Quantitation of guanidine derivatives as representative persistent and mobile organic compounds in water: method development.

Persistent and mobile organic compounds (PMOCs) are highly soluble in water, thereby posing a threat to water resource quality. Currently, there are no methods that can accurately quantify guanidine derivative PMOCs, other than 1,3-diphenylguanidine (DPG) and cyanoguanidine (CG), in aqueous media. In this study, we developed a quantitation method that combines solid-phase extraction and liquid chromatography (LC)-tandem mass spectrometry to detect seven guanidine derivatives in aquatic environments and applied it to environmental water samples. Five LC columns were examined, and among them, a hydrophilic interaction liquid chromatography column was chosen owing to its suitable instrument detection limit and retention factor. Method precision was assessed using seven replicate analyses of river water. The corresponding analyte recoveries ranged from 73 to 137% (coefficient of variation = 2.1-5.8%). DPG and CG were detected in ultrapure water samples at levels up to 0.69 and 150 ng L-1, respectively; DPG and CG levels up to 44 and 2600 ng L-1, respectively, were detected in lake water, river water, sewage effluent, and tap water sampled in Western Japan. This is the first reported detection of DPG in the surface water of Japan, revealing that DPG and CG are ubiquitous compounds in aquatic environments. Moreover, this is the first study to detect 1-(o-tolyl)biguanide and N,N'''-1,6-hexanediylbis(N'-cyanoguanidine) in water. This study provides a foundation for further research on the distribution, fate, and emission source of these pollutants, which is critical to maintain high water quality and to determine regulatory limits for these pollutants.

Inhomogeneity of sediment samples in analysis of hexabromocyclododecane.

The repeatability test of the analytical method for hexabromocyclododecane (HBCD) was conducted with sediment sample. The maximum HBCD concentration exceeded the minimum by a factor of 90 even though the identical sediment samples were used. Therefore, we examined which step of the analytical method was the factor causing variability. We examined the blank test, and confirmation test of the extraction and purified procedure. From these results, we confirmed that there was nothing wrong with the accuracy of our analytical method. These results indicate that the variability of HBCD concentration in the repeatability test was attributed not to the analytical method, but to the inhomogeneity of the sediment sample. Aluminum, silicon, and organic carbon in sediments were measured to compare the variability of these concentrations with that of HBCD concentration. These concentrations were similar values within identical samples which showed variability in HBCD concentration. HBCD concentration in several samples did not correlate with organic carbon content. These results suggests that sediment samples were homogeneous by itself, and HBCD was heterogeneously distributed in spite of homogeneity of organic carbon in sediment. The sediment sample with variability in HBCD concentration showed different HBCD diastereomer compositions in identical sediment. It implies that the sample contained HBCD derived from different histories or point sources. Even though we increased sample amounts to analyze the homogeneity of the sample, HBCD concentration varied within identical samples if the sample had a hot spot. Past monitoring data may contain overestimation or underestimation of HBCD concentration in sediment.

Hexabromocyclododecane in riverine and estuarine sediments from Osaka, Japan: spatial distribution and concentration variability within identical samples.

In this study, hexabromocyclododecane (HBCD) in riverine and estuarine sediments was investigated in Osaka, Japan. The mean total HBCD concentration detected in sediments ranged from < 0.50 to 130 ng g-1 dry weight. This exceeded the ubiquitous HBCD contamination level found globally but was lower than that in areas affected by point sources, such as textile industries and expanded polystyrene plants. Sewage effluent was one of the suspected point sources of HBCD in the study area. The HBCD concentrations in sediments were highly dependent on certain factors, such as the location of the sampling site (proximity to possible emission sources), sediment properties (silt or sand), and organic substance content. The range of the diastereomer composition of α- and γ-HBCD was wider than that in other studies. Repeatability tests (n = 3) were conducted for all samples to assess the variability in the HBCD concentrations within identical sediment samples. Some variations were observed in the HBCD concentrations and diastereomer compositions within the repeatability test results at some sampling sites; nevertheless, the same samples were extracted and analyzed in triplicate. The bromine contents of the extracts of these samples were analyzed by X-ray fluorescence, and the results agreed well with those estimated from the LC-MS/MS results. From these results, it was confirmed that several sediment samples contained heterogeneously distributed HBCD. The risk characterization ratios (predicted environmental concentration/predicted no-effect concentration) of sites with high HBCD concentrations ranged from 0.1 to 1; thus, further information is required, and the sediment HBCD levels in this region should be continuously studied.

