Advanced oxidation technologies based on periodate (PI, IO4−) have garnered significant attention in water decontamination. In this work, we found that electrochemical activation using graphite electrodes (E-GP) can significantly accelerate the degradation of micropollutants by PI. The E-GP/PI system achieved almost complete removal of bisphenol A (BPA) within 15 min, exhibited unprecedented pH tolerance ranging from pH 3.0 to 9.0, and showed more than 90% BPA depletion after 20 h of continuous operation. Additionally, the E-GP/PI system can realize the stoichiometric transformation of PI into iodate, dramatically decreasing the formation of iodinated disinfection by-products. Mechanistic studies confirmed that singlet oxygen (1O2) is the primary reactive oxygen species in the E-GP/PI system. A comprehensive evaluation of the oxidation kinetics of 1O2 with 15 phenolic compounds revealed a dual descriptor model based on quantitative structure−activity relationship (QSAR) analysis. The model corroborates that pollutants exhibiting strong electron-donating capabilities and high pKa values are more susceptible to attack by 1O2 through a proton transfer mechanism. The unique selectivity induced by 1O2 in the E-GP/PI system allows it to exhibit strong resistance to aqueous matrices. Thus, this study demonstrates a green system for the sustainable and effective elimination of pollutants, while providing mechanistic insights into the selective oxidation behaviour of 1O2.

Evaluation and strategy for improving the quality of desalinated water.

Seawater desalination is practiced in many coastal countries, which is accepted as clean water by the general populations. The untreated seawater reported high concentrations of bromide (50,000 - 80,000µg/L) and iodide (21 - 60µg/L) ions, which are reduced to non-detectable levels during thermal desalination while the concentrations of bromide and iodide ions were reduced to 250-600µg/L and < 4-16µg/L, respectively during reverse osmosis processes. During the treatment and/or disinfection, many brominated and iodinated disinfection byproducts (Br-DBPs and I-DBPs) are formed in desalinated water, some of which are genotoxic and cytotoxic to the mammalian cells and possible/probable human carcinogens. In this paper, DBPs' formation in desalinated and blended water from source to tap, toxicity to the mammalian cells, their risks to humans and the strategies to control DBPs were investigated. The lifetime excess cancer risks from groundwater, and desalinated and blended water sourced DBPs were 4.15 × 10-6 (4.72 × 10-7 - 1.30 × 10-5), 1.75 × 10-5 (2.58 × 10-6 - 5.25 × 10-5) and 2.59 × 10-5 (4.02 × 10-6 - 8.35 × 10-5) respectively, indicating higher risks from desalinated and blended water (2.56 and 4.51 times respectively) than groundwater systems. Few emerging DBPs in desalinated/blended water showed higher cyto- and genotoxicity in the mammalian cells. The findings were compared with safe drinking water standards and strategies to produce cleaner desalinated water were demonstrated.

Impacts of hydraulic fracturing wastewater from oil and gas industries on drinking water: Quantification of 69 disinfection by-products and calculated toxicity

Oil and gas production generates large amounts of brine wastewater called “produced water” with various geogenic and synthetic contaminants. These brines are generally used in hydraulic fracturing operations to stimulate production. They are characterized by elevated halide levels, particularly geogenic bromide and iodide. Such salt concentrations in produced water may be as high as thousands of mg/L of bromide and tens of mg/L of iodide. Large volumes of produced water are stored, transported, reused in production operations, and ultimately disposed of by deep well injection into saline aquifers. Improper disposal may potentially contaminate shallow freshwater aquifers and impact drinking water sources. Because conventional produced water treatment typically does not remove halides, produced water contamination of groundwater aquifers may cause the formation of brominated and iodinated disinfection by-products (I-DBPs) at municipal water treatment plants. These compounds are of interest because of their higher toxicity relative to their chlorinated counterparts. This study reports a comprehensive analysis of 69 regulated and priority unregulated DBPs in simulated drinking waters fortified with 1 % (v/v) oil and gas wastewater. Impacted waters produced 1.3×–5× higher levels of total DBPs compared to river water after chlorination and chloramination. Individual DBP levels ranged from (<0.1–122 μg/L). Overall, chlorinated waters formed highest levels, including trihalomethanes that would exceed the U.S. EPA regulatory limit of 80 μg/L. Chloraminated waters had more I-DBP formation and highest levels of haloacetamides (23 μg/L) in impacted water. Calculated cytotoxicity and genotoxicity were higher for impacted waters treated with chlorine and chloramine than corresponding treated river waters. Chloraminated impacted waters had the highest calculated cytotoxicity, likely due to higher levels of more toxic I-DBPs and haloacetamides. These findings demonstrate that oil and gas wastewater if discharged to surface waters could adversely impact downstream drinking water supplies and potentially affect public health.

