Pharmaceutical and personal care products (PPCPs) in urban receiving waters

The transport pathways of pharmaceutical and personal care products (PPCP) discharges within the urban water cycle include both combined and separate sewer systems with only the former receiving treatment. The dry-weather flow dilution patterns for selected PPCPs following discharge from a sewage treatment works (STW) to a North London stream indicate a persistent downstream increase in concentration. The dilution ratio analysis also indicates that the STW's final effluent only contributes a dilution of the endogenous concentrations already present in the river flow which reflects a progressive PPCP load with increasing urbanization; "worst-case" scenarios being probably related to wet-weather conditions. Maximum PPCP concentrations fall above the reported PEC levels and the analysis highlights the deficiencies of conventional acute toxicity for the evaluation of long-term effects of episodic urban discharges. Groundwater analysis points to sewer exfiltration which is limited in terms of PPCP impact to 25-50 cm depths.     

Assessment of the environmental fate of linear alkylbenzenesulphonates

Fugacity models, as developed previously, are applied to the chemical linear alkylbenzenesulphonate (LAS) to predict its ultimate fate in the environment. The behaviour of LAS is illustrated using unit worlds or evaluative environments at three successive levels of complexity (Levels I, II, and III). LAS is shown to have a short environmental life of two days attributable to rapid biodegradation in water. Reported concentration data for LAS in Rapid Creek, South Dakota, downstream from a municipal sewage treatment plant, are compared to expected concentrations as generated by the QWASI (Quantitative Water Air Sediment Interaction) fugacity model; the model being based solely on the physical, chemical, reactivity and transport properties of LAS and the emission rate of the chemical into the river. The data are found to fit the model when a sediment-water mass transfer coefficient of 7.80 × 10⁻³ m/h and an effective sediment bed depth of 3 mm are used. The generally satisfying agreement between environmental observations and the QWASI fugacity models lends credibility to the use of evaluative models.     

European risk assessment of LAS in agricultural soil revisited: species sensitivity distribution and risk estimates

Linear alkylbenzene sulphonate (LAS) is used at a rate of approximately 430,000 tons/y in Western Europe, mainly in laundry detergents. It is present in sewage sludge (70-5,600 mg/kg; 5-95th percentile) because of its high usage per capita, its sorption and precipitation in primary settlers, and its lack of degradation in anaerobic digesters. Immediately after amendment, calculated and measured concentrations are <1 to 60 mg LAS/kg soil. LAS biodegrades rapidly in soil with primary and ultimate half-lives of up to 7 and 30 days, respectively. Calculated residual concentrations after the averaging time (30 days) are 0.24-18 mg LAS/kg soil. The long-term ecotoxicity to soil microbiota is relatively low (EC10 >or=26 mg sludge-associated LAS/kg soil). An extensive review of the invertebrate and plant ecotoxicological data, combined with a probabilistic assessment approach, led to a PNEC value of 35 mg LAS/kg soil, i.e. the 5th percentile (HC5) of the species sensitivity distribution (lognormal distribution of the EC10 and NOEC values). Risk ratios were identified to fall within a range of 0.01 (median LAS concentration in sludge) to 0.1 (95th percentile) and always below 0.5 (maximum LAS concentration measured in sludge) according to various scenarios covering different factors such as local sewage influent concentration, water hardness, and sewage sludge stabilisation process. Based on the present information, it can be concluded that LAS does not represent an ecological risk in Western Europe when applied via normal sludge amendment to agricultural soil.     

Comparison between the polar organic chemical integrative sampler and the solid-phase extraction for estimating herbicide time-weighted average concentrations during a microcosm experiment

Polar organic chemical integrative samplers (POCIS) were exposed for 9 days in two different microcosms that contained river waters spiked with deethylterbuthylazine, terbuthylazine and isoproturon. The experiment was performed with natural light and strong turbulence (flow velocities of about 15-50cms(-1)) for reproducing natural conditions. The concentrations were kept relatively constant in the first microcosm (2.6-3.6mugl(-1)) and were variable in the second microcosm (peak concentrations ranged from 15 to 24mugl(-1) during the 3 day pulse phase). The time-weighted average (TWA) concentrations were determined with both POCIS and repetitive grab sampling followed by solid-phase extraction. The results showed a systematic and significant overestimation of the TWA concentrations with the POCIS most probably due to the use of sampling rates derived under low flow scenario. The results showed also that peak concentrations of pollutants are fully integrated by this passive sampler. Even if the POCIS should not provide very accurate concentration estimates without the application of adequate sampling rate values or the use of performance reference compounds, it can be a really useful tool for detecting episodic or short-term pollution events (e.g. increased herbicide concentrations during a flood), which may be missed with classical and low frequency grab sampling.     

