Neutral degradates of chloroacetamide herbicides: occurrence in drinking water and removal during conventional water treatment

Treated drinking water samples from 12 water utilities in the Midwestern United States were collected during Fall 2003 and Spring 2004 and were analyzed for selected neutral degradates of chloroacetamide herbicides, along with related compounds. Target analytes included 20 neutral chloroacetamide degradates, six ionic chloroacetamide degradates, four parent chloroacetamide herbicides, three triazine herbicides, and two neutral triazine degradates. In the fall samples, 17 of 20 neutral chloroacetamide degradates were detected in the finished drinking water, while 19 of 20 neutral chloroacetamide degradates were detected in the spring. Median concentrations for the neutral chloroacetamide degradates were ∼2-60 ng/L during both sampling periods. Concentrations measured in the fall samples of treated water were nearly the same as those measured in source waters, despite the variety of treatment trains employed. Significant removals (average of 40% for all compounds) were only found in the spring samples at those utilities that employed activated carbon.     

Formation and removal of mutagenic activity during drinking water preparation

The influence of different treatment processes on the mutagenic activity (Ames test) and some chemical parameters in water were investigated in a few waterworks. Application of a chlorine treatment generally increased the direct and promutagenic activity, but the extent increase proved to be dependent on the type of water chlorinated. The use of ozone in the preparation of drinking water decreased the mutagenic activity in the water. The extent reduction was also dependent on the type of water ozonated. Dune filtration greatly reduced the mutagenic activity. Slow sand filtration could not be evaluated, because of the toxicity of the organic concentrates for the bacterial strains. Granular activated carbon filters, in operation for about 1 year, reduced the mutagenic activity below the detection level. A similar filter which has operated for more than 1.5 years in a pilot plant, showed a breakthrough of mutagenic activity, suggesting that carbon filters are able to remove organic mutagens for a limited period. The results of the chemical parameters measured before and after the different treatment processes showed that none of these parameters were a reliable indicator for the mutagenic activity.     

Occurrence and removal of pharmaceuticals and hormones through drinking water treatment

The occurrence of fifty-five pharmaceuticals, hormones and metabolites in raw waters used for drinking water production and their removal through a drinking water treatment were studied. Thirty-five out of fifty-five drugs were detected in the raw water at the facility intake with concentrations up to 1200 ng/L. The behavior of the compounds was studied at each step: prechlorination, coagulation, sand filtration, ozonation, granular activated carbon filtration and post-chlorination; showing that the complete treatment accounted for the complete removal of all the compounds detected in raw waters except for five of them. Phenytoin, atenolol and hydrochlorothiazide were the three pharmaceuticals most frequently found in finished waters at concentrations about 10 ng/L. Sotalol and carbamazepine epoxide were found in less than a half of the samples at lower concentrations, above 2 ng/L. However despite their persistence, the removals of these five pharmaceuticals were higher than 95%.     

Organic arsenic removal from drinking water

Arsenic occurs in both inorganic and organic forms in water. Although various methods have been adopted to remove inorganic species of arsenic from drinking water, not much emphasis has been given to the removal of organic species of arsenic. In the present study column studies were conducted using manganese greensand (MGS), iron oxide-coated sand (IOCS-1 and IOCS-2) and ion exchange resin in Fe³⁺ form, to examine the removal of organic arsenic (dimethylarsinate) spiked to required concentrations in tap water. Batch studies were conducted with IOCS-2, and the results showed that the organic arsenic adsorption capacity was 8 μg/g IOCS-2. Higher bed volumes (585 BV) and high arsenic removal capacity (5.7 μg/cm³) were achieved by the ion exchange resin among all the media studied. Poor performance was observed with MGS and IOCS-1.     

Endotoxins, algae and Limulus amoebocyte lysate test in drinking water

Field and laboratory studies were conducted to determine the distribution of algae and bacteria, and investigate sources of endotoxins (lipopolysaccharides) in drinking water. The field survey was performed on five drinking water systems located in Allegheny County, Pennsylvania during the spring and summer of 1978. The highest concentrations of phytoplankton were found in uncovered finished water reservoirs. The major source of “endotoxic” response as measured by the Limulus amoebocyte lysate (LAL) gelation test was a non-specific reaction caused by algae. This was documented by a highly positive correlation of phytoplankton concentrations occurring in the reservoirs with respective LAL titers. Chlorella vulgaris (Chlorophyta) was the most common alga, whereas Schizothrix calcicola was the most dominant Cyanobacterium found in the five water systems. LAL gelation test with C. vulgaris grown in the laboratory verified the phenomenon observed on samples collected in the field and indicated a non-specific reaction, whereas S. calcicola cultures under identical conditions produced a specific response. Alkali and lysozyme treatments were successful in distinguishing specific and non-specific LAL reactions. These two techniques in conjunction with LAL test are recommended for drinking water quality assessment.     

