Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin. Part I: Drug Residues and other Polar Contaminants in Berlin Surface and Groundwater

Several polar contaminants were found in screening analyses of 30 representative surface water samples collected from rivers, lakes, and canals in Berlin. Residues of pharmaceuticals and N-(phenylsulfonyl)-sarcosine originating from various sewage treatment plants effluents were found at concentrations up to the μg/L-level in the surface water, whereas the concentrations of polar pesticides such as dichlorprop and mecoprop were always below 0.1 μg/L. The pharmaceuticals most frequently detected in the surface water samples include clofibric acid, diclofenac, ibuprofen, propiphenazone, and two other drug metabolites. Additional investigations of groundwater wells of a drinking water plant have shown that polar contaminants such as drug residues or N-(phenylsulfonyl)-sarcosine easily leach through the subsoil into the groundwater aquifers when contaminated surface water is used for groundwater recharge in drinking water production.     

Determination of Antibiotic Residues in Manure,Soil, and Surface Waters

In the last years more and more often detections of antimicrobially active compounds (“antibiotics”) in surface waters have been reported. As a possible input pathway in most cases municipal sewage has been discussed. But as an input from the realm of agriculture is conceivable as well, in this study it should be investigated if an input can occur via the pathway application of liquid manure on fields with the subsequent mechanisms surface run‐off/interflow, leaching, and drift. For this purpose a series of surface waters, soils, and liquid manures from North Rhine‐Westphalia (Northwestern Germany) were sampled and analyzed for up to 29 compounds by HPLC‐MS/MS. In each of the surface waters antibiotics could be detected. The highest concentrations were found in samples from spring (300 ng/L of erythromycin). Some of the substances detected (e.g., tylosin), as well as characteristics in the landscape suggest an input from agriculture in some particular cases. In the investigation of different liquid manure samples by a fast immunoassay method sulfadimidine could be detected in the range of 1…2 mg/kg. Soil that had been fertilized with this liquid manure showed a content of sulfadimidine extractable by accelerated solvent extraction (ASE) of 15 μg/kg dry weight even 7 months after the application. This indicates the high stability of some antibiotics in manure and soil.     

Pesticides in the River Rhine Pestizide im Rhein

Since 1987 significant decrease of pesticide concentrations in the river Rhine has been observed. This is due to the improvement of waste water treatment processes and the closing of some pesticide production sites in the Rhine basin area. Whereas in the last years point pollution from waste water effluents was the dominant source for pesticide input into the river, nowadays the nonpoint pollution (diffuse runoff) becomes more and more important. This leads to seasonal occurrence or to higher concentration peaks after application in agriculture. Only for atrazine and its metabolite desethylatrazine very low ?background”?-levels could regularly be found along the river and all over the year. Furthermore pesticide metabolites and byproducts seem to be interesting for evaluating pesticide pollution in the river Rhine.     

Simultaneous Analysis of Natural Free Estrogens and Their Sulfate Conjugates in Wastewater

Natural estrogens from humans increasingly attract attention because of their strong endocrine disrupting potency. The discharge of sewage water is considered as the most important source of these endocrine disrupting chemicals (EDCs) in the environment. Therefore, a GC‐MS method was developed for the simultaneous analysis of six natural free estrogens and their sulfate conjugates in municipal wastewater, in which natural free estrogens and sulfate conjugates were successfully separated from an Oasis HLB solid phase extraction (SPE) cartridge with two different eluents, and the sulfate conjugates were then transformed to their corresponding free estrogens by acid solvolysis. Before the analysis with GC‐MS, samples were derivatized by N,O‐bis (trimethylsilyl) trifluoroacetamide (BSTFA) plus 1% trimethylchlorosilane (TMCS) at 80°C for 40 min. Satisfactory recoveries ranging from 64 to 112.3% were obtained by spiking ultra‐purified water, raw, and treated municipal wastewater with the six estrogens at 50, 100, and 50 ng/L, respectively. The method was successfully applied to wastewater samples from one WWTP, which suggested that E1 was the dominant natural estrogens in effluent and E3‐3S was one of the conjugates possibly occurring in the effluent.     

