氮化物在土层中的迁移与转化的研究

通过摸拟实验,研究了氮化物在土层中的迁移与转化作用。结果表明,土层对NH_4~+有很强的吸附作用,NH_4~+难以通过土层进入地下水中:NO_3~--N基本上不被土层吸附,能顺利通过土层进入地下水,故是地下水氮污染的主要形式。     

Concentration levels of disinfection by-products in 14 swimming pools of China

Swimming has become a popular exercising and recreational activity in China but little is known about the disinfection by-products (DBPs) concentration levels in the pools. This study was conducted as a survey of the DBPs in China swimming pools, and to establish the correlations between the DBP concentrations and the pool water quality parameters. A total of 14 public indoor and outdoor pools in Beijing were included in the survey. Results showed that the median concentrations for total trihalomethanes (TTHM), nine haloacetic acids (HAA9), chloral hydrate (CH), four haloacetonitriles (HAN4), 1,1-dichloropropanone, 1,1,1-trichloropropanone and trichloronitromethane were 33.8, 109.1, 30.1, 3.2, 0.3, 0.6 µg∙L⁻¹ and below detection limit, respectively. The TTHM and HAA9 levels were in the same magnitude of that in many regions of the world. The levels of CH and nitrogenous DBPs were greatly higher than and were comparable to that in typical drinking water, respectively. Disinfection by chlorine dioxide or trichloroisocyanuric acid could substantially lower the DBP levels. The outdoor pools had higher TTHM and HAA9 levels, but lower trihaloacetic acids (THAA) levels than the indoor pools. The TTHM and HAA9 concentrations could be moderately correlated with the free chlorine and total chlorine residuals but not with the total organic carbon (TOC) contents. When the DBP concentration levels from other survey studies were also included for statistical analysis, a good correlation could be established between the TTHM levels and the TOC concentration. The influence of chlorine residual on DBP levels could also be significant.     

饮用水有机类消毒副产物毒理学研究方法进展

伴随着饮用水消毒技术的改进,有机类消毒副产物(DBPs)的种类日趋多样化,其生物毒性和健康风险受到广泛关注。基于国内外对DBPs毒理学效应的研究成果,结合消毒技术的发展历程,对有机类DBPs进行了系统的分类,针对含碳消毒副产物(C-DBPs)和含氮消毒副产物(N-DBPs)中典型的DBPs的毒理学研究方法进行了详细的介绍,在此基础上分析了相关研究的不足之处和发展趋势,对今后的研究方向提出了建议。     

Assesment of disinfection by‐products removal by ozonation coupled with adsorption

This research work was performed to evaluate ozonation and granular activated carbon adsorption processes from the view‐point of controlling the formation of disinfection by products (DBPs). Both the humic acid and raw water were first preozonated and then adsorbed on the activated carbon to assess the potency for removal of total organic carbon (TOC) and DBPs. The disinfection by‐product including THMs and HAAs, in principle, can be successfully removed through a use of the ozonation and granular activated carbon (GAC) adsorption processes. However, in practice dealing with the raw water, it is necessary to introduce the pilot‐plant to obtain the design and operation guidelines for the water treatment plant through the ICA (Instrumentation Control and Automation) program in our future research work.     

Influencing factors of disinfection byproducts formation during chloramination of Cyclops metabolite solutions

Effects of reaction time, chlorine dosage, pH and temperature on the formation of disinfection byproducts(DBPs), were investigated during the chloramination of Cyclops metabolite solutions. The results showed that some species of DBPs like trichloromethane(TCM), dichloroacetic acid(DCAA) and trichloroacetic acid(TCAA) could accumulate to their respective stable values with a progressive elevation in reaction time and monochloramine concentration. And 1,1,1-2-trichloropropanone(1,1,1-TCP) content decreased correspondingly with a continuous increase of reaction time. The amounts of chloral hydrate(CH), chloropicrin(TCNM), 1,1,1-TCP and DCAA firstly increased and then decreased with increasing monochloramine doses. Higher temperature resulted in a decrease of CH, dichloroacetonitrile(DCAN), 1,1-dichloropropanone(1,1-DCP), 1,1,1-TCP, DCAA and TCAA concentration. pH affected the formation of the different DBPs distinctly. TCM accumulateded with the increase of pH under 9, and DCAA, TCAA, CH and 1,1-DCP decreased continuously with increasing pH from 5 to 10, and other DBPs had the maximum concentrations at pH 6–7.     

