Relationship between volatile organohalogen compounds in drinking water and human urine in Poland

Selected volatile organohalogen compounds (VOX) were investigated in urine samples from people living in different areas of the Gdańsk-Sopot-Gdynia TriCity (Poland). The analytes were isolated and preconcentrated using the so-called thin layer headspace technique with autogenous generation of the liquid sorbent. Final gas chromatographic determination was carried out by direct aqueous injection with electron capture detection. Analyte concentrations in drinking water ranged from not detected to approximately 8 microg/l (chloroform), depending on the source of drinking water in a given part of the TriCity (underground, surface or mixed). The corresponding urine levels were typically lower by about an order of magnitude. VOX levels in urine of people living in the parts of the TriCity supplied with drinking water containing elevated levels of the analytes were higher than the levels in urine of people whose drinking water originated from deep underground wells. The linear correlation coefficients for the relationships between total VOX and chloroform levels in drinking water and in urine were r2=0.65 and 0.88, respectively. The fraction of VOX excreted with urine in unchanged form did not exceed 20%.     

Occurrence of perfluorooctanoate and perfluorooctanesulfonate in the Korean water system: implication to water intake exposure

Perfluorinated compounds (PFCs) measured in surface running waters indicated the existence of different emission sources in eight main city basins. The tap water reflected the contamination pattern and levels in their corresponding source water basins. The daily intakes through tap water consumption ranged from <0.01 to 0.73 ng kg⁻¹ d⁻¹ for perfluorooctanoate (PFOA) and <0.01 to 0.08 ng kg⁻¹ d⁻¹ for perfluorooctanesulfonate (PFOS). Tap water intake-derived exposure accounted for 8.6%-101% (for PFOA) and while <10% (for PFOS) of total daily exposure, which was estimated from Korean serum concentrations using a pharmacokinetic model. Our findings indicate that tap water intake could be an important contributor to PFOA exposure in Korean populations; accordingly, additional efforts are necessary to improve the removal efficiency of perfluorinated compounds (PFCs) in the water purification process. However, more fundamentally the aim would be to reduce the discharge of PFCs from potential sources within the basin.     

Monitoring PCDD/Fs and other organic substances in workers of a hazardous waste incinerator: a case study

The aim of this study was to measure, 6 years after regular operations, the concentrations of a number of organic substances in blood and urine of 19 workers employed at a hazardous waste incinerator (HWI) in Spain, and to establish the temporal variation with respect to baseline data and previously performed surveys. This facility was the first, and so far the only HWI in that country. The levels of hexachlorobenzene (HCB), polychlorinated biphenyls (PCB 28, 52, 101, 138, 153 and 180) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analyzed in six composite plasma samples, while concentrations of di-, tri, and pentachlorophenols, as well those of 1-hydroxypyrene were measured in the urine of these workers. The current mean PCDD/F concentration, 10.4 ng I-TEQ/kg lipid, was significantly lower than that found in the baseline survey, 26.7 ng I-TEQ/kg lipid and similar to that found in the previous (2004) study (7.7 ng I-TEQ/kg lipid). PCDD/F levels in plasma were similar or even lower than those recently reported for various non-exposed populations. For the remaining analyzed substances in plasma and urine, there was not any significant increase in comparison with the levels found in the baseline survey. On the other hand, no marked differences between the concentrations of organic substances in plasma or urine were found according to the respective workplace (plant, laboratory and administration). The results of the present survey indicate that after 6 years of regular operation, the workers at the HWI are not occupationally exposed to PCDD/Fs and other organic substances in their workplaces.     

