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.     

Determination and occurrence of phthalates, alkylphenols, bisphenol A, PBDEs, PCBs and PAHs in an industrial sewage grid discharging to a Municipal Wastewater Treatment Plant

Industrial and urban discharges release organic contaminants which might affect the quality of receiving waters if not properly eliminated in Wastewater Treatment Plants (WWTP). This study is aimed to evaluate the source, transport and fate of contaminants of industrial origin in a sewage grid discharging to a WWTP and finally to the sea. The sampling network covered an industrial and urban area and wastewaters, influents and effluents of a WWTP were analyzed using a newly developed multiresidual method to capture a wide range contaminants (phthalates, alkylphenols, bisphenol A, PBDEs, PCBs and PAHs). Alkylphenols and phthalates followed by PAHs were the main compounds detected at levels between 0.01 to 698 µg l^− 1 in the sewage pipelines. At the WWTP influent they were detected at concentrations up to 345 µg l^− 1. The contaminant load was eliminated in a 64-92% during the primary and secondary treatment of the plant. However, alkylphenols, phthalates bisphenol A and traces of PAHs were discharged with the effluent, producing a total net input of 825 g d^− 1 to the sea. The study of wastewaters herein proposed can be used to better predict the loads into WWTP to improve treatment conditions according to specific sewage inputs and to assess the risks associated with the continuous discharge of contaminants to receiving plants.     

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.     

Effects of chromium on activated sludge and on the performance of wastewater treatment plants: A review

Chromium is a heavy metal of commercial importance, thus significant amounts are released in wastewaters. Chromium in wastewaters and in the aquatic environment is primarily encountered in oxidation stages +3 (Cr^(III)) and +6 (Cr^(VI)). Recent publications suggest that Cr^(VI) compounds are more toxic than Cr^(III) ones, while Cr^(III) has been identified as trace element, at least for complex organisms. With respect to chromium species mobility, Cr^(VI) can cross cellular membranes, which then may be oxidized to Cr^(III) and react with intracellular biomolecules. Clear conclusions cannot be derived about the critical chromium concentrations that affect activated sludge growth, as the latter is a function of a number of factors. Broadly, may be supported that activated sludge growth is stimulated at Cr^(III) concentrations up to 15 mg L⁻¹, above which is inhibited, with lethal doses lying above 160 mg Cr^(III) L⁻¹. On the other hand, literature data on Cr^(VI) effects on activated sludge are even more controversial. A number of reports support that Cr^(VI) is toxic to activated sludge at concentrations above 5 mg L⁻¹, while others report growth stimulation at concentrations up to 25 mg L⁻¹. However, all reports agree that Cr^(VI) is definitely an activated sludge growth inhibitor at higher concentrations, while 80 mg Cr^(VI) L⁻¹ have been identified as lethal dose. A number of factors have been identified to influence chromium toxicity on activated sludge, such as, pH, biomass concentration, presence of organic substances or other heavy metals, acclimation process, exposure time, etc. Naturally, the presence of chromium species in wastewaters may affect the performance of wastewater treatment plants often causing malfunctions, particularly for industrial wastewaters containing relatively high chromium concentrations. The present work reviews in a critical way the published literature on chromium effects on activated sludge, and on the operation of wastewater treatment plants.     

Fate of N-nitrosodimethylamine in recycled water after recharge into anaerobic aquifer

