Reconnaissance of selected PPCP compounds in Costa Rican surface waters

Eighty-six water samples were collected in early 2009 from Costa Rican surface water and coastal locations for the analysis of 34 pharmaceutical and personal care product compounds (PPCPs). Sampling sites included areas receiving treated and untreated wastewaters, and urban and rural runoff. PPCPs were analyzed using a combination of solid phase extraction and liquid chromatography tandem mass spectrometry. The five most frequently detected compounds were doxycycline (77%), sulfadimethoxine (43%), salicylic acid (41%), triclosan (34%) and caffeine (29%). Caffeine had the maximum concentration of 1.1 mg L⁻¹, possibly due to coffee bean production facilities upstream. Other compounds found in high concentrations include: doxycycline (74 μg L⁻¹), ibuprofen (37 μg L⁻¹), gemfibrozil (17 μg L⁻¹), acetominophen (13 μg L⁻¹) and ketoprofen (10 μg L⁻¹). The wastewater effluent collected from an oxidation pond had similar detection and concentrations of compounds compared to other studies reported in the literature. Waters receiving runoff from a nearby hospital showed higher concentrations than other areas for many PPCPs. Both caffeine and carbamazepine were found in low frequency compared to other studies, likely due to enhanced degradation and low usage, respectively. Overall concentrations of PPCPs in surface waters of Costa Rica are inline with currently reported occurrence data from around the world, with the exception of doxycycline.     

Transparent exopolymer particle removal in different drinking water production centers

Transparent exopolymer particles (TEP) have recently gained interest in relation to membrane fouling. These sticky, gel-like particles consist of acidic polysaccharides excreted by bacteria and algae. The concentrations, expressed as xanthan gum equivalents L⁻¹ (μg X_eq L⁻¹), usually reach hundred up to thousands μg X_eq L⁻¹ in natural waters. However, very few research was performed on the occurrence and fate of TEP in drinking water, this far. This study examined three different drinking water production centers, taking in effluent of a sewage treatment plant (STP), surface water and groundwater, respectively. Each treatment step was evaluated on TEP removal and on 13 other chemical and biological parameters. An assessment on TEP removal efficiency of a diverse range of water treatment methods and on correlations between TEP and other parameters was performed. Significant correlations between particulate TEP (>0.4 μm) and viable cell concentrations were found, as well as between colloidal TEP (0.05-0.4 μm) and total COD, TOC, total cell or viable cell concentrations. TEP concentrations were very dependent on the raw water source; no TEP was detected in groundwater but the STP effluent contained 1572 μg X_eq L⁻¹ and the surface water 699 μg X_eq L⁻¹. Over 94% of total TEP in both plants was colloidal TEP, a fraction neglected in nearly every other TEP study. The combination of coagulation and sand filtration was effective to decrease the TEP levels by 67%, while the combination of ultrafiltration and reverse osmosis provided a total TEP removal. Finally, in none of the installations TEP reached the final drinking water distribution system at significant concentrations. Overall, this study described the presence and removal of TEP in drinking water systems.     

Remediation of groundwater contaminated with MTBE and benzene: the potential of vertical-flow soil filter systems