Colloids as a sink for certain pharmaceuticals in the aquatic environment

Background, aim, and scope  

The occurrence and fate of pharmaceuticals in the aquatic environment is recognized as one of the emerging issues in environmental chemistry and as a matter of public concern. Existing data tend to focus on the concentrations of pharmaceuticals in the aqueous phase, with limited studies on their concentrations in particulate phase such as sediments. Furthermore, current water quality monitoring does not differentiate between soluble and colloidal phases in water samples, hindering our understanding of the bioavailability and bioaccumulation of pharmaceuticals in aquatic organisms. In this study, an investigation was conducted into the concentrations and phase association (soluble, colloidal, suspended particulate matter or SPM) of selected pharmaceuticals (propranolol, sulfamethoxazole, meberverine, thioridazine, carbamazepine, tamoxifen, indomethacine, diclofenac, and meclofenamic acid) in river water, effluents from sewage treatment works (STW), and groundwater in the UK.     

Statistical evaluation of the influence of flow conditions and sampling techniques on water quality data.

The purpose of this study is to statistically evaluate the influence of various sampling methodologies and flow conditions on the quality and comparability of total phosphorus concentration data collected over the course of 27 months at the South Florida Water Management District (SFWMD) S-65E structure. The data was obtained from the following sampling methodologies: U.S. Geological Survey (USGS) (Reston, Virginia) equal width increment spatially composite grab samples, USGS replicate samples, SFWMD grab samples, and SFWMD autosampler samples. Both significant and insignificant differences were reported from these comparisons. Parametric and nonparametric standard statistical tests for significance were carried out to evaluate the differences between the data. To avoid invalid conclusions of insignificant differences, we conducted tests for equivalence of the means and variances. The results from the data analysis revealed that both flow conditions and sampling methodology affected the water quality data.     

Partitioning and availability of sediment-bound metals following final sewage effluent release to a lowland river

A simple partitioning scheme was used to assess the partitioning and behaviour of copper, cadmium, iron, lead and manganese within the surface waters and sediments of the River Yare, Norfolk, UK, following the discharge of final effluent to the water course from municipal sewage treatment works (STW). Sewage effluent discharges were shown to increase metal concentrations and complexation capacities in receiving waters, but the tidal nature of the river meant that surface water monitoring could not accurately pinpoint the contamination source or the main metal partitioning trends. Sediments formed a more stable base on which to perform contaminant studies: these revealed that metals discharged from the STW rapidly accumulated in bottom deposits in relative stable chemical forms.     

Pharmaceuticals in the river Elbe and its tributaries

Medicinal drugs were found to be ubiquitous in the river Elbe, its tributary the river Saale and in other tributaries at their points of entry into the Elbe. The distribution of concentration peaks along the investigated river stretches provides an indication that they are mainly due to the emission of treated waste water from municipal sewage treatment works. This leads to the conclusion that medicinal substances can be regarded as faecal indicators for water pollution caused by human activity. The main substances found in the Elbe in 1998 were diclofenac, ibuprofen and carbamazepine as well as various antibiotics and lipid regulators in the concentration range of <20-140 ng/l. The more thorough investigations carried out in 1999 and 2000 show that in addition to the drugs (phenazone, isopropyl-phenazone and paracetamol) metabolite concentrations contributed significantly to the total concentration of pharmaceuticals in the Elbe. The metamizole metabolites N-acetyl-4-aminoantipyrine (AAA) and N-formyl-4-aminoantipyrine (FAA) were found in concentrations from <20 to 939 ng/l. A multivariate statistical analysis revealed a high correlation in respect of the distribution of persistent substances. The metoprolol distribution throughout the Saale demonstrated that the tributaries cause either an increase (Weisse Elster, Unstrut, Ilm) or a reduction (Wipper, Bode) in the concentration, depending on the respective load of waste water. Wide scale sampling in Saxony during 2002 showed the ubiquitous occurrence of carbamazepine in surface waters. The ecotoxicological effects of this contamination cannot be assessed at present. This is due to the fact that no legal framework in respect of these medicinal drugs for human consumption has been established and therefore little research and no risk assessment has been carried out. Therefore it is urgently necessary to include at least the quantitatively most significant substances in the new assessment concept of the EC White Paper.     

