Contamination by arsenic and other trace elements of tube-well water along the Mekong River in Lao PDR

Arsenic and other trace element concentrations were determined for tube-well water collected in the Lao PDR provinces of Attapeu, Bolikhamxai, Champasak, Savannakhet, Saravane, and Vientiane. Water samples, especially from floodplain areas of central and southern Laos, were significantly contaminated not only with As, but with B, Ba, Mn, U, and Fe as well. Total As concentrations ranged from <0.5 μg L⁻¹ to 278 μg L⁻¹, with over half exceeding the WHO guideline of 10 μg L⁻¹. 46% of samples, notably, were dominated by As(III). Samples from Vientiane, further north, were all acceptable except on pH, which was below drinking water limits. A principal component analysis found associations between general water characteristics, As, and other trace elements. Causes of elevated As concentrations in Lao tube wells were considered similar to those in other Mekong River countries, particularly Cambodia and Vietnam, where young alluvial aquifers give rise to reducing conditions.     

Partitioning of arsenic in soil-crop systems irrigated using groundwater: a case study of rice paddy soils in southwestern Taiwan

The accumulation of As in rice due to groundwater irrigation in paddy fields represents a serious health hazard in South and Southeast Asia. In Taiwan, the fate of As in long-term irrigated paddy fields is poorly understood. Groundwater, surface soil, and rice samples were collected from a paddy field that was irrigated with As-containing groundwater in southwestern Taiwan. The purpose of this study is to elucidate the source and sink of As in the paddy field by comparing the As fractions in the soils that were obtained by a sequential extraction procedure (SEP) with the As uptake of rice. The risks associated with eating rice from the field can thus be better understood. The concentration of As in groundwater varied with time throughout the growing seasons of rice, but always exceeded the permitted maximum (10 μg L⁻¹) for drinking water by the WHO. The As concentration increased with the concentration of Fe in the groundwater, supporting the claim that a large amount of As was concentrated in the Fe flocs collected from the internal wall of the groundwater pump. The results of the SEP revealed that As bound with amorphous and crystalline hydrous oxides exhibited high availability in the soils. The root of rice accumulated the largest amount of As, followed by the straw, husk, and grain. Although the As concentration in the rice grain was less than 1.0 mg kg⁻¹, the estimated intake level was close to the maximum tolerable daily intake of As, as specified by the WHO.     

Hydrogeological and biogeochemical constrains of arsenic mobilization in shallow aquifers from the Hetao basin, Inner Mongolia

Little is known about the importance of drainage/irrigation channels and biogeochemical processes in arsenic distribution of shallow groundwaters from the Hetao basin. This investigation shows that although As concentrations are primarily dependent on reducing conditions, evaporation increases As concentration in the centre of palaeo-lake sedimentation. Near drainage channels, groundwater As concentrations are the lowest in suboxic-weakly reducing conditions. Results demonstrate that both drainage and irrigation channels produce oxygen-rich water that recharges shallow groundwaters and therefore immobilize As. Groundwater As concentration increases with a progressive decrease in redox potential along the flow path in an alluvial fan. A negative correlation between SO₄²⁻ concentrations and δ³⁴S values indicates that bacterial reduction of SO₄²⁻ occurs in reducing aquifers. Due to high concentrations of Fe (>0.5 mg L⁻¹), reductive dissolution of Fe oxides is believed to cause As release from aquifer sediments. Target aquifers for safe drinking water resources are available in alluvial fans and near irrigation channels.     