Field investigations on the treatment of MTBE and benzene from contaminated groundwater in pilot or full-scale constructed wetlands are lacking hugely. The aim of this study was to develop a biological treatment technology that can be operated in an economic, reliable and robust mode over a long period of time. Two pilot-scale vertical-flow soil filter eco-technologies, a roughing filter (RF) and a polishing filter (PF) with plants (willows), were operated independently in a single-stage configuration and coupled together in a multi-stage (RF + PF) configuration to investigate the MTBE and benzene removal performances. Both filters were loaded with groundwater from a refinery site contaminated with MTBE and benzene as the main contaminants, with a mean concentration of 2970 ± 816 and 13,966 ± 1998 μg L⁻¹, respectively. Four different hydraulic loading rates (HLRs) with a stepwise increment of 60, 120, 240 and 480 L m⁻² d⁻¹ were applied over a period of 388 days in the single-stage operation. At the highest HLR of 480 L m⁻² d⁻¹, the mean concentrations of MTBE and benzene were found to be 550 ± 133 and 65 ± 123 μg L⁻¹ in the effluent of the RF. In the effluent of the PF system, respective mean MTBE and benzene concentrations of 49 ± 77 and 0.5 ± 0.2 μg L⁻¹ were obtained, which were well below the relevant MTBE and benzene limit values of 200 and 1 μg L⁻¹ for drinking water quality. But a dynamic fluctuation in the effluent MTBE concentration showed a lack of stability in regards to the increase in the measured values by nearly 10%, which were higher than the limit value. Therefore, both (RF + PF) filters were combined in a multi-stage configuration and the combined system proved to be more stable and effective with a highly efficient reduction of the MTBE and benzene concentrations in the effluent. Nearly 70% of MTBE and 98% of benzene were eliminated from the influent groundwater by the first vertical filter (RF) and the remaining amount was almost completely diminished (∼100% reduction) after passing through the second filter (PF), with a mean MTBE and benzene concentration of 5 ± 10 and 0.6 ± 0.2 μg L⁻¹ in the final effluent. The emission rate of volatile organic compounds mass into the air from the systems was less than 1% of the inflow mass loading rate. The results obtained in this study not only demonstrate the feasibility of vertical-flow soil filter systems for treating groundwater contaminated with MTBE and benzene, but can also be considered a major step forward towards their application under full-scale conditions for commercial purposes in the oil and gas industries.     

Microbial community distribution and activity dynamics of granular biomass in a CANON reactor

The application of microelectrodes to measure oxygen and nitrite concentrations inside granules operated at 20 °C in a CANON (Complete Autotrophic Nitrogen-removal Over Nitrite) reactor and the application of the FISH (Fluorescent In Situ Hybridization) technique to cryosectioned slices of these granules showed the presence of two differentiated zones inside of them: an external nitrification zone and an internal anammox zone. The FISH analysis of these layers allowed the identification of Nitrosomonas spp. and Candidatus Kuenenia Stutgartiensis as the main populations carrying out aerobic and anaerobic ammonia oxidation, respectively.Concentration microprofiles measured at different oxygen concentrations in the bulk liquid (from 1.5 to 35.2 mg O₂ L⁻¹) revealed that oxygen was consumed in a surface layer of 100-350 μm width. The obtained consumption rate of the most active layers was of 80 g O₂ (L_granule)⁻¹ d⁻¹. Anammox activity was registered between 400 and 1000 μm depth inside the granules. The nitrogen removal capacity of the studied sequencing batch reactor containing the granular biomass was of 0.5 g N L⁻¹ d⁻¹. This value is similar to the mean nitrogen removal rate obtained from calculations based on in- and outflow concentrations.Information obtained in the present work allowed the establishment of a simple control strategy based on the measurements of NH₄⁺ and NO₂⁻ in the bulk liquid and acting over the dissolved oxygen concentration in the bulk liquid and the hydraulic retention time of the reactor.     

Changes in herbicide concentrations in Midwestern streams in relation to changes in use, 1989-1998

Water samples were collected from Midwestern streams in 1994-1995 and 1998 as part of a study to help determine if changes in herbicide use resulted in changes in herbicide concentrations since a previous reconnaissance study in 1989-1990. Sites were sampled during the first significant runoff period after the application of pre-emergent herbicides in 1989-1990, 1994-1995, and 1998. Samples were analyzed for selected herbicides, two atrazine metabolites, three cyanazine metabolites, and one alachlor metabolite. In the Midwestern USA, alachlor use was much greater in 1989 than in 1995, whereas acetochlor was not used in 1989 but was commonly used in 1995. The use of atrazine, cyanazine, and metolachlor was approximately the same in 1989 and 1995. The median concentrations of atrazine, alachlor, cyanazine, and metolachlor were substantially higher in 1989-1990 than in 1994-1995 or 1998. The median acetochlor concentration was higher in 1998 than in 1994 or 1995.     