Modelling the removal of p-TSA (para-toluenesulfonamide) during rapid sand filtration used for drinking water treatment

A finite element model was set-up to determine degradation rate constants for p-TSA during rapid sand filtration (RSF). Data used for the model originated from a column experiment carried out in the filter hall of a drinking water treatment plant in Berlin (Germany). Aerated abstracted groundwater was passed through a 1.6 m long column-shaped experimental sand filter applying infiltration rates from 2 to 6 m h⁻¹. Model results were fitted to measured profiles and breakthrough curves of p-TSA for different infiltration rates using both first-order reaction kinetics and Michaelis-Menten kinetics. Both approaches showed that degradation rates varied both in space and time. Higher degradation rates were observed in the upper part of the column, probably related to higher microbial activity in this zone. Measured and simulated breakthrough curves revealed an adaption phase with lower degradation rates after infiltration rates were changed, followed by an adapted phase with more elevated degradation rates. Irrespective of the mathematical approach and the infiltration rate, degradation rates were very high, probably owing to the fact that filter sands have been in operation for decades, receiving high p-TSA concentrations with the raw water.     

New chlorinated amphetamine-type-stimulants disinfection-by-products formed during drinking water treatment

Previous studies have demonstrated high removal rates of amphetamine-type-stimulants (ATSs) through conventional drinking water treatments; however the behaviour of these compounds through disinfection steps and their transformation into disinfection-by-products (DBPs) is still unknown. In this work, for the first time, the reactivity of some ATSs such as amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA) and 3,4-methylenedioxyethylamphetamine (MDEA) with chlorine has been investigated under simulated and real drinking water treatment conditions in order to evaluate their ability to give rise to transformation products. Two new DBPs from these illicit drugs have been found. A common chlorinated-by-product (3-chlorobenzo)-1,3-dioxole, was identified for both MDA and MDEA while for MDMA, 3-chlorocatechol was found. The presence of these DBPs in water samples collected through drinking water treatment was studied in order to evaluate their formation under real conditions. Both compounds were generated through treatment from raw river water samples containing ATSs at concentration levels ranging from 1 to 15 ng/L for MDA and from 2.3 to 78 ng/L for MDMA. One of them, (3-chlorobenzo)-1,3-dioxole, found after the first chlorination step, was eliminated after ozone and GAC treatment while the MDMA DBP mainly generated after the postchlorination step, showed to be recalcitrant and it was found in final treated waters at concentrations ranging from 0.5 to 5.8 ng/L.     

Characterization of bromate-reducing bacterial isolates and their potential for drinking water treatment

The objective of the current study was to isolate and characterize several bromate-reducing bacteria and to examine their potential for bioaugmentation to a drinking water treatment process. Fifteen bromate-reducing bacteria were isolated from three sources. According to 16S rRNA gene sequencing, the bromate-reducing bacteria are phylogenetically diverse, representing the Actinobacteria, Bacteroidetes, Firmicutes, and α-, β-, and γ-Proteobacteria. The broad diversity of bromate-reducing bacteria suggests the widespread capability for microbial bromate reduction. While the cometabolism of bromate via nitrate reductase and (per)chlorate reductase has been postulated, five of our bromate-reducing isolates were unable to reduce nitrate or perchlorate. This suggests that a bromate-specific reduction pathway might exist in some microorganisms. Bioaugmentation of activated carbon filters with eight of the bromate-reducing isolates did not significantly decrease start-up time or increase bromate removal as compared to control filters. To optimize bromate reduction in a biological drinking water treatment process, the predominant mechanism of bromate reduction (i.e., cometabolic or respiratory) needs to be assessed so that appropriate measures can be taken to improve bromate removal.     

Polar nitrogen compounds and their behaviour in the drinking water treatment process

Aliphatic and alicyclic amines as well as ethanolamines are extremely polar compounds, frequently found in the environment, and some of them have high toxicity. To address the contamination of selected German surface waters examined and the importance of bank filtration in Eastern Germany, investigations on the behaviour of polar organic nitrogen compounds during water treatment were carried out. Test conditions were designed appropriately for drinking water treatment conditions, and the tests were carried out using model water as well as bank filtrate. Test filter studies of microbial degradation of selected compounds demonstrated the following order of biodegradability: ethanolamine > dimethylamine > pyrrolidine > ethylenediamine. piperidine > diethylamine > morpholine > piperazine > cyclohexylamine. Flocculation tests using iron salts as well as aluminium salts as coagulants showed very low removal rates for the amines. The best results for the removal of the polar organic nitrogen compounds from the water were obtained using ozonation. Based on the reaction-rate constants, the order of degradation by ozone is: piperazine > morpholine > ethylenediamine > piperidine, cyclohexylamine > dimethylamine > ethanolamine > pyrrolidine > diethylamine. Disinfection by chlorine-containing agents under drinking water treatment conditions did not give effective elimination of the selected polar nitrogen compounds.     