Concentrations of cyclic volatile methylsiloxanes in biosolid amended soil,influent, effluent,receiving water,and sediment of wastewater treatment plants in Canada

A comprehensive surveillance program was conducted to determine the occurrence of three cyclic volatile methylsiloxanes (cVMS) octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in environmental compartments impacted by wastewater effluent discharges. Eleven wastewater treatment plants (WWTPs), representative of those found in Southern Ontario and Southern Quebec, Canada, were investigated to determine levels of cVMS in their influents and effluents. In addition, receiving water and sediment impacted by WWTP effluents, and biosolid-amended soil from agricultural fields were also analyzed for a preliminary evaluation of the environmental exposure of cVMS in media impacted by wastewater effluent and solids. A newly-developed large volume injection (septumless head adapter and cooled injection system) gas chromatography – mass spectrometry method was used to avoid contamination originating from instrumental analysis. Concentrations of D4, D5, and D6 in influents to the 11 WWTPs were in the range 0.282–6.69 μg L⁻¹, 7.75–135 μg L⁻¹, and 1.53–26.9 μg L⁻¹, respectively. In general, wastewater treatment showed cVMS removal rates of greater than 92%, regardless of treatment type. The D4, D5, and D6 concentration ranges in effluent were <0.009–0.045 μg L⁻¹, <0.027–1.56 μg L⁻¹, and <0.022–0.093 μg L⁻¹, respectively. The concentrations in receiving water influenced by effluent, were lower compared to those in effluent in most cases, with the ranges <0.009–0.023 μg L⁻¹, <0.027–1.48 μg L⁻¹, and <0.022–0.151 μg L⁻¹ for D4, D5, and D6, respectively. Sediment concentrations ranged from <0.003–0.049 μg g⁻¹ dw, 0.011–5.84 μg g⁻¹ dw, and 0.004–0.371 μg g⁻¹ dw for D4, D5, and D6, respectively. The concentrations in biosolid-amended soil, having values of <0.008–0.017 μg g⁻¹ dw, <0.007–0.221 μg g⁻¹ dw, and <0.009–0.711 μg g⁻¹ dw for D4, D5, and D6, respectively, were lower than those in sediment impacted by wastewater effluent in most cases. In comparison with the no-observed-effected concentrations (NOEC) and IC50 (concentration that causes 50% inhibition of the response) values, the potential risks to aquatic, sediment-dwelling, and terrestrial organisms from these reported concentrations are low.     

Levels and speciation of arsenic in the atmosphere in Beijing, China

Arsenic levels and speciation in the total suspended particles (TSPs) were quantitatively determined by high performance liquid chromatography on-line coupled with hydride generation atomic fluorescence spectrometry in Beijing, China from February 2009 to March 2011. The high TSP levels fluctuated between 0.07 and 0.79 mg m⁻³, with a mean level of 0.32 ± 0.17 mg m⁻³. The total arsenic concentrations ranged from 0.03 to 0.31 μg m⁻³ (mean: 0.13 ± 0.06 μg m⁻³) in Beijing‘s air. The concentrations of As(III) and As(V) ranged from 0.73 to 20 ng m⁻³ (mean: 4.7 ± 3.6 ng m⁻³) and from 14 to 2.5 × 10² ng m⁻³ (mean: 67 ± 35 ng m⁻³), respectively. As levels and speciation demonstrated relative higher levels in spring and autumn and lower values in summer and winter. As(V) accounted for 81-99% of the extractable species in the TSP samples which showed that As(V) was the major fraction of the extractable As. Organoarsenic species, monomethylarsonate (MMA) and dimethylarsinate (DMA) were not found in all samples. Higher values of enrichment factors demonstrated that arsenic in TSP mainly come from anthropogenic sources. High As and its species levels in air and respiratory exposure (0.30-0.84 μg d⁻¹) attributed to higher excess cancer risk ((4.2 ± 2.0) × 10⁻⁴) for people in Beijing.     

