Volatile organohalogen compounds in human urine: the effect of environmental exposure

The paper presents the results of determination of volatile organohalogen compounds (VOX) in urine samples from subjects exposed to these compounds in their workplaces and through consumption of chlorinated tap water. The analytes were isolated and preconcentrated from the complex urine samples using the thin layer headspace (TLHS) technique with autogenous generation of the liquid sorbent. Final gas chromatographic determination was carried out by direct aqueous injection with electron capture detection (DAI-ECD). The results indicate that only a small fraction (<4%) of the VOX input is excreted with urine in the non-metabolized form. A positive correlation was found between the occupational levels of VOX in the workplace and their levels in urine. VOX levels in the urine of subjects not exposed to them in the workplace were significantly lower. Their presence in the organisms was most probably related to consumption of tap water produced by chlorination of surface waters.     

Contamination status of arsenic and other trace elements in drinking water and residents from Tarkwa, a historic mining township in Ghana

This study was conducted to assess the contamination status of 22 trace elements, especially As in water and residents in Tarkwa, a historic mining town in Ghana. Drinking water and human urine samples were collected from Tarkwa in addition to control samples taken from Accra, the capital of Ghana in March, 2004. Concentrations of As and Mn in some drinking water samples from Tarkwa were found above the WHO drinking water guidelines posing a potential health risk for the people. A potential health risk of As and Mn is a concern for the people consuming the contaminated water in this area. No significant difference of As concentrations in human urine between mining town (Tarkwa) and control site (Accra) was observed. Although As concentrations in drinking water in Tarkwa were low, urinary As levels were comparable to those reported in highly As-affected areas in the world. These results suggest the presence of other sources of As contamination in Ghana. This is the first study on multi-elemental contamination in drinking water and human from a mining town in Ghana.     

松花江饮用水氯消毒中氯仿形成的优化控制

通过对松花江水进行大量实验 ,找出TOC的含量、投氯量、温度和 pH值等对氯仿形成的定量关系 ,确定了饮用水氯化的优化条件 ,使饮用水氯化过程中形成的氯仿含量不超过国家饮用水的标准     

Formation of halogenated acetaldehydes, and occurrence in Canadian drinking water

Controlled laboratory chlorination of acetaldehyde (ACD) under typical drinking water conditions (pH 6.7, 7.6 and 8.8, and temperature 4 degrees C and 21 degrees C) revealed that the formation of chloral hydrate (CH), the most common halogenated acetaldehyde (HAs), increased with contact time (0-10 days). However, at increased pH and temperature, CH reached maximum levels and subsequently broke down partially to chloroform and other unidentified compounds. After 10 days contact time, a maximum of 63% (molar) of the initial ACD consumed were converted into CH or chloroform (TCM). Various surveys of drinking water systems indicated that ACD is not the only precursor of CH. A suite of aldehydes (including ACD), and chlorinated disinfection by-products (including TCM and CH) were found in most distribution systems. The levels of bromide in source water impacted speciation of HAs. In addition to CH, brominated and other mixed (Cl/Br) acetaldehydes were detected in most samples; the speciation of HAs and THMs followed comparable trends. Similar to chloroform for trihalomethanes, CH contributed from as low as 5% to up to 60% of the total HAs. The bromine incorporation factors (BIF) in THMs and HAs were shown to increase with increasing bromide ion concentrations in the source water. Brominated THMs are more readily formed than their HA analogues; in fact, BIF values for THMs were 2-3 times higher than for the HAs. It was found that HAs may be as high as THMs in some drinking waters. As a result, the determination of the other target HAs, in addition to CH, is necessary for a better assessment of the pool of disinfection by-products in drinking water.     

Disinfection by-products in Finnish drinking waters

Disinfection by-products (DBPs) were measured in plant effluents of 35 Finnish waterworks, which utilized different treatment processes and raw water sources. DBPs were measured also from the distribution systems of three waterworks. Di- and trichloroacetic acids, and chloroform were the major DBPs found in treated water samples. The concentration of six haloacetic acids (HAA6) exceeded the concentrations of trihalomethanes (THMs). Chlorinated drinking waters (DWs) originating from surface waters contained the highest concentration of HAA6 and THMs: 108 and 26 microg/l, respectively. The lowest concentrations of DBPs were measured from ozonated and/or activated carbon filtrated and chloraminated DWs. Higher concentrations of HAA6, THMs, and adsorbable organic halogens were measured in summer compared to winter. The levels of chlorinated acetic acids, chloroform, and bromodichloromethane correlated positively with mutagenicity. Past mutagenicity levels of DWs were examined. A major reduction in the use of prechlorination, increased use of chloramine disinfection, and better removal of organic carbon were the most important reasons for the 69% decrease in mutagenicity from 1985 to 1994.     