The mutagenic potentials of tap water samples in Shanghai

The tap water samples were collected from the users' ends in several areas of Shanghai, which is located in Taihu Lake basin, Eastern China. Source water samples were also collected from two municipal source water facilities at the same time. Samples were assayed by three different short-term mutagenicity test systems: Salmonella/microsome assay (Ames test), the Arabinose resistance test (Ara test) and the SOS/umu test. The data showed that two source water samples did not display direct mutagenic potentials. Two tap water samples from city north, which were directly from Yangtze River, were also not mutagenic. Water samples from city south and middle which used source water originating from Taihu Lake were proved to be contaminated with mutagenic potentials by three different assay techniques. The boiled water displayed an even stronger mutagenic potential compared to its original tap water. The molecular mechanism of mutagenicity was associated with a reading frame-shifting potential. GC-MS analysis of tap water extracts from city middle and corresponding source water was compared. Qualitatively similar spectra were observed except for the peaks of three chlorinated aromatic hydrocarbon compounds, which existed only in the tap water. Since the water source has been polluted, raw water was heavily chlorinated in order to sterilize. More toxic compounds, including mutagens, might form during the multi-chlorination. Caution about the possibility of elevated cancer risks in the population that consumes heavily chlorinated water should be kept in mind. A cohort study in the residents of Shanghai is required.     

Ultrasound-assisted emulsification-microextraction of fragrance allergens in water

A method based on ultrasound-assisted emulsification-microextraction (USAEME) and gas chromatography-mass spectrometry (GC-MS) has been developed for the analysis of regulated fragrance allergens in water. Extraction conditions such as the type of solvent, extraction temperature, irradiation time, and salting-out effect were optimized using a multivariate approach. Compounds were extracted during 2 min in an acoustically emulsified media formed by 100 μL chloroform and 10 mL sample. The USAEME process provided an efficient and exhaustive extraction (enrichment factor ～100) and, after centrifugation, the extract was ready for GC analysis. Validation was performed using spiked ultrapure water as well as other most complex matrices such as sewage water. Recoveries between 75% and 110% were generally obtained, and precision was characterized by RSD values <10% in most cases. The limits of detection (LODs) were at the sub-nanogram per millilitre level. The proposed procedure was applied to the determination of allergens in several real samples including tap water, baby bathwater, recreational place water, public washing place water, and sewage water. The presence of some of the target compounds was confirmed in all the samples excluding tap water, demonstrating the ubiquity of this group of cosmetic and personal care products ingredients.     

A rapid, sensitive screening test for polycyclic aromatic hydrocarbons applied to Antarctic water

We describe a rapid, sensitive, fluorescence screening test for polycyclic aromatic hydrocarbons in water samples that avoids more costly time-consuming methods. The screening test works by detecting benzo[a]pyrene. It runs without the need for any pre-concentration step, thus rendering it suitable for routine use in water-quality-control laboratories. The test recognizes contaminated samples rapidly (150 s) and inexpensively with a cut-off level of 10 ng l(-1), which is the value that the European Union and World Health Organization (WHO) have laid down in its assessment of the quality of water for human consumption. This was first ascertained by analysing tap and waste-water samples before studying environmental water samples from the Antarctic region. The reliability of the screening test was 2% false positives and 4% false negatives in 200 samples of tap and waste-water. The applicability was confirmed by the fact that the predictions of the screening test coincided exactly with results obtained with gas chromatography-mass spectrometry assays. We also discuss the polluted Antarctic samples and the possible sources of the contamination involved.     

VOC concentrations measured in personal samples and residential indoor,outdoor and workplace microenvironments in EXPOLIS-Helsinki,Finland

