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%.     

Rejection of pharmaceuticals in nanofiltration and reverse osmosis membrane drinking water treatment

This paper investigates the removal of a broad range of pharmaceuticals during nanofiltration (NF) and reverse osmosis (RO) applied in a full-scale drinking water treatment plant (DWTP) using groundwater. Pharmaceutical residues detected in groundwater used as feed water in all five sampling campaigns were analgesics and anti-inflammatory drugs such as ketoprofen, diclofenac, acetaminophen and propyphenazone, beta-blockers sotalol and metoprolol, an antiepileptic drug carbamazepine, the antibiotic sulfamethoxazole, a lipid regulator gemfibrozil and a diuretic hydrochlorothiazide. The highest concentrations in groundwater were recorded for hydrochlorothiazide (58.6-2548ngL(-1)), ketoprofen (85%). Deteriorations in retentions on NF and RO membranes were observed for acetaminophen (44.8-73 %), gemfibrozil (50-70 %) and mefenamic acid (30-50%). Furthermore, since several pharmaceutical residues were detected in the brine stream of NF and RO processes at concentrations of several hundreds nanogram per litre, its disposal to a near-by river can represent a possible risk implication of this type of treatment.     

Release of organic matter in a discontinuously chlorinated drinking water network

The effects of discontinuous chlorination on the characteristics of the water in a pilot drinking water distribution network were investigated. The release or consumption of organic matter (as dissolved organic carbon, DOC) following chlorination and non-chlorination periods were estimated, as were changes in bacterial cell production. In each unchlorinated network 0.3 mg DOCl(-1) was consumed and the average cell production was approximately 1.3 x 10(5) cells ml(-1). In discontinously chlorinated networks (chlorine treatment: 3.3 mg Cl2l(-1), chlorine residual: 0.1 mg Cl2l(-1)) the DOC release (DOCout-DOCin) was between 0.1 and 0.2 mg Cl(-1). Biomass production (cells(out)-cells(in)) during this chlorination period was lower (approximately 2 x 10(4) cells ml(-1)). The delay before DOC was released in chlorinated networks appeared to be less than 24 h, which corresponds to one hydraulic residence time. Likewise, when chlorination was stopped, 24 h or less were required before an efficient DOC removal was resumed. When chlorination was prolonged the observed release of DOC was progressively reduced from 0.2 mg l(-1) to zero, thus after 6 weeks of continuous chlorination the DOCin was equivalent to the DOCout.     

Persistence and decontamination of surrogate radioisotopes in a model drinking water distribution system

Contamination of a model drinking water system with surrogate radioisotopes was examined with respect to persistence on and decontamination of infrastructure surfaces. Cesium and cobalt chloride salts were used as surrogates for cesium-137 and cobalt-60. Studies were conducted in biofilm annular reactors containing heavily corroded iron surfaces formed under shear and constantly submerged in drinking water. Cesium was not detected on the corroded iron surface after equilibration with 10 and 100 mg L⁻¹ solutions of cesium chloride, but cobalt was detected on corroded iron coupons at both initial concentrations. The amount of adhered cobalt decreased over the next six weeks, but was still present when monitoring stopped. X-ray absorption near-edge spectroscopy (XANES) showed that adhered cobalt was in the III oxidation state. The adsorbed cobalt was strongly resistant to decontamination by various physicochemical methods. Simulated flushing, use of free chlorine and dilute ammonia were found to be ineffective whereas use of aggressive methods like 14.5 M ammonia and 0.36 M sulfuric acid removed 37 and 92% of the sorbed cobalt, respectively.     

Ozone oxidation of pharmaceuticals, endocrine disruptors and pesticides during drinking water treatment