Uptake and elimination kinetics of trifluralin and pendimethalin in Pheretima spp. and Eisenia spp.

The purpose of this study was to clarify the kinetic bioaccumulation potential of herbicides in the earthworm, Pheretima spp., the most common earthworms throughout Asia, and Eisenia spp., litter-feeding earthworms included in the test species recommended by the Organization for Economic Co-operation and Development. The kinetic bioaccumulation factors of trifluralin and pendimethalin were estimated from an uptake test for 10 or 12 days and from an elimination test for 10 days. The time required to reach a steady state following herbicide exposure was 7 days for both herbicides in Eisenia spp. and 1 day in Pheretima spp. The uptake rate constant (g-soil/g-worm/day) and elimination rate constant (per day) for trifluralin were 2.1 and 0.23 in Eisenia spp. and 0.42 and 0.45 in Pheretima spp., respectively, and those for pendimethalin were 1.5 and 0.26 in Eisenia spp. and 0.27 and 1.0 in Pheretima spp., respectively. Kinetic bioaccumulation factors of both herbicides were relatively close to bioaccumulation factors in steady state and were higher in Eisenia spp. (8.9 for trifluralin and 5.7 for pendimethalin) than in Pheretima spp. (0.95 and 0.26). These results demonstrated that the herbicide bioaccumulation risk is lower for Pheretima spp. than for Eisenia spp. because of the lower uptake rate and higher elimination rate in Pheretima spp.

Herbicide discharge from rice paddy fields by surface runoff and percolation flow: A case study in paddy fields in the Lake Biwa basin, Japan.

The transport of three herbicides, pyriminobac-methyl, imazosulfuron and pyraclonil from a watershed that includes 40 ha of paddy fields to a drainage canal was monitored in the Lake Biwa basin, Japan. Based on the intensive monitoring of all paddy plots and in the drainage canal conducted on 3 days during and after the application period, the passage of herbicide discharge from the paddy fields to the drainage canal was separated into surface runoff obtained from field observations and percolation flow calculated from the herbicide mass balance. Surface runoff from paddy plots immediately after herbicide application, discharging a large volume of paddy water, or both processes in conjunction had a significant effect on herbicide discharge. Without surface runoff, paddy fields discharged a consistently high amount of herbicide gradually by percolation flow. These results suggest that considerable amounts of herbicides were discharged into the drainage canal through percolation even if appropriate water management to prevent herbicide surface runoff was practiced.

A Bayesian approach for estimating hexabromocyclododecane (HBCD) diastereomer compositions in water using data below limit of quantification.

We developed a statistical model that quantitatively incorporated the stochastic fluctuations of values, which were estimated as Bayesian credible intervals (BCIs), to analyze environmental monitoring data. We used α-hexabromocyclododecane (α-HBCD) diastereomer compositions of water samples that included data points below limit of quantification. To avoid replacing "not detected (ND)" values with irrelevant values in data analysis, we substituted ND with observed values from the measurement system upon examination of the model. In our study, it was assumed that the magnitude of stochastic fluctuations of observed values in environmental samples was identical to that in iterative measurements of a standard solution at the lowest concentration. Using this model, α-HBCD diastereomer compositions could be estimated along with BCIs even for samples collected from sites where concentrations of α-HBCD were ND or near limit of quantification. The brackish areas in our study showed relatively wide ranges in composition for the 95% BCIs compared with samples from fresh water areas. In the brackish areas, concentrations of HBCD were frequently ND or near limit of quantification. Using this model, it was unnecessary to replace ND with zero or limit of quantification in data analysis, and an environmental assessment could be achieved using all of the data. Therefore, this model is considered to be a widely applicable approach in the analysis of environmental monitoring data including ND.

Concentration and loading of pesticide residues in Lake Biwa basin (Japan).

