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.     

Processes releasing arsenic to groundwater in the Caldes de Malavella geothermal area, NE Spain

Arsenic concentrations exceeding the World Health Organization drinking water guideline (10 μg/L) have been measured in thermal and non-thermal groundwaters from the Caldes de Malavella geothermal area (La Selva graben, NE Spain). The CO₂-rich Na-HCO₃ thermal waters (up to 60 °C at the spring) have elevated arsenic concentrations ([As_T] from 50 to 80 μg/L). The non-thermal waters are of Ca-Na-HCO₃-Cl type and have [As_T] between <1 and 200 μg/L, defining a hot-spot distribution. The present-day contribution of As from CO₂-rich thermal waters to non-thermal aquifers is very limited, as shown by the concentration of geothermal tracers such as Li and B. Redox-controlling processes appear to govern the mobility of As in the non-thermal waters. Arsenate is clearly predominant in most oxidizing groundwaters (>85% of As(V) over total As), whereas reducing, high-As groundwater reaches up to 100% in arsenite. The reductive dissolution of Fe(III) oxyhydroxides and the coupled release and reduction of adsorbed As explain the elevated dissolved arsenite (up to 190 μg/L) and Fe (up to 14 mg/L) content in the more reducing non-thermal groundwater. Conversely, the high levels of nitrate (up to 136 mg/L) ensure an oxidizing environment in most non-thermal groundwaters ([As_T] between <1 and 60 μg/L). Under these conditions, Fe(III) oxyhydroxides are stable and As release to groundwater is not related to their dissolution. Instead, dissolved arsenate concentrations up to 60 μg/L are explained by a competition for sorption sites with other species, mainly bicarbonate and silicic acid, while arsenate desorption due to pH increase is not considered a major process.     

Perfluorinated compounds in surface waters and WWTPs in Shenyang, China: mass flows and source analysis

Concentrations of 10 perfluorinated chemicals (PFCs) were investigated in the Hun River (HR), four canals, ten lakes, and influents and effluents from four main municipal wastewater treatment plants (WWTPs) in Shenyang, China. Mass flows of four main PFCs were calculated to elucidate the contribution from different sections of the HR. Overall, perfluorooctanoic acid (PFOA) and perfluorohexanoic acid (PFHxA) were the major PFCs in the HR, with ranges of 2.68-9.13 ng/L, and 2.12-11.3 ng/L, respectively, while perfluorooctane sulfonate (PFOS) was detected at lower levels, ranging from 0.40 to 3.32 ng/L. The PFC concentrations in the HR increased after the river passes through two cities (Shenyang and Fushun), indicating cities are an important contributor for PFCs. Mass flow analysis in the HR revealed that PFC mass flows from Fushun are 1.65-5.50 kg/year for C6-C8 perfluorinated acids (PFCAs) and 1.29 kg/year for PFOS, while Shenyang contributed 2.83-5.18 kg C6-C8 PFCAs/year, and 3.65 kg PFOS/year. The concentrations of PFCs in four urban canals were higher than those in the HR, with the maximum total PFCs of 240 ng/L. PFOA and PFOS showed different trends along these canals, suggesting different sources for the two PFCs. Total PFCs in ten lakes from Shenyang were at low levels, with the greatest concentration (56.2 ng/L) detected in a heavily industrialized area. The PFC levels in WWTP effluents were higher than those in surface waters with concentrations ranging from 18.4 to 41.1 ng/L for PFOA, and 1.69-3.85 ng/L for PFOS. Similar PFC profiles between effluents from WWTPs and urban surface waters were found. These results indicate that WWTPs are an important PFC source in surface water. Finally, we found that the composition profiles of PFCs in surface waters were similar to those in tap water, but not consistent with those in adult blood from Shenyang. The calculation on total daily intake of PFOS by adults from Shenyang showed that the contribution of drinking water to human exposure was minor.     

Poor elimination rates in waste water treatment plants lead to continuous emission of deoxynivalenol into the aquatic environment

Deoxynivalenol (DON) is one of the most prominent mycotoxins generated by fungi of the generus Fusarium on crops. Its presence in surface waters was recently demonstrated. Here, we elucidate the occurrence and behaviour of DON in three Swiss waste water treatment plants (WWTP) as a result of human consumption and excretion. DON was shown to be omnipresent in the primary effluent samples of these WWTP in concentrations from 32 to 118 ng/L. Corresponding loads were a factor of 1.3–2.3 higher than predicted based on human excretion data from the literature. DON elimination rates in WWTP ranged from 33 to 57%. These rather low percentages were confirmed with a further, more detailled study conducted at WWTP Kloten/Opfikon (average elimination rate 32%). The relative importance of WWTP as a source of DON in surface waters was compared with agricultural emissions due to runoff from Fusarium infected crops. Both sources seem to contribute equally to the total DON exposure of surface waters of a few ng/L, however, their input dynamics vary considerably in space and time.     