This study investigates the oxidation of pharmaceuticals, endocrine disrupting compounds and pesticides during ozonation applied in drinking water treatment. In the first step, second-order rate constants for the reactions of selected compounds with molecular ozone (k_O3) were determined in bench-scale experiments at pH 8.10: caffeine (650 ± 22 M⁻¹ s⁻¹), progesterone (601 ± 9 M⁻¹ s⁻¹), medroxyprogesterone (558 ± 9 M⁻¹ s⁻¹), norethindrone (2215 ± 76 M⁻¹ s⁻¹) and levonorgestrel (1427 ± 62 M⁻¹ s⁻¹). Compared to phenolic estrogens (estrone, 17β-estradiol, estriol and 17α-ethinylestradiol), the selected progestogen endocrine disruptors reacted far slower with ozone. In the second part of the study, bench-scale experiments were conducted with surface waters spiked with 16 target compounds to assess their oxidative removal using ozone and determine if bench-scale results would accurately predict full-scale removal data. Overall, the data provided evidence that ozone is effective for removing trace organic contaminants from water with ozone doses typically applied in drinking water treatment. Ozonation removed over 80% of caffeine, pharmaceuticals and endocrine disruptors within the CT value of about 2 mg min L⁻¹. As expected, pesticides were found to be the most recalcitrant compounds to oxidize. Caffeine can be used as an indicator compound to gauge the efficacy of ozone treatment.     

Ozone treatment and the depletion of detectable pharmaceuticals and atrazine herbicide in drinking water sourced from the upper Detroit River, Ontario, Canada

The depletion and degradation of pharmacologically active compounds (PhACs) and pesticides as a function of ozonation in drinking water treatment processes is not well studied. The A.H. Weeks drinking water treatment plant (DWTP) serves the City of Windsor, Ontario Canada, and incorporates ozone treatment into the production of drinking water. This DWTP also operates a real-time, scaled down pilot plant, which has two parallel streams, conventional and ozone plus conventional treatments. In this study water samples were collected from key points in the two streams of the pilot plant system to determine the depletion and influence of seasonal changes in water processing parameters on eighteen major PhACs (and metabolites) and seven s-triazines herbicides. However, only carbamazepine (antiepileptic), caffeine (stimulant), cotinine (metabolite of nicotine) and atrazine were consistently detectable in the raw water intake (low to sub-ng/L level). Regardless of the seasonality, the flocculation-coagulation and dual media filtration steps without ozone treatment resulted in no decrease in analyte concentrations, while decreases of 66-100% (undetectable, method detection limits 0.05-1 ng/L) of the analyte concentrations were observed when ozone treatment was part of the water processing. These findings demonstrate that ozone treatment is highly effective in depleting carbamazepine, caffeine, cotinine, and atrazine, and thus is highly influential in the fate of these compounds in drinking water treatment regardless of the seasonal time frame. Currently very few Canadian DWTPs incorporate ozonation into conventional treatment, which suggests that human exposure to these compounds via drinking water consumption may be an issue in affected communities.     

Manganese-oxidizing and -reducing microorganisms isolated from biofilms in chlorinated drinking water systems

The interaction of chemical, physical and biological factors that affect the fate, transport and redox cycling of manganese in engineered drinking water systems is not clearly understood. This research investigated the presence of Mn-oxidizing and -reducing bacteria in conventional water treatment plants exposed to different levels of chlorine. Mn(II)-oxidizing and Mn(IV)-reducing bacteria, principally Bacillus spp., were isolated from biofilm samples recovered from four separate drinking water systems. Rates of Mn-oxidation and -reduction for selected individual isolates were represented by pseudo-first-order kinetics. Pseudo-first-order rate constants were obtained for Mn-oxidation (range: 0.106-0.659 days⁻¹), aerobic Mn-reduction (range: 0.036-0.152 days⁻¹), and anaerobic Mn-reduction (range: 0.024-0.052 days⁻¹). The results indicate that microbial-catalyzed Mn-oxidation and -reduction (aerobic and anaerobic) can take place simultaneously in aqueous environments exposed to considerable oxygen and chlorine levels and thus affect Mn-release and -deposition in drinking water systems. This has important implications for Mn-management strategies, which typically assume Mn-reduction is not possible in the presence of chlorine and oxidizing conditions.     

Investigation of pharmaceuticals in Missouri natural and drinking water using high performance liquid chromatography-tandem mass spectrometry

A comprehensive method has been developed and validated in two different water matrices for the analysis of 16 pharmaceutical compounds using solid phase extraction (SPE) of water samples, followed by liquid chromatography coupled with tandem mass spectrometry. These 16 compounds include antibiotics, hormones, analgesics, stimulants, antiepileptics, and X-ray contrast media. Method detection limits (MDLs) that were determined in both reagent water and municipal tap water ranged from 0.1 to 9.9 ng/L. Recoveries for most of the compounds were comparable to those obtained using U.S. EPA methods. Treated and untreated water samples were collected from 31 different water treatment facilities across Missouri, in both winter and summer seasons, and analyzed to assess the 16 pharmaceutical compounds. The results showed that the highest pharmaceutical concentrations in untreated water were caffeine, ibuprofen, and acetaminophen, at concentrations of 224, 77.2, and 70 ng/L, respectively. Concentrations of pharmaceuticals were generally higher during the winter months, as compared to those in the summer due, presumably, to smaller water quantities in the winter, even though pharmaceutical loadings into the receiving waters were similar for both seasons.     