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin. Part III: Determination of Synthetic Musks in Berlin Surface Water Applying Solid-phase Microextraction (SPME) and Gas Chromatography-Mass Spectrometry (GC-MS)

Polycyclic musks and nitro musks were found as environmental pollutants in screening analyses of 30 representative surface water samples collected from rivers, lakes, and canals in Berlin. These synthetic musks, which are used as fragrances in cosmetics, detergents, and other products, are discharged by the municipal sewage treatment plants into Berlinπs surface waters. In particular, the polycyclic musks 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyrane (HHCB; Galaxolide®, Abbalide®) and 7-acetyl-1,1,3,4,4,6-hexamethyltetraline (AHTN; Tonalide®, Fixolide®) were found in the receiving surface waters at considerable concentrations up to the μg/L-level. In the Wuhle, a small brook almost totally consisting of sewage effluents, maximum concentrations were 12.5 μg/L for HHCB and 6.8 μg/L for AHTN. Additionally, the polycyclic musk 4-acetyl-1,1-dimethyl-6-tert-butylindane (ADBI; Celestolide®, Crysolide®) and 1-tert-butyl-3,5-dimethyl-2,6-dinitro-4-acetylbenzene (musk ketone) were detected at low concentrations in most of the samples. Two other nitro musks, namely 1,1,3,3,5-pentamethyl-4,6-dinitroindene (musk moskene) and 1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene (musk xylene), were only detected in a single surface water sample. Solid-phase microextraction (SPME) with detection by gas chromatography-mass spectrometry (GC-MS) has proven to be a rapid and reliable tool for the screening of synthetic musks in surface and sewage water samples. Internal calibration with a suitable internal standard enables reproducible quantitation of the analytes down to the low ng/L-level.     

Sorption of ortho‐Phenylphenol to Soils

Conflicting sorption coefficients for ortho‐phenylphenol (OPP) have been reported in the literatures, which resulted in the conflicting assessments on OPP mobility in soil. To ascertain the sorption coefficient of OPP, batch experiments were performed based on OECD guideline 106, using three types of soils. Headspace solid‐phase microextraction (HS‐SPME) and GC‐MS were applied to the determination of OPP concentration in the liquid phase. The sorption isotherms obtained for all three soils under equilibrium conditions were described well, assuming linear sorption. The organic carbon normalized distribution coefficients (K_oc) ranged from 894 to 1703 L kg^?1, which suggested that OPP is moderately mobile in soil. The results also showed that the K_oc value of OPP can be predicted precisely from K_ow, whereas it was underestimated by one order of magnitude when water solubility is used.     

Vorkommen natürlicher und synthetischer östrogener Steroide in Wässern des süd‐ und mitteldeutschen Raumes

Distribution of Natural and Synthetic Estrogenic Steroid Hormones in Water Samples from Southern and Middle Germany Natural and synthetic hormones can reach surface waters via domestic sewage effluents. For drinking water production, bank filtration of river waters is a common procedure and hormone contaminations can potentially reach groundwater levels and drinking water sources. In order to analyse steroid hormones in the different aquatic compartments (raw sewage and effluent, surface water, groundwater, raw and drinking water) of South and Middle Germany, a sensitive analytical method was developed and employed to detect the natural steroid hormones estradiol (E2) and estrone and the synthetic estrogen ethinylestradiol (EE2). Samples which were taken in two subsequent series were subjected to clean‐up and enrichment procedure and subsequently analysed by HPLC‐MS. The limit of quantitation for the method was determined to be 0.05 to 0.5 ng/L, depending on the matrix. By treating the samples with glucuronidases/arylsulfatases, conjugates were amenable to analysis and the sum of conjugates and unconjugated steroids was calculated. In raw sewage, the median of the concentrations of the unconjugated steroids was 7 ng/L for EE2, 1.5 ng/L for E2, and 5.5 ng/L for estrone. After cleavage of conjugates, the medians of total steroids were 9.5 ng/L (EE2), 3 ng/L (E2), and 13 ng/l (estrone). Conjugates therefore contributed up to 50 % of the total steroid concentration in raw sewage. In treated effluents, the concentrations of steroids were much lower than in the raw sewage. The medians of free steroids were determined to be 0.3 ng/L for EE2, 0.2 ng/L for E2, and 2.5 ng/L for estrone. Overall the medians in the effluent were thus less than 10% of those in the influent. Conjugates still contributed significantly (40% and more) to the steroid concentrations (medians: EE2: 0.5 ng/L, E2: 0.8 ng/L, and estrone: 8 ng/L).     