Thirty target volatile organic compounds (VOC) were analyzed in personal 48-h exposure samples and residential indoor, residential outdoor and workplace indoor microenvironment samples as a component of EXPOLIS-Helsinki, Finland. Geometric mean residential indoor concentrations were higher than geometric mean residential outdoor concentrations for all target compounds except hexane, which was detected in 40% of residential outdoor samples and 11% of residential indoor samples, respectively. Geometric mean residential indoor concentrations were significantly higher than personal exposure concentrations, which in turn were significantly higher than workplace concentrations for compounds that had strong residential indoor sources (d-limonene, alpha pinene, 3-carene, hexanal, 2-methyl-1-propanol and 1-butanol). 40% of participants in EXPOLIS-Helsinki reported personal exposure to environmental tobacco smoke (ETS). Participants in Helsinki that were exposed to ETS at any time during the 48-h sampling period had significantly higher personal exposures to benzene, toluene, styrene, m,p-xylene, o-xylene, ethylbenzene and trimethylbenzene. Geometric mean ETS-free workplace concentrations were higher than ETS-free personal exposure concentrations for styrene, hexane and cyclohexane. Geometric mean personal exposures of participants not exposed to ETS were approximately equivalent to time weighted ETS-free indoor and workplace concentrations, except for octanal and compounds associated with traffic, which showed higher geometric mean personal exposure concentrations than any microenvironment (o-xylene, ethylbenzene,benzene, undecane, nonane, decane, m,p-xylene, and trimethylbenzene). Considerable differences in personal exposure concentrations and residential levels of compounds with mainly indoor sources suggested differences in product types or the frequency of product use between Helsinki, Germany and the United States.     

Determination of 2,4-dichlorophenoxyacetic acid (2,4-D) in human urine with mass selective detection.

Method development and validation studies have been completed on an assay that will allow the determination of 2,4-dichlorophenoxyacetic acid (2,4-D) in human urine. The accurate determination of 2,4-D in urine is an important factor in monitoring worker and population exposure. These studies successfully validated a method for the detection of 2,4-D in urine at a limit of quantitation (LOQ) of 5.00 ppb (parts per billion) using gas chromatography with mass selective detection (GC/MSD). The first study involved the determination of 2,4-D in control human urine and urine samples fortified with 2,4-D. Due to chromatographic interference, a second study was conducted using 14C-2,4-D to verify the recoverability of 2,4-D from human urine at low levels using the GC/MSD method. The second study supports the results of the original data. The 2,4-D was extracted from human urine using a procedure involving hydrolysis using potassium hydroxide, followed by a liquid-liquid extraction into methylene chloride. The extracted samples were derivatized with diazomethane. The methylated fraction was analyzed by GC/MSD. Quantitation was made by comparison to methylated reference standards of 2,4-D. Aliquots fortified at 5-, 50-, and 500-ppb levels were analyzed. The overall mean recovery for all fortified samples was 90.3% with a relative standard deviation of 14.31%.     

Levels of perfluorochemicals in water samples from Catalonia,Spain: is drinking water a significant contribution to human exposure?

Background, aim, and scope  In recent years, due to a high persistence, biomagnification in food webs, presence in remote regions, and potential toxicity, perfluorochemicals (PFCs) have generated a considerable interest. The present study was aimed to determine the levels of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and other PFCs in drinking water (tap and bottled) and river water samples from Tarragona Province (Catalonia, Spain). Materials and methods  Municipal drinking (tap) water samples were collected from the four most populated towns in the Tarragona Province, whereas samples of bottled waters were purchased from supermarkets. River water samples were collected from the Ebro (two samples), Cortiella, and Francolí Rivers. After pretreatment, PFC analyses were performed by HPLC-MS. Quantification was done using the internal standard method, with recoveries between 68% and 118%. Results  In tap water, PFOS and PFOA levels ranged between 0.39 and 0.87 ng/L (0.78 and 1.74 pmol/L) and between 0.32 and 6.28 ng/L (0.77 and 15.2 pmol/L), respectively. PFHpA, PFHxS, and PFNA were also other detected PFCs. PFC levels were notably lower in bottled water, where PFOS could not be detected in any sample. Moreover, PFHpA, PFHxS, PFOA, PFNA, PFOS, PFOSA, and PFDA could be detected in the river water samples. PFOS and PFOA concentrations were between <0.24 and 5.88 ng/L (<0.48 and 11.8 pmol/L) and between <0.22 and 24.9 ng/L (<0.53 and 60.1 pmol/L), respectively. Discussion  Assuming a human water consumption of 2 L per day, the daily intake of PFOS and PFOA by the population of the area under evaluation was calculated (0.78–1.74 and 12.6 ng, respectively). It was found that drinking water might be a source of exposure to PFCs as important as the dietary intake of these pollutants. Conclusions  The contribution of drinking water (tap and bottled) to the human daily intake of various PFCs has been compared for the first time with data from dietary intake of these PFCs. It was noted that in certain cases, drinking water can be a source of exposure to PFCs as important as the dietary intake of these pollutants although the current concentrations were similar or lower than those reported in the literature for surface water samples from a number of regions and countries. Recommendations and perspectives  Further studies should be carried out in order to increase the knowledge of the role of drinking water in human exposure to PFCs.     