Degradation of carbamazepine by Trametes versicolor in an air pulsed fluidized bed bioreactor and identification of intermediates

The paper describes the aerobic degradation of carbamazepine (CBZ), an anti-epileptic drug widely found in aquatic environment, from Erlenmeyer flask to bioreactor by the white-rot fungus Trametes versicolor. In Erlenmeyer flask, CBZ at approximately 9 mg L⁻¹ was almost completely eliminated (94%) after 6 d, while at near environmentally relevant concentrations of 50 μg L⁻¹, 61% of the contaminant was degraded in 7 d. Acridone, acridine, 10,11-dihydro-10,11-dihydroxy-CBZ, and 10, 11-epoxy-CBZ were identified as major metabolites, confirming the degradation of CBZ. The degradation process was then carried out in an air pulsed fluidized bioreactor operated in batch and continuous mode. Around 96% of CBZ was removed after 2 days in batch mode operation, and 10,11-dihydro-10,11-epoxycarbamazepine was found as unique metabolite. In bioreactor operated in continuous mode with a hydraulic retention time of 3 d, 54% of the inflow concentration (approx. 200 μg L⁻¹) was reduced at the steady state (25 d) with a CBZ degradation rate of 11.9 μg CBZ g⁻¹ dry weight d⁻¹. No metabolite was detected in the culture broth. Acute toxicity tests (Microtox) indicated that the final culture broth in both batch and continuous mode operation were non toxic, with 15 min EC50 values of 24% and 77%, respectively.     

Fate of N-nitrosomorpholine in an anaerobic aquifer used for managed aquifer recharge: a column study

The fate of N-nitrosomorpholine (NMOR) was evaluated at microgram and nanogram per litre concentrations. Experiments were undertaken to simulate the passage of groundwater contaminants through a deep anaerobic pyritic aquifer system, as part of a managed aquifer recharge (MAR) strategy. Sorption studies demonstrated the high mobility of NMOR in the Leederville aquifer system, with retardation coefficients between 1.2 and 1.6. Degradation studies from a 351 day column experiment and a 506 day stop-flow column experiment showed an anaerobic biologically induced reductive degradation process which followed first order kinetics. A biological lag-time of less than 3 months and a transient accumulation of morpholine (MOR) were also noted during the degradation. Comparable half-life degradation rates of 40-45 days were observed over three orders of magnitude in concentration (200 ng L⁻¹ to 650 μg L⁻¹). An inhibitory effect on microorganism responsible to the biodegradation of NMOR at 650 μg L⁻¹ or a threshold effect at 200 ng L⁻¹ was not observed during these experiments.     

Influence of manganese and ammonium oxidation on the removal of 17 alpha-ethinylestradiol (EE2)

Flow-through reactors with manganese oxides were examined for their capacity to remove 17α-ethinylestradiol (EE2) at μg L⁻¹ and ng L⁻¹ range from synthetic wastewater treatment plant (WWTP) effluent. The mineral MnO₂ reactors removed 93% at a volumetric loading rate (B_V) of 5 μg EE2 L⁻¹ d⁻¹ and from a B_V of 40 μg EE2 L⁻¹ d⁻¹ on, these reactors showed 75% EE2 removal. With the biologically produced manganese oxides, only 57% EE2 was removed at 40 μg EE2 L⁻¹ d⁻¹. EE2 removal in the ng L⁻¹ range was 84%. The ammonium present in the influent (10 mg N L⁻¹) was nitrified and ammonia-oxidizing bacteria (AOB) were found to be of prime importance for the degradation of EE2. Remarkably, EE2 removal by AOB continued for a period of 4 months after depleting NH₄⁺ in the influent. EE2 removal by manganese-oxidizing bacteria was inhibited by NH₄⁺. These results indicate that the metabolic properties of nitrifiers can be employed to polish water containing EE2 based estrogenic activity.     