Occurrence and fate modeling of MTBE and BTEX compounds in a Swiss Lake used as drinking water supply

Emissions of fuel components from boating use on multiple-use lakes and reservoirs are of high concern with regard to the drinking water supply from such water bodies. We report results of a detailed study on the occurrence, sources and fate of aromatic hydrocarbons and methyl tert-butyl ether (MTBE) in a typical holomictic lake, Lake Zurich, that supplies drinking water for the largest Swiss city. Emphasis of the investigation was on the fuel oxygenate MTBE, which was found in concentrations up to 1.4 microg/L in the epilimnion and up to 0.05microg/L in the hypolimnion of the lake. The concentration difference was due to the stratification of the lake during the boating season with very limited water exchange across the thermocline. MTBE and BTEX nearly completely volatilized before vertical lake mixing occurred in winter. Spatial and temporal variations of MTBE concentrations in the lake were observed and successfully predicted using two complementary box models (MASAS Light and Aquasim). The drinking water supply from holomictic lakes is not at risk for the scenarios studied if water is extracted from well below the thermocline. Since emissions of unburned gasoline into such water bodies are caused predominantly by boating activities, restrictions of highly emitting two-stroke engines could substantially reduce the MTBE and BTEX load of the epilimnion during the boating season.     

Investigation of assimilable organic carbon (AOC) in flemish drinking water

The aim of the study was to investigate the drinking water supplied to majority of residents of Flanders in Belgium. Over 500 water samples were collected from different locations, after particular and complete treatment procedure to evaluate the efficiency of each treatment step in production of biologically stable drinking water. In this study assimilable organic carbon (AOC) was of our interest and was assumed as a parameter responsible for water biostability. The influence of seasons and temperature changes on AOC content was also taken into account. The AOC in most of the non-chlorinated product water of the studied treatment plants could not meet the biostability criteria of 10 mug/l, resulting in the mean AOC concentration of 50 microg/l. However, majority of the examined chlorinated water samples were consistent with proposed criteria of 50--100 microg/l for systems maintaining disinfectant residual. Here, mean AOC concentration of 72 microg/l was obtained. Granular activated carbon filtration was helpful in diminishing AOC content of drinking water; however, the nutrient removal was enhanced by biological process incorporated into water treatment (biological activated carbon filtration). Disinfection by means of chlorination and ozonation increased the water AOC concentration while the ultraviolet irradiation showed no impact on the AOC content. Examination of seasonal AOC variations showed similar fluctuations in six units with the highest values in summer and lowest in winter.     

Occurrence, oral exposure and risk assessment of volatile organic compounds in drinking water for Izmir

Concentrations of volatile organic compounds (VOCs) were measured in the drinking water in Province of Izmir, Turkey, and associated health risks due to ingestion of these compounds were investigated using population weighted random samples. A total of 100 houses were visited in different districts of Izmir and drinking water samples were collected from consumers' drinking water source. Questionnaires were administered to one participant in each house to determine demographics and drinking water consumption rates. Oral exposure and risks were estimated for each participant and Izmir population by deterministic and probabilistic approaches, respectively. The four trihalomethane (THM) species (i.e., chloroform, bromodichloromethane, dibromochloromethane, and bromoform), benzene, toluene, p-xylene, and naphthalene were the most frequently detected VOCs with concentrations ranging from below detection limit to 35 microg/l. The risk estimates were found to be less than the values reported in the literature with few exceptions. Noncarcinogenic risks attributable to ingestion of VOCs for Izmir population were negligible, whereas the mean carcinogenic risk estimates for bromodichloromethane and dibromochloromethane were above the de minimis level of one in a million (10(-6)). For all VOCs, the concentrations measured in metropolitan area were greater than those in other districts. All THM species were detected in higher concentrations in tap water, whereas nontap water contained more benzene, toluene, p-xylene, and naphthalene. Therefore, the concentrations of the latter four compounds and associated risks increased with increasing income and education level since bottled water was used in larger proportions within these subgroups. The results of this study showed that oral exposure to drinking water contaminants and associated risks may be higher than the acceptable levels even if the concentrations fall below the standards.     