Monitoring of iodinated X-ray contrast media in surface water

A monitoring programme was carried out in order to determine iodinated X-ray contrast media (ICM) in the River Danube and to investigate the raw water quality for drinking water production at Langenau waterworks. The study revealed that the maximum concentrations of ICM (over 500 ng l(-1) for diatrizoic acid and iopamidol) were found in 2h-composite samples taken from the downstream of the Ulm/Neu-Ulm metropolitan area. By means of a concentration profile over one month the highest ICM concentrations were observed on weekdays. The extended data evaluation with principal component analysis shows that the upstream and downstream samples had different pattern of variations in ICM concentration and also demonstrates a clear change in ICM composition by the discharge of municipal wastewater. In addition to load profiles of ICM, time-dependent plots of principal component 1 exhibited peaks, indicating a short-term discharge of ICM between the two sampling sites. In conclusion, a point source for ICM contamination between the sampling sites in Ulm upstream and Leipheim downstream seems to be the reasonable explanation for peak ICM concentrations. Due to the observed high variations of ICM concentrations in river, the evaluation of natural waters by means of a single analysis is not representative.     

Biological and chemical tools in the toxicological risk assessment of Jarama River, Madrid, Spain

Four river water samples (R) and three sewage samples (S) were collected at different points in the Jarama River, Spain. Organic concentrates were tested on the RTG-2 in vitro cytotoxicity test and analyzed by HPLC and GC/MS. The cytotoxicity assessment demonstrated a progressive increase in the toxicity of the river water when moving downstream. A wide range, from slightly harmful to highly toxic, was observed for sewage samples. The most toxic samples produced decreases of 95% to 100% in the ATP content, cell viability and cell detachment (a parameter to estimate mortality). The most toxic organic concentrates (the sewage from an urban + industrial effluent collected in Paracuellos, Madrid, Spain, and the river 100 m downstream from the discharge of this effluent) were fractioned by an HPLC system. Each chromatographic peak was collected as a fraction of the whole concentrate. The cytotoxicity of each fraction was also assessed on RTG-2 cells. A toxic peak with a retention time of 38.3 min was detected in both samples; this time belongs to the PAHs retention time interval under our chromatographic conditions. Analytical procedures identified fluorene (0.62 microg/l) and benz(a)anthracene (0.44 microg/l) in the sewage and anthracene (0.40 microg/l) and benz(a)anthracene (0.14 microg/l) in the river water. However, the observed cytotoxicity could not be explained by the PAH concentrations. Five additional toxic peaks were observed in each sample. Results suggest that the combination of HPLC with cost-effective toxicity tests produces a useful tool to define environmental management decisions when the chemical analysis cannot identify the substances responsible for the environmental risk.     

Development of solid phase adsorption toxin tracking (SPATT) for monitoring anatoxin-a and homoanatoxin-a in river water

Sampling and monitoring for cyanotoxins can be problematic as concentrations change with environmental and hydrological conditions. Current sampling practices (e.g. grab samples) provide data on cyanotoxins present only at one point in time and may miss areas or times of highest risk. Recent research has identified the widespread distribution of anatoxin-producing benthic cyanobacteria in rivers highlighting the need for development of effective sampling techniques. In this study we evaluated the potential of an in situ method known as solid phase adsorption toxin tracking (SPATT) for collecting and concentrating anatoxin-a (ATX) and homoanatoxin-a (HTX) in river water. Fifteen different adsorption substrates were screened for efficiency of ATX uptake, nine of which retained high proportions (>70%) of ATX. Four substrates were then selected for a 24-h trial in a SPATT bag format in the laboratory. The greatest decrease in ATX in the water was observed with powdered activated carbon (PAC) and Strata-X (a polymeric resin) SPATT bags. A 3-d field study in a river containing toxic benthic cyanobacterial mats was undertaken using PAC and Strata-X SPATT bags. ATX and HTX were detected in all SPATT bags. Surface grab samples were taken throughout the field study and ATX and HTX were only detected in one of the water samples, highlighting the limitations of this currently used method. Both Strata-X and PAC were found to be effective absorbent substrates. PAC has the advantage that it is cheap and readily available and appears to continue to sorb toxins over longer periods than Strata-X. SPATT has the potential to be integrated into current cyanobacterial monitoring programmes and would be a very useful and economical tool for early warning of ATX and HTX contamination in water.     