Human exposure to fluoride from tea (Camellia sinensis) in a volcanic region—Canary Islands,Spain

Fluoride is highly present in the environment, especially in water and its derivatives. Excessive fluoride contribution to diet poses a health risk. Tea leaves accumulate fluoride and the consumption of tea (Camellia sinensis) could pose a risk to human by the excessive fluoride intake. Ninety tea samples were analyzed by potentiometry using a selective fluoride ion electrode. Mixed tea samples (2.82?±?1.11 mg/L) and black tea samples (2.28?±?0.79 mg/L) recorded the highest fluoride levels. The contribution of drinking water is important for increasing fluoride levels in teas. The daily consumption of two cups (250 mL per cup) of mixed and black teas prepared with La Laguna tap water does pose a health risk for children (4–8 years old) because of the high contribution percentages (74.4% and 63.6%, respectively) of the Tolerable Upper Intake Level set in 2.5 mg/day by the EFSA (European Food Safety Authority). A minor consumption in children (4–8 years old) and adults during pregnancy is advisable.

     

Organic contaminates in water

Abstract

The carbon adsorption method was used for separating organic matter from large samples of drainage, river and tap water. The carbon chloroform extract (CCE) was separated into different solubility fractions and the neutral fraction was separated into aliphatic, aromatic and oxy‐compounds using column chromatography. The aromatic fraction was subjected to TLC, IR and UV analysis. The pesticide endrin was present in both river and tap water at concentrations of 0.7 and 1.5 ppb, respectively.     

颗粒活性炭去除水中甲基叔丁基醚的可行性研究

随着甲基叔丁基醚（MTBE）作为汽油添加剂被持续大量使用，其已成为一种地下水中常见的有机污染物。本文通过纯净水、自来水和地下水中MTBE的平衡吸附容量和微型快速穿透实验（MCRB），比较了5种不同种类活性炭对MTBE的吸附性能。结果显示，苯酚值可准确预测活性炭样品对MTBE的平衡吸附容量大小次序，而丹宁酸值则可大致估计活性炭在实际处理应用时的吸附速度和吸附容量利用率。水样中共存的有机成分降低了活性炭对纯净水中MTBE的吸附容量，在背景TOC较低的去离子水中，活性炭对于MTBE的吸附性能反而比在地下水中降低得更多。穿透实验数据显示双柱串联的处理方式是高效应用活性炭吸附水中MTBE的优选工艺。使用环境友好的竹质活性炭去除地下水中MTBE具有良好的可行性和较高的性价比。     

Determination of phenolic and steroid endocrine disrupting compounds in environmental matrices