Development and validation of a drinking water temperature model in domestic drinking water supply systems

Domestic drinking water supply systems (DDWSs) are the final step in the delivery of drinking water to consumers. Temperature is one of the rate-controlling parameters for many chemical and microbiological processes and is, therefore, considered as a surrogate parameter for water quality processes. In this study, a mathematical model is presented that predicts temperature dynamics of the drinking water in DDWSs. A full-scale DDWS resembling a conventional system was built and run according to one year of stochastic demands with a time step of 10 s. The drinking water temperature was measured at each point-of-use in the systems and the data-set was used for model validation. The temperature model adequately reproduced the temperature profiles, both in cold and hot water lines, in the full-scale DDWS. The model showed that inlet water temperature and ambient temperature have a large effect on the water temperature in the DDWSs.     

Human health risk assessment of chlorinated disinfection by-products in drinking water using a probabilistic approach

The presence of chlorinated disinfection by-products (DBPs) in drinking water is a public health issue, due to their possible adverse health effects on humans. To gauge the risk of chlorinated DBPs on human health, a risk assessment of chloroform (trichloromethane (TCM)), bromodichloromethane (BDCM), dibromochloromethane (DBCM), bromoform (tribromomethane (TBM)), dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) in drinking water was carried out using probabilistic techniques. Literature data on exposure concentrations from more than 15 different countries and adverse health effects on test animals as well as human epidemiological studies were used. The risk assessment showed no overlap between the highest human exposure dose (EXP(D)) and the lowest human equivalent dose (HED) from animal test data, for TCM, BDCM, DBCM, TBM, DCAA and TCAA. All the HED values were approximately 10(4)-10(5) times higher than the 95th percentiles of EXP(D). However, from the human epidemiology data, there was a positive overlap between the highest EXP(D) and the lifetime average daily doses (LADD(H)) for TCM, BDCM, DCAA and TCAA. This suggests that there are possible adverse health risks such as a small increased incidence of cancers in males and developmental effects on infants. However, the epidemiological data comprised several risk factors and exposure classification levels which may affect the overall results.     

Multivariate distributions of disinfection by-products in chlorinated drinking water

Drinking water disinfection by-product (DBP) occurrence research is important in supporting risk assessment and regulatory performance assessment. Recent DBP occurrence surveys have expanded their scope to include non-regulated priority DBPs as well as regulated DBPs. This study applies a Box-Cox transformed multivariate normal model and data augmentation methods for left-censored and missing observations to US EPA Information Collection Rule (ICR) drinking water data to describe the variability in the trihalomethane (THM4), trihaloacetic acid (THAA), dihaloacetic acid (DHAA), and dihaloacetonitrile (DHAN) DBP classes, the relationship between class-sum and the occurrence of individual DBPs within these classes. Inferences about bromine incorporation in these classes are then compared to those made by Obolensky and Singer (2005). Results reported herein show that class-based and individual DBP concentrations are strongly related to bromine substitution, and that speciation and bromine substitution patterns are consistent across DBP classes. In addition, the multiple imputation approach employed reveals that uncertainties related to missing and left-censored DBPs have important implications for understanding bromine substitution in the THAA class. These concerns should be considered through alternative approaches to DBP regulation in subsequent Stage II D/DBP assessment and revisions, where appropriate.     

Formation equation of halogenated organic compounds when water is chlorinated

Various halogenated organic compounds are formed by chlorination of water. In this study, formation of organic compounds halogenated from a reagent humic acid and extract of a leaf mold were examined under various conditions. The following overall formation equation was obtained from empirical data under the practical wide range when free chlorine remained.

[TOX]=k_TOX[TOC][Cl₂]_ot^β.

Here, [TOX] is the concentration of total organic halogen after t h in units of mg chlorine per liter; [TOC] and [Cl₂]_o are concentrations of total organic carbon and dosed chlorine in units of mg per liter; k_TOX is the rate constant and and β are parameters. From the values of k_TOX, and β, the character of organic substances i.e. precursor of halogenated organic compounds, in water can be evaluated. The values k_TOX, and β for humic acid are 0.053, 0.28 and 0.13, and the values for extract of the leaf mold are 0.032, 0.36 and 0.15, respectively. The activation energies are 10 kJ mol⁻¹ and 11 kJ mol⁻¹ for the reactions of humic acid and leaf mold extract, respectively.     