A study of ground water contamination by arsenic in the residential area of Behala, Calcutta due to industrial pollution

Due to the discharge of industrial effluent after production of the insecticide Paris-Green [Copper acetoarsenite Cu(CH(3)COO)(2).3Cu(AsO(2))(2)] by a local factory at the P. N. Mitra Lane, Behala, ground water has become contaminated with arsenic. More than seven thousand people were using this arsenic contaminated tube-well water for drinking and house-hold purposes. Many people of the area were hospitalised and symptoms of arsenic toxicity were visible amongst a large number of the population. Analytical study reveals that soil around the area of effluent dumping point, which is at the middle of the locality, contains a very high concentration of arsenic and copper. For the last 20 years this factory had been producing 20 tons of Paris-Green per year and had been dumping its effluent in that area. It seems, the effluent treatment for arsenic removal was not adequate and finally arsenic percolated to the underground aquifers. Consequently, arsenic concentration in the ground water is very high. Both arsenite and arsenate are present in ground water. An alternate source of water other than the ground water is immediately necessary for the people of P. N. Mitra Lane.     

Trihalomethane formation during water disinfection in four water supplies in the Somes river basin in Romania

Background, aim and scope

After the discovery of chloroform in drinking water, an extensive amount of work has been dedicated to the factors influencing the formation of halogenated disinfections by-products (DBPs). The disinfection practice can vary significantly from one country to another. Whereas no disinfectant is added to many water supplies in Switzerland or no disinfectant residual is maintained in the distribution system, high disinfectant doses are applied together with high residual concentrations in the distribution system in other countries such as the USA or some southern European countries and Romania. In the present study, several treatment plants in the Somes river basin in Romania were investigated with regard to chlorine practice and DBP formation (trihalomethanes (THMs)). Laboratory kinetic studies were also performed to investigate whether there is a relationship between raw water dissolved organic matter, residual chlorine, water temperature and THM formation.

Materials and methods

Drinking water samples were collected from different sampling points in the water treatment plant (WTP) from Gilau and the corresponding distribution system in Cluj-Napoca and also from Beclean, Dej and Jibou WTPs. The water samples were collected once a month from July 2006 to November 2007 and stored in 40-mL vials closed with Teflon lined screw caps. Water samples were preserved at 4°C until analysis after sodium thiosulfate (Na₂S₂O₃) had been added to quench residual chlorine. All samples were analysed for THMs using headspace GC-ECD between 1 and 7 days after sampling. The sample (10 mL) was filled into 20-mL headspace vials and closed with a Teflon-lined screw cap. Thereafter, the samples were equilibrated in an oven at 60°C for 45 min. The headspace (1 mL) was then injected into the GC (Cyanopropylphenyl Polysiloxane column, 30 m × 53 mm, 3 μm film thickness, Thermo Finnigan, USA). The MDLs for THMs were determined from the standard deviation of eight standards at 1 μg/L. The MDLs for CHCl₃, CHBrCl₂, CHBr₂Cl and CHBr₃ were 0.3, 0.2, 0.3 and 0.6 μg/L, respectively. All kinetic laboratory studies were carried out only with water from the WTP Gilau. The experiments were conducted under two conditions: baseline conditions (pH 7, 21°C, 2.5 mg/L Cl₂) to gain information about the change of the organic matter in the raw water and seasonally variable conditions to simulate the actual process at the treatment plant and the distribution system.