Evaluation of methane oxidation activity in waste biocover soil during landfill stabilization

The results of a nationwide survey of uranium in Swiss drinking water are reported. Elevated concentrations of uranium in groundwater are found mainly in the alpine regions and can be traced back to the geology of the bedrock. Water sources were systematically surveyed and analysed for the presence of Li, B, Si, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Cd, Sn, Sb, Ba, Tl, Pb and U and the results were analysed to determine if any correlation with uranium concentration was apparent. No correlation was found. The results are interpreted in relation to the current WHO guideline and those of other countries with a view to determining which areas would be affected if a maximum value were to be adopted and which areas require further investigation. Uranium content varied considerably, from below the limit of detection to almost 100 μg L⁻¹. Of the 5548 data samples, 98% are below the 2004 WHO provisional guideline value of 15 μg L⁻¹ and 99.7% below the revised (2011) value of 30 μg L⁻¹.     

Root porosity and radial oxygen loss related to arsenic tolerance and uptake in wetland plants

The rates of radial oxygen loss (ROL), root porosity, concentrations of arsenic (As), iron (Fe) and manganese (Mn) in shoot and root tissues and on root surfaces, As tolerances, and their relationships in different wetland plants were investigated based on a hydroponic experiment (control, 0.8, 1.6 mg As L⁻¹) and a soil pot trail (control, 60 mg As kg⁻¹). The results revealed that wetland plants showed great differences in root porosity (9-64%), rates of ROL (55-1750 mmo1 O₂ kg⁻¹ root d.w. d⁻¹), As uptake (e.g., 8.8-151 mg kg⁻¹ in shoots in 0.8 mg As L⁻¹ treatment), translocation factor (2.1-47% in 0.8 mg As L⁻¹) and tolerance (29-106% in 0.8 mg As L⁻¹). Wetland plants with higher rates of ROL and root porosity tended to form more Fe/Mn plaque, possess higher As tolerance, higher concentrations of As on root surfaces and a lower As translocation factor so decreasing As toxicity.     

Emerging pollutants in sewage, surface and drinking water in Galicia (NW Spain)

A monitoring programme was carried out on wastewater, surface and drinking water on the NW area of Spain during the four seasons of a year period (November 2007-September 2008). This study covered a series of emerging pollutants of different classes, including pharmaceuticals, neutral and acidic organophosphorus flame retardant/plasticizers (OPs), triclosan, phenoxy-herbicides, insect repellents and UV filters. From the total set of 53 compounds, 19 were found in raw wastewater with median concentrations higher than 0.1 μg L⁻¹. Among them, salicylic acid, ibuprofen and the UV filter benzophenone-4 (BP-4) were the most concentrated, exceeding the 1 μg L⁻¹ median value. Subsequently, 11 of these contaminants are not efficiently enough removed in the small WWTPs tested and their median concentrations in effluents still surpassed the 0.1 μg L⁻¹, so that they can spread through surface water. These chemicals are the pharmaceuticals naproxen, diclofenac and atenolol; the OPs tri(2-chloroethyl) phosphate (TCEP), tri(chloropropyl) phosphate (TCPP), tri-n-butyl phosphate (TnBP), diphenyl phosphate (DPhP) and diethylhexyl phosphate (DEHP); and the sulphonate UV filters BP-4 and 2-phenylbenzimidazole-5-sulphonic acid (PBSA). These OPs were then the dominant emerging pollutants occurring in surface and drinking water, where they are detected in the 20-200 ng L⁻¹ range. Pharmaceuticals and UV filters are typically below the 10 ng L⁻¹ level. Finally, herbicides were only detected in the last sampling campaign under the 100 ng L⁻¹ drinking water European Union limit.     

Effects of root anatomy and Fe plaque on arsenic uptake by rice seedlings grown in solution culture

Hydroponic experiments were carried out to investigate the effects of root anatomy, induced by aeration and stagnation, and Fe plaque on arsenic (III&V) uptake and translocation by rice plants. The results showed that As uptake in rice plants (Gui Chao-2) treated by aeration was decreased due to lower root specific surface area. Rice roots with larger specific surface area tended to form more Fe plaque, and Fe plaque affected As uptake kinetics by changing As influx curves from linear to hyperbolic for As(III) and from hyperbolic to S-curve for As(V). Fe plaque increased As(III&V) adsorption and minimized the effects of root anatomy characteristics on As uptake into roots and subsequently translocation to shoots. Fe plaque increased As(III) uptake rate at As(III) concentrations of 0.5∼8 mg L⁻¹, reduced As(V) uptake rate at low As(V) concentrations (<2 mg L⁻¹), but increased As uptake rate at high As(V) concentrations (>6 mg L⁻¹).     