Detection and estimation of potentially toxic cyanobacteria in raw water at the drinking water treatment plant by in vivo fluorescence method

In vivo fluorescence methods have been accepted as a quick, simple, and useful tool for quantification of phytoplankton organisms. In this paper, we present a case study in which fluorescence methods were employed for the selective detection of potentially toxic cyanobacteria in raw water at the drinking water treatment plant. The occurrence of cyanobacteria in the drinking water reservoir and in raw water was monitored by phycocyanin fluorescence measurements and by standard methods for phytoplankton quantification (cell counts, chlorophyll a). A special attention was paid to the most critical parts of the season -- spring recruitment of cyanobacteria from sediment to water column and autumn bloom collapse. All methods showed similar patterns within the season. Phycocyanin fluorescence was found to be a simple and sensitive indicator of cyanobacteria in water and can serve as a tool that can provide an early warning about the presence of potentially toxic cyanobacterial metabolites in water.     

Phototransformation of selected pharmaceuticals during UV treatment of drinking water

The kinetics of Ultraviolet C (UV-C)-induced direct phototransformation of four representative pharmaceuticals, i.e., 17alpha-ethinylestradiol (EE2), diclofenac, sulfamethoxazole, and iopromide, was investigated in dilute solutions of pure water buffered at various pH values using a low-pressure and a medium-pressure mercury arc lamp. Except for iopromide, pH-dependent rate constants were observed, which could be related to acid-base equilibria. Quantum yields for direct phototransformation were found to be largely wavelength-independent, except for EE2. This compound, which also had a rather inefficient direct phototransformation, mainly underwent indirect phototransformation in natural water samples, while the UV-induced depletion of the other pharmaceuticals appeared to be unaffected by the presence of natural water components. At the UV-C (254 nm) drinking-water disinfection fluence (dose) of 400 Jm(-2), the degree of depletion of the select pharmaceuticals at pH=7.0 in pure water was 0.4% for EE2, 27% for diclofenac, 15% for sulfamethoxazole, and 15% for iopromide, indicating that phototransformation should be seriously taken into account when evaluating the possibility of formation of UV transformation products from pharmaceuticals present as micropollutants.     

Organic micropollutant removal from wastewater effluent-impacted drinking water sources during bank filtration and artificial recharge

Natural treatment systems such as bank filtration (BF) and artificial recharge (via an infiltration basin) are a robust barrier for many organic micropollutants (OMPs) and may represent a low-cost alternative compared to advanced drinking water treatment systems. This study analyzes a comprehensive database of OMPs at BF and artificial recharge (AR) sites located near Lake Tegel in Berlin (Germany). The focus of the study was on the derivation of correlations between the removal efficiencies of OMPs and key factors influencing the performance of BF and AR. At the BF site, shallow monitoring wells located close to the Lake Tegel source exhibited oxic conditions followed by prolonged anoxic conditions in deep monitoring wells and a production well. At the AR site, oxic conditions prevailed from the recharge pond along monitoring wells to the production well. Long residence times of up to 4.5 months at the BF site reduced the temperature variation during soil passage between summer and winter. The temperature variations were greater at the AR site as a consequence of shorter residence times. Deep monitoring wells and the production well located at the BF site were under the influence of ambient groundwater and old bank filtrate (up to several years of age). Thus, it is important to account for mixing with native groundwater and other sources (e.g., old bank filtrate) when estimating the performance of BF with respect to removal of OMPs. Principal component analysis (PCA) was used to investigate correlations between OMP removals and hydrogeochemical conditions with spatial and temporal parameters (e.g., well distance, residence time and depth) from both sites. Principal component-1 (PC1) embodied redox conditions (oxidation-reduction potential and dissolved oxygen), and principal component-2 (PC2) embodied degradation potential (e.g., total organic carbon and dissolved organic carbon) with the calcium carbonate dissolution potential (Ca²⁺ and HCO₃⁻) for the BF site. These two PCs explained a total variance of 55% at the BF site. At the AR site, PCA revealed redox conditions (PC1) and degradation potential with temperature (PC2) as principal components, which explained a total variance of 56%.     