Determination of antibiotic substances in hospital sewage water using solid phase extraction and liquid chromatography/mass spectrometry and group analogue internal standards

A method for determination of antibiotics in hospital sewage water has been developed and validated. Analogue internal standards for fluoroquinolones, sulfonamides, trimethoprim, beta-lactams (penicillins and cephalosporins), nitroimidazoles and tetracyclines were successfully used for calibration and shown to generally improve precision compared to external calibration. Matrix components caused ion suppression/enhancement effects during the MS detection for all analytes studied. Two effects were observed: general suppression and short-term variations in the MS response. In the hospital sewage water large temporal variations in the analyte concentration were observed during the course of the sampling period (seven grab samples in 13 h). Analyte concentrations varied within the following ranges (in microg l(-1)): ciprofloxacin, 3.6-101.0; metronidazole, 0.1-90.2; sulfamethoxazole, 0.4-12.8; ofloxacin, 0.2-7.6; trimethoprim, 0.6-7.6; and doxycycline, 0.6-6.7.     

Prognosis of environmental concentrations by geo-referenced and generic models: a comparison of GREAT-ER and EUSES exposure simulations for some consumer-product ingredients in the Itter

The aim of this study was the comparison between predicted environmental concentrations (PEC) derived using a generic aspacial model, European Union System for the Evaluation of Substances (EUSES), and a geo-referenced model, the Geo-referenced Regional Environmental Assessment Tool for European Rivers (GREAT-ER). The PECs of some consumer-product ingredients (boron, LAS) and professional uses (EDTA, NTA and Triclosan) were calculated for the river catchment of the Itter, a small tributary to the river Rhine. The PEClocal and PECregional for the water compartment generated by EUSES (default scenario) were subsequently refined with data that realistically reflects the region of North Rhine-Westphalia (NRW scenario) and the Itter catchment (Itter scenario). The results of the three scenarios were then compared with the PECinitial and PECcatchment calculated by GREAT-ER, that was designed as a higher-tiered exposure assessment tool, and with concrete concentrations in the Itter, measured as 24-h composite samples. While the PECregional of all scenarios was close to the lower end of the measured concentrations, the geo-referenced PECs described equally well the real spacial situation. The measured environmental concentrations confirmed the built-in conservatism of the PEClocal calculations by EUSES showing for all investigated chemicals an unrealistically high PEClocal (default). The refinement in the more realistic scenarios could not provide a straight forward general improvement of the PEClocal. In conclusion, when the EUSES prognosis is refined using more detailed substance and regional specific data, it may provide a fairly accurate modelling especially of substances that are not eliminated in the environment. However, in the case of eliminable substances, it does not match the accuracy of higher-tiered geo-referenced exposure models like GREAT-ER.     

Occurrences and potential risks of 16 fragrances in five German sewage treatment plants and their receiving waters

Fragrances are used in a wide array of everyday products and enter the aquatic environment via wastewater. While several musk compounds have been studied in detail, little is known about the occurrence and fate of other fragrances. We selected 16 fragrance compounds and scrutinized their presence in Bavarian sewage treatment plants (STP) influents and effluents and discussed their ecological risks for the receiving surface waters. Moreover, we followed their concentrations along the path in one STP by corresponding time-related water sampling and derived the respective elimination rates in the purification process. Six fragrance substances (OTNE, HHCB, lilial, acetyl cedrene, menthol, and, in some grab samples, also methyl-dihydrojasmonate) could be detected in the effluents of the investigated sewage treatment plants. The other fragrances under scrutiny were only found in the inflow and were eliminated in the purification process. Only OTNE and HHCB were found in the receiving surface waters of the STP in congruent concentrations, which exceeded the preliminary derived environmental thresholds by a factor of 1.15 and 1.12, respectively, indicating potential risks. OTNE was also detected in similar concentration ranges as HHCB in muscles and livers of fish from surface waters and from ponds that are supplied with purified wastewater. The findings show that some fragrance compounds undergo high elimination rates, whereas others—not only musks—are present in receiving surface water and biota and may present a risk to local aquatic biota. Hence, our results suggest that the fate and potential effects of fragrance compounds in the aquatic environment deserve more attention.     