Residues and dynamics of pymetrozine in rice field ecosystem

The fate of pymetrozine was studied in rice field ecosystem, and a simple and reliable analytical method for determination of pymetrozine in soil, rice straw, paddy water and brown rice was developed. Pymetrozine residues were extracted from samples, cleaned up by solid phase extraction (SPE) and then determined by high-performance liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS). The average recovery was 81.2-88.1% from soil, 83.4-88.6% from rice straw, 87.3-94.1% from paddy water and 82.9-85.3% from brown rice. The relative standard deviation (RSD) was less than 15%. The limits of detection (LODs) of pymetrozine calculated as a sample concentration were 0.0003 mg kg⁻¹ (mg L⁻¹) for soil and paddy water, 0.001 mg kg⁻¹ for brown rice and rice straw. The results of kinetics study of pymetrozine residue showed that pymetrozine degradation in water, soil, and rice straw coincided with C = 0.194e^−0.986t, C = 0.044e^−0.099t, and C = 0.988e^−0.780t, respectively; the half-lives were about 0.70 d, 7.0 d and 0.89 d, respectively. The degradation rate of pymetrozine in water was the fastest, followed by rice straw. The highest final pymetrozine residues in brown rice were 0.01 mg kg⁻¹, which was lower than the EU’s upper limit of 0.02 mg kg⁻¹ in rice. Therefore, a dosage of 300-600 g a.i.hm⁻² was recommended, which could be considered as safe to human beings and animals.     

A human health risk assessment of rare earth elements in soil and vegetables from a mining area in Fujian Province,Southeast China

Contaminated food through dietary intake has become the main potential risk impacts on human health. This study investigated concentrations of rare earth elements (REEs) in soil, vegetables, human hair and blood, and assessed human health risk through vegetables consumption in the vicinity of a large-scale mining area located in Hetian Town of Changting County, Fujian Province, Southeast China. The results of the study included the following mean concentrations for total and bio-available REEs of 242.92 ± 68.98 (135.85–327.56) μg g⁻¹ and 118.59 ± 38.49 (57.89–158.96) μg g⁻¹ dry weight (dw) in agricultural soil, respectively, and total REEs of 3.58 ± 5.28 (0.07–64.42) μg g⁻¹ dw in vegetable samples. Concentrations of total REEs in blood and hair collected from the local residents ranged from 424.76 to 1274.80 μg L⁻¹ with an average of 689.74 ± 254.25 μg L⁻¹ and from 0.06 to 1.59 μg g⁻¹ with an average of 0.48 ± 0.59 μg g⁻¹ of the study, respectively. In addition, a significant correlation was observed between REEs in blood and corresponding soil samples (R² = 0.6556, p < 0.05), however there was no correlation between REEs in hair and corresponding soils (p > 0.05). Mean concentrations of REEs of 2.85 (0.59–10.24) μg L⁻¹ in well water from the local households was 53-fold than that in the drinking water of Fuzhou city (0.054 μg L⁻¹). The health risk assessment indicated that vegetable consumption would not result in exceeding the safe values of estimate daily intake (EDI) REEs (100−110 μg kg⁻¹ d⁻¹) for adults and children, but attention should be paid to monitoring human beings health in such rare earth mining areas due to long-term exposure to high dose REEs from food consumptions.     