Results and discussion

This study shows that the current chlorination practice in the investigated plants complies with the THM drinking water standards of the EU. The THM concentrations in all samples taken in the four treatment plants and distributions systems were below the EU drinking water standard for TTHMs of 100 μg/L. Due to the low bromide levels in the raw waters, the main THM formed in the investigated plants is chloroform. It could also be seen that the THM levels were typically lower in water supplies with groundwater as their water resource. In one plant (Dej) with a pre-ozonation step, a significantly lower (50%) THM formation during post-chlorination was observed. Laboratory chlorination experiments revealed a good correlation between chloroform formation and the consumed chlorine dose. Also, these experiments allowed a semi-quantative prediction of the chloroform formation in the distribution system of Cluj-Napoca.

Conclusions

CHCl₃ was the most important trihalomethane species observed after the chlorination of water in all of the sampled months. However, TTHM concentrations did not exceed the maximum permissible value of 100 μg/L (EU). The THM formation rates in the distribution system of Cluj-Napoca have a high seasonal variability. Kinetic laboratory experiments could be used to predict chloroform formation in the Cluj-Napoca distribution system. Furthermore, an empirical model allowed an estimation of the chloroform formation in the Gilau water treatment plant.

     

Determination of pesticides of different chemical classes in drinking water of the state of Santa Catarina (Brazil) using solid-phase microextraction coupled to chromatographic determinations

The evaluation of the concentration of pesticides in drinking water presents a real concern. In this study, a simple and rapid method based on solid-phase microextraction (SPME) followed by gas chromatography–mass spectrometry and electron capture detectors was developed aiming at multiclass determination of 23 pesticides regulated by the Brazilian legislation. The extraction was carried out by direct immersion mode (DI-SPME) using DVB/Car/PDMS fiber coating. In order to improve the extraction efficiency, parameters such as temperature, salting-out effect, and extraction time were optimized. The method was evaluated using drinking water samples spiked with the analytes at different concentrations, and it showed good linearity in the range studied. The values obtained for limits of quantification (LOQ) were below the limits established by Brazilian regulations. Accuracy and precision of the method exhibited satisfactory results, providing relative recoveries from 70 to 123.34% at three spiked levels, and the relative standard deviations ranged from 0.53 to 24.8%. The method was applied in 20 drinking water samples from 13 cities in the State of Santa Catarina, Brazil.

     

Distribution of polycyclic aromatic hydrocarbons in surface water and sediment near a drinking water reservoir in Northeastern China

The levels of polycyclic aromatic hydrocarbons (PAHs) in the water and the sediment samples collected near the Mopanshan Reservoir—the most important drinking water resource of Harbin City in Northeast China—were examined. A total of 16 PAHs were concurrently identified and quantified in the three water bodies tested (Lalin River, Mangniu River, and Mopanshan Reservoir) and in the Mopanshan drinking water treatment plant during the high- and low water periods. The total PAH concentrations in the water and sediment samples ranged from 122.7 to 639.8 ng/L and from 89.1 to 749.0 ng/g dry weight, respectively. Similar spatial and temporal trends were also found for both samples. The lowest Σ₁₆PAH concentration of the Mopanshan Reservoir was obtained during the high water period; by contrast, the Lalin River had the highest concentration during the low water period. The PAH profiles resembling the three water bodies, with high percentages of low-molecular weight PAHs and dominated by two- to three-ring PAHs (78.4 to 89.0 %). Two of the molecular indices used reflected the possible PAH sources, indicating the main input from coal combustion, especially during the low water period. The conventional drinking water treatment operations resulted in a 20.7 to 67.0 % decrease in the different-ringed PAHs in the Mopanshan-treated drinking water. These findings indicate that human activities negatively affect the drinking water resource. Without the obvious removal of the PAHs in the waterworks, drinking water poses certain potential health risks to people.     

自来水二氧化氯消毒控制三氯甲烷研究

对自来水二氧化氯消毒控制三氯甲烷形成进行了试验研究 ,二氧化氯预消毒替代预氯化消毒可以降低水中的三氯甲烷 ,预消毒处理后形成三氯甲烷的反应受温度和反应时间的影响。使用二氧化氯与氯配制的混合消毒剂消毒时 ,随二氧化氯含量增加 ,水中的三氯甲烷将明显减少。     

Formation of disinfection by-products in chlorinated swimming pool water.