Occurrence and fate of the angiotensin II receptor antagonist transformation product valsartan acid in the water cycle – A comparative study with selected β-blockers and the persistent anthropogenic wastewater indicators carbamazepine and acesulfame

The substantial transformation of the angiotensin II receptor antagonist valsartan to the transformation product 2′-(2H-tetrazol-5-yl)-[1,1′-biphenyl]-4-carboxylic acid (referred to as valsartan acid) during the activated sludge process was demonstrated in the literature and confirmed in the here presented study. However, there was a severe lack of knowledge regarding the occurrence and fate of this compound in surface water and its behavior during drinking water treatment. In this work a comparative study on the occurrence and persistency of valsartan acid, three frequently used β-blockers (metoprolol, atenolol, and sotalol), atenolol acid (one significant transformation product of atenolol and metoprolol), and the two widely distributed persistent anthropogenic wastewater indicators carbamazepine and acesulfame in raw sewage, treated wastewater, surface water, groundwater, and tap water is presented. Median concentrations of valsartan acid in the analyzed matrices were 101, 1,310, 69, <1.0, and 65 ng L⁻¹, respectively. Treated effluents from wastewater treatment plants were confirmed as significant source. Regarding concentration levels of pharmaceutical residues in surface waters valsartan acid was found just as relevant as the analyzed β-blockers and the anticonvulsant carbamazepine. Regarding its persistency in surface waters it was comparable to carbamazepine and acesulfame. Furthermore, removal of valsartan acid during bank filtration was poor, which demonstrated the relevance of this compound for drinking water suppliers. Regarding drinking water treatment (Muelheim Process) the compound was resistant to ozonation but effectively eliminated (≥90%) by subsequent activated carbon filtration. However, without applying activated carbon filtration the compound may enter the drinking water distribution system as it was demonstrated for Berlin tap water.     

Monitoring of opiates, cannabinoids and their metabolites in wastewater, surface water and finished water in Catalonia, Spain

The occurrence of several opiates and cannabinoids in wastewaters and surface waters has been investigated. Most of the compounds (8 out of 11) were identified in both influent and effluents of fifteen wastewater treatment plants (WWTPs). Codeine, morphine, EDDP and methadone were detected in almost all samples with median values of 69 ng/L; 63 ng/L; 28 ng/L and 18 ng/L, respectively, whereas the main cannabinoid metabolite THC-COOH presented a median value of 57 ng/L in influents. A rough estimate of heroin and cannabis consumption was performed from the analysis of target urinary metabolites in wastewater influents. Data obtained from influents of rural and urban WWTPs gave 0.07% of heroin consumption (0.67% for the largest urban WWTP) and 4% consumption of cannabinoids, respectively for the population aged between 15 and 64 years old. The presence of opiates and cannabinoids in surface waters used for drinking water production showed the presence of the same compounds identified in wastewater effluents at concentrations up to 76 ng/L for codeine; 31 ng/L for EDDP; 12 ng/L for morphine and 9 ng/L for methadone at the intake of the DWTP. A complete removal of all studied drugs present in surface water was achieved during the potabilization process except for methadone and EDDP (91% and 87% removal, respectively).     

Occurrence and fate of the antidiabetic drug metformin and its metabolite guanylurea in the environment and during drinking water treatment