Laboratory and field experiments were undertaken to assess the fate of N-nitrosodimethylamine (NDMA) in aerobic recycled water that was recharged into a deep anaerobic pyritic aquifer, as part of a managed aquifer recharge (MAR) strategy. Laboratory studies demonstrated a high mobility of NDMA in the Leederville aquifer system with a retardation coefficient of 1.1. Anaerobic degradation column and ¹⁴C-NDMA microcosm studies showed that anaerobic conditions of the aquifer provided a suitable environment for the biodegradation of NDMA with first-order kinetics. At microgram per litre concentrations, inhibition of biodegradation was observed with degradation half-lives (260 ± 20 days) up to an order of magnitude greater than at nanogram per litre concentrations (25-150 days), which are more typical of environmental concentrations. No threshold effects were observed at the lower ng L⁻¹ concentrations with NDMA concentrations reduced from 560 ng L⁻¹ to <6 ng L⁻¹ over a 42 day ¹⁴C-NDMA aerobic microcosm experiment.Aerobic ¹⁴C-NDMA microcosm studies were also undertaken to assess potential aerobic degradation, likely to occur close to the recharge bore. These microcosm experiments showed a faster degradation rate than anaerobic microcosms, with a degradation half-life of 8 ± 2 days, after a lag period of approximately 10 days.Results from a MAR field trial recharging the Leederville aquifer with aerobic recycled water showed that NDMA concentrations reduced from 2.5 ± 1.0 ng L⁻¹ to 1.3 ± 0.4 ng L⁻¹ between the recharge bore and a monitoring location 20 m down gradient (an estimated aquifer residence time of 10 days), consistent with data from the aerobic microcosm experiment. Further down gradient, in the anaerobic zone of the aquifer, NDMA degradation could not be assessed, as NDMA concentrations were too close to their analytical detection limit (<1 ng L⁻¹).     

Relationship between phenol degradation efficiency and microbial community structure in an anaerobic SBR

Phenol is a common wastewater contaminant from various industrial processes, including petrochemical refineries and chemical compounds production. Due to its toxicity to microbial activity, it can affect the efficiency of biological wastewater treatment processes. In this study, the efficiency of an Anaerobic Sequencing Batch Reactor (ASBR) fed with increasing phenol concentrations (from 120 to 1200 mg L⁻¹) was assessed and the relationship between phenol degradation capacity and the microbial community structure was evaluated. Up to a feeding concentration of 800 mg L⁻¹, the initial degradation rate steadily increased with phenol concentration (up to 180 mg L⁻¹ d⁻¹) and the elimination capacity remained relatively constant around 27 mg phenol removed?gVSS⁻¹ d⁻¹. Operation at higher concentrations (1200 mg L⁻¹) resulted in a still efficient but slower process: the elimination capacity and the initial degradation rate decreased to, respectively, 11 mg phenol removed?gVSS⁻¹ d⁻¹ and 154 mg L⁻¹ d⁻¹. As revealed by Denaturing Gradient Gel Electrophoresis (DGGE) analysis, the increase of phenol concentration induced level-dependent structural modifications of the community composition which suggest an adaptation process. The increase of phenol concentration from 120 to 800 mg L⁻¹ had little effect on the community structure, while it involved drastic structural changes when increasing from 800 to 1200 mg L⁻¹, including a strong community structure shift, suggesting the specialization of the community through the emergence and selection of most adapted phylotypes. The thresholds of structural and functional disturbances were similar, suggesting the correlation of degradation performance and community structure. The Canonical Correspondence Analysis (CCA) confirmed that the ASBR functional performance was essentially driven by specific community traits. Under the highest feeding concentration, the most abundant ribotype probably involved in successful phenol degradation at 1200 mg L⁻¹ was affiliated to the Anaerolineaceae family.     

Electrochemical sulfide removal from synthetic and real domestic wastewater at high current densities

Hydrogen sulfide generation is the key cause of sewer pipe corrosion, one of the major issues in water infrastructure. Current abatement strategies typically involve addition of various types of chemicals to the wastewater, which incurs large operational costs. The transport, storage and application of these chemicals also constitute occupational and safety hazards. In this study, we investigated high rate electrochemical oxidation of sulfide at Ir/Ta mixed metal oxide (MMO) coated titanium electrodes as a means to remove sulfide from wastewater. Both synthetic and real wastewaters were used in the experiments. Electrochemical sulfide oxidation by means of indirect oxidation with in-situ produced oxygen appeared to be the main reaction mechanism at Ir/Ta MMO coated titanium electrodes. The maximum obtained sulfide removal rate was 11.8 ± 1.7 g S m⁻² projected anode surface h⁻¹ using domestic wastewater at sulfide concentrations of ≥30 mg L⁻¹ or higher. The final products of the oxidation were sulfate, thiosulfate and elemental sulfur. Chloride and acetate concentrations did not entail differences in sulfide removal, nor were the latter two components affected by the electrochemical oxidation. Hence, the use of electrodes to generate oxygen in sewer systems may constitute a promising method for reagent-free removal of sulfide from wastewater.     

