Occurrence of selected pharmaceuticals at drinking water purification plants in Japan and implications for human health.

The present study was performed to determine the occurrence of 64 pharmaceuticals and metabolites in source water and finished water at 6 drinking water purification plants and 2 industrial water purification plants across Japan. The analytical methods employed were sample concentration using solid-phase extraction cartridges and instrumental analysis by liquid chromatography with tandem mass spectrometry (LC-MS/MS), liquid chromatography with mass spectrometry (LC/MS), or trimethylsilyl derivatization followed by gas chromatography with mass spectrometry (GC/MS). Thirty-seven of the 64 target substances were detected in the source water samples. The maximum concentrations in the source water were mostly below 50 ng/L except for 13 substances. In particular, residual concentrations of iopamidol (contrast agent) exceeded 1000 ng/L at most facilities. Most of the residual pharmaceuticals and metabolites in the source water samples were removed in the course of conventional and/or advanced drinking water treatments, except for 7 pharmaceuticals and 1 metabolite, i.e., amantadine, carbamazepine, diclofenac, epinastine, fenofibrate, ibuprofen, iopamidol, and oseltamivir acid. The removal ratios of the advanced water treatment processes including ozonation and granular activated carbon filtration were typically much higher than those of the conventional treatment processes. The margins of exposure estimated by the ratio of daily minimum therapeutic dose to daily intake via drinking water were substantial, and therefore the pharmacological and physiological impacts of ingesting those residual substances via drinking water would be negligible.

Effects of introducing energy recovery processes to the municipal solid waste management system in Ulaanbaatar, Mongolia.

Currently, most developing countries have not set up municipal solid waste management systems with a view of recovering energy from waste or reducing greenhouse gas emissions. In this article, we have studied the possible effects of introducing three energy recovery processes either as a single or combination approach, refuse derived fuel production, incineration and waste power generation, and methane gas recovery from landfill and power generation in Ulaanbaatar, Mongolia, as a case study. We concluded that incineration process is the most suitable as first introduction of energy recovery. To operate it efficiently, 3Rs strategies need to be promoted. And then, RDF production which is made of waste papers and plastics in high level of sorting may be considered as the second step of energy recovery. However, safety control and marketability of RDF will be required at that moment.

Modelling climate change impacts on the seasonality of water resources in the Upper Ca River Watershed in Southeast Asia.

The impact of climate change on the seasonality of water resources in the Upper Ca River Watershed in mainland Southeast Asia was assessed using downscaled global climate models coupled with the SWAT model. The results indicated that temperature and evapotranspiration will increase in all months of future years. The area could warm as much as 3.4(°)C in the 2090 s, with an increase of annual evapotranspiration of up to 23% in the same period. We found an increase in the seasonality of precipitation (both an increase in the wet season and a decrease in the dry season). The greatest monthly increase of up to 29% and the greatest monthly decrease of up to 30% are expected in the 2090 s. As a result, decreases in dry season discharge and increases in wet season discharge are expected, with a span of ± 25% for the highest monthly changes in the 2090 s. This is expected to exacerbate the problem of seasonally uneven distribution of water resources: a large volume of water in the wet season and a scarcity of water in the dry season, a pattern that indicates the possibility of more frequent floods in the wet season and droughts in the dry season.

Assessment of thyroid hormone activity of halogenated bisphenol A using a yeast two-hybrid assay.

The thyroid hormone agonist/antagonist activities of halogenated derivatives of bisphenol A (BPA) were assessed using a yeast two-hybrid assay incorporating the human thyroid hormone α (TRα), both with and without possible metabolic activation by rat liver S9 preparation. In the absence of the rat liver S9 preparation, 3,3',5,5'-tetrabromobisphenol A (TBBPA), 3,3',5,5'-tetrachlorobisphenol A (TCBPA), and 3,3',5-trichlorobisphenol A (3,3',5-triClBPA) exhibited agonist activity, whereas 3-chlorobisphenol A (3-ClBPA), 3,5-dichlorobisphenol A (3,5-diClBPA), 3,3'-dichlorobisphenol A (3,3'-diClBPA), and BPA did not. The activities of TBBPA and TCBPA increased markedly (7.6-fold and 3.1-fold, respectively) after their metabolic activation with the rat liver S9 preparation. TBBPA, TCBPA, and 3,3',5-triClBPA inhibited the binding of triiodothyronine (T3) to TRα at 2×10(-5) M without rat liver S9 treatment and 4×10(-6) M with rat liver S9 treatment, demonstrating their T3 antagonist activity. These results revealed that metabolic activation by rat liver S9 significantly increased the agonist/antagonist potential of some halogenated BPAs.