The concentrations and loading rates of pesticides used in paddy fields were investigated over a period of 5 years in the Seta River, which is the only natural outlet of Lake Biwa. The lake's water catchment area is 3,174 km2, 20% of which contains paddy fields. Water samples were also collected in six rivers flowing into the lake in order to compare the contamination level and concentration profile. The pesticides analyzed were four herbicides (molinate, simetryn, oxadiazon, and thiobencarb), one fungicide (isoprothiolane), and two insecticides (diazinon and fenitrothion). Molinate, simetryn, oxadiazon and isoprothiolane were found at the higher frequencies with maximum concentrations of 1.1, 0.4, 0.1 and 0.5 microg,/l in the effluent river, one or two order of magnitude higher than that of effluent in influent rivers. These peak concentrations were observed during the application period in influent rivers and two or three weeks after that in effluent river. The frequency of occurrence of thiobencarb, diazinon, and fenitrothion was relatively low and their maximum concentrations in the effluent remained below 0.1 microg/l. The decrease of molinate, simetryn and oxadiazon concentrations in the effluent river were approximated by two straight lines plotted on semilogarithmic scale. Increased loading was induced by intense rainfall, which took place during the application period. Simetryn and isoprothiolane persisted in relatively high concentrations through the year were also influenced on its loading by the heavy rainfall in the following months. The percentages of the total amount of pesticides released through Lake Biwa to the basin in downstream were estimated to be 1.3-2.9% for molinate, 5.4-10.0% for simetryn, 0.6-1.3% for oxadiazon, 0.2-0.9% for thiobencarb, 1.8-6.6% for isoprothiolane, 0.3-2.1% for diazinon. and 0% for fenitrothion.

Algal growth inhibition by river water pollutants in the agricultural area around Lake Biwa, Japan.

An ecotoxicological study of river water discharged from the agricultural area around Lake Biwa was performed by using algal bioassays to guide chemical analysis. Water samples were collected once a week, at least, for 1 year starting in April 1997 and continuing until April 1998. The toxicities of the dissolved and particulate-adsorbed extracts of water samples were evaluated by the algal growth inhibition test and concentrations of individual pesticides were determined. Most of the river water that was collected during the periods when pesticides were applied to the paddy fields caused algal growth inhibition. Some extracts were found to contain herbicides (molinate, mefenacet, simetryn, or esprocarb) as major compounds. According to chemical assay and bioassay, simetryn was identified as the most toxic compound that caused algal growth inhibition.

Distribution and pollutant load of hexabromocyclododecane (HBCD) in sewage treatment plants and water from Japanese Rivers.

Hexabromocyclododecane diastereoisomers (α-, ß-, γ-, δ-, and ε-HBCD) were investigated in river water, sewage influent, and sewage effluent from the Yodo River basin, Japan. The mean annual values of HBCDs ranged from 0.19 to 14ngL(-1) in river water. We observed that the concentrations of HBCDs in the brackish water area were low compared with that in the fresh water area. It was implied that, when the flow of the river stagnated in the estuarine area, HBCDs settled with suspended matter because of their hydrophobic character. In the sewage treatment plants, HBCDs ranged from 16 to 400ngL(-1) in sewage influent, whereas they ranged from 0.39 to 12ngL(-1) in sewage effluent. Over 90% of HBCDs were removed from the wastewater in the sewage treatment plants. By using these results, we estimated the pollutant load of HBCDs that flows into Osaka Bay from the study area. It was estimated that approximately 15kg of HBCDs flow into Osaka Bay from the study area in a year. This value is five orders of magnitude lower than the 2010 market demand for HBCDs (3019 metrictons) in Japan.

Comparison of the effects of di(2-ethylhexyl)phthalate, a peroxisome proliferator, on the vitamin metabolism involved in the energy formation in rats fed with a casein or gluten diet.

In order to find an alleviation method for the adverse effect of environmental endocrine disrupters, we studied the effects of the putative endocrine disrupter and peroxisome proliferator, di(2-ethylhexyl)phthalate (DEHP), on animal growth and vitamin metabolism. It is known that the effects of chemical compounds such as xenobiotics differ according to the dietary protein source. We compared the effects of dietary DEHP administration on rats fed with a diet containing milk casein or wheat gluten. The increased conversion ratio of tryptophan to nicotinamide by DEHP administration was significantly higher in the casein group than in the gluten group. We also investigated the effects of DEHP on the urinary excretion of other vitamins. DEHP administration resulted in decreased urinary excretion of vitamin B(1), vitamin B(2), and pantothenic acid.