The formation of five volatile disinfection by-products (DBPs: chloroform, bromodichloromethane, chloral hydrate, dichloroacetonitrile, and 1,1,1-trichloropropanone) by the chlorination of the materials of human origin (MHOs: hair, lotion, saliva, skin, and urine) in a swimming pool model system was examined. Chlorination reactions took place with a sufficient supply of chlorine residuals (0.84 mg Cl2/l < total chlorine < 6.0 mg Cl2/l) in 300 ml glass bottles containing either ground water or surface water as a reaction medium at 30 degrees C and pH 7.0, for either 24 or 72 h. A longer reaction period of 72 h or a higher content of organic materials led to the increased formation of DBPs. Of the DBPs formed by the reaction, chloroform was a major compound found in both ground and surface waters. The formation of chloroform and bromodichloromethane per unit total organic carbon (TOC) concentration was suppressed when all types of MHOs were added to the surface water that already contained DBP precursors such as humic substances. However, the formation of dichloroacetonitrile was promoted, probably due to the increased degradation reactions of nitrogen-containing compounds such as urea and proteins of human origin. In conclusion, the materials of swimmers' origin including hair, lotion, saliva, skin, and urine add to the levels of DBPs in swimming pool water, and any mitigation measures such as periodic change of water are needed to protect swimmers from elevated exposures to these compounds.     

Human pharmaceuticals, antioxidants, and plasticizers in wastewater treatment plant and water reclamation plant effluents.

The primary objective of this study was to determine the presence of unregulated organic chemicals in reclaimed water using complementary targeted and broad spectrum approaches. Eleven of 12 targeted human pharmaceuticals, antioxidants, and plasticizers, and 27 tentatively identified non-target organic chemicals, were present in secondary effluent entering tertiary treatment trains at a wastewater treatment plant and two water reclamation facilities. The removal of these compounds by three different tertiary treatment trains was investigated: coagulant-assisted granular media filtration (California Title-22 water, 22 CCR 60301-60357; Barclay [2006]), lime clarification/reverse osmosis (lime/ RO), and microfiltration-reverse osmosis (MF/RO). Carbamazepine, clofibric acid, gemfibrozil, ibuprofen, p-toluenesulfonamide, caffeine, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), and N-butyl benzenesulfonamide (N-BBSA) were present at low to high nanogram-per-liter levels in Title 22 water. The lime/RO product waters contained lower concentrations of clofibric acid, ibuprofen, caffeine, BHA, and N-BBSA (<10 to 71 ng/L) than their Title 22 counterparts. The MF/RO treatment reduced concentrations to levels below their detection limits, although BHT was present in MF/RO product water from one facility. The presence of the target analytes in two surface waters used as raw drinking water sources and a recharged groundwater was also examined. Surface waters used as raw drinking water sources contained caffeine, BHA, BHT, and N-BBSA, while recharged groundwater contained BHT, BHA, and N-BBSA. Nontarget compounds in recharged groundwater appeared to be attenuated with increased residence time in the aquifer.     

Mutagenicity and organic halogen determination in body fluids and tissues of rats treated with drinking water and pulp mill bleachery effluent concentrates

Concentrates of either drinking water or chlorination stage pulp mill effluent were injected intraperitonally into rats. Urine, feces, liver, and adipose tissues were tested for mutagenic activity and analysed for organic halogen. For both sample types nearly all the organic halogen taken up, eighteen percent from the chlorination stage sample and four percent from the drinking water sample, was excreted via the urine during the first day. Weak mutagenic activity could only be found in the urine collected the first day from animals treated with the highest dose of drinking water.     

MTBE in California's Drinking Water: A Comparison of Groundwater Versus Surface Water Sources