Zamzam water: concentration of trace elements and other characteristics

Many Muslims drink Zamzam water for use either medicinally or religiously. Millions of pilgrims drink it and take bottles of it to their home countries. Heated scientific and political debates appeared after BBC reported in May 2011 that Zamzam water is poisonous, because of the high levels of arsenic. The World Health Organizations classifies arsenic as a human carcinogen, but some types of arsenic are also used as medicines. Adequate scientific studies on the Zamzam water are absent. This paper will provide, for the first time, basic and comprehensive information regarding the geochemical properties of Zamzam water for more than 30 indicators and using the state-of-the-art laboratory facilities. The data will help us to understand the sources of pollution under discussion, reactions at both local and international levels; and will highlight the potential healing capacity of Zamzam water. Thirty Zamzam water samples were collected by three distinct methods; from 10 pilgrims living in different locations in Germany in 2007, 10 samples from shops in Frankfurt and Berlin in 2011, and 10 samples directly from Makkah in 2011. The samples were analyzed 2 weeks after collection for more than 30 indicators: pH, EC, Eh, Cl, F, Br, NO₃, PO₄, SO₄, HCO₃, Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn beside others. Four major instruments were used; the IC, the ICPOES, the ICPMS and the HGAAS. The quality of the water did not change for 2 years and there was an excellent agreement among the results of the 30 water samples as well as between the results of the 2 years for the same samples analyzed in 2007 and 2008. The water is alkaline (average pH is 8) with an average Li concentration of 15 μg L⁻¹. The average concentrations of As and NO₃ showed values three times higher than the WHO standards (27 μg L⁻¹ and 150 mg L⁻¹, respectively). The averages of Ca and K were 95 and 50 mg L⁻¹, respectively. Very urgent steps are required to scientifically screen for the elevated parameters As, NO₃, Ca, and K in all Zamzam water sources and locations with full transparency. The resultant information should be made available to the public, and the relationship between pollution and human health should be addressed. The alkalinity of Zamzam water and the presence of trace amounts of As and Li may cause the healing power. However, a scientific strategy should be developed and adopted to enable further research and studies on toxicology and treatment technologies could be applied if needed.     

Zerovalent iron encapsulated chitosan nanospheres - a novel adsorbent for the removal of total inorganic arsenic from aqueous systems

Evaluation of Chitosan zerovalent Iron Nanoparticle (CIN) towards arsenic removal is presented. Addition of chitosan enhances the stability of Fe(0) nano particle. Prepared adsorbent was characterized by FT-IR, SEM EDX, BET and XRD. It was found that, with an initial dose rate of 0.5 g L⁻¹, concentrations of As (III) and As (V) were reduced from 2 mg L⁻¹ to <5 μg L⁻¹ in less than 180 min and the adsorbent was found to be applicable in wide range of pH. Langmuir monolayer adsorption capacity was found to be 94 ± 1.5 mg g⁻¹ and 119 ± 2.6 mg g⁻¹ at pH 7 for As (III) and As (V) respectively. Major anions including sulfate, phosphate and silicate did not cause significant interference in the adsorption behavior of both arsenite and arsenate. The adsorbent was successfully recycled five times and applied to the removal of total inorganic arsenic from real life groundwater samples.     

Effects of calcium peroxide on arsenic uptake by celery (Apium graveolens L.) grown in arsenic contaminated soil

The ability of calcium peroxide (CaO₂) to immobilize As of contaminated soil was studied using pot and field experiments. In pot experiment, CaO₂ applied at 2.5 and 5 g kg⁻¹ significantly increased celery shoot weight and decreased shoot As accumulation, which was ascribed to the formation of stable crystalline Fe and Al oxides bound As and the reduction of labile As fractions in the soil. The labile As fractions were pH dependent and it followed a “V” shaped profile with the change of pH. In field experiment, the dose of CaO₂ application at 750 kg ha⁻¹ was optimal and at which the celery was found to produce the highest biomass (63.4 Mg ha⁻¹) and lowest As concentration (0.43 mg kg⁻¹). CaO₂ probably has a promising potential as soil amendment to treat As contaminated soils.     