Controlling toxic cyanobacteria: effects of dredging and phosphorus-binding clay on cyanobacteria and microcystins

Sediment dredging and Phoslock^® addition were applied individually and in combination in an enclosure experiment in a Dutch hypertrophic urban pond. These measures were applied to control eutrophication and reduce the risk of exposure to cyanobacterial toxins. Over the 58 days course of the experiment, cyanobacteria (predominantly Microcystis aeruginosa) gradually decreased until they dropped below the level of detection in the combined treated enclosures, they were reduced in dredged enclosures, but remained flourishing in controls and Phoslock^® treated enclosures. Cyanobacteria were, however, less abundant in the enclosures (medians chlorophyll-a 30-87 μg l⁻¹) than in the pond (median chlorophyll-a 162 μg l⁻¹), where also a thick surface scum covered one-third of the pond for many weeks.Soluble reactive phosphorus (SRP), total phosphorus and total nitrogen concentrations were significantly lower in the combined dredged and Phoslock^® treated enclosures than in controls. Median SRP concentrations were 24 μg P l⁻¹ in the combined treatment, 58 μg P l⁻¹ in dredged enclosures, and 90 μg P l⁻¹ in controls and 95 μg P l⁻¹ in Phoslock^® treated enclosures. Hence, the combined treatment was most effective in decreasing SRP and TP, and in lowering cyanobacterial biomass.Microcystin (MC) concentrations were analyzed by LC-MS/MS. MC concentrations and cyanobacterial biomass were positively correlated in all treatments. Mean MC concentrations in controls (71 μg l⁻¹), Phoslock^® treated enclosures (37 μg l⁻¹) and dredged enclosures (25 μg l⁻¹) exceeded the provisional guideline of 20 μg l⁻¹, whereas mean MC concentrations were 13 μg l⁻¹ in the combined treated enclosures. All samples contained the MC variants dmMC-RR, MC-RR, MC-YR, dmMC-LR and MC-LR; traces of MC-LY and nodularin were detected in few samples. The different treatments did not change the relative contribution of the variants to the MC pool; MC profiles in all treatments and the pond showed dominance of MC-RR followed by MC-LR. In the surface scum of the pond, total MC concentration was extremely high (64000 μg l⁻¹ or 1300 μg g⁻¹ DW), which poses a serious health hazard to children playing on the banks of the pond. Based on our results and pond characteristics, we propose combined sediment dredging and Phoslock^® addition, fish removal and strong reduction of duck feeding by the neighborhood as most promising measures controlling cyanobacterial hazards in this pond.     

Particle concentrations and effectiveness of free-standing air filters in bedrooms of children with asthma in Detroit,Michigan

Asthma can be exacerbated by environmental factors including airborne particulate matter (PM) and environmental tobacco smoke (ETS). We report on a study designed to characterize PM levels and the effectiveness of filters on pollutant exposures of children with asthma. 126 households with an asthmatic child in Detroit, Michigan, were recruited and randomized into control or treatment groups. Both groups received asthma education; the latter also received a free-standing high efficiency air filter placed in the child’s bedroom. Information regarding the home, emission sources, and occupant activities was obtained using surveys administered to the child’s caregiver and a household inspection. Over a one week period, we measured PM, carbon dioxide (CO₂), environmental tobacco smoke (ETS) tracers, and air exchange rates (AERs). Filters were installed at midweek. Before filter installation, PM concentrations averaged 28 μg m⁻³, number concentrations averaged 70,777 and 1471 L⁻¹ in 0.3–1.0 and 1–5 μm size ranges, respectively, and the median CO₂ concentration was 1018 ppm. ETS tracers were detected in 23 of 38 homes where smoking was unrestricted and occupants included smokers and, when detected, PM concentrations were elevated by an average of 15 μg m⁻³. Filter use reduced PM concentrations by an average of 69–80%. Simulation models representing location conditions show that filter air flow, room volume and AERs are the key parameters affecting PM removal, however, filters can achieve substantial removal in even "worst" case applications. While PM levels in homes with asthmatic children can be high, levels can be dramatically reduced using filters.     