Metformin, an antidiabetic drug with one of the highest consumption rates of all pharmaceuticals worldwide, is biologically degraded to guanylurea in wastewater treatment plants. Due to high metformin influent concentrations of up to 100 μg/L and its high but incomplete degradation both compounds are released in considerable amounts of up to several tens of μg/L into recipient rivers. This is the first systematic study on their environmental fate and the effectiveness of treatment techniques applied in waterworks to remove metformin and guanylurea from surface water influenced raw waters. The concentrations in surface waters depend strongly on the respective wastewater burden of rivers and creeks and are typically in the range of about 1 μg/L for metformin and several μg/L for guanylurea but can reach elevated average concentrations of more than 3 and 20 μg/L, respectively. Treatment techniques applied in waterworks were investigated by an extended monitoring program in three facilities and accompanied by laboratory-scale batch tests. Flocculation and activated carbon filtration proved to be ineffective for removal of metformin and guanylurea. During ozonation and chlorination experiments with waterworks-relevant ozone and chlorine doses they were partly transformed to yet unknown compounds. The effectiveness of the treatment steps under investigation can be ordered chlorination > ozonation > activated carbon filtration > flocculation. However, most effective for removal of both compounds at the three full-scale waterworks studied proved to be an underground passage (riverbank filtration or artificial groundwater recharge). A biological degradation is most likely as sorption can be neglected. This is based on laboratory batch tests conducted with three different soil materials according to OECD guideline 106. Since such treatment steps were implemented in all three drinking water treatment plants, even traces of metformin and its metabolite guanylurea could not be detected at the end of the treatment trains. Both can only be expected in finished drinking water if surface influenced raw water is used by direct abstraction without underground passage.     

Occurrence of perchlorate in drinking water sources of metropolitan area in Japan

The occurrence of perchlorate in the Tone River Basin was investigated using an ion chromatograph (IC) coupled with a tandem mass spectrometer (MS/MS). Perchlorate was found at high concentrations in the upper Tone River and its tributary, Usui River, and the maximum concentrations were 340 and 2300 microg/L, respectively. The possible sources of perchlorate in two areas were attributable to industrial effluents. In case of the upper Tone River, perchlorate concentration in an effluent was 1100 microg/L and its concentrations in a tributary (or waterway) directly downstream of the outlet of the effluent ranged from 44 to 1500 microg/L. In case of the Usui River, perchlorate concentration in another effluent was 15,000 microg/L and its concentrations downstream of the outlet of the effluent were 1100-3900 microg/L. Due to the discharge of perchlorate in the upper Tone River Basin, perchlorate concentrations in the river waters of the middle and lower Tone River Basin were generally 10-20 microg/L. Perchlorate concentrations in 30 tap water samples were investigated. Water sources of three tap water samples were other than the Tone River Basin and their perchlorate concentrations were 0.16-0.87 microg/L. On the other hand, water sources of the remaining 27 samples were the upper, middle and lower Tone River Basin and their perchlorate concentrations were 0.06-37 microg/L. Perchlorate concentrations were more than 1 microg/L in 19 tap water samples and more than 10 microg/L in 13 samples. It was shown that tap waters in the Tone River Basin were widely contaminated with perchlorate. To our knowledge, this study was the first to report on perchlorate contamination of environmental and drinking waters in Japan.     

Chemical water quality in Thailand and its impacts on the drinking water production in Thailand

In Thailand, surface water and groundwater are the main water sources for tap water and drinking water production. Thirty-six different samples from surface waters from Chao Praya and Mae Klong rivers, tap waters, bottled drinking waters, groundwaters and commercial ice cubes from around the Bangkok area were collected. Water samples were also taken from two waterworks in the Chonburi province. The extensive survey showed that, overall in all water samples investigated, there was only a minor pollution which could be traced back to the analyses performed including amongst others total organic carbon, inorganics and heavy metals, pesticides, organochlorine compounds, volatile organic compounds, surfactants, pharmaceuticals and disinfection by-products. However, whenever organic micropollutants could be detected in surface water, such as, e.g. the herbicide atrazine, they were also present in the tap water produced thereof proving that the present treatment steps are not sufficient for removal of such pollutants. The concentration of disinfection by-products was higher in tap water produced from Chao Praya river than from Mae Klong river. Disinfection by-products were also found in bottled drinking water. Commercial ice cubes contained anionic surfactants and their metabolites at elevated concentrations. The data of this study constitute the first set of homogenous data for the chemical water quality and also aid development of new water quality criteria in Thailand.     

Occurrence and removal of pharmaceuticals and hormones through drinking water treatment

The occurrence of fifty-five pharmaceuticals, hormones and metabolites in raw waters used for drinking water production and their removal through a drinking water treatment were studied. Thirty-five out of fifty-five drugs were detected in the raw water at the facility intake with concentrations up to 1200 ng/L. The behavior of the compounds was studied at each step: prechlorination, coagulation, sand filtration, ozonation, granular activated carbon filtration and post-chlorination; showing that the complete treatment accounted for the complete removal of all the compounds detected in raw waters except for five of them. Phenytoin, atenolol and hydrochlorothiazide were the three pharmaceuticals most frequently found in finished waters at concentrations about 10 ng/L. Sotalol and carbamazepine epoxide were found in less than a half of the samples at lower concentrations, above 2 ng/L. However despite their persistence, the removals of these five pharmaceuticals were higher than 95%.     