Simultaneous removal of arsenite and fluoride via an integrated electro-oxidation and electrocoagulation process

An integrated electro-oxidation and electrocoagulation system was designed and used to remove As(III) and F⁻ ions from water simultaneously. Dimensionally stable anodes (DSA), Fe electrodes, and Al electrodes were combined into an electrochemical system. Two pieces of DSA electrodes were assigned as the outside of the Fe and Al electrodes and were directly connected to the power supply as anode and cathode, respectively. The Fe and Al ions were generated by electro-induced process simultaneously. Subsequently, hydroxides of Fe and Al were formed. Arsenic ions are mainly removed by iron hydroxides and F⁻ ions are mainly removed by the Al oxides. At the initial concentration of 1.0 mg L⁻¹, most of As(III) was transferred into As(V) within 40 min at current density of 4 mA cm⁻², whereas F⁻ ions can be efficiently removed simultaneously. The effect of the ratio of Fe and Al plate electrodes and current density on the removal of As(III) and F⁻ was investigated. With one piece of Fe plate electrode and three pieces of Al plate electrodes, it is observed that As(III) with concentration of 1 mg L⁻¹ and F⁻ with concentration of 4.5 mg L⁻¹ can be removed and their final concentrations were below the values of 10 μg L⁻¹ and 1.0 mg L⁻¹, respectively within 40 min. Removal efficiency of As(III) increases with the increase of solution pH. However, in the pH range of 6-7, removal efficiency of F⁻ is the largest.     

Fates and transport of PPCPs in soil receiving reclaimed water irrigation

Fates and transport of 9 commonly found PPCPs of the reclaimed water were simulated based on the HYDRUS-1D software that was validated with data generated from field experiments. Under the default scenario in which the model parameters and input data represented the typical conditions of turf grass irrigation in southern California, the adsorption, degradation, and volatilization of clofibric acid, ibuprofen, 4-tert-octylphenol, 4-n-nonylphenol, naproxen, triclosan, diclofenac sodium, bisphenol A and estrone in the receiving soils were tracked for 10 years. At the end, their accumulations in the 90 cm soil profile varied from less than 1 ng g⁻¹ to about 140 ng g⁻¹ and their concentrations in the drainage water in the 90 cm soil depth varied from nil to μg L⁻¹ levels. The adsorption and microbial degradation processes interacted to contain the PPCPs entirely within surface 40 cm of the soil profiles. Leaching and volatilization were not significant processes governing the PPCPs in the soils. The extent of accumulations in the soils did not appear to produce undue ecological risks to the soil biota. PPCPs did not represent any potential environmental harm in reclaimed water irrigation.     

Variation of As concentration between soil types and rice genotypes and the selection of cultivars for reducing As in the diet

Human exposure to toxic heavy metals via the food chain is of increasing concern. In the present study, the effects of soil type and genotype on variation in arsenic (As) concentrations of different organs were investigated by using nine rice cultivars grown in two soils, with two levels of As contamination. There were significant genotypic differences (P < 0.05) in As concentrations of all organs, and As concentrations of polished grain were significantly affected by genotype and soil type. The As concentration in polished grain was higher in red paddy soil under As treatment, with range from 0.24 to 1.03 mg kg⁻¹, and the As concentration of three cultivars exceeded the concentration of Chinese Food Hygiene Standard (0.7 mg kg⁻¹). The As concentrations in stems, leaves and polished grain were all significantly and positively correlated. The As concentrations in polished grain were positively and significantly (P < 0.01) correlated with As root-grain translocation factor. The results indicated that As concentration in grain was partially governed by As uptake and the transfer of As from root to grain. The grain As concentration of the nine cultivars was significantly correlated between the two soil types at different levels of As contamination. Some genotypes, such as japonica rice (e.g. Ning jing 1 and Nan jing 32) had consistently low grain As concentrations. The results suggest the possibility of breeding the As rice cultivars to produce grain for safe consumption from soils with slight and moderate levels of As.     