Endocrine disruptors in freshwater streams of Hesse, Germany: changes in concentration levels in the time span from 2003 to 2005

Four small freshwater streams in the region known as Hessisches Ried in Germany were investigated with respect to the temporal and spatial concentration variations of the endocrine disruptors bisphenol A (BPA), 4-tert-octylphenol (4-tert-OP), and the technical isomer mixture of 4-nonylphenol (tech.-4-NP). Measured concentrations of the target compounds in the river water samples ranged from <20 ng/l to 1927 ng/l, <10 ng/l to 770 ng/l, and <10 ng/l to 420 ng/l for BPA, 4-tert-OP and tech.-4-NP, respectively. BPA levels were, with the exception of two samples, below the predicted no-effect concentration (PNEC) for water organisms. Tech.-4-NP concentrations showed a significant tendency of decreasing concentrations during the sampling period. This is mainly attributed to the implementation of the European Directive 2003/53/EG, which restricts both the marketing and use of nonylphenols. Results from the analysis of additionally collected water samples from sewage treatment plant (STP) effluents indicate that the STPs cannot be the only sources for tech.-4-NP found in the river water.     

Existence of nonpoint source of perfluorinated compounds and their loads in the Tsurumi River basin, Japan

Products containing perfluorinated compounds (PFCs) have been widely used during the last 50 years. As a result, worldwide environmental pollution by PFCs has been reported. The sources of PFC pollution in the aquatic environment have been poorly understood. In this study, river water and sewage treatment plant (STP) effluent were sampled along the stretch of the Tsurumi River and also at a fixed station in the river. The concentrations of perfluorooctanesulfonate (PFOS), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) were measured. With an increase in river flow rate, it was observed that the PFC concentrations in the river water at fixed station were remained the same or increased for PFOS (179.9+/-34.4-179.6+/-69.5 ng l(-1)), PFHxA (5.5+/-0.8-9.0+/-2.6 ng l(-1)), PFHpA (3.1+/-0.3-4.4+/-1.0 ng l(-1)), and PFOA (15.9+/-0.3-13.4+/-2.5 ng l(-1)) whereas the concentration of PFNA (38.0+/-3.3-15.4+/-3.0 ng l(-1)) and PFDA (3.9+/-0.3-2.1+/-0.3 ng l(-1)) were decreased. On the other hand, the loads of every PFC increased with an increase in river flow rate. The loads of PFCs in rain runoff were estimated to be 2-11 times greater than those in STP effluents that are discharged into the river. These results indicate the existence of a PFC nonpoint source (NPS) and its impact to the total PFC load of river is significant.     

Grab and passive sampling applied to pesticide analysis in the São Lourenço river headwater in Campo Verde – MT,Brazil

In this study, the quality of surface water in the headwaters of São Lourenço River in Mato Grosso, Brazil, was evaluated in relation to contamination by pesticides. For this purpose, samples were collected between December 2015 and June 2016 by grab sampling and by passive sampling using an integrative polar organic compound sampler installed in the field during four 14-day cycles between March and June 2016. The analyses were performed by gas chromatography (CG/MS) and by liquid chromatography (UPLC-MS/MS). The results showed the detection of two pesticides (atrazine and pyraclostrobin) of the five analyzed by passive sampling and eight active principles among the 20 analyzed (malathion, diuron, carbofuran, carbendazim, trifluralin, imidacloprid, metolachlor, and acetamiprid) by grab sampling. The detection of 10 pesticides, even almost a decade after the beginning of a recovery process of the ciliary forest, confirms the headwaters' vulnerability to these contaminants and passive sampling proved to be an important tool in capturing small concentrations of pesticides constituting an interesting complement to grab sampling.     