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.     

Assessing granular media filtration for the removal of chemical contaminants from wastewater

Granular media filtration was evaluated for the removal of a suite of chemical contaminants that can be found in wastewater. Laboratory- and pilot-scale sand and granular activated carbon (GAC) filters were trialled for their ability to remove atrazine, estrone (E1), 17α-ethynylestradiol (EE2), N-nitrosodimethylamine (NDMA), N-nitrosomorpholine (NMOR) and N-nitrosodiethylamine (NDEA). In general, sand filtration was ineffective in removing the contaminants from a tertiary treated wastewater, with the exception of E1 and EE2, where efficient removals were observed after approximately 150 d. Batch degradation experiments confirmed that the removal of E1 was through biological activity, with a pseudo-first-order degradation rate constant of 7.4 × 10⁻³ h⁻¹. GAC filtration was initially able to effectively remove all contaminants; although removals decreased over time due to competition with other organics present in the water. The only exception was atrazine where removal remained consistently high throughout the experiment. Previously unreported differences were observed in the adsorption of the three nitrosamines, with the ease of removal following the trend, NDEA > NMOR > NDMA, consistent with their hydrophobic character. In most instances the removals from the pilot-scale filters were generally in agreement with the laboratory-scale filter, suggesting that there is potential in using laboratory-scale filters as monitoring tools to evaluate the performance of pilot- and possibly full-scale sand and GAC filters at wastewater treatment plants.     

Soil aquifer treatment of artificial wastewater under saturated conditions

A 2000 mm long saturated laboratory soil column was used to simulate soil aquifer treatment under saturated conditions to assess the removal of chemical and biochemical oxygen demand (COD and BOD), dissolved organic carbon (DOC), nitrogen and phosphate, using high strength artificial wastewater. The removal rates were determined under a combination of constant hydraulic loading rates (HLR) and variable COD concentrations as well as variable HLR under a constant COD. Within the range of COD concentrations considered (42 mg L⁻¹-135 mg L⁻¹) it was found that at fixed hydraulic loading rate, a decrease in the influent concentrations of dissolved organic carbon (DOC), biochemical oxygen demand (BOD), total nitrogen and phosphate improved their removal efficiencies. At the high COD concentrations applied residence times influenced the redox conditions in the soil column. Long residence times were detrimental to the removal process for COD, BOD and DOC as anoxic processes and sulphate reduction played an important role as electron acceptors. It was found that total COD mass loading within the range of 911 mg d⁻¹-1780 mg d⁻¹ applied as low COD wastewater infiltrated coupled with short residence times would provide better effluent quality than the same mass applied as a COD with higher concentration at long residence times. The opposite was true for organic nitrogen where relatively high concentrations coupled with long residence time gave better removal efficiency.     

Treatment of estrogens and androgens in dairy wastewater by a constructed wetland system

Constructed wetland systems (CWS) have been used as a low cost bio-filtration system to treat farm wastewater. While studies have shown that CWS are efficient in removing organic compounds and pathogens, there is limited data on the presence of hormones in this type of treatment system.The objective of this study was to evaluate the ability of the CWS to reduce estrogenic and androgenic hormone concentration in dairy wastewater. This was achieved through a year long study on dairy wastewater samples obtained from a surface flow CWS. Analysis of hormonal levels was performed using a solid phase extraction (SPE) sample clean-up method, combined with reporter gene assays (RGAs) which incorporate relevant receptors capable of measuring total estrogenic or androgenic concentrations as low as 0.24 ng L⁻¹ and 6.9 ng L⁻¹ respectively. Monthly analysis showed a mean removal efficiency for estrogens of 95.2%, corresponding to an average residual concentration of 3.2 ng L⁻¹ 17β-estradiol equivalent (EEQ), below the proposed lowest observable effect concentration (LOEC) of 10 ng L⁻¹. However, for one month a peak EEQ concentration of 115 ng L⁻¹ was only reduced to 18.8 ng L⁻¹. The mean androgenic activity peaked at 360 ng L⁻¹ and a removal efficiency of 92.1% left an average residual concentration of 32.3 ng L⁻¹ testosterone equivalent (TEQ).The results obtained demonstrate that this type of CWS is an efficient system for the treatment of hormones in dairy wastewater. However, additional design improvements may be required to further enhance removal efficiency of peak hormone concentrations.     