Herbicides and herbicide degradates in shallow groundwater and the Cedar River near a municipal well field, Cedar Rapids, Iowa

Water samples were collected near a Cedar Rapids, Iowa municipal well field from June 1998 to August 1998 and analyzed for selected triazine and acetanilide herbicides and degradates. The purpose of the study was to evaluate the occurrence of herbicides and herbicide degradates in the well field during a period following springtime application of herbicides to upstream cropland. The well field is in an alluvial aquifer adjacent to the Cedar River. Parent herbicide concentrations generally were greatest in June, and decreased in July and August. Atrazine was most frequently detected and occurred at the greatest concentrations; acetochlor, cyanazine and metolachlor also were detected, but at lesser concentrations than atrazine. Triazine degradate concentrations were relatively small (< 0.50 microg/l) and generally decreased from June to August. Although the rate of groundwater movement is relatively fast (approx. 1 m per day) in the alluvial aquifer near the Cedar River, deethylatrazine (DEA) to atrazine ratios in groundwater samples collected near the Cedar River indicate that atrazine and DEA probably are gradually transported into the alluvial aquifer from the Cedar River. Deisopropylatrazine (DIA) to DEA ratios in water samples indicate most DIA in the Cedar River and alluvial aquifer is produced by atrazine degradation, although some could be from cyanazine degradation. Acetanilide degradates were detected more frequently and at greater concentrations than their corresponding parent herbicides. Ethanesulfonic-acid (ESA) degradates comprised at least 80% of the total acetanilide-degradate concentrations in samples collected from the Cedar River and alluvial aquifer in June, July and August; oxanilic acid degradates comprised less than 20% of the total concentrations. ESA-degradate concentrations generally were smallest in June and greater in July and August. Acetanilide degradate concentrations in groundwater adjacent to the Cedar River indicate acetanilide degradates are transported into the alluvial aquifer in a manner similar to that indicated for atrazine and DEA.     

Immediate and long-term impacts of UV-C irradiation on photosynthetic capacity, survival and microcystin-LR release risk of Microcystis aeruginosa

In this study, the immediate and long-term impacts of shortwave ultraviolet (UV-C) irradiation on photosynthetic capacity, survival, and recovery of Microcystis aeruginosa were investigated. The risk of microcystin-LR (MC-LR) release during irradiation was also estimated. The cell density was determined by a flow cytometry, and typical chlorophyll fluorescence parameters, including the effective quantum yield, photosynthetic efficiency and maximal electron transport rate, were measured by a pulse amplitude modulated (PAM) fluorometer. Under various UV-C dosages (140-4200 mJ cm⁻²), photosynthetic capacities were reduced, to different degrees, accompanied by slight cytoclasis and complete degradation of extracellular MC-LR immediately after irradiation. In a 6-d cultivation following UV-C irradiation, cell density and extracellular MC-LR in the samples treated by 140 mJ cm⁻² UV-C irradiation increased from 4.0 × 10⁶ cells mL⁻¹ and 8 μg L⁻¹ to 5.1 × 10⁶ cells mL⁻¹ and 20 μg L⁻¹, respectively. Significant M. aeruginosa cytoclasis (cell density from 4.0 × 10⁶ to 1.0 × 10⁶ cells mL⁻¹) and MC-LR release (2-25 μg L⁻¹) occurred when the UV-C dosage reached 350 mJ cm⁻². Cell cytoclasis and MC-LR release were enhanced in the cultivated samples under higher UV-C dosages. Results revealed that photosynthetic parameters were useful tools to predict the recovery profiles of M. aeruginosa cells, and the MC-LR release risk should be considered after UV-C inactivation.     

Health risk assessment of inorganic arsenic intake of Cambodia residents through groundwater drinking pathway