Overlooked Iodo-Disinfection Byproduct Formation When Cooking Pasta with Iodized Table Salt.

Iodized table salt provides iodide that is essential for health. However, during cooking, we found that chloramine residuals in tap water can react with iodide in table salt and organic matter in pasta to form iodinated disinfection byproducts (I-DBPs). While naturally occurring iodide in source waters is known to react with chloramine and dissolved organic carbon (e.g., humic acid) during the treatment of drinking water, this is the first study to investigate I-DBP formation from cooking real food with iodized table salt and chloraminated tap water. Matrix effects from the pasta posed an analytical challenge, necessitating the development of a new method for sensitive and reproducible measurements. The optimized method utilized sample cleanup with Captiva EMR-Lipid sorbent, extraction with ethyl acetate, standard addition calibration, and analysis using gas chromatography (GC)-mass spectrometry (MS)/MS. Using this method, seven I-DBPs, including six iodo-trihalomethanes (I-THMs) and iodoacetonitrile, were detected when iodized table salt was used to cook pasta, while no I-DBPs were formed with Kosher or Himalayan salts. Total I-THM levels of 11.1 ng/g in pasta combined with cooking water were measured, with triiodomethane and chlorodiiodomethane dominant, at 6.7 and 1.3 ng/g, respectively. Calculated cytotoxicity and genotoxicity of I-THMs for the pasta with cooking water were 126- and 18-fold, respectively, compared to the corresponding chloraminated tap water. However, when the cooked pasta was separated (strained) from the pasta water, chlorodiiodomethane was the dominant I-THM, and lower levels of total I-THMs (retaining 30% of the I-THMs) and calculated toxicity were observed. This study highlights an overlooked source of exposure to toxic I-DBPs. At the same time, the formation of I-DBPs can be avoided by boiling the pasta without a lid and adding iodized salt after cooking.

Unraveling the role of iodide in periodate-based water decontamination: Accelerated selective oxidation and formation of iodinated products

Periodate (PI)-based oxidation processes are garnering worldwide increasing attention in the oxidative water treatment field. Unfortunately, the influence of water constituents on the transformation-driven product formation and risks of organic micropollutants remains largely unknown. This study firstly reports that naturally occurring iodide (I−) greatly enhances the PI oxidation of multiple phenolic compounds (e.g., bisphenol A) under different application scenarios (e.g., solution pH and high salinity). Furthermore, an improved bacterial inactivation with 3-log reduction is found after 30 min of PI treatment in the presence of I−. Comparatively, such enhancement is not observed during PI/I− treatment of six non-phenolic contaminants such as sulfadiazine, atrazine, and carbamazepine. Multi-evidence explorations demonstrate hypoiodous acid (HOI) as the dominant oxidizing species for accelerated phenolic oxidation. Based on the high-resolution mass spectroscopic analysis, PI/I−-mediated transformation of bisphenols and 4-chlorophenol yields different iodinated aromatic products with enhanced persistence, bioaccumulation, and toxicity. Taken together, this investigation unveils that I− could selectively alter phenolics’ transformation behaviors and fate when using PI-based oxidation strategies in water. Particular concern should be concentrated on the treatment-driven secondary risks of iodinated aromatic products, which also behave as the precursors of highly toxic iodinated disinfection byproducts during water disinfection.

Fate and removal of iodinated X-ray contrast media in membrane bioreactor: Microbial dynamics and effects of different operational parameters

Iodinated X-ray contrast media (ICM) are mainly used in medical sector, and their presence in environmental waters is a cause of concern as they are capable of forming highly toxic iodinated disinfection byproducts. In the present study, the removal mechanisms of the three ICM- iohexol, iopromide, and iopamidol were elucidated in a lab-scale aerobic membrane bioreactor (MBR). At steady-state operation (solids retention time (SRT)- 70 days, organic loading rate (OLR)- 0.80 KgCOD/m3-day, nitrogen loading rate (NLR)- 0.08 KgNH4-N/m3-day, hydraulic retention time (HRT)- 12 h), the average removal of iohexol and iopromide was found to be 34.9 and 45.2 %, respectively, whereas iopamidol proved to be highly recalcitrant in aerobic conditions of the MBR (removal <10 % in all phases of the MBR operation). Further, through batch kinetic studies and mass balance analysis, it was observed that ICM were primarily biotransformed in the MBR system and biosorption (Kd < 10 L/Kg) was negligible. The biodegradation rate coefficient values (Kbiol) of the ICM were found to be <0.65 L/g-d which indicate that biotransformation rate of ICM was slow. Increased OLR (1.60 KgCOD/m3-day) and reduced SRT (20 days) were found to negatively affect the removal of the ICM. Further, the removal of ICM was found to depend on its initial concentration, and the increment in the ammonium loading (0.16 KgNH4-N/m3-day) did not favor its removal. The dosing of ICM altered the microbial dynamics of the mixed liquor and reduced the microbial diversity and richness. Bdellovibrio, Zoogloea, and bacteria belonging to TM7-3 class, Cryomorphaceae and Hyphomonadaceae families may contribute in ICM biotransformation.