Effect of pathogen concentrations on removal of Cryptosporidium and Giardia by conventional drinking water treatment

The presence of waterborne enteric pathogens in municipal water supplies contributes risk to public health. To evaluate the removal of these pathogens in drinking water treatment processes, previous researchers have spiked raw waters with up to 10(6) pathogens/L in order to reliably detect the pathogens in treated water. These spike doses are 6-8 orders of magnitude higher than pathogen concentrations routinely observed in practice. In the present study, experiments were conducted with different sampling methods (i.e., grab versus continuous sampling) and initial pathogen concentrations ranging from 10(1) to 10(6) pathogens/L. Results showed that Cryptosporidium oocyst and Giardia cyst removal across conventional treatment were dependent on initial pathogen concentrations, with lower pathogen removals observed when lower initial pathogen spike doses were used. In addition, higher raw water turbidity appeared to result in higher log removal for both Cryptosporidium oocysts and Giardia cysts.     

Dispersion of C60 in natural water and removal by conventional drinking water treatment processes

The first objective of this study is to examine the fate of C₆₀ under two disposal scenarios through which pristine C₆₀ is introduced to water containing natural organic matter (NOM). A method based on liquid-liquid extraction and HPLC to quantify nC₆₀ in water containing NOM was also developed. When pristine C₆₀ was added to water either in the form of dry C₆₀ or in organic solvent, it formed water stable aggregates with characteristics similar to nC₆₀ prepared by other methods reported in the literature. The second objective of this study is to examine the fate of the nC₆₀ in water treatment processes, which are the first line of defense against ingestion from potable water - a potential route for direct human consumption. Results obtained from jar tests suggested that these colloidal aggregates of C₆₀ were efficiently removed by a series of alum coagulation, flocculation, sedimentation and filtration processes, while the efficiency of removal dependent on various parameters such as pH, alkalinity, NOM contents and coagulant dosage. Colloidal aggregates of functionalized C₆₀ could be well removed by the conventional water treatment processes but with lesser efficiency compared to those made of pristine C₆₀.     

Relating freshwater organic matter fluorescence to organic carbon removal efficiency in drinking water treatment

Monthly raw and clarified water samples were obtained for 16 UK surface water treatment works. The fluorescence excitation-emission matrix (EEM) technique was used for the assessment of total organic carbon (TOC) removal and organic matter (OM) characterisation. The impact of algae presence in water on TOC removal, and its relationship with fluorescence, was analysed. Fluorescence peak C intensity was found to be a sensitive and reliable measure of OM content. Fluorescence peak C emission wavelength and peak T intensity (reflecting the degree of hydrophobicity and the microbial fraction, respectively) were found to characterize the OM; the impact of both on TOC removal efficiency was apparent. OM fluorescence properties were shown to predict TOC removal, and identify spatial and temporal variations. Previous work indicates that the trihalomethane (THM) concentration of treated water can be predicted from the raw water TOC concentration. The simplicity, sensitivity, speed of analysis and low cost, combined with potential for incorporation into on-line monitoring systems, mean that fluorescence spectroscopy offers a robust analytical technique to be used in conjunction with, or in place of, other approaches to OM characterisation and THM formation prediction.     

纳滤用于饮用水深度处理的研究

采用纳滤膜对某市自来水进行深度处理试验,研究了纳滤对自来水中有机物及离子等的去除效果.结果表明,采用一级纳滤工艺,在回收率为70%的情况下,能有效去除自来水中的有机物、离子、内分泌干扰物和细菌等.对CODMn浊度、Cr6+和阿特拉津的平均去除率分别为81.06%,85.47%,77.20%和83.90%;对总硬度和阴离子的去除率保持在一个适中的水平;出水中未检测出细菌.     

饮用水的臭氧氧化技术

通过介绍臭氧在饮用水处理中的应用，分析了臭氧处理系统的功能及其与污染物的反应机理。臭氧氧化技术与其他处理方法的联用在给水深度净化领域有十分广阔的应用前景。     

Formation of linear aldehydes during surface water preozonization and their removal in water treatment in relation to mutagenic activity and sum parameters

Low molecular weight aldehydes were formed during surface water preozonization, their levels showing a positive correlation with increasing ozone dose applied and with increasing water temperature. A strong negative correlation was observed between aldehyde levels and U.V. absorbance at 254 nm.Coagulation had no influence on the aldehydes present and the influence of rapid double layer filtration varied strongly with temperature : significant removals were only observed above 10°C.Mutagenic activity generated by preozonization in Salmonella typhimurium TA98 shows an ozone dose depending relationship different from the formation of linear aldehydes. Its removal by coagulation is not effective but rapid double layer filtration reduces mutagenic activity to marginal levels.In this respect too no clear parallel can be drawn between the presence of low molecular weight aldehydes and mutagenic activity.