The occurrence of antibiotics in an urban watershed: From wastewater to drinking water

The presence of 28 antibiotics in three hospital effluents, five wastewater treatment plants (WWTPs), six rivers and a drinking water storage catchment were investigated within watersheds of South-East Queensland, Australia. All antibiotics were detected at least once, with the exception of the polypeptide bacitracin which was not detected at all. Antibiotics were found in hospital effluent ranging from 0.01-14.5 μg L^− 1, dominated by the β-lactam, quinolone and sulphonamide groups. Antibiotics were found in WWTP influent up to 64 μg L^− 1, dominated by the β-lactam, quinolone and sulphonamide groups. Investigated WWTPs were highly effective in removing antibiotics from the water phase, with an average removal rate of greater than 80% for all targeted antibiotics. However, antibiotics were still detected in WWTP effluents in the low ng L^− 1 range up to a maximum of 3.4 μg L^− 1, with the macrolide, quinolone and sulphonamide antibiotics most prevalent. Similarly, antibiotics were detected quite frequently in the low ng L^− 1 range, up to 2 μg L^− 1 in the surface waters of six investigated rivers including freshwater, estuarine and marine samples. The total investigated antibiotic concentration (TIAC) within the Nerang River was significantly lower (p < 0.05) than all other rivers sampled. The absence of WWTP discharge to this river is a likely explanation for the significantly lower TIAC and suggests that WWTP discharges are a dominant source of antibiotics to investigated surface waters. A significant difference (p < 0.001) was identified between TIACs at surface water sites with WWTP discharge compared to sites with no WWTP discharge, providing further evidence that WWTPs are an important source of antibiotics to streams. Despite the presence of antibiotics in surface waters used for drinking water extraction, no targeted antibiotics were detected in any drinking water samples.     

Investigation of pharmaceuticals in Missouri natural and drinking water using high performance liquid chromatography-tandem mass spectrometry

A comprehensive method has been developed and validated in two different water matrices for the analysis of 16 pharmaceutical compounds using solid phase extraction (SPE) of water samples, followed by liquid chromatography coupled with tandem mass spectrometry. These 16 compounds include antibiotics, hormones, analgesics, stimulants, antiepileptics, and X-ray contrast media. Method detection limits (MDLs) that were determined in both reagent water and municipal tap water ranged from 0.1 to 9.9 ng/L. Recoveries for most of the compounds were comparable to those obtained using U.S. EPA methods. Treated and untreated water samples were collected from 31 different water treatment facilities across Missouri, in both winter and summer seasons, and analyzed to assess the 16 pharmaceutical compounds. The results showed that the highest pharmaceutical concentrations in untreated water were caffeine, ibuprofen, and acetaminophen, at concentrations of 224, 77.2, and 70 ng/L, respectively. Concentrations of pharmaceuticals were generally higher during the winter months, as compared to those in the summer due, presumably, to smaller water quantities in the winter, even though pharmaceutical loadings into the receiving waters were similar for both seasons.     

Analysis of environmental endocrine disrupting chemicals using the E-screen method and stir bar sorptive extraction in wastewater treatment plant effluents

Endocrine disrupting chemicals (EDCs) have become a major issue in the field of environmental science due to their ability to interfere with the endocrine system. Recent studies show that surface water is contaminated with EDCs, many released from wastewater treatment plants (WWTP). This pilot study used biological (E-screen assay) and chemical (stir bar sorptive extraction-GC-MS) analyses to quantify estrogenic activity in effluent water samples from a municipal WWTP and in water samples of the recipient river, upstream and downstream of the plant.The E-screen assay was performed on samples after solid phase extraction (SPE) to determine total estrogenic activity; the presence of estrogenic substances can be evaluated by measuring the 17-β-estradiol equivalency quantity (EEQ). Untreated samples were also assayed with an acute toxicity test (Vibrio fischeri) to study the correlation between toxicity and estrogenic disruption activity.Mean EEQs were 4.7 ng/L (± 2.7 ng/L) upstream and 4.4 ng/L (± 3.7 ng/L) downstream of the plant, and 11.1 ng/L (± 11.7 ng/L) in the effluent. In general the WWTP effluent had little impact on estrogenicity nor on the concentration of EDCs in the river water. The samples upstream and downstream of the plant were non-toxic or weakly toxic (0 < TU < 0.9) while the effluent was weakly toxic or toxic (0.4 < TU < 7.6). Toxicity and estrogenic activity were not correlated.At most sites, industrial mimics, such as the alkylphenols and phthalates, were present in higher concentrations than natural hormones. Although the concentrations of the detected xenoestrogens were generally higher than those of the steroids, they accounted for only a small fraction of the EEQ because of their low estrogenic potency. The EEQs resulting from the E-screen assay and those calculated from the results of chemical analyses using estradiol equivalency factors were comparable for all samples and closely correlated.     