Degradation of iopamidol in the permanganate/sulfite process: Evolution of iodine species and effect on the subsequent formation of disinfection by-products

Permanganate/sulfite (Mn(VII)/S(IV)) process is a promising pre-oxidation technology for sequestering the emerging organic contaminants in drinking water treatment plant. Iopamidol (IPM), a representative of iodinated X-ray contrast media, has been widely detected in water sources and has the risk of forming iodinated disinfection byproducts (I-DBPs) in water treatment system. In this study, we investigated the evolution of iodine species during the IPM degradation by the Mn(VII)/S(IV) process and its effect on the subsequent formation of I-DBPs during chlorination at pH 7.0 and 8.0. IPM could be effectively degraded in the Mn(VII)/S(IV) process at environmentally relevant pH (pH 7.0 and 8.0). The results of quenching and competitive oxidation kinetic experiments revealed that SO4·– was the major reactive oxidizing species contributing to the degradation of IPM whereas the contributions of HO· and reactive manganese species were negligible in the Mn(VII)/S(IV) process. I– and IO3– were generated while no HOI was detected during the degradation of IPM in the Mn(VII)/S(IV) process. The effects of IPM oxidation by Mn(VII)/S(IV) on the subsequent formation of chlorinated disinfection by-products (Cl-DBPs) during chlorination were related to the category of Cl-DBPs. The pre-oxidation of IPM by Mn(VII)/S(IV) resulted in the generation of I-DBPs during the disinfection process although no I-DBPs were detected if no pre-oxidation was applied. The finding of this study suggested that attention should be paid to the toxicity of DBPs when water containing iodinated organic contaminants is treated by Mn(VII)/S(IV) process or other pre-oxidation technologies.

Fe3+-enhanced zero valent iron/peroxymonosulfate (ZVI/PMS) process for the transformation of iopamidol during coagulation and reduction of iodinated disinfection by-products

The traditional coagulation process in drinking water treatment cannot effectively remove the organic precursors of highly toxic iodinated disinfection by-products (I-DBPs). This study proposes a combination of zero-valent iron (ZVI) and peroxymonosulfate (PMS) to remove the organic precursor of I-DBPs during the coagulation stage. This study investigated the degradation of iopamidol (IPM), a typical organic precursor of I-DBPs, by the combination of ZVI/peroxymonosulfate (PMS) and the influence on the generation of I-DBPs during disinfection. IPM was effectively decomposed by ZVI/PMS, because of the formation of hydroxyl (HO•) and sulfate (SO4•−) radicals. SO4•− was a major contributor (>64.7 %) to the degradation. The anions (Cl− and SO42−) in the conventional coagulants have a weak effect on the removal of IPM by the ZVI/PMS process, while the common cations (Fe3+) further enhance the removal of IPM by the ZVI/PMS process. The formation of I-THMs was obviously decreased during the chlorination of IPM in the presence of the ZVI/PMS process (14.4 μg/L) compared to that in the presence of the ZVI process (258.1 μg/L) and the chlorination alone process (29.7 μg/L). The formation of I-THMs was increased by more than 1.7-fold in the presence of natural organic matter (NOM). The presence of Fe3+ further reduced the formation of I-DBPs to below the limit of quantitation (LOQ). Therefore, it is feasible to use the ZVI/PMS process to degrade IPM in the coagulation stage of drinking water treatment, and it can also reduce the I-DBPs formed by subsequent disinfection.