In order to compare the magnitudes and health impacts of arsenic and other toxic trace elements in well water, groundwater and hair samples were collected from three areas with different arsenic exposure scenarios in the Mekong River basin of Cambodia. Ampil commune in Kampong Cham province was selected as an uncontaminated area, Khsarch Andaet commune in Kratie province was selected as a moderately contaminated area, and Kampong Kong commune in Kandal Province was selected as an extremely contaminated area. Results of ICP-MS analyses of the groundwater samples revealed that As, Mn, Fe and Ba concentrations were significantly different among the three study areas (Kruskal-Wallis test, p < 0.0001). Out of 46 observed wells in the Kandal province study area, 100% detected As > 50 μg L⁻¹ and Fe > 300 μg L⁻¹; 52.17% had Mn > 400 μg L⁻¹ and 73.91% found Ba > 700 μg L⁻¹. In the Kratie province study area (n = 12), 25% of wells showed elevated arsenic levels above 10 μg L⁻¹ and 25% had Mn > 400 μg L⁻¹, whereas samples from Kampong Cham province study area (n = 18) were relatively clean, with As < 10 μg L⁻¹. A health risk assessment model derived from the USEPA was applied to calculate individual risks resulting from drinking groundwater. Computational results indicated that residents from Kandal Province study area (n = 297) confronted significantly higher non-carcinogenic and carcinogenic risks than those in Kratie (n = 89) and Kampong Cham (n = 184) province study areas (Kruskal-Wallis test, p < 0.0001). 98.65% of respondents from the Kandal province study area were at risk for the potential non-cancer effect and an average cancer risk index was found to be 5 in 1000 exposure. The calculations also indicated that, in the Kratie province study area, 13.48% of respondents were affected by non-cancer health risks and 33.71% were threatened by cancer, whereas none of respondents in the Kampong Cham province study area appeared to have non-carcinogenic effect. Positively significant correlations of the arsenic content in scalp hair (As_h) with both arsenic levels in groundwater (As_w) (r_s (304) = 0.757, p < 0.0001) and individual average daily doses (ADD) of arsenic (r_s (304) = 0.763, p < 0.0001) undoubtedly indicated that arsenic accumulation in the bodies of Cambodia residents in the Mekong River basin was mainly through a groundwater drinking pathway. To the best of our knowledge, this is the first comprehensive report comparing individual health risk assessments of arsenic exposure through a groundwater drinking pathway to enriched arsenic levels from groundwater in the Mekong River basin, Cambodia. This study indicates that elevated arsenic concentrations in groundwater may lead to thousands of cases of arsenicosis in the near future if mitigating actions are not taken.     

Occurrence and load of selected herbicides and metabolites in the lower Mississippi River

Analyses of water samples collected from the Mississippi River at Baton Rouge, Louisiana, during 1991-1997 indicate that hundreds of metric tons of herbicides and herbicide metabolites are being discharged annually to the Gulf of Mexico. Atrazine, metolachlor, and the ethane-sulfonic acid metabolite of alachlor (alachlor ESA) were the most frequently detected herbicides and, in general, were present in the largest concentrations. Almost 80% of the annual herbicide load to the Gulf of Mexico occurred during the growing season from May to August. The concentrations and loads of alachlor in the Mississippi River decreased dramatically after 1993 in response to decreased use in the basin. In contrast, the concentrations and loads of acetochlor increased after 1994, reflecting its role as a replacement for alachlor. The peak annual herbicide load occurred in 1993, when approximately 640 metric tons (t) of atrazine, 320 t of cyanazine, 215 t of metolachlor, 53 t of simazine, and 50 t of alachlor were discharged to the Gulf of Mexico. The annual loads of atrazine and cyanazine were generally 1-2% of the amount annually applied in the Mississippi River drainage basin; the annual loads of acetochlor, alachlor, and metolachlor were generally less than 1%. Despite a reduction in atrazine use, historical data do not indicate a long-term downward trend in the atrazine load to the Gulf of Mexico. Although a relation (r2 = 0.62) exists between the atrazine load and stream discharge during May to August, variations in herbicide use and rainfall patterns within subbasins can have a large effect on herbicide loads in the Mississippi River Basin and probably explain a large part of the annual variation in atrazine load to the Gulf of Mexico.     

Behavior, mass inventories and modeling evaluation of xenobiotic endocrine-disrupting chemicals along an urban receiving wastewater river in Henan Province, China