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.     

Degradation of fifteen emerging contaminants at μg L initial concentrations by mild solar photo-Fenton in MWTP effluents

The degradation of 15 emerging contaminants (ECs) at low concentrations in simulated and real effluent of municipal wastewater treatment plant with photo-Fenton at unchanged pH and Fe = 5 mg L⁻¹ in a pilot-scale solar CPC reactor was studied. The degradation of those 15 compounds (Acetaminophen, Antipyrine, Atrazine, Caffeine, Carbamazepine, Diclofenac, Flumequine, Hydroxybiphenyl, Ibuprofen, Isoproturon, Ketorolac, Ofloxacin, Progesterone, Sulfamethoxazole and Triclosan), each with an initial concentration of 100 μg L⁻¹, was found to depend on the presence of CO₃²⁻ and HCO₃⁻ (hydroxyl radicals scavengers) and on the type of water (simulated water, simulated effluent wastewater and real effluent wastewater), but is relatively independent of pH, the type of acid used for release of hydroxyl radicals scavengers and the initial H₂O₂ concentration used. Toxicity tests with Vibrio fisheri showed that degradation of the compounds in real effluent wastewater led to toxicity increase.     

Biodegradability enhancement of a pesticide-containing bio-treated wastewater using a solar photo-Fenton treatment step followed by a biological oxidation process

This work proposes an efficient combined treatment for the decontamination of a pesticide-containing wastewater resulting from phytopharmaceutical plastic containers washing, presenting a moderate organic load (COD = 1662-1960 mg O₂ L⁻¹; DOC = 513-696 mg C L⁻¹), with a high biodegradable organic carbon fraction (81%; BOD₅ = 1350-1600 mg O₂ L⁻¹) and a remaining recalcitrant organic carbon mainly due to pesticides. Nineteen pesticides were quantified by LC-MS/MS at concentrations between 0.02 and 45 mg L⁻¹ (14-19% of DOC). The decontamination strategy involved a sequential three-step treatment: (a) biological oxidation process, leading to almost complete removal of the biodegradable organic carbon fraction; (b) solar photo-Fenton process using CPCs, enhancing the bio-treated wastewater biodegradability, mainly due to pesticides degradation into low-molecular-weight carboxylate anions; (c) and a final polishing step to remove the residual biodegradable organic carbon, using a biological oxidation process. Treatment performance was evaluated in terms of mineralization degree (DOC), pesticides content (LC-MS/MS), inorganic ions and low-molecular-weight carboxylate anions (IC) concentrations. The estimated phototreatment energy necessary to reach a biodegradable wastewater, considering pesticides and low-molecular-weight carboxylate anions concentrations, Zahn-Wellens test and BOD₅/COD ratio, was only 2.3 kJ_UV L⁻¹ (45 min of photo-Fenton at a constant solar UV power of 30 W m⁻²), consuming 16 mM of H₂O₂, which pointed to 52% mineralization and an abatement higher than 86% for 18 pesticides. The biological oxidation/solar photo-Fenton/biological oxidation treatment system achieved pesticide removals below the respective detection limits and 79% mineralization, leading to a COD value lower than 150 mg O₂ L⁻¹, which is in agreement with Portuguese discharge limits regarding water bodies.     