Insights into the formation and mitigation of iodinated disinfection by-products during household cooking with Laminaria japonica (Haidai)

Iodinated disinfection by-products (I-DBPs) have attracted extensive interests because of their higher cytotoxicity and genotoxicity than their chlorinated and brominated analogues. Our recent studies have firstly demonstrated that cooking with seaweed salt could enhance the formation of I-DBPs with several tens of μg/L level. Here, I-DBP formation and mitigation from the reaction of disinfectant with Laminaria japonica (Haidai), an edible seaweed with highest iodine content, upon simulated household cooking process was systematically investigated. The total iodine content in Haidai ranged from 4.6 mg-I/g-Haidai to 10.0 mg-I/g-Haidai, and more than 90% of iodine is soluble iodide. During simulated cooking, the presence of disinfectant simultaneously decreased iodide by 15.0–32.8% to 2.7–5.8 mg/L and increased total organic iodine by 1.3–10.9 times to 0.5–1.8 mg/L in Haidai soup, proving I-DBP formation. The concentrations of iodinated trihalomethanes and haloacetic acids were at the levels of several hundreds of μg/L and several μg/L, respectively, which are 2–3 orders and 1–2 orders of magnitude more than those in drinking water. Effects of key factors including disinfectant specie, disinfectant dose, temperature and time on I-DBP formation were also ascertained, and temperature and disinfectant specie played a decisive role in the formation and speciation of I-DBPs. In order to avoid the potential health risk from the exposure of I-DBPs in Haidai soup, it is prerequisite to soak and wash dry Haidai sample over 30.0 min before cooking, which could effectively remove major soluble iodide. In general, this study provided the new insight into I-DBP formation from daily household cooking with Haidai and the corresponding enlightenment for inhabitants to eat Haidai in daily life.

Oxidation of iodide by PbO2, the major lead pipe corrosion product: Kinetics, mechanism and formation of toxic iodinated disinfection by-products

Lead oxide (PbO2) formed by the oxidation of lead pipes and lead-containing plumbing materials is an important corrosion product in some drinking water distribution systems. Under certain conditions it acts as an oxidant, and we report here the effects of pH on the oxidation of I¯ by PbO2, which leads to the formation of iodine (I2) and iodate (IO3¯) as well as dissolution of Pb2+. Oxidation of I¯ by PbO2 is a multi-step pH-dependent reaction, the rate of which can be expressed as: R = 6.92 × 109 × [SA]0.67 × [I¯]2.19 × [H+]0.59 (where SA is the PbO2 surface area). I2 was the major intermediate product formed along with some HOI, and was then further oxidized to IO3¯. Based on these results, a kinetic model was developed to simulate the evolution of I¯, I2 and IO3¯ in the PbO2/I¯ reaction system. In addition, the formation of iodinated disinfection by-products (I-DBPs) in the PbO2/I¯/NOM system was evaluated under different water quality conditions, and was found to be influenced by the form of the lead corrosion products in the order: Pb3O4 > PbO2 > Pb(CO3)2(OH)2 > PbCO3. Iodoform and monoiodoacetic acid were identified as the main I-DBPs, and their formation decreased with increasing pH. It is concluded that oxidation of I¯ by lead oxides in water distribution pipes probably contributes to the formation of I-DBPs as well as Pb2+ in tap water.

Fate and transformation of iodine species during Mn(VII)/sulfite treatment in iodide-containing water.

During oxidative treatment of iodide (I- )-containing waters, I- is easy to be oxidized into hypoiodous acid (HOI) by various oxidants and the further reaction of HOI with organic compounds can lead to the formation of iodinated disinfection by-products (I-DBPs). Oxidation of HOI to iodate (IO3 - ) or reduction of HOI to I- has been proposed to reduce the formation of I-DBPs. Because the reaction of HOI with sulfite proceeds rapidly, this study examined the fate of iodine and the formation of I-DBPs in Mn(VII)/sulfite process. Results showed that I- was oxidized to HOI but the further formation of IO3 - was suppressed due to the fast reduction of HOI to I- by sulfite. The reactions of HOI with SO3 2- and IO- with SO3 2- are the major pathways with species-specific second-order rate constants determined to be 1.12 × 105 M-1 s-1 and 9.43 × 107 M-1 s-1 , respectively. The rapid reaction of HOI with sulfite plays an essential role in minimizing the formation of iodinated products in HOI- and phenol-containing solutions. The toxic risk analysis showed that the toxicity of the generated DBPs from Mn(VII)/sulfite pre-oxidation followed by chlorination only changed slightly. PRACTITIONER POINTS: The decay of I- was negligible in Mn(VII)/sulfite process. The rapid reaction of HOI with SO3 2- resulted in the negligible generation of IO3 - . Mn(VII)/sulfite process exerted slight influence on the formation of I-DBPs. Mn(VII)/sulfite process is promising for the pretreatment of I- -containing water.

