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.     

饮用水中溴酸盐控制方法和去除技术研究进展

溴酸盐是一种潜在致癌物,通常产生于含溴离子水源水的臭氧消毒过程中,我国和世界卫生组织饮用水标准中规定溴酸盐的最高浓度为10μg/L。重点综述了近7年来溴酸盐生成的控制方法(如优化臭氧投加量、降低溶液pH值、加氨等)以及溴酸盐离子去除技术(如吸附法、还原法、离子交换法、生物法等)的研究进展,并对各种技术的优缺点进行了评述。     

Inhibition of bromate formation by reduced graphene oxide supported cerium dioxide during ozonation of bromide-containing water

GO or RGO promotes bromate formation during ozonation of bromide-containing water. CeO₂/RGO significantly inhibits bromate formation compared to RGO during ozonation. CeO₂/RGO shows an enhancement on DEET degradation efficiency during ozonation. Ozone (O₃) is widely used in drinking water disinfection and wastewater treatment. However, when applied to bromide-containing water, ozone induces the formation of bromate, which is carcinogenic. Our previous study found that graphene oxide (GO) can enhance the degradation efficiency of micropollutants during ozonation. However, in this study, GO was found to promote bromate formation during ozonation of bromide-containing waters, with bromate yields from the O₃/GO process more than twice those obtained using ozone alone. The promoted bromate formation was attributed to increased hydroxyl radical production, as confirmed by the significant reduction (almost 75%) in bromate yield after adding t-butanol (TBA). Cerium oxide (less than 5 mg/L) supported on reduced GO (xCeO₂/RGO) significantly inhibited bromate formation during ozonation compared with reduced GO alone, and the optimal Ce atomic percentage (x) was determined to be 0.36%, achieving an inhibition rate of approximately 73%. Fourier transform infrared (FT-IR) spectra indicated the transformation of GO into RGO after hydrothermal treatment, and transmission electron microscope (TEM) results showed that CeO₂ nanoparticles were well dispersed on the RGO surface. The X-ray photoelectron spectroscopy (XPS) spectra results demonstrated that the Ce³⁺/Ce⁴⁺ ratio in xCeO₂/RGO was almost 3‒4 times higher than that in pure CeO₂, which might be attributed to the charge transfer effect from GO to CeO₂. Furthermore, Ce³⁺ on the xCeO₂/RGO surface could quench Br⋅ and BrO⋅ to further inhibit bromate formation. Meanwhile, 0.36CeO₂/RGO could also enhance the degradation efficiency of N,N-diethyl-m-toluamide (DEET) in synthetic and reclaimed water during ozonation.     

离子色谱法测定水体中溴酸根

采用离子色谱法测定水中溴酸盐的浓度。该方法操作简单,对水中溴酸盐进行了准确的定量分析,SUPPER5分离柱可以有效的使溴酸盐与其它阴离子分离。     

离子色谱法测定地表水和饮用水中亚氯酸盐、溴酸盐和氯酸盐

采用KOH梯度淋洗离子色谱法测定地表水和饮用水中ClO2-、BrO3-和ClO3-,在试验确定的条件下,3种离子与F-、Cl-、NO2-、NO3-、SO2-4、Br-、I-等7种离子分离度良好。 ClO2-、BrO3-、ClO3-在50．0μg/L～1000μg/L范围内线性良好,检出限分别为5．2μg/L、8．9μg/L、7．6μg/L,环境水样加标平行测定的RSD分别为2．1％～5．4％、4．1％～5．4％、2．5％～4．8％,两个质量浓度水平加标的平均回收率分别为93．7％～96．5％、90．3％～94．8％、98．7％～111％。     

Catalytic reduction of water pollutants: knowledge gaps,lessons learned,and new opportunities

● Advances, challenges, and opportunities for catalytic water pollutant reduction. ● Cases of Pd-based catalysts for nitrate, chlorate, and perchlorate reduction. ● New functionalities developed by screening and design of catalytic metal sites. ● Facile catalyst preparation approaches for convenient catalyst optimization. ● Rational design and non-decorative effort are essential for future work. In this paper, we discuss the previous advances, current challenges, and future opportunities for the research of catalytic reduction of water pollutants. We present five case studies on the development of palladium-based catalysts for nitrate, chlorate, and perchlorate reduction with hydrogen gas under ambient conditions. We emphasize the realization of new functionalities through the screening and design of catalytic metal sites, including (i) platinum group metal (PGM) nanoparticles, (ii) the secondary metals for improving the reaction rate and product selectivity of nitrate reduction, (iii) oxygen-atom-transfer metal oxides for chlorate and perchlorate reduction, and (iv) ligand-enhanced coordination complexes for substantial activity enhancement. We also highlight the facile catalyst preparation approach that brought significant convenience to catalyst optimization. Based on our own studies, we then discuss directions of the catalyst research effort that are not immediately necessary or desirable, including (1) systematic study on the downstream aspects of under-developed catalysts, (2) random integration with hot concepts without a clear rationale, and (3) excessive and decorative experiments. We further address some general concerns regarding using H₂ and PGMs in the catalytic system. Finally, we recommend future catalyst development in both “fundamental” and “applied” aspects. The purpose of this perspective is to remove major misconceptions about reductive catalysis research and bring back significant innovations for both scientific advancements and engineering applications to benefit environmental protection.     

The role of metal oxides on oxidant decay and disinfection byproduct formation in drinking waters: Relevance to distribution systems

Maintaining a residual disinfectant/oxidant (e.g., chlorine and chlorine dioxide), is a generally used strategy to control microbial contaminants and bacterial regrowth in distribution systems. Secondarily oxidant, such as hypobromous acid (HOBr), can be formed during chlorination of bromide-containing waters. The decay of oxidants and formation of disinfection byproducts (DBPs) due to the interaction between oxidants and selected metal oxides were studied. Selected metal oxides generally enhanced the decay of these halogen-containing oxidants via three pathways: (1) catalytic disproportionation to yield an oxidized form of halogen (i.e., halate) and reduced form (halide for chlorine and bromine or chlorite for chlorine dioxide), (2) oxygen formation, and (3) oxidation of a metal in a reduced form (e.g., cuprous oxide) to a higher oxidation state. Cupric oxide (CuO) and nickel oxide (NiO) showed significantly strong abilities for the first pathway, and oxygen formation was a side reaction. Cuprous oxide can react with oxidants via the third pathway, while goethite was not involved in these reactions. The ability of CuO on catalytic disproportionation of HOBr remained stable up to four cycles. In chlorination process, bromate formation tends to be important (exceeding 10 µg/L) when initial bromide concentration is above 400 µg/L in the presence of dissolved organic matter. Increasing initial bromide concentrations increased the formation of DBPs and calculated cytotoxicity, and the maximum was observed at pH 8.6 during chlorination process. Therefore, the possible disinfectant loss and DBP formation should be carefully considered in drinking water distribution systems.     

离子色谱双通道同时分析矿泉水中阴阳离子

建立了一种离子色谱双通道同时检测矿泉水中阴阳离子的方法。阴离子通道选择摘要SH-Anion-013的阴离子色谱柱,洗脱液为3.6mmol/LNa3CO2,流速0.7mL/min,采用抑制电导的检测模式。阳离子通道选择,SH-Cation-012的阳离子色谱柱,洗脱液为3.0mmol/L甲烷磺酸,流速1.0mL/min,采用直接电导的检测方法。结果表明,待测离子线性范围宽,相关性好(R>0.999)精密度高(RSD≤2.35%)实际样品加标回收率在92.5%~103.8%之间,完全满足检测要求,适用于矿泉水中阴阳离子的检测。