Historically, the locations of cities mainly depend on the available water source and the urban river not only supplies the fresh water to city but also receives its wastewaters. To analyze the influences of urban zone on its receiving water river, the Jialu River in Henan Province, China, a typical urban river was chosen. Water and sediment samples were collected along the river in 2007 to analyze the concentrations of xenobiotic endocrine-disrupting chemicals (XEDCs) including nonylphenol (NP), octylphenol (OP) and bisphenol A (BPA) in surface water and sediment. The results showed that the concentrations of OP, NP and BPA in surface water were 20.9-63.2 ng L⁻¹ (mean 39.8 ng L⁻¹), 75.2-1520 ng L⁻¹ (mean 645 ng L⁻¹), 410-2990 ng L⁻¹ (mean 1535 ng L⁻¹), respectively. The lowest and highest concentrations of XEDCs in surface water were found in the upper stream and downstream of Zhengzhou urban zone, which was regarded as the major discharge source of these chemicals to this river. The concentrations of OP, NP and BPA in the sediment were 15.9-31.1 ng g⁻¹, 145-349 ng g⁻¹ and 626-3584 ng g⁻¹ with the average concentrations of 21.4 ng g⁻¹, 257 ng g⁻¹ and 2291 ng g⁻¹, respectively. The results of in situ sediment-water partition of XEDCs showed that the partition coefficients (log K_oc′) in the downstream were higher than that in the upstream, which was mainly caused by the retransfer of surface sediment from the upper stream to the downstream. Comparison of measured and theoretical inventories of XEDCs in sediment indicated that the residual time of XEDCs in sediment in the river was about 5 years, which was in the same order of magnitude with its big flood frequency. In order to predict concentration variances of XEDCs in surface water, a fugacity-hydrodynamic model was developed according to the concept of in series completely stirred tank reactors (CSTR). The model results showed that about 29-65% of XEDCs derived from the urban zone (about 2.0 t yr⁻¹) would finally dissipate from aqueous phase in the 170 km downstream of the river. Assuming the discharge amount of XEDCs from the urban zone remaining constant, the predicted concentrations of the total XEDCs in the over 90% river reach would be higher than 1.0 μg L⁻¹ under all normal, high water and low water season in 2007.     

Determination of arsenic leaching from glazed and non-glazed Turkish traditional earthenware

Glazed and non-glazed earthenware is traditionally and widely used in Turkey and most of the Mediterranean and the Middle East countries for cooking and conservation of foodstuff. Acid-leaching tests have been carried out to determine whether the use of glazed and non-glazed earthenware may constitute a human health hazard risk to the consumers. Earthenware was leached with 4% acetic acid and 1% citric acid solutions, and arsenic in the leachates was measured using hydride generation atomic absorption spectrometry. Arsenic concentrations in the leach solution of non-glazed potteries varied from 30.9 to 800 μg L^− 1, while the glazed potteries varied generally from below the limit of detection (0.5 μg L^− 1) to 30.6 μg L^− 1, but in one poorly glazed series it reached to 110 μg L^− 1. Therefore, the risk of arsenic poisoning by poorly glazed and non-glazed potteries is high enough to be of concern. It appears that this is the first study reporting arsenic release from earthenware into food.     

The distribution of depleted uranium contamination in Colonie, NY, USA

Uranium oxide particles were dispersed into the environment from a factory in Colonie (NY, USA) by prevailing winds during the 1960s and '70s. Uranium concentrations and isotope ratios from bulk soil samples have been accurately measured using inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) without the need for analyte separation chemistry. The natural range of uranium concentrations in the Colonie soils has been estimated as 0.7-2.1 μg g^− 1, with a weighted geometric mean of 1.05 μg g^− 1; the contaminated soil samples comprise uranium up to 500 ± 40 μg g^− 1. A plot of ²³⁶U/²³⁸U against ²³⁵U/²³⁸U isotope ratios describes a mixing line between natural uranium and depleted uranium (DU) in bulk soil samples; scatter from this line can be accounted for by heterogeneity in the DU particulate. The end-member of DU compositions aggregated in these bulk samples comprises (2.05 ± 0.06) × 10^− 3235U/²³⁸U, (3.2 ± 0.1) × 10^− 5236U/²³⁸U, and (7.1 ± 0.3) × 10^− 6234U/²³⁸U. The analytical method is sensitive to as little as 50 ng g^− 1 DU mixed with the natural uranium occurring in these soils. The contamination footprint has been mapped northward from site, and at least one third of the uranium in a soil sample from the surface 5 cm, collected 5.1 km NNW of the site, is DU. The distribution of contamination within the surface soil horizon follows a trend of exponential decrease with depth, which can be approximated by a simple diffusion model. Bioturbation by earthworms can account for dispersal of contaminant from the soil surface, in the form of primary uranium oxide particulates, and uranyl species that are adsorbed to organic matter. Considering this distribution, the total mass of uranium contamination emitted from the factory is estimated to be c. 4.8 tonnes.     