During the last decade, the fuel oxygenate methyl tertiary butyl ether (MTBE) has received widespread attention as a potential threat to water quality, primarily due to leaking underground gasoline storage tanks and watercraft with two-stroke engines. In this article, we examine the annual detection frequency, number of new source detections, and concentration of MTBE detected in California's public drinking water groundwater and surface water sources from 1995 to 2002. This work builds on our previous evaluations of California's water quality monitoring database. However, it is unique in that it includes separate evaluations for groundwater and surface water sources that are of greatest concern to regulators, and which are likely being used for current public consumption. Our evaluations also include full-year data for 2002 (which have not been published previously) and an analysis of how the sampling and reported detections of MTBE vary by geographic location. We find that MTBE was generally detected (at any level) in approximately 0.5-0.9% and 0.2-0.4% of all groundwater sources assuming a one-detection and two-detection criterion, respectively. The overall detection frequency for MTBE in surface water sources is significantly higher than for groundwater sources, although these surface water detections appear to have substantially declined since 1996 (e.g., 7-9% for all surface water sources during 1996 to 1999 and 4% for all surface water sources during 2000 to 2002, assuming a one-detection criterion). The detection frequency of MTBE concentrations at or above the state drinking water standards in all drinking water sources (both groundwater and surface water sources) and the subset of drinking water sources that are likely to currently be delivered to consumers is markedly lower (and often zero). Despite the significant increase in water sampling over time, the number of new drinking water sources found to contain MTBE in California has not increased at the same rate and appears to have remained relatively stable or to have decreased since 1998. The data also show that nearly all of the 58 counties in California have routinely sampled at least some of their groundwater and surface water sources for MTBE over the last 8 years. Geographical evaluations show that MTBE has been detected (at least once) in groundwater sources in 34 counties and in surface water sources in 18 counties but has only been detected routinely (i.e., for 3 or more years) in 16 and 7 counties, respectively. Detected concentrations of MTBE are also generally below state drinking water standards, particularly for surface water sources. In short: (1) MTBE is rarely found in California groundwater or surface water sources that are of greatest concern to regulators or the public, and (2) drinking water detections of MTBE are expected to decline in the future due to the pending phase-out of MTBE and recent regulatory programs aimed at controlling gasoline releases from underground storage tanks and two-stroke-engine watercraft.     

Chloroform in the environment: occurrence,sources, sinks and effects

The chloroform flux through the environment is apparently constant at some 660±220 Gg yr⁻¹ (±1σ) and about 90% of the emissions are natural in origin: the largest single source being in offshore sea water (contributing 360±90 Gg yr⁻¹), with soil processes the next most important (220±100 Gg yr⁻¹). Other natural sources, mainly volcanic and geological, account for less than 20 Gg yr⁻¹. The non-natural sources total 66±23 Gg yr⁻¹ and are much better characterised than the natural sources. They are predominantly the result of using strong oxidising agent on organic material in the presence of chloride ion, a direct parallel with the natural processes occurring in soils.

Chloroform partitions preferentially into the atmosphere; the equilibrium distribution is greater than 99% and the average global atmospheric concentration has been calculated to be 18.5 pmol mol⁻¹. Atmospheric oxidation, the principal removal process, is approximately in balance with the identified source fluxes. Chloroform is widely dispersed in the aquatic environment (even naturally present in some mineral waters). Consequently, it is also widely dispersed in the tissue of living creatures and in foodstuffs but there is little evidence of bioaccumulation and the quantities in foodstuffs and drinking water are not problematical for human ingestion at the highest concentrations found. Definitive studies have shown that current environmental concentrations of chloroform do not present an ecotoxicological risk, even to fish at the embryonic and larval stages when they are most susceptible.

By virtue of the very small amounts that actually become transported to the stratosphere, chloroform does not deplete ozone materially, nor is it a photochemically active volatile organic compound (VOC). It has a global warming potential that is less than that of the photochemically active VOCs and is not classed as a greenhouse gas.     

Dietary arsenic consumption and urine arsenic in an endemic population: response to improvement of drinking water quality in a 2-year consecutive study