Kinetic Studies and Anaerobic Co‐digestion of Vegetable Market Waste and Sewage Sludge

The effect of anaerobic co‐digestion of vegetable market waste and sewage sludge was studied extensively. The effects of co‐digestion were compared with the separate digestion of vegetable market waste and sewage sludge. The batch studies were carried out using three bench scale reactors having 1.5 L working volume. The cumulative biogas production shows that the organic waste available from the vegetable waste contains easily biodegradable organic matter compared with the sewage sludge. First order reaction kinetics is maintained throughout the methanation fermentation. The reductions in volatile solids (VS) in the three reactors were in the range of 63–65 %. The specific gas production for vegetable waste was higher (0.75 L biogas/g VS_in and 1.17 L biogas/g VS_des) than for the sewage sludge (0.43 L biogas/g VS_in and 0.68 L biogas/g VS_des). Consequently, the specific gas production for the co‐digestion of the mixture of vegetable waste and sewage sludge (0.68 L biogas/g VS_in and 1.04 L biogas/g VS_des) was considerably higher than for the sewage sludge only. Batch kinetics of anaerobic digestion is useful in predicting the performance of digesters and for the design of appropriate digesters.     

Die gaschromatographische Bestimmung von Diethylentriaminpentaessigsäure in Oberflächenwasser

Gaschromatographic Determination of Diethylenetriaminepentaacetic Acid in Surface Water. A method for the determination of diethylenetriaminepentaacetic acid (DTPA) is reported. The determination is based on the preconcentration on a strong base anion exchange resin, esterification with n-propanol and following gaschromatographic separation using a N-selective detector. The sensitivity of the method, including enrichment, is 1 μg/L in river water. The identity of DTPA in river water was proved by mass spectrography. The method can be used also for the quantitative determination of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), cyclohexanediaminetetraacetic acid (CDTA) and ethyleneglycolbis-(2-aminoethylether)-N,N,N′,N′-tetraacetic acid (EGTA). The method was used to examine river water. An investigation along the river Rhine, taking grab samples from January and february 1992 showed that DTPA was present in some sampling places in similiar concentrations as NTA and EDTA.     

Problems and Solutions in Pesticide Analysis Using Solid‐phase Extraction (SPE) and Gas Chromatography Ion‐trap Mass Spectrometry Detection (GC‐MS)

In the present study an analytical method was tested for the determination of selected pesticides and metabolites using solid‐phase extraction (SPE) and gas chromatography ion‐trap mass spectrometry (GC‐MS). The extraction efficiency of C18, Isolut ENV+, and Lichrolut EN for SPE was compared for trifluralin, fenitrothion, endosulfan, propargite, 2,4‐D, 3‐methyl‐4‐nitrophenol, 2‐(4‐tert‐butylphenoxy)cyclohexanol, endosulfan sulfate, and 2,4‐dichlorophenol. Isolut ENV+ and C18 showed good results as sorbents and acetone as an elution solvent for SPE for the selected pesticides. Recoveries varied between 36% and 176% with a relative standard deviation of 2...18%. Because of coextracts from the SPE materials, recovery values higher than 100% were obtained for fenitrothion, endosulfan sulfate, and 2,4‐D with C18 as well as for endosulfan sulfate and 3‐methyl‐4‐nitrophenol with Isolut ENV+. A standard addition method was used to verify the occurrence of coextracts in the sample after SPE.     