Identification of antiyellowing agents as precursors of N-nitrosodimethylamine production on ozonation from sewage treatment plant influent.

In Japan, N-nitrosodimethylamine (NDMA) formation associated with ozonation at a relatively high concentration has been reported only at a small number of water treatment plants (WTPs) in the western part of Japan for which the source water is the Yodo River. In the present study, the formation of relatively high concentrations of NDMA was found upon ozonation of water samples taken from sewage treatment plants (STPs) located upstream of the water intake points of the WTPs in the Yodo River basin. NDMA concentrations before and after ozonation were 16-290 and 14-280 ng/L, respectively. At least some of the STPs investigated receive industrial effluents. At one STP in this area, an extremely high concentration of NDMA (10,000ng/L) was found in one influent water sample after ozonation. To identify potential NDMA precursors upon ozonation in the influent at this STP, the concentrated extracts of the influent were fractionated by high-performance liquid chromatography (HPLC). Ultraperformance liquid chromatography coupled with tandem mass spectrometry (UPLC/MS/MS) identified 4,4'-hexamethylenebis(1,1-dimethylsemicarbazide) (HDMS) and 1,1,1',1'-tetramethyl-4,4'-(methylene-di-p-phenylene)disemicarbazide (TMDS) as precursors of NDMA on ozonation of the influent. Both HDMS and TMDS are used as antiyellowing agents in polyurethane fibers and as light stabilizers in polyamide resins. Their contributions to NDMA production on ozonation of water samples at STPs were up to 17%. The remaining unidentified NDMA precursors may be hydrophilic compounds that were not trapped by the cartridges used for extraction of the water samples. HDMS and TMDS were frequently present in surface waters and STP effluents in the Yodo River basin and were also detected in surface waters from several other areas in Japan.

Application of real-time PCR assays to genotyping of F-specific phages in river water and sediments in Japan.

Genotyping of F-specific RNA phages is currently one of the most promising approaches to differentiate between human and animal fecal contamination in aquatic environments. In this study, a total of 18 river water and sediment samples were collected from the Tonegawa River basin, Japan, in order to describe the genogroup distribution of F-specific RNA and DNA phages using genogroup-specific real-time PCR assays. F-specific phages were detected in nine (100%) river water and six (67%) sediment samples. Eighty-five phage plaques were isolated from these samples and subjected to real-time PCR assays specific for the phages. F-specific RNA phages of human genogroups (II and III) were detected in 32 (38%) plaques, whereas those of animal genogroups (I and IV) were detected in 17 (20%) plaques. No correlation was observed between the genogroup distribution of F-specific RNA phages and the occurrence of human adenovirus genomes, suggesting that genotyping of the phages alone is inadequate for the evaluation of the occurrence of viruses in aquatic environments. SYBR Green-based real-time PCR assay revealed the presence of F-specific DNA phages in four (5%) plaques, which were further classified into two genogroups (fd- and f1-like phages) by sequence analysis. Thirty-two (38%) plaques were not classified as the F-specific phage genogroups, indicating the limited applicability of these real-time PCR assays to a wide range of aquatic environmental samples worldwide.

Simultaneous determination of tetracyclines and their degradation products in environmental waters by liquid chromatography-electrospray tandem mass spectrometry.

A sensitive method was developed for the trace determination of six tetracyclines and ten of their degradation products in influent, effluent, and river waters using liquid chromatography-electrospray tandem mass spectrometry detection, combined with Oasis hydrophilic-lipophilic balance (HLB) cartridge extraction and Oasis mixed-mode strong anion exchange (MAX) cartridge cleanup. Tetracyclines and their products were separated by liquid chromatography in 9.5min, and the instrument detection limits were generally between 0.03 and 0.1microg/L except for minocycline (0.5microg/L). The chromatograms were improved through the MAX cleanup and no apparent matrix effect was found. The recoveries of all the target compounds except for 4-epianhydrochlortetracycline and anhydrochlortetracycline (34-52%) were 75-120% for influent, 61-103% for effluent, and 64-113% for river waters. The method detection limits (MDLs) of the analytes varied in the range of 0.8-17.5ng/L in all studied matrices. The method was applied for the determination of tetracyclines and their products in a sewage treatment plant (STP) and surface waters in Beijing, China. Oxytetracycline (3.8-72.5ng/L), tetracycline (1.9-16.5ng/L), and five products including 4-epitetracycline, 4-epioxytetracycline, isochlortetracycline, anhydrotetracycline, and 4-epianhydrochlortetracycline (5.7-25.3ng/L) were detected in wastewater, while only oxytetracycline and tetracycline (2.2 and 2.1ng/L) were detected in surface water samples.