Phosphorus addition reverses the positive effect of zebra mussels (Dreissena polymorpha) on the toxic cyanobacterium, Microcystis aeruginosa

We tested the hypothesis that zebra mussels (Dreissena polymorpha) have positive effects on the toxin-producing cyanobacterium, Microcystis aeruginosa, at low phosphorus (P) concentrations, but negative effects on M. aeruginosa at high P, with a large-scale enclosure experiment in an oligotrophic lake. After three weeks, mussels had a significantly positive effect on M. aeruginosa at ambient P (total phosphorus, TP ∼10 μg L⁻¹), and a significantly negative effect at high P (simulating a TP of ∼40 μg L⁻¹ in lakes). Positive and negative effects were strong and very similar in magnitude. Thus, we were able to ameliorate a negative effect of Dreissena invasion on water quality (i.e., promotion of Microcystis) by adding P to water from an oligotrophic lake. Our results are congruent with many field observations of Microcystis response to Dreissena invasion across ecosystems of varying P availability.     

Sublethal toxicity of commercial insecticide formulations and their active ingredients to larval fathead minnow (Pimephales promelas)

Toxic effect concentrations of insecticides are generally determined using the technical grade or pure active ingredient. Commercial insecticide formulations, however, contain a significant proportion (> 90%) of so-called inert ingredients, which may alter the toxicity of the active ingredient(s). This study compares the sublethal toxicity of two insecticides, the pyrethroid bifenthrin, and the phenylpyrazole fipronil, to their commercial formulations, Talstar® and Termidor®. Both insecticides are used for landscape treatment and structural pest control, and can be transported into surface water bodies via stormwater and irrigation runoff. We used larval fathead minnow (Pimephales promelas), to determine effects on growth and swimming performance after short-term (24 h) exposure to sublethal concentrations of pure insecticides and the respective formulations. Significantly enhanced 7 d growth was observed at 10% of the 24 h LC₁₀ (53 μg L⁻¹) fipronil. Swimming performance was significantly impaired at 20% of the 24 h LC₁₀ (0.14 μg L⁻¹) of bifenthrin and 10% of the 24 h LC₁₀ of Talstar® (0.03 μg L⁻¹). Fipronil and Termidor® led to a significant impairment of swimming performance at 142 μg L⁻¹ and 148 μg L⁻¹ respectively, with more pronounced effects for the formulation. Our data shows that based on dissolved concentrations both formulations were more toxic than the pure active ingredients, suggesting that increased toxicity due to inert ingredients should be considered in risk assessments and regulation of insecticides.     

Environmental occurrence and degradation of the herbicide n-chloridazon

A sampling campaign was carried out for n-chloridazon (n-CLZ) and its degradation product desphenyl-chloridazon (DPC) in the Hesse region (Germany) during the year 2007: a total of 548 environmental samples including groundwater, surface water and wastewater treatment plant (WWTP) effluent were analysed. Furthermore, aerobic degradation of n-CLZ has been studied utilising a fixed bed bioreactor (FBBR).In surface water, n-CLZ was detected at low concentrations (average 0.01 ± 0.06 μg L⁻¹; maximum 0.89 μg L⁻¹) with a seasonal peak, whereas DPC was present throughout the year at much higher concentrations (average 0.72 ± 0.81 μg L⁻¹; maximum 7.4 μg L⁻¹). Higher n-CLZ concentrations were observed in the North compared with South Hesse, which is ascribed to a higher density of agricultural areas. Furthermore, methylated DPC (Me-DPC), another degradation product, was detected in surface water.In the degradation test, n-CLZ was completely converted to DPC at all concentrations tested (Me-DPC was not formed under the test conditions). DPC was resistant to further degradation during the whole experimental period of 98 days. The results obtained suggest persistence and high dispersion of DPC in the aquatic environment.