We assessed the association between arsenic intake through water and diet, and arsenic levels in first morning-void urine under variable conditions of water contamination. This was done in a 2-year consecutive study in an endemic population. Exposure of arsenic through water and diet was assessed for participants using arsenic-contaminated water (≥50 μg L^?1) in a first year (group I) and for participants using water lower in arsenic (<50 μg L^?1) in the next year (group II). Participants with and without arsenical skin lesions were considered in the statistical analysis. Median dose of arsenic intake through drinking water in groups I and II males was 7.44 and 0.85 μg kg body wt.^?1 day^?1 (p <0.0001). In females, it was 5.3 and 0.63 μg kg body wt.^?1 day^?1 (p <0.0001) for groups I and II, respectively. Arsenic dose through diet was 3.3 and 2.6 μg kg body wt.^?1 day^?1 (p?=?0.088) in males and 2.6 and 1.9 μg kg body wt.^?1 day^?1 (p?=?0.0081) in females. Median arsenic levels in urine of groups I and II males were 124 and 61 μg L^?1 (p?=?0.052) and in females 130 and 52 μg L^?1 (p?=?0.0001), respectively. When arsenic levels in the water were reduced to below 50 μg L^?1 (Indian permissible limit), total arsenic intake and arsenic intake through the water significantly decreased, but arsenic uptake through the diet was found to be not significantly affected. Moreover, it was found that drinking water mainly contributed to variations in urine arsenic concentrations. However, differences between male and female participants also indicate that not only arsenic uptake, but also many physiological factors affect arsenic behavior in the body and its excretion. As total median arsenic exposure still often exceeded 3.0 μg kg body wt.^?1 day^?1 (the permissible lower limit established by the Joint Expert Committee on Food Additives) after installation of the drinking water filters, it can be concluded that supplying the filtered water only may not be sufficient to minimize arsenic availability for an already endemic population.     

Application of semipermeable membrane device for assessing toxicity in drinking water

Semipermeable membrane devices (SPMDs) mimic passive diffusive transport of bioavailable hydrophobic organic compounds through biological membranes and their partitioning between lipids and environmental levels. Our study was developed on a surface water treatment plant based in Turin, Northern Italy. The investigated plant treats Po River surface water and it supplies about 20% of the drinking water required by Turin city (about one million inhabitants). Surface water (input) and drinking water (output) were monitored with SPMDs from October 2001 to January 2004, over a period of 30 days. The contaminant residues, monthly extracted from SPMDs by dialysis in organic solvent, were tested with the Microtox^TM acute toxic test and with the Ames mutagenicity test. Same extracts were also analyzed with gaschromatography—mass spectrometry technique in order to characterise the organic pollutants sampled, especially Polycyclic Aromatic Hydrocarbons (PAHs).

Although the PAHs mean concentration is about one hundred times lower in the output samples, the mean toxic units are similar in drinking and surface water.

Our data indicate that the SPMD is a suitable tool to assess the possible toxicity in drinking water.     

Relationship of urinary arsenic metabolites to intake estimates in residents of the Red River Delta, Vietnam

This study investigated the status of arsenic (As) exposure from groundwater and rice, and its methylation capacity in residents from the Red River Delta, Vietnam. Arsenic levels in groundwater ranged from <1.8 to 486 μg/L. Remarkably, 86% of groundwater samples exceeded WHO drinking water guideline of 10 μg/L. Also, estimated inorganic As intake from groundwater and rice were over Provisional Tolerable Weekly Intake (15 μg/week/kg body wt.) by FAO/WHO for 92% of the residents examined. Inorganic As and its metabolite (monomethylarsonic acid and dimethylarsinic acid) concentrations in human urine were positively correlated with estimated inorganic As intake. These results suggest that residents in these areas are exposed to As through consumption of groundwater and rice, and potential health risk of As is of great concern for these people. Urinary concentration ratios of dimethylarsinic acid to monomethylarsonic acid in children were higher than those in adults, especially among men, indicating greater As methylation capacity in children.     

Factors affecting the performance of a solar still and productivity enhancement methods: A review

Environmental Science and Pollution Research - Good-quality drinking water is an essential requirement for a healthy and sustainable future. In the current scenario, people living in remote areas...     

A global health problem caused by arsenic from natural sources

Arsenic is a carcinogen to both humans and animals. Arsenicals have been associated with cancers of the skin, lung, and bladder. Clinical manifestations of chronic arsenic poisoning include non-cancer end point of hyper- and hypo-pigmentation, keratosis, hypertension, cardiovascular diseases and diabetes. Epidemiological evidence indicates that arsenic concentration exceeding 50 microg l(-1) in the drinking water is not public health protective. The current WHO recommended guideline value for arsenic in drinking water is 10 microg l(-1), whereas many developing countries are still having a value of 50 microg l(-1). It has been estimated that tens of millions of people are at risk exposing to excessive levels of arsenic from both contaminated water and arsenic-bearing coal from natural sources. The global health implication and possible intervention strategies were also discussed in this review article.