Critical Limits for Hg(II) in soils, derived from chronic toxicity data

Published chronic toxicity data for Hg(II) added to soils were assembled and evaluated to produce a data set comprising 52 chronic end-points, five each for plants and invertebrates and 42 for microbes. With end-points expressed in terms of added soil Hg(II) contents, Critical Limits were derived from the 5th percentiles of species sensitivity distributions, values of 0.13 μg (g soil)⁻¹ and 3.3 μg (g soil organic matter)⁻¹ being obtained. The latter value exceeds the currently recommended Critical Limit, used to determine Hg(II) Critical Loads in Europe, of 0.5 μg (g soil organic matter)⁻¹. We also applied the WHAM/Model VI chemical speciation model to estimate concentrations of Hg²⁺ in soil solution, and derived an approximate Critical Limit Function (CLF) that includes pH; log [Hg²⁺]_crit = −2.15 pH −17.10. Because they take soil properties into account, the soil organic matter-based limit and the CLF provide the best assessment of toxic threat for different soils. For differing representative soils, each predicts a range of up to 100-fold in the dry weight-based content of mercury that corresponds to the Critical Limit.     

Endocrine disrupting activities in sewage effluent and river water determined by chemical analysis and in vitro assay in the context of granular activated carbon upgrade

As part of endocrine disruption in catchments (EDCAT) programme, this work aims to assess the temporal and spatial variations of endocrine disrupting chemicals (EDCs) in River Ray, before and after the commissioning of a full-scale granular activated carbon (GAC) plant at a sewage treatment works (STW). Through spot and passive sampling from effluent and river sites, estrogenic and anti-androgenic activities were determined by chemical analysis and in vitro bio-assay. A correlation was found between chemical analyses of the most potent estrogens (estrone (E1), 17β-estradiol (E2), 17α-ethinylestradiol (EE2)) and yeast estrogen screen (YES) measurement, both showing clearly a reduction in estrogenic activity after the commissioning of the GAC plant at the STW. During the study period, the annual average concentrations of E1, E2 and EE2 had decreased from 3.5 ng L⁻¹, 3.1 ng L⁻¹ and 0.5 ng L⁻¹ to below their limit of detection (LOD), respectively, with a concentration reduction of at least 91%, 81% and 60%. Annual mean estrogenic activity measured by YES of spot samples varied from 1.9 ng L⁻¹ to 0.4 ng L⁻¹ E2 equivalent between 2006 and 2008 representing a 79% reduction. Similarly, anti-androgenic activity measured by yeast anti-androgen screen (anti-YAS) of spot samples was reduced from 148.8 to 22.4 μg flutamide L⁻¹, or by 85%. YES and anti-YAS values were related to each other, suggesting co-existence of both types of activities from chemical mixtures in environmental samples. The findings confirm the effectiveness of a full-scale GAC in removing both estrogenic and anti-androgenic activities from sewage effluent.     

Stability considerations of aspartame in the direct analysis of artificial sweeteners in water samples using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS)

A HPLC-MS/MS method is presented for the simultaneous determination of frequently used artificial sweeteners (ASs) and the main metabolite of aspartame (ASP), diketopiperazine (DKP), in environmental water samples using the direct-injection (DI) technique, thereby achieving limits of quantification (LOQ) of 10 ng L⁻¹. For a reliable quantification of ASP pH should be adjusted to 4.3 to prevent formation of the metabolite. Acesulfame (ACE), saccharin (SAC), cyclamate (CYC) and sucralose (SUC) were ubiquitously found in water samples. Highest concentrations up to 61 μg L⁻¹ of ACE were found in wastewater effluents, followed by surface water with concentrations up to 7 μg L⁻¹, lakes up to 600 ng L⁻¹ and groundwater and tap water up to 70 ng L⁻¹. The metabolite DKP was only detected in wastewater up to 200 ng L⁻¹ and at low detection frequencies.