Characterization of halogenated DBPs and identification of new DBPs trihalomethanols in chlorine dioxide treated drinking water with multiple extractions

Chlorine dioxide(ClO_2) is a widely used alternative disinfectant due to its high biocidal efficiency and low-level formation of trihalomethanes and haloacetic acids. A major portion of total organic halogen(TOX), a collective parameter for all halogenated DBPs, formed in ClO_2-treated drinking water is still unknown. A commonly used pretreatment method for analyzing halogenated DBPs in drinking water is one-time liquid–liquid extraction(LLE), which may lead to a substantial loss of DBPs prior to analysis. In this study, characterization and identification of polar halogenated DBPs in a ClO_2-treated drinking water sample were conducted by pretreating the sample with multiple extractions. Compared to one-time LLE, the combined four-time LLEs improved the recovery of TOX by 2.3 times. The developmental toxicity of the drinking water sample pretreated with the combined four-time LLEs was 1.67 times higher than that pretreated with one-time LLE.With the aid of ultra-performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry, a new group of polar halogenated DBPs, trihalomethanols,were detected in the drinking water sample pretreated with multiple extractions; two of them,trichloromethanol and bromodichloromethanol, were identified with synthesized standard compounds. Moreover, these trihalomethanols were found to be the transformation products of trihalomethanes formed during ClO_2disinfection. The results indicate that multiple LLEs can significantly improve extraction efficiencies of polar halogenated DBPs and is a better pretreatment method for characterizing and identifying new polar halogenated DBPs in drinking water.     

Total organic halogen (TOX) in human urine: A halogen-specific method for human exposure studies

Disinfection by-products(DBPs) are a complex mixture of compounds unintentionally formed as a result of disinfection processes used to treat drinking water. Effects of long-term exposure to DBPs are mostly unknown and were the subject of recent epidemiological studies. However,most bioanalytical methods focus on a select few DBPs. In this study, a new comprehensive bioanalytical method has been developed that can quantify mixtures of organic halogenated compounds, including DBPs, in human urine as total organic chlorine(TOCl), total organic bromine(TOBr), and total organic iodine(TOI). The optimized method consists of urine dilution, adsorption to activated carbon, pyrolysis of activated carbon, absorption of gases in an aqueous solution, and halide analysis with ion chromatography and inductively coupled plasma-mass spectrometry. Spike recoveries for TOCl, TOBr, and TOI measurements ranged between 78% and 99%. Average TOCl, TOBr, and TOI concentrations in five urine samples from volunteers who consumed tap water were 1850, 82, and 21.0 μg/L as X~-, respectively.Volunteers who consumed spring water(control) had TOCl, TOBr, and TOI average concentrations in urine of 1090, 88, and 10.3 μg/L as X~-, respectively. TOCl and TOI in the urine samples from tap water consumers were higher than the control. However, TOBr was slightly lower in tap water urine samples compared to mineral water urine samples, indicating other sources of environmental exposure other than drinking water. A larger sample population that consumes tap water from different cities and mineral water is needed to determine TOCl, TOBr, and TOI exposure from drinking water.     

TIC-Tox: A preliminary discussion on identifying the forcing agents of DBP-mediated toxicity of disinfected water

The disinfection of drinking water is a major public health achievement; however, an unintended consequence of disinfection is the generation of disinfection by-products (DBPs). Many of the identified DBPs exhibit in vitro and in vivo toxicity, generate a diversity of adverse biological effects, and may be hazards to the public health and the environment. Only a few DBPs are regulated by several national and international agencies and it is not clear if these regulated DBPs are the forcing agents that drive the observed toxicity and their associated health effects. In this study, we combine analytical chemical and biological data to resolve the forcing agents associated with mammalian cell cytotoxicity of drinking water samples from three cities. These data suggest that the trihalomethanes (THMs) and haloacetic acids may be a small component of the overall cytotoxicity of the organic material isolated from disinfected drinking water. Chemical classes of nitrogen-containing DBPs, such as the haloacetonitriles and haloacetamides, appear to be the major forcing agents of toxicity in these samples. These findings may have important implications for the design of epidemiological studies that primarily rely on the levels of THMs to define DBP exposure among populations. The TIC-Tox approach constitutes a beginning step in the process of identifying the forcing agents of toxicity in disinfected water.     