Formation of N-nitrosodimethylamine (NDMA) by ozonation of dyes and related compounds.

Formation of N-nitrosodimethylamine (NDMA) by ozonation of commercially available dyes and related compounds was investigated. Ozonation was conducted using a semi-batch type reactor, and ozone concentration in gas phase and the ozone gas flow were 10 mg L(-1) and 1.0 L min(-1), respectively. NDMA was formed by 15 min of ozonation of seven out of eight selected target compounds (0.05 mM) at pH 7. All the target compounds with N,N-dimethylamino functions were NDMA precursors in ozonation. The lowest and highest NDMA concentrations after ozonation of the target compounds were 13 ng L(-1) for N,N-dimethylformamide (DMF) and 1600 ng L(-1) for N,N-dimethyl-p-phenylenediamine (DMPD), respectively. NDMA concentrations after 15 min of ozonation of 0.05 mM methylene blue (MB) and DMPD increased with an increase in pH in its range of 6-8. The effects of coexisting compounds on NDMA concentrations after 15 min of ozonation of 0.05 mM MB and DMPD were examined at pH 7. NDMA concentrations after ozonation of MB and DMPD increased by the presence of 0.05 mM (0.7 mg L(-1) as N) nitrite (NO(2)(-)); 5000 ng L(-1) for MB and 4000 ng L(-1) for DMPD. NDMA concentration after MB ozonation decreased by the presence of 5mM tertiary butyl alcohol (TBA), a hydroxyl radical (HO.) scavenger, but that after DMPD ozonation was increased by the presence of TBA. NDMA concentrations after ozonation of MB and DMPD were not affected by the presence of 0.16 mM (5.3 mg L(-1)) hydrogen peroxide (H(2)O(2)). When 0.05 mM MB and DMPD were added to the Yodo and Tone river water samples, NDMA concentrations after 15 min of their ozonation at pH 7 increased compared with those in the case of addition to ultrapure water samples.

Trace analysis of androgens and progestogens in environmental waters by ultra-performance liquid chromatography-electrospray tandem mass spectrometry.

A sensitive ultra-performance liquid chromatography-electrospray tandem mass spectrometry method, combined with solid-phase extraction and silica cartridge cleanup, was established for nine androgens (androstenedione, 19-nor-4-androstene-3,17-diol, androsterone, epiandrosterone, testosterone, methyltestosterone, trenbolone, nandrolone, stanozolol) and nine progestogens (progesterone, 17alpha-hydroxyprogesterone, 21alpha-hydroxyprogesterone, 6alpha-methyl-hydroxyprogesterone, 17alpha,20beta-dihydroxy-4-pregnene-3-one, megestrol acetate, norethindrone, norgestrel, medroxyprogesterone acetate) in environmental waters. For the various water matrices considered, the overall method recoveries were from 78 to 100%, and no apparent signal suppression was found. The method detection limits for the eighteen analytes in the influent, effluent and surface water samples were 0.20-50, 0.04-20 and 0.01-12 ng/L, respectively. This method was used to analyze the residual androgens and progestogens in the wastewater and surface water samples from Japan, and ten analytes (0.03 (medroxyprogesterone acetate)-1441 ng/L (androsterone)) were detected in the wastewater samples, and four analytes (0.06 (progesterone)-0.46 ng/L (androstenedione)) were detected in the surface water samples.

Simultaneous analysis of 16 sulfonamide and trimethoprim antibiotics in environmental waters by liquid chromatography-electrospray tandem mass spectrometry.

A sensitive liquid chromatography-electrospray tandem mass spectrometry method combined with solid-phase extraction and silica cartridge cleanup was established for 16 sulfonamides and trimethoprim in various water matrices. Signal suppression of all target analytes in sewage treatment plant influent, effluent and river water was improved by this method developed in this study. The method detection limits for 17 analytes were 20-200 pg/L for influent, 16-120 pg/L for effluent and 8.0-60 pg/L for river water with overall mean recoveries of 62-102% in all studied matrices. This method was used to analyze residual sulfonamides and trimethoprim in wastewater and river samples from Japan, and 8 analytes (0.08 (sulfadimethoxine)-161 ng/L (sulfapyridine) in wastewater and 10 (0.03 (sulfamethizol)-8.9 ng/L (sulfaquinoxaline) in river samples were detected.