Removal of phenolic compounds from raw industrial wastewater by Achromobacter sp. isolated from a hydrocarbon‐contaminated area

The discharge of raw industrial wastewaters, specifically coking wastewater, represents a severe environmental problem. In this work, a phenol‐degrading aerobic strain isolated from a hydrocarbon contaminated site, Achromobacter sp. C‐1, was tested for degrading raw coking wastewater to explore its potential for use in biological treatment. Initially, phenol degradation was reached after 24 h of inoculation in synthetic wastewater [600 mg/L of phenol]. The maximum specific degradation rate was 0.436 h^–1 found in the concentration 300 mg/L. In a raw industrial wastewater containing a mixture of phenols as carbon source [phenol 370 mg/L, m‐cresol 100 mg/L and o‐cresol 60 mg/L], 90% biodegradation of a mixture of phenols was achieved after 80 h of inoculation. Following the biodegradation process to remove the colour from the wastewater, polishing was performed by activated carbon adsorption, resulting in a clear wastewater (without colour and contaminants) ready for industrial reuse purposes. These results provided useful information about use of the phenol‐degrading bacteria for bioaugmentation in industrial wastewater treatment improving the quality of final wastewater. The quality of the resulting wastewater was confirmed by mass spectrometry analysis. This work shows the biodegradation process could be a cost‐effective and promising solution for the treatment and reuse of phenolic wastewater.      

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.     

Significance of urban and agricultural land use for biocide and pesticide dynamics in surface waters

Biocides and pesticides are designed to control the occurrence of unwanted organisms. From their point of application, these substances can be mobilized and transported to surface waters posing a threat to the aquatic environment. Historically, agricultural pesticides have received substantially more attention than biocidal compounds from urban use, despite being used in similar quantities.This study aims at improving our understanding of the influence of mixed urban and agricultural land use on the overall concentration dynamics of biocides and pesticides during rain events throughout the year. A comprehensive field study was conducted in a catchment within the Swiss plateau (25 km²). Four surface water sampling sites represented varying combinations of urban and agricultural sources. Additionally, the urban drainage system was studied by sampling the only wastewater treatment plant (WWTP) in the catchment, a combined sewer overflow (CSO), and a storm sewer (SS). High temporal resolution sampling was carried out during rain events from March to November 2007.The results, based on more than 600 samples analyzed for 23 substances, revealed distinct and complex concentration patterns for different compounds and sources. Five types of concentration patterns can be distinguished: a) compounds that showed elevated background concentrations throughout the year (e.g. diazinon >50 ng L⁻¹), indicating a constant household source; b) compounds that showed elevated concentrations driven by rain events throughout the year (e.g. diuron 100-300 ng L⁻¹), indicating a constant urban outdoor source such as facades; c) compounds with seasonal peak concentrations driven by rain events from urban and agricultural areas (e.g. mecoprop 1600 ng L⁻¹ and atrazine 2500 ng L⁻¹ respectively); d) compounds that showed unpredictably sharp peaks (e.g. atrazine 10,000 ng L⁻¹, diazinon 2500 ng L⁻¹), which were most probably due to improper handling or even disposal of products; and finally, e) compounds that were used in high amounts but were not detected in surface waters (e.g. isothiazolinones).It can be safely concluded that in catchments of mixed land use, the contributions of biocide and pesticide inputs into surface waters from urban areas are at least as important as those from agricultural areas.     

Removal of organics in constructed wetlands with horizontal sub-surface flow: a review of the field experience