Water Security in Uzbekistan: Implication of Return Waters on the Amu Darya Water Quality

- DOI: http://dx.doi.org/10.1065/espr2006.01.007 Goal, Scope and Background Amu Darya river, one of the main water resources of Uzbekistan, shows a relevant longitudinal enrichment of soluble contents which strongly limits the human uses of its waters. Because of the low natural run-off processes, salts and pollutants are mainly driven to the river by the return waters used for washing and irrigating the surrounding lands. The influence of return waters on stream quality is dramatically relevant in the lower reaches of the river where almost all the flowing waters have been previously used for the agriculture practises. To provide analytical evidence on the potential effects of return waters on the quality of the Amu Darya river, the paper reports and comments data on salinity and metals contents of the waters flowing in the artificial channel network of Bukhara and in the Amu Darya river, from Bukhara up to the dam forming the Tuyamuyn Hydro Complex (THC). Methods A total of 15 sampling sites were selected for the analytical survey: Two sites were located on the Amu Darya river downstream from the inflow of the return waters from Bukhara, two in the river entering in the THC, and three downstream from the dam forming the reservoir complex. The waters entering and leaving the Bukhara agricultural area were sampled in two main collectors, while the waters flowing in the channel system were sampled in six distinct collectors. The following parameters were considered in the survey: pH, Oxygen, Hardness, Salinity, Conductivity, P-PO4 3–, P tot, N tot, N-NO3 2–, N-NO2 –, COD, Ca2+, Mg2+, Fe, Mn, Zn, Cr, Cu, Ni, Cd, Pb. Results and Discussion Salt concentrations below 1000 mg/l were measured in the Amu Darya waters upstream to Bukhara. In the drainage system, salinity exceeds the palatability limit and reaches the maximum peak of 3200 mg/l in the outflow collector. Due to dilution effects, salinity returns to lower values (400–700 mg/l) along the Amu Darya river downstream from Bukhara; calcium and magnesium resulted the major constituents of the overall salinity. No serious metal contaminations were detected in the waters entering and leaving the examined channel system. Differently, the Amu Darya waters upstream to the THC showed a relevant metal contamination, with Cr, Ni, Fe concentrations exceeding the limits for human consumption. In the downstream sites, located in the Tuyamuyn Hydro Complex and in the Amu Darya river flowing out from this reservoir, excluding Fe, all the examined metals showed lover concentrations and values below the normative limits. Conclusion The direct human consumption of the lower Amu Darya waters is strongly limited by salinity and by metal contamination. Although the salinity of the return waters from the Bukhara drainage system results in above normal limits, no corresponding increases were measured in the Amu Darya river downstream from the return water inflow at the time of the survey. As for the metal contamination of the Amu Darya river, the survey revealed the presence of relevant sources of metal contamination downstream from Bukhara external to the agricultural drainage system. This contamination resulted in reduced sedimentation processes taking place in the limnetic zones of the Amu Darya river upstream to the dam forming the Tuyamuyn Hydro Complex. Recommendation and Outlook To fully understand the longitudinal increase of Amu Darya salinity, an evaluation of the cumulative effects of the loads from the main agricultural areas is required, also by using mass-balance models. As for the metals, an investigation should be addressed to identify the anthropogenic sources of contaminations present in the lower Amu Darya region and the metal loads should be diverted.     

Occurrence and temporal variations of TMDD in the river Rhine,Germany

Background, aim, and scope

The chemical substance 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD) is a non-ionic surfactant used as an industrial defoaming agent and in various other applications. Its commercial name is Surynol 104® and the related ethoxylates are also available as Surfynol® 420, 440, 465 and 485 which are characterized by different grades of ethoxylation of TMDD at both hydroxyl functional groups. TMDD and its ethoxylates offer several advantages in waterborne industrial applications in coatings, inks, adhesives as well as in paper industries. TMDD and its ethoxylates can be expected to reach the aquatic environment due its widespread use and its physico-chemical properties. TMDD has previously been detected in several rivers of Germany with concentrations up to 2.5?µg/L. In the United States, TMDD was also detected in drinking water. However, detailed studies about its presence and distribution in the aquatic environment have not been carried out so far. The aim of the present study was the analysis of the spatial and temporal concentration variations of TMDD in the river Rhine at the Rheingütestation Worms (443.3 km). Moreover, the transported load in the Rhine was investigated during two entire days and 7 weeks between November 2007 and January 2008.