Simultaneous Analysis of Natural Free Estrogens and Their Conjugates in Wastewater by GC‐MS

A solid‐phase extraction (SPE)‐gas chromatography (GC)‐mass spectrometry (MS) analytical method was developed for the simultaneous analysis of natural free estrogens and their conjugates in wastewater samples. Natural free estrogens and their conjugates in wastewater were successfully separated by the oasis hydrophilic‐lipophilic balance solid phase extraction (Oasis HLB SPE) method, and the conjugates were initially enzyme hydrolyzed by β‐glucuronidase or arylsulfatase from Helix pomatia prior to derivatization. N‐methyl‐N‐(tert‐butyldimethylsilyl)trifluoroacetamide (MTBSTFA) plus 1% tert‐butyldimetheylchlorosilane (TBDMCS) was chosen as the derivatization reagent, and the most appropriate conditions of derivatization were determined to be at 95°C for 90 min. The recovery ratios of nine target chemicals were determined by spiking them in 1 L of ultra‐purified water or the influent of a wastewater treatment plant (WWTP). The recovery ratios of six out of nine for the analytes ranged from 73.3–114.9% with relative standard deviations (RSD) from 1.6–19.9%. The established method was successfully applied to environmental wastewater samples which were collected from one municipal wastewater treatment plant (WWTP) in Osaka, Japan, for the determination of natural free estrogens and their conjugates. In the influent sample, E1, E2, E1‐3S, E3‐3S, and E1‐3G were detected at concentrations of 16.6, 9.6, 8.2, 21.9, and 3.2 ng L^–1, respectively. However, only E1 was detected at a high concentration of 44 ng L^–1 in the effluent sample, suggesting that it is the dominant natural free estrogen in the effluent.     

Effect of Preozonation on the Formation of Chlorinated Disinfection By‐products for River Ruhr

The purpose of the study is to gain a better understanding about the formation of THM (trihalomethanes), HAA (haloacetic acids), and AOX (adsorbable organic halogen) in river water (river Ruhr, Essen) through a chlorination kinetics approach. The effect of chlorination time and preozonation on the formation of THM, HAA, and AOX substances was studied. Preozonation can reduce the chlorine demand and the precursors for AOX and THM. THM generation was reduced further, when the ozone dosage consumed increased from 3.5 to 12.5 mg in the 1.4 L reaction vessel. AOX and TCAA (trichloroacetic acid) concentrations also decreased dramatically when 3.5 mg of ozone had reacted with the river water, but a higher dose of ozone did not further reduce AOX and TCAA formations. Besides, the characteristics of organic matter in raw water, ozonated water, and preozonated/chlorinated water was investigated. The results suggest the formation of low‐molecular‐weight acids with low UV absorbance when high‐molecular refractive matter is oxidized.     

Fate of Lignin in the Process of Aerobic Biological Treatment of Paper Mill Wastewater

Although lignin is known to be not readily biodegradable the concentration of dissolved lignin decreased during aerobic biological treatment of paper mill wastewater performed in sequencing batch reactors (SBR). Systematic lab scale batch tests were conducted to clarify whether the observed removal of lignin was the result of biodegradation or adsorption onto the activated sludge. For the batch tests, sludge samples were taken from sequencing batch reactors operated at solid retention times (SRT) of 10, 15, 20, 30, and 40 days, respectively. The amount of lignin present in the bulk liquid and in the sludge samples was quantified by an analytical procedure comprising pyrolysis, gas chromatography and mass spectrometry (py‐GC/MS analysis). It was found that lignin adsorbs onto the activated sludge by up to 30%[TH]w/w. This demonstrates the sludge excellent adsorption properties. The ultimate removal of lignin is achieved by sludge wasting. The highest overall removal rate was found when sludge was used from the SBR run at SRT of 20 days.     

Rapid Analysis of 1,4‐Dioxane in Groundwater by Frozen Micro‐Extraction with Gas Chromatography/Mass Spectrometry

An innovative micro‐extraction of aqueous samples coupled with gas chromatography/mass spectrometry in selected ion‐monitoring mode (GC/MS‐SIM) was developed to selectively analyze for 1,4‐dioxane with low part‐per‐billion detection sensitivity. Recoveries of 1,4‐dioxane ranged from 93% to 117% for both spiked laboratory reagent water and natural groundwater matrices, the later having elevated organic carbon content (8.34 ± 0.31 mg/L as total organic carbon). We observed that freezing the aqueous sample along with the extraction solvent enhanced the extraction efficiency, minimized physical interferences, and improved sensitivity resulting in a limit of detection for 1,4‐dioxane to approximately 1.6 μg/L. This method substantially reduces the labor, time, reagents and cost, and uses instruments that are commonly found in analytical laboratories. This method requires a relatively small sample volume (200 μL), and can be considered a green analytical method as it minimizes the use of toxic solvents and the associated laboratory wastes.     