BACKGROUND, AIM AND SCOPE: Many pollutants have received significant attention due to their potential estrogenic effect and are classified as endocrine disrupting compounds (EDCs). EDCs comprise many classes of organic compounds. The development or optimization of analytical protocols for the simultaneous determination of EDCs in environmental samples is an analytical challenge because these compounds exhibit different physicochemical characteristics, they occur in the aquatic environment in relatively low concentrations and, furthermore, environmental samples are considered as complex matrices. The aim of this study is the development of analytical methods for the simultaneous determination of phenolic and steroid EDCs in aqueous and solid samples. The target compounds are 4-nonylphenol, 4-octylphenol, their ethoxylate oligomers (mono- and di-ethoxylates of nonylphenol and octylphenol), bisphenol A, the estrogens (estriol, estrone, 17beta-estradiol, 17alpha-estradiol) and the synthetic steroids (mestranol and 17alpha-ethynylestradiol). MATERIALS AND METHODS: Solid phase extraction employing Oasis HLB cartridges and different elution solvents was used for the recovery studies of the target compounds from various types of water samples (ultrapure water, artificial seawater, river water and seawater). Ultrasonic assisted extraction was applied for the recovery of the target EDCs from the solid samples. The recoveries were assessed using various solvents for the extraction and the elution of EDCs from different SPE cartridges used for clean up. Gas chromatography-mass spectrometry after derivatization with N,O-bis(trimethylsilyl)-trifluoroacetamide was employed for the determination of these compounds. RESULTS AND DISCUSSION: The recovery rates of three elution solvents (methanol, acetone and ethylacetate) for the extraction of target EDCs from artificial seawater were assessed after preconcentration on SPE cartridges. Acetone showed better recoveries and was further tested for its extraction efficiency in different water types (river water, seawater). Ultrasonic assisted extraction was used for the recovery of target EDCs from solid matrices. Acetone, methanol, mixture of acetone-methanol (1:1) and ethylacetate were used as extraction solvents. Ethylacetate and the mixture of acetone-methanol (1:1) exhibited better extraction efficiencies. An additional clean up step was necessary for sediment samples. Different SPE cartridges were employed for clean up of the extracts (Oasis HLB, C18, Florisil, silica, combination of silica and alumina). Florisil cartridges were finally used. The proposed methods were further validated on the determination of target EDCs in field collected samples (river water, seawater, wastewater, total suspended solids and sediments) from the major area of Thessaloniki, Greece. CONCLUSIONS: Efficient and accurate integrated methods for the simultaneous determination of alkylphenols (nonylphenol, octylphenol), their ethoxylate oligomers (mono- and di-ethoxylate of nonylphenol and octylphenol), bisphenol A and steroids (estriol, estrone, 17beta-estradiol, 17alpha-estradiol, mestranol and 17alpha-ethynylestradiol) in aqueous and solid samples were developed. The proposed methods were applied for the determination of the target compounds in representative environmental samples in the area of Thessaloniki, Northern Greece. RECOMMENDATIONS AND PERSPECTIVES: This study confirms the occurrence of selected EDCs in inland and marine waters in the area of Thessaloniki, Northern Greece. Since there is no previous data on the occurrence of the target EDCs in the major area, an extended survey is in progress to evaluate the occurrence and fate of these compounds.     

Pilot study on the contamination of drinking water by organotin compounds from PVC materials

Raw and treated water samples and tap water samples from four to six houses located on distribution lines where PVC pipe/tubing had been recently installed were collected in five Canadian municipalities for the analysis of organotin compounds. After derivatisation with sodium tetraethylborate the ethylated organotin compounds were extracted with hexane and analysed by gas chromatography-microwave induced plasma atomic emission spectrometry using a wavelength (326.234 nm) specific for tin. Organotin compounds, mainly methyltin and dimethyltin at concentrations ranging respectively from 0.5 to 257 ng Sn/L and from 0.5 to 6.5 ng Sn/L, were detected in samples from ten of the twenty-two houses. No organotin compounds were detected in raw water or treated water leaving the treatment plant, indicating that the organotin compounds were leaching into the water from some component of the distribution system.     

Gross alpha and beta activities in tap waters in Eastern Black Sea region of Turkey

Gross alpha and gross beta activities were determined for 27 different tap water samples collected from Eastern Black Sea region of Turkey. The instrumentation used to count the gross alpha and gross beta activities was a alpha/beta counter of the low background multiple detector type with 10 sample detectors (Berthold LB770). The obtained results showed that natural activity concentrations of alpha- and beta-emitting radionuclides in tap water samples did not exceed WHO and ITS recommended levels. Concentrations ranging from 0.2 mBq/l to 15 mBq/l and from 25.2 mBq/l to 264.4 mBq/l were observed for the gross alpha and gross beta activities, respectively. For all samples the gross beta activities were higher than the corresponding gross alpha activities.     