Sonochemical degradation of chlorinated organic compounds, phenolic compounds and organic dyes - A review

Sonochemical processes have been widely used in chemistry and chemical engineering field. Recently, these processes have found new applications in the environmental field, because of advantages in terms of operational simplicity, secondary pollutant formation and safety. Several studies have reported on sonochemical degradation of organic compounds that are toxic in nature. The objective of this review was to identify and examine some of the studies on sonochmical degradation of chlorinated organic compounds, phenolic compounds and organic dyes. This review also examines the basic theory of sonochemical reactions and the use of sonochemical reactors for environmental applications.     

Impacts of emerging organic contaminants on freshwater resources: review of recent occurrences, sources, fate and effects

Rapid urbanization and frequent disposal of wastewater to surface water cause widespread contamination of freshwater supplies with emerging contaminants, such as pharmaceuticals, insecticides, surfactants, endocrine disruptors, including hormones. Although these organic contaminants may be present at trace levels, their adverse effects on aquatic life, animals and even humans are a growing concern. Numerous studies have been published on the occurrence and fate of emerging organic contaminants in different parts of the world, spanning a wide range of sources and aquatic environments including freshwater catchments, effluent wastewater streams, lakes, rivers, reservoirs, estuaries and marine waters. This paper reviews recent studies on the occurrence and fate of frequently detected pharmaceuticals and hormones and identifies areas that merit further research.     

Bioassays as a tool for evaluating advanced oxidation processes in water and wastewater treatment

Advanced oxidation processes (AOPs) have been widely used in water and wastewater treatment for the removal of organic and inorganic contaminants as well as to improve biodegradability of industrial wastewater. Unfortunately, the partial oxidation of organic contaminants may result in the formation of intermediates more toxic than parent compounds. In order to avoid this drawback, AOPs are expected to be carefully operated and monitored, and toxicity tests have been used to evaluate whether effluent detoxification takes place. In the present work, the effect of AOPs on the toxicity of aqueous solutions of different classes of contaminants as well as actual aqueous matrices are critically reviewed. The dualism toxicity-biodegradability when AOPs are used as pre-treatment step to improve industrial wastewater biodegradability is also discussed. The main conclusions/remarks include the followings: (i) bioassays are a really useful tool to evaluate the dangerousness of AOPs as well as to set up the proper operative conditions, (ii) target organisms for bioassays should be chosen according to the final use of the treated water matrix, (iii) acute toxicity tests may be not suitable to evaluate toxicity in the presence of low/realistic concentrations of target contaminants, so studies on chronic effects should be further developed, (iv) some toxicity tests may be not useful to evaluate biodegradability potential, in this case more suitable tests should be applied (e.g., activated sludge bioassays, respirometry).     

Volatile organic components migrating from plastic pipes (HDPE,PEX and PVC) into drinking water

High-density polyethylene pipes (HDPE), crossbonded polyethylene pipes (PEX) and polyvinyl chloride (PVC) pipes for drinking water were tested with respect to migration of volatile organic components (VOC) to water. The odour of water in contact with plastic pipes was assessed according to the quantitative threshold odour number (TON) concept. A major migrating component from HDPE pipes was 2,4-di-tert-butyl-phenol (2,4-DTBP) which is a known degradation product from antioxidants such as Irgafos 168(R). In addition, a range of esters, aldehydes, ketones, aromatic hydrocarbons and terpenoids were identified as migration products from HDPE pipes. Water in contact with HDPE pipes was assessed with respect to TON, and values > or =4 were determined for five out of seven brands of HDPE pipes. The total amount of VOC released to water during three successive test periods were fairly constant for the HDPE pipes. Corresponding migration tests carried out for PEX pipes showed that VOC migrated in significant amounts into the test water, and TON >/=5 of the test water were observed in all tests. Several of the migrated VOC were not identified. Oxygenates predominated the identified VOC in the test water from PEX pipes. Migration tests of PVC pipes revealed few volatile migrants in the test samples and no significant odour of the test water.