Removal of iodide anions in water by silver nanoparticles supported on polystyrene anion exchanger

The removal of iodide (I−) from source waters is an effective strategy to minimize the formation of iodinated disinfection by-products (DBPs), which are more toxic than their brominated and chlorinated analogues. In this work, a nanocomposite Ag-D201 was synthesized by multiple in situ reduction of Ag-complex in D201 polymer matrix, to achieve highly efficient removal of iodide from water. Scanning electron microscope /energy dispersive spectrometer characterization showed that uniform cubic silver nanoparticles (AgNPs) evenly dispersed in the D201 pores. The equilibrium isotherms data for iodide adsorption onto Ag-D201 was well fitted with Langmuir isotherm with the adsorption capacity of 533 mg/g at neutral pH. The adsorption capacity of Ag-D201 increased with the decrease of pH in acidic aqueous solution, and reached the maximum value of 802 mg/g at pH 2. This was attributed to the oxidization of I−, by dissolved oxygen under the catalysis of AgNPs, to I2 which was finally adsorbed as AgI3. However, the aqueous solutions at pH 7 – 11 could hardly affect the iodide adsorption. The adsorption of I− was barely affected by real water matrixes such as competitive anions (SO42−, NO3−, HCO3−, Cl−) and natural organic matter, of which interference of NOM was offset by the presence of Ca2+. The proposed synergistic mechanism for the excellent performance of iodide adsorption by the absorbent was ascribed to the Donnan membrane effect caused by the D201 resin, the chemisorption of I− by AgNPs, and the catalytic effect of AgNPs.

Effects of ultrasonication on the DBP formation and toxicity during chlorination of saline wastewater effluents

Chlorine disinfection of saline wastewater effluents rich in bromide and iodide forms relatively toxic brominated and iodinated disinfection byproducts (DBPs). Ultrasonication is a relatively new water treatment technology, and it is less sensitive to suspended solids in wastewaters. In this study, we examined the effects of ultrasonication (in terms of reactor type and combination mode with chlorination) on the DBP formation and toxicity in chlorinated primary and secondary saline wastewater effluents. Compared with the chlorinated wastewater effluent samples without ultrasonication, ultrasonic horn pretreatment of the wastewater effluent samples reduced the total organic halogen (TOX) levels in chlorination by ∼30%, but ultrasonic bath pretreatment of the wastewater samples did not significantly change the TOX levels in chlorination, which might be attributed to the higher energy utilization and decomposition extent of organic DBP precursors in the ultrasonic horn reactor. Moreover, the TOX levels in the chlorinated samples with ultrasonic horn pretreatment (USH–chlorination), simultaneous treatment (chlorination+USH) and subsequent treatment (chlorination–USH) were also significantly reduced, with the maximum TOX reductions occurring in the samples with ultrasonic horn pretreatment. A toxicity index was calculated by weighting and summing the levels of total organic chlorine, total organic bromine and total organic iodine in each treated sample. The calculated toxicity index values of the chlorinated wastewater effluent samples followed a descending rank order of “chlorination” > “chlorination+USH” > “chlorination–USH” > “USH–chlorination”, with the lowest toxicity occurring in the samples with ultrasonic horn pretreatment. Then, a developmental toxicity bioassay was conducted for each treated sample. The measured toxicity index values of the chlorinated wastewater samples followed the same descending rank order.

Synergistic cytotoxicity of binary combinations of inorganic and organic disinfection byproducts assessed by real-time cell analysis

Chlorine, chlorine dioxide, and ozone are widely used as disinfectants in drinking water treatments. However, the combined use of different disinfectants can result in the formation of various organic and inorganic disinfection byproducts (DBPs). The toxic interactions, including synergism, addition, and antagonism, among the complex DBPs are still unclear. In this study, we established and verified a real-time cell analysis (RTCA) method for cytotoxicity measurement on Chinese hamster ovary (CHO) cell. Using this convenient and accurate method, we assessed the cytotoxicity of a series of binary combinations consisting of one of the 3 inorganic DBPs (chlorite, chlorate, and bromate) and one of the 32 regulated and emerging organic DBPs. The combination index (CI) of each combination was calculated and evaluated by isobolographic analysis to reflect the toxic interactions. The results confirmed the synergistic effect on cytotoxicity in the binary combinations consisting of chlorite and one of the 5 organic DBPs (2 iodinated DBPs (I-DBPs) and 3 brominated DBPs (Br-DBPs)), chlorate and one of the 4 organic DBPs (3 aromatic DBPs and dibromoacetonitrile), and bromate and one of the 3 organic DBPs (2 I-DBPs and dibromoacetic acid). The possible synergism mechanism of organic DBPs on the inorganic ones may be attributed to the influence of organic DBPs on cell membrane and cell antioxidant system. This study revealed the toxic interactions among organic and inorganic DBPs, and emphasized the latent adverse outcomes in the combined use of different disinfectants.