Characteristics of typical dissolved black carbons and their influence on the formation of disinfection by-products in chlor(am)ination

● The physicochemical and structural properties of DBC were characterized. ● The effects of DBC on DBPs and DBPFP generation during disinfection were evaluated. ● The DBPs and DBPFP generation during chlor(am)ination were compared. Dissolved black carbon (DBC) released from biochar can be one of the potential disinfection by-products (DBPs) precursors in the dissolved organic matter pool. However, the physiochemical and structural properties of DBC and the effects on the development of DBPs and DBP formation potential (DBPFP) during the disinfection process remain unclear. In this study, the characteristics of two kinds of DBC, namely, animal-derived DBC (poultry litter DBC, PL-DBC) and plant-derived DBC (wheat straw DBC, WS-DBC), were investigated. The effects of different kinds of DBC on the evolution of DBPs and DBPFP in chlorine and chloramine disinfection processes were compared with natural organic matter (NOM). The results showed that the total DBPs concentrations derived from PL-DBC, WS-DBC and NOM were similar during chlorination (i.e., 61.23 μg/L, 64.59 μg/L and 64.66 μg/L, respectively) and chloramination (i.e., 44.63 μg/L, 44.42 μg/L and 45.58 μg/L, respectively). The lower total DBPs and DBPFP concentrations in chloramination could be attributed to the fact that the introduction of ammonia in chloramine inhibited the breaking of the bond between the disinfectant and the active group of the precursor. Additionally, DBC presented much lower total DBPFP concentrations than NOM in both chlorination and chloramination. However, both kinds of DBC tended to form more monochloroacetic acids and haloacetamides than NOM, which could result from the higher organic strength, higher protein matter, and nitrogen-rich soluble microbial products of DBC.     

Formation of disinfection by-products during sodium hypochlorite cleaning of fouled membranes from membrane bioreactors

•HAAs was dominant among the DBPs of interest. •Rising time, dose, temperature and pH raised TCM and HAAs but reduced HANs and HKs. •Low time, dose and temperature and non-neutrality pH reduced toxic risks of DBPs. •The presence of EPS decelerated the production of DBPs. •EPS, particularly polysaccharides were highly resistant to chlorine. Periodic chemical cleaning with sodium hypochlorite (NaClO) is essential to restore the membrane permeability in a membrane bioreactor (MBR). However, the chlorination of membrane foulants results in the formation of disinfection by-products (DBPs), which will cause the deterioration of the MBR effluent and increase the antibiotic resistance in bacteria in the MBR tank. In this study, the formation of 14 DBPs during chemical cleaning of fouled MBR membrane modules was investigated. Together with the effects of biofilm extracellular polymeric substances (EPS), influences of reaction time, NaClO dosage, initial pH, and cleaning temperature on the DBP formation were investigated. Haloacetic acids (HAAs) and trichloromethane (TCM), composed over 90% of the DBPs, were increasingly accumulated as the NaClO cleaning time extended. By increasing the chlorine dosage, temperature, and pH, the yield of TCM and dichloroacetic acid (DCAA) was increased by up to a factor of 1‒14, whereas the yields of haloacetonitriles (HANs) and haloketones (HKs) were decreased. Either decreasing in the chlorine dosage and cleaning temperature or adjusting the pH of cleaning reagents toward acidic or alkaline could effectively reduce the toxic risks caused by DBPs. After the EPS extraction pretreatment, the formation of DBPs was accelerated in the first 12 h due to the damage of biofilm structure. Confocal laser scanning microscopy (CLSM) images showed that EPS, particularly polysaccharides, were highly resistant to chlorine and might be able to protect the cells exposed to chlorination.