Polycyclic aromatic hydrocarbons in sewage,mussels and tap water

Polycyclic aromatic hydrocarbons (PAH) have been determined in sewage discharge, mussels and tap water by glass capillary gas chromatography. Up to 30 PAH compounds have been identified. The concentration levels are low, respectively 0.8 – 7.7μg/1, 0.5–1.1 μg/g and 0.002 – 0.2μg/1 of sum PAH have been determined in sewage discharge, mussels and tap water. The accumulation rate in mussels seems to be rather slow at the ambient water concentrations.     

Integrated biological responses of zebrafish (Danio rerio) to analyze water quality in regions under anthropogenic influence

This study analyzed water quality in regions around Patos lagoon (Southern Brazil) that are under anthropogenic pressure. Water samples were collected from five different sites, including one used as a source for human consumption (COR) and others known to be influenced by human activities (IP). Danio rerio (Teleostei, Cyprinidae) organisms were exposed for 24 h to these water samples, plus a control group. It was observed that: (1) reactive oxygen species levels were lower in COR and IP than in the control group; (2) glutamate-cysteine ligase (catalytic subunit) expression was higher in COR than in other sites; (3) exposure to all water samples affected long-term memory (LTM) when compared to control group. Thus, some water samples possess the ability to modulate the antioxidant system and to induce a decline in cognitive functions, as measured by LTM. The obtained results indicate that a combination of variables of different organization level (molecular, biochemical and behavioral) can be employed to analyze water quality in impacted regions.     

Novel polymer monolith microextraction using a poly-(methyl methacrylate-co-ethylene dimethacrylate) monolith and its application to the determination of polychlorinated biphenyls in water samples

A novel and simple method based on polymer monolith microextraction (PMME) coupled to gas chromatography with electron-capture detection (GC-ECD) was developed for the determination of six polychlorinated biphenyls (PCBs) residues in water samples. The proposed method used poly-(methyl methacrylate-co-ethylene dimethacrylate) (MMA-co-EDMA) monolith as extraction media. Several factors affecting experiments such as sample flow rate, sample volume, the type of eluent, eluent volume, eluent flow rate, effect of salt addition and carry over effect were investigated and optimized systematically. The limits of detection (LODs) for six PCBs were 0.028-0.043 ng mL⁻¹ in water samples. The intra-day and inter-day precisions (R.S.D.) were less than 9.2% and 9.6%, respectively. The proposed method was successfully applied to the determination of six PCBs in tap water, lake water and industrial waste water and the trueness has been evaluated by recovery experiments. The obtained relative recoveries were in the range of 63.3-105.6%.     

Response of microbial growth to orthophosphate and organic carbon influx in copper and plastic based plumbing water systems

Consequences of orthophosphate addition for corrosion control in water distribution pipes with respect to microbial growth were investigated using batch and dynamic tests. Batch tests showed that the release of copper in either low or high organic carbon content water was decreased by 69% and 56% with addition 206 microg PO(4)-P, respectively. Dosing of orthophosphate against corrosion did not increase microbial growth potential in the water and in the biofilm in both corroded and uncorroded systems receiving tap water with a low content of organic carbon and of biodegradable organic fraction. However, in tap water having a high concentration of organic carbon from acetate addition, orthophosphate addition promoted the growth of bacteria, allowed more bacteria to assemble on corroded and uncorroded surfaces, and increased the consumption of organic carbon. Orthophosphate consumption did not exceed 1% of the amount of easily biodegradable organic carbon required for microbial growth, and the orthophosphate demand for corrosion control greatly exceeded the nutritional requirement of microbial growth. The results of the dynamic tests demonstrated that there was a significant effect of interaction between biodegradable organic carbon and orthophosphate on biofilm growth, whereby the effect of orthophosphate flux on microbial growth was dependent on the levels of biodegradable organic carbon. Controlling an easily biodegradable organic carbon would be therefore necessary to minimize the microbial growth potential induced by orthophosphate-based anticorrosion treatment.