Constructed wetlands with horizontal sub-surface flow (HF CWs) have successfully been used for treatment various types of wastewater for more than four decades. Most systems have been designed to treat municipal sewage but the use for wastewaters from agriculture, industry and landfill leachate in HF CWs is getting more attention nowadays. The paper summarizes the results from more than 400 HF CWs from 36 countries around the world. The survey revealed that the highest removal efficiencies for BOD₅ and COD were achieved in systems treating municipal wastewater while the lowest efficiency was recorded for landfill leachate. The survey also revealed that HF CWs are successfully used for both secondary and tertiary treatment. The highest average inflow concentrations of BOD₅ (652 mg l^− 1) and COD (1865 mg l^− 1) were recorded for industrial wastewaters followed by wastewaters from agriculture for BOD₅ (464 mg l^− 1) and landfill leachate for COD (933 mg l^− 1). Hydraulic loading data reveal that the highest loaded systems are those treating wastewaters from agriculture and tertiary municipal wastewaters (average hydraulic loading rate 24.3 cm d^− 1). On the other hand, landfill leachate systems in the survey were loaded with average only 2.7 cm d^− 1. For both BOD₅ and COD, the highest average loadings were recorded for agricultural wastewaters (541 and 1239 kg ha^− 1 d^− 1, respectively) followed by industrial wastewaters (365 and 1212 kg ha^− 1 d^− 1, respectively). The regression equations for BOD₅ and COD inflow/outflow concentrations yielded very loose relationships. Much stronger relationships were found for inflow/outflow loadings and especially for COD. The influence of vegetation on removal of organics in HF CWs is not unanimously agreed but most studies indicated the positive effect of macrophytes.     

Occurrence and removal of pharmaceuticals, caffeine and DEET in wastewater treatment plants of Beijing, China

The occurrence and removal of 13 pharmaceuticals and 2 consumer products, including antibiotic, antilipidemic, anti-inflammatory, anti-hypertensive, anticonvulsant, stimulant, insect repellent and antipsychotic, were investigated in four wastewater treatment plants (WWTPs) of Beijing, China. The compounds were extracted from wastewater samples by solid-phase extraction (SPE) and analyzed by ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). Most of the target compounds were detected, with the concentrations of 4.4 ng L⁻¹-6.6 μg L⁻¹ and 2.2-320 ng L⁻¹ in the influents and secondary effluents, respectively. These concentrations were consistent with their consumptions in China, and much lower than those reported in the USA and Europe. Most compounds were hardly removed in the primary treatment, while their removal rates ranging from −12% to 100% were achieved during the secondary treatment. In the tertiary treatment, different processes showed discrepant performances. The target compounds could not be eliminated by sand filtration, but the ozonation and microfiltration/reverse osmosis (MF/RO) processes employed in two WWTPs were very effective to remove them, showing their main contributions to the removal of such micro-pollutants in wastewater treatment.     

Performance of conventional multi-barrier drinking water treatment plants for the removal of four artificial sweeteners

Due to incomplete removal of artificial sweeteners in wastewater treatment plants some of these compounds end up in receiving surface waters, which are used for drinking water production. The sum of removal efficiency of single treatment steps in multi-barrier treatment systems affects the concentrations of these compounds in the provided drinking water. This is the first systematic study revealing the effectiveness of single treatment steps in laboratory experiments and in waterworks. Six full-scale waterworks using surface water influenced raw water were sampled up to ten times to study the fate of acesulfame, saccharin, cyclamate and sucralose. For the most important treatment technologies the results were confirmed by laboratory batch experiments. Saccharin and cyclamate proved to play a minor role for drinking water treatment plants as they were eliminated by nearly 100% in all waterworks with biologically active treatment units like river bank filtration (RBF) or artificial groundwater recharge. Acesulfame and sucralose were not biodegraded during RBF and their suitability as wastewater tracers under aerobic conditions was confirmed. Sucralose proved to be persistent against ozone and its transformation was <20% in lab and field investigations. Remaining traces were completely removed by subsequent granular activated carbon (GAC) filters. Acesulfame readily reacts with ozone (pseudo first-order rate constant k = 1.3 × 10⁻³ s⁻¹ at 1 mg L⁻¹ ozone concentration). However, the applied ozone concentrations and contact times under typical waterworks conditions only led to an incomplete removal (18-60%) in the ozonation step. Acesulfame was efficiently removed by subsequent GAC filters with a low throughput of less than 30 m³ kg⁻¹, but removal strongly depended on the GAC preload. Thus, acesulfame was detected up to 0.76 μg L⁻¹ in finished water.