Occurrence of perchlorate in drinking water sources of metropolitan area in Japan.

The occurrence of perchlorate in the Tone River Basin was investigated using an ion chromatograph (IC) coupled with a tandem mass spectrometer (MS/MS). Perchlorate was found at high concentrations in the upper Tone River and its tributary, Usui River, and the maximum concentrations were 340 and 2300 microg/L, respectively. The possible sources of perchlorate in two areas were attributable to industrial effluents. In case of the upper Tone River, perchlorate concentration in an effluent was 1100 microg/L and its concentrations in a tributary (or waterway) directly downstream of the outlet of the effluent ranged from 44 to 1500 microg/L. In case of the Usui River, perchlorate concentration in another effluent was 15,000 microg/L and its concentrations downstream of the outlet of the effluent were 1100-3900 microg/L. Due to the discharge of perchlorate in the upper Tone River Basin, perchlorate concentrations in the river waters of the middle and lower Tone River Basin were generally 10-20 microg/L. Perchlorate concentrations in 30 tap water samples were investigated. Water sources of three tap water samples were other than the Tone River Basin and their perchlorate concentrations were 0.16-0.87 microg/L. On the other hand, water sources of the remaining 27 samples were the upper, middle and lower Tone River Basin and their perchlorate concentrations were 0.06-37 microg/L. Perchlorate concentrations were more than 1 microg/L in 19 tap water samples and more than 10 microg/L in 13 samples. It was shown that tap waters in the Tone River Basin were widely contaminated with perchlorate. To our knowledge, this study was the first to report on perchlorate contamination of environmental and drinking waters in Japan.

Transformation of pyrene in aqueous chlorination in the presence and absence of bromide ion: kinetics, products, and their aryl hydrocarbon receptor-mediated activities.

To assess the endocrine-disrupting activity stemming from the presence of pyrene in drinking water, the kinetics of chlorination of pyrene was investigated at room temperature, the products of its aqueous chlorination with and without bromide ion were identified, and their aryl hydrocarbon receptor (AhR)-mediated activities were determined. It was found that the presence of bromide ion greatly promoted the reaction rate of chlorination of pyrene accompanied with the formation of brominated products. While the main product was 1-Cl-pyrene without the addition of bromide ion, di-Br-pyrene and 1-Br-pyrene became the main products in the presence of bromide ion. GC-MS and NMR analysis identified three structures of dibromopyrene in chlorination with the addition of bromide ion as 1,3-di-Br-pyrene, 1,6-di-Br-pyrene, and 1,8-di-Br-pyrene, and their molar ratio was determined to be approximately 0.3:1:1. Finally, 1-Br-pyrene, 1,3-di-Br-pyrene, a mixture of 1,6-di-Br-pyrene and 1,8-di-Br-pyrene (di-Br-pyrene), 1-Cl-pyrene, and a mixture of 1,6-di-Cl-pyrene and 1,8-di-Cl-pyrene (di-Cl-pyrene) were fractionated by HPLC, and their AhR-mediated activities were assessed by a yeast assay. It was found that the effective molar concentrations (or mass concentration) showing half-maximal transcriptional response, EC50, for pyrene, 1-Br-pyrene, 1-Cl-pyrene, di-Cl-pyrene, and di-Br-pyrene were 5632 (1.14), 3089 (0.86), 1942 (0.46), 597.2 (0.21), and 147.3 (0.04) nM (mg/L), respectively.

Risk of adverse reproductive outcomes associated with proximity to municipal solid waste incinerators with high dioxin emission levels in Japan.

BACKGROUND: Great public concern about health effects of dioxins emitted from municipal solid waste incinerators has increased in Japan. This paper investigates the association of adverse reproductive outcomes with maternal residential proximity to municipal solid waste incinerators. METHODS: The association of adverse reproductive outcomes with mothers living within 10 km from 63 municipal solid waste incinerators with high dioxin emission levels (above 80 ng international toxic equivalents TEQ/m3) in Japan was examined. The numbers of observed cases were compared with the expected numbers calculated from national rates adjusted regionally. Observed/expected ratios were tested for decline in risk or peak-decline in risk with distance up to 10 km. RESULTS: In the study area within 10 km from the 63 municipal solid waste incinerators in 1997-1998, 225,215 live births, 3,387 fetal deaths, and 835 infant deaths were confirmed. None of the reproductive outcomes studied here showed statistically significant excess within 2 km from the incinerators. However, a statistically significant peak-decline in risk with distance from the incinerators up to 10 km was found for infant deaths (p=0.023) and infant deaths with all congenital malformations combined (p=0.047), where a "peak" is detected around 1-2 km. CONCLUSION: Our study shows a peak-decline in risk with distance from the municipal solid waste incinerators for infant deaths and infant deaths with all congenital malformations combined. However, due to the lack of detailed exposure information to dioxins around the incinerators, the observed trend in risk should be interpreted cautiously and there is a need for further investigation to accumulate good evidence regarding the reproductive health effects of waste incinerator exposure.