Polar pollutants in municipal wastewater and the water cycle: Occurrence and removal of benzotriazoles

1H-benzo-1,2,3-triazole (BTri) and its methylated analogues (tolyltriazole, TTri) are corrosion inhibitors used in many industrial applications, but also in households in dishwashing agents and in deicing fluids at airports and elsewhere. BTri and one of the TTri-isomers (4-TTri) are typical examples of polar and poorly degradable trace pollutants. Benzotriazole elimination in four wastewater treatment plants (WWTP) in Berlin ranged from 20 to 70% for 5-TTRi over 30 to 55% for BTri to insignificant for 4-TTri. WWTP effluent concentrations were in the range of 7-18 μg/L of BTri, 1-5 μg/L of 4-TTri and 0.8-1.2 μg/L of 5-TTri. BTri and 4-TTri proved to be omnipresent in surface waters of the rivers Rhine and Elbe with concentrations increasing from <0.05 μg/L to around 0.5 μg/L of BTri and 0.2-0.5 μg/L of 4-TTri over 600-700 km. Bank filtration is an important process to generate raw water for drinking water production from surface waters. Even after residence times of several months BTri and 4-TTri were determined in concentrations of a few hundred ng/L in bank filtration water. Isotherm data from batch experiments indicate that activated carbon filtration should be suitable to avoid intrusion of TTri into drinking water in partially closed water cycles. For BTri, however, sorption to activated carbon appears to be too weak and ozonation may be mandatory to remove it from raw waters.     

Relative importance of wastewater treatment plants and non-point sources of perfluorinated compounds to Washington State rivers

Perfluorinated compounds (PFCs) were measured in 10 Washington State rivers and 4 wastewater treatment plants (WWTPs) under periods of low and high flows to investigate the relative importance of point and non-point sources to rivers. PFCs were detected in all samples with summed values ranging from 1.11 to 74.9 ng/L in surface waters and 62.3-418 ng/L in WWTP effluent. Concentrations in 6 of the 10 rivers exhibited a positive relationship with flow, indicating runoff as a contributing source, with PFC loads greatest at all 10 waterbodies during high flows. Perfluoroheptanoic acid:perfluorooctanoic acid homologue ratios suggest atmospheric contributions to the waterbodies are important throughout the year. Principal component analysis (PCA) indicated distinct homologue profiles for high flow, low flow, and effluent samples. The PCA demonstrates that during the spring when flows and loads are at their greatest; WWTP discharges are not the primary sources of PFCs to the river systems. Taken together, the evidence provided signifies non-point inputs are a major pathway for PFCs to surface waters in Washington State.     

Lake responses following lanthanum-modified bentonite clay (Phoslock) application: An analysis of water column lanthanum data from 16 case study lakes

Phoslock^® is a lanthanum (La) modified bentonite clay that is being increasingly used as a geo-engineering tool for the control of legacy phosphorus (P) release from lake bed sediments to overlying waters. This study investigates the potential for negative ecological impacts from elevated La concentrations associated with the use of Phoslock^® across 16 case study lakes. Impact-recovery trajectories associated with total lanthanum (TLa) and filterable La (FLa) concentrations in surface and bottom waters were quantified over a period of up to 60 months following Phoslock^® application. Both surface and bottom water TLa and FLa concentrations were <0.001 mg L⁻¹ in all lakes prior to the application of Phoslock^®. The effects of Phoslock^® application were evident in the post-application maximum TLa and FLa concentrations reported for surface waters between 0.026 mg L⁻¹–2.30 mg L⁻¹ and 0.002 mg L⁻¹ to 0.14 mg L⁻¹, respectively. Results of generalised additive modelling indicated that recovery trajectories for TLa and FLa in surface and bottom waters in lakes were represented by 2nd order decay relationships, with time, and that recovery reached an end-point between 3 and 12 months post-application. Recovery in bottom water was slower (11–12 months) than surface waters (3–8 months), most probably as a result of variation in physicochemical conditions of the receiving waters and associated effects on product settling rates and processes relating to the disturbance of bed sediments. CHEAQS PRO modelling was also undertaken on 11 of the treated lakes in order to predict concentrations of La³⁺ ions and the potential for negative ecological impacts. This modelling indicated that the concentrations of La³⁺ ions will be very low (<0.0004 mg L⁻¹) in lakes of moderately low to high alkalinity (>0.8 mEq L⁻¹), but higher (up to 0.12 mg L⁻¹) in lakes characterised by very low alkalinity. The effects of elevated La³⁺ concentrations following Phoslock^® applications in lakes of very low alkalinity requires further evaluation. The implications for the use of Phoslock^® in eutrophication management are discussed.     