Materials and methods

The sampling was carried out at three different sampling points across the river. Sampling point MWL1 is located in the left part of the river, MWL2 in the middle part, and MWL4 in the right part. One more sampling site (MWL3) was run by the monitoring station until the end of 2006, but was put out of service due to financial constrains. The water at the left side of the river Rhine (MWL1) is influenced by sewage from a big chemical plant in Ludwigshafen and by the sewage water from this city. The water at the right side of the river Rhine (MWL4) is largely composed of the water inflow from river Neckar, discharging into Rhine 14.9 km upstream from the sampling point and of communal and industrial wastewater from the city Mannheim. The water from the middle of the river (MWL2) is largely composed of water from the upper Rhine. Water samples were collected in 1-L bottles by an automatic sampler. The water samples were concentrated by use of solid-phase extraction (SPE) using Bond Elut PPL cartridges and quantified by use of gas chromatography-mass spectrometry (GC-MS). The quantification was carried out with the internal standard method. Based on these results, concentration variations were determined for the day profiles and week profiles. The total number of analyzed samples was 219.

Results

The results of this study provide information on the temporal concentration variability of TMDD in river Rhine in a cross section at one particular sampling point (443.3 km). TMDD was detected in all analyzed water samples at high concentrations. The mean concentrations during the 2 days were 314 ng/L in MWL1, 246 ng/L in MWL2, and 286 ng/L in MWL4. The variation of concentrations was low in the day profiles. In the week profiles, a trend of increasing TMDD concentrations was detected particularly in January 2008, when TMDD concentrations reached values up to 1,330 ng/L in MWL1. The mean TMDD concentrations during the week profiles were 540 ng/L in MWL1, 484 ng/L in MWL2, and 576 ng/L in MWL4. The loads of TMDD were also determined and revealed to be comparable in all three sections of the river. The chemical plant located at the left side of the Rhine is not contributing additional TMDD to the river. The load of TMDD has been determined to be 62.8 kg/d on average during the entire period. By extrapolation of data obtained from seven week profiles the annual load was calculated to 23 t/a.

Discussion

The permanent high TMDD concentrations during the investigation period indicate an almost constant discharge of TMDD into the river. This observation argues for effluents of municipal wastewater treatment plants as the most likely source of TMDD in the river. Another possible source might be the degradation of ethoxylates of TMDD (Surfynol® series 400), in the WWTPs under formation of TMDD followed by discharge into the river. TMDD has to be considered as a high-production-volume (HPV) chemical based on the high concentrations found in this study. In the United States, TMDD is already in the list of HPV chemicals from the Environmental Protection Agency (EPA). However, the amount of TMDD production in Europe is unknown so far and also the biodegradation rates of TMDD in WWTPs have not been investigated.

Conclusions

TMDD was found in high concentrations during the entire sampling period in the Rhine river at the three sampling points. During the sampling period, TMDD concentrations remained constant in each part of the river. These results show that TMDD is uniformly distributed in the water collected at three sampling points located across the river. ‘Waves’ of exceptionally high concentrations of TMDD could not be detected during the sampling period. These results indicate that the effluents of WWTPs have to be considered as the most important sources of TMDD in river Rhine.

Recommendations and perspectives

Based also on the occurrence of TMDD in different surface waters of Germany with concentrations up to 2,500 ng/L and its presence in drinking water in the USA, more detailed investigations regarding its sources and distribution in the aquatic environment are required. Moreover, the knowledge with respect to its ecotoxicity and its biodegradation pathway is scarce and has to be gained in more detail. Further research is necessary to investigate the rate of elimination of TMDD in municipal and industrial wastewater treatment plants in order to clarify the degradation rate of TMDD and to determine to which extent effluents of WWTPs contribute to the input of TMDD into surface waters. Supplementary studies are needed to clarify whether the ethoxylates of TMDD (known as Surfynol 400® series) are hydrolyzed in the aquatic environment resulting in formation of TMDD similar to the well known cleavage of nonylphenol ethoxylates into nonylphenols. The stability of TMDD under anaerobic conditions in groundwater is also unknown and should be studied.