Products of aqueous chlorination of 17beta-estradiol and their estrogenic activities.

To assess the estrogenic activity potentially stemming from 17beta-estradiol (E2) in drinking water, ESI-LC-MS was used to identifythe products of its aqueous chlorination under the following conditions: 50 microg/L E2, 1.46 mg/L sodium hypochlorite, pH 7.5, 25 degrees C. Seven products, including 2,4-dichloro-17beta-estradiol, monochloroestrone, 2,4-dichloroestrone, and the four byproducts such as 4-[2-(2,6-dichloro-3-hydroxyphenyl)ethyl]-7alpha-methyloctahydroinden-5-one (product C in the text) were identified in chlorinated E2 solution. The estrogenic activities of the aqueous chlorinated E2 solution at 10, 30, 60, 120, and 180 min contact time were assessed by a yeast two-hybrid system based on the ligand-dependent interaction of two proteins, a human estrogen receptor (ER) and a coactivator. All five solutions elicited transcriptional activation induction. The maximal beta-galactosidase activities induced by the chlorinated solution at 10, 30, and 60 min were similar and slightly lower than those before chlorination, while the activities of the chlorinated solution at 120 and 180 min were about 40% of those before chlorination. Finally, 4-chloro-17beta-estradiol (4-chloro-E2) (we failed to synthesize the 2-chloroestrone (2-chloro-E1)), 2,4-dichloro-17beta-estradiol (2,4-dichloro-E2), and 2,4-dichloroestrone (2,4-dichloro-E1) were synthesized, and product C was fractionated by HPLC. It was found that 4-chloro-E2 elicited strong estrogenic activity, at almost the same level as that of estrone (EC50 = 10(2) nM), while 2,4-dichloro-E2 elicited weaker beta-galactosidase activity compared with that of 4-chloro-E2. The EC50 was ca. 10(3) nM. The maximal beta-galactosidase activity for 2,4-dichloro-E1 was lower than that of 2,4-dichloro-E2, while its EC50 was similar to that of 2,4-dichloro-E2. In addition, product C, 4-[2-(2,6-dichloro-3-hydroxyphenyl)ethyl]-7alpha-methyloctahydroinden-5-one, induced high beta-galactosidase activity at the relatively higher concentration of 3.5 x 10(5) nM. On the basis of the dose-response curve of a single byproduct of chlorinated E2, the estrogenic activity at 120 and 180 min appears to be induced mainly by 2,4-dichloro-E2 and 2,4-dichloro-E1.

Prevalence of Cryptosporidium oocysts and giardia cysts in the drinking water supply in Japan.

A one-year monitoring of Cryptosporidium oocysts and Giardia cysts was conducted at a water purification plant. A total of 13 samples of 50 L river source water and 26 samples of 2,000 L-filtered water, treated by coagulation flocculation, sedimentation and rapid filtration, were tested. Prior to conducting a survey of a water purification plant, we developed a method for concentrating Cryptosporidium oocysts from a large volume of raw or filtered water using a hollow fiber ultrafiltration (UF) membrane, and this procedure was adapted to survey a water purification plant. Cryptosporidium oocysts were detected in all of the 13 raw water samples. The geometric mean concentration was 40 oocysts 100 L. Giardia cysts were detected in 12 of 13 raw water samples (92%) and the geometric mean concentration was 17 cysts/100 L. Probability distributions of both Cryptosporidium oocyst and Giardia cyst concentration in raw water were nearly lognormal. In filtered water samples, Cryptosporidium oocysts were detected in 9 of the 26 samples (35%) with the geometric mean concentration of 1.2 oocysts /1,000 L and Giardia cysts in 3 samples (12%) with 0.8 cysts/1,000 L. The estimated log10 removal efficiency of Cryptosporidium oocysts and Giardia cysts by rapid-sand filtration was 2.47 and 2.53, respectively. Empty particles were removed at a higher log10 than intact oocysts and cysts. The efficiency of particle removal in the rapid sand filtration process tends to be reduced under cold-water conditions. Close management is necessary in the winter when the water temperature is low.