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.     

Fate of hormones and pharmaceuticals during combined anaerobic treatment and nitrogen removal by partial nitritation-anammox in vacuum collected black water

Vacuum collected black (toilet) water contains hormones and pharmaceuticals in relatively high concentrations (μg/L to mg/L range) and separate specific treatment has the potential of minimizing their discharge to surface waters. In this study, the fate of estrogens (natural and synthetical hormones) and pharmaceuticals (paracetamol, metoprolol, propranolol, cetirizine, doxycycline, tetracycline, ciprofloxacin, trimethoprim, carbamazepine, ibuprofen and diclofenac) in the anaerobic treatment of vacuum collected black water followed by nitrogen removal by partial nitritation-anammox was investigated. A new analytical method was developed to detect the presence of several compounds in the complex matrix of concentrated black water. Detected concentrations in black water ranged from 1.1 μg/L for carbamazepine to >1000 μg/L for paracetamol. Anaerobic treatment was only suitable to remove the majority of paracetamol (>90%). Metoprolol was partly removed (67%) during aerobic treatment. Deconjugation could have affected the removal efficiency of ibuprofen as concentrations even increased during anaerobic treatment and only after the anammox treatment 77% of ibuprofen was removed. The presence of persistent micro-pollutants (diclofenac, carbamazepine and cetirizine), which are not susceptible for biodegradation, makes the application of advanced physical and chemical treatment unavoidable.     

Bromide concentration in Swedish precipitation, surface and ground waters

The occurrence of bromide in precipitation, surface and ground waters in Sweden has been investigated (300 samples). The concentration of bromide in precipitation is 0.05–0.15 μM in the south and <0.05 μM in the north of Sweden. The concentrations of bromide and chloride are well correlated. For river water the same areal distribution pattern as for precipitation is found, but the concentrations are 2–4 times higher. The molar ratio Br/Cl is 1 × 10⁻³ which is lower than that for sea water (1.54 × 10⁻³) and, most likely, also lower than for precipitation. A detailed study of Lake Mälaren has been made. The north-eastern feeder streams, passing an area of post-glacial clay, showed unusually high bromide concentrations (0.3–3 μM) and Br/Cl quotients (2 × 10⁻³-8 × 10⁻³). No correlation between the concentrations of bromide and chloride was found. Rough calculations indicate that fertilizers and chemicals added to the fields could only contribute a minor fraction of the bromide found. Analysis of 18 ground water samples indicated increased bromide levels as compared to surface waters.     

Determination of iodide,iodate and organo-iodine in waters with a new total organic iodine measurement approach

The dissolved iodine species that dominate aquatic systems are iodide, iodate and organo-iodine. These species may undergo transformation to one another and thus affect the formation of iodinated disinfection byproducts during disinfection of drinking waters or wastewater effluents. In this study, a fast, sensitive and accurate method for determining these iodine species in waters was developed by derivatizing iodide and iodate to organic iodine and measuring organic iodine with a total organic iodine (TOI) measurement approach. Within this method, organo-iodine was determined directly by TOI measurement; iodide was oxidized by monochloramine to hypoiodous acid and then hypoiodous acid reacted with phenol to form organic iodine, which was determined by TOI measurement; iodate was reduced by ascorbic acid to iodide and then determined as iodide. The quantitation limit of organo-iodine or sum of organo-iodine and iodide or sum of organo-iodine, iodide and iodate was 5 μg/L as I for a 40 mL water sample (or 2.5 μg/L as I for an 80 mL water sample, or 1.25 μg/L as I for a 160 mL water sample). This method was successfully applied to the determination of iodide, iodate and organo-iodine in a variety of water samples, including tap water, seawater, urine and wastewater. The recoveries of iodide, iodate and organo-iodine were 91–109%, 90–108% and 91–108%, respectively. The concentrations and distributions of iodine species in different water samples were obtained and compared.