Estimation of Organic Pesticide Residues in Wines of Moldova

This paper presents the study of pesticide residues in Moldovan wine products originating from traditional agriculture because the appreciation of these compounds is an important aspect of food safety. During 2007–2010, about 3000 analyses of wine samples using GC‐MS were investigated. Persistent organic pollutants (POPs), i.e., α‐, β‐, γ‐HCH, aldrine, and heptachlor were not found in any of the samples. Insignificant quantities of metalaxyl and mefenoxam were found in some wine samples. The missing of POPs in wine products represents an important quality feature. The study showed that if growers comply with rules of phytosanitary treatments and the waiting period is respected, the content of pesticide residues can be reduced to safe limits. Also, the list of approved pesticides must be regularly revised, taking into account the degree of toxicity. Additionally, growers are to be constantly informed about effectuated changes.     

Quantitation of Nonextractable Anthropogenic Quantitation of Nonextractable Anthropogenic Sediments after Chemical Degradation

Four highly contaminated sediment samples obtained from three sampling locations of the Teltow Canal, Berlin, were investigated by quantitation of extractable and nonextractable organic contaminants. The selection of the anthropogenic contaminants (including chlorinated and brominated naphthalenes, 2, 4, 6‐tribromoaniline, phthalates, tri‐n‐butylphosphate, 2, 2, 4‐trimethyl‐1, 3‐pentanediol diisobutyrate, bisphenol A, butylated nitrophenols, 4‐nitrobenzoic acid, galaxolide, and tonalide) based on the results of extended GC‐MS screening analyses applied to the extracts of the sediment samples as well as to the extracts derived from selective chemical degradation procedures. In detail, alkaline hydrolyses, BBr₃‐treatment and RuO₄‐oxidation were applied to the pre‐extracted sediment samples in both a separate and a sequential mode.     

Cloud Point Extraction for the Preconcentration of Silver and Palladium in Real Samples and Determination by Atomic Absorption Spectrometry

A cloud point extraction procedure is presented for the preconcentration and simultaneous determination of Ag⁺ and Pd²⁺ in various samples. After complexation with 2‐((2‐((1H‐benzo[d]imidazole‐2‐yl)methoxy)phenoxy)methyl)‐1H‐benzo[d]imidazol (BIMPI), which was used as a new chelating agent, analyte ions were quantitatively extracted to a phase rich in Triton X‐114 following centrifugation, and determination was carried out by flame atomic absorption spectrometry (FAAS). Under the optimum experimental conditions (i. e., pH = 7.0, 15.0·10^–5 mol/L BIMPI and 0.036% (w/v) Triton X‐114), calibration graphs were linear in the range of 28.0–430.0 μg/L and 57.0–720.0 μg/L with detection limits of 10.0 and 25.0 μg/L for Ag⁺ and Pd²⁺, respectively. The enrichment factors were 35.0 and 28.0 for Ag⁺ and Pd²⁺, respectively. The method has been successfully applied to evaluate these metals in some real samples, including waste water, soil and hydrogenation catalyst samples.     

Removal of Natural Free Estrogens and their Conjugates in a Municipal Wastewater Treatment Plant

Removal of natural free estrogens and estrogen conjugates in a municipal wastewater treatment plant (WWTP) was investigated and analyzed by GC‐MS, in which estrogen conjugates were first transformed to their corresponding free estrogens with an acid solvolysis procedure before their analysis. Natural free estrogens, E1‐3‐sulfate (E1‐3S), and E3‐3‐sulfate (E3‐3S) were detected with high concentrations in both the influent and effluent of the primary settling tank (PS), while no estrogen glucuronides were detected in any of the monitored wastewater samples. Regarding their removal efficiencies, all were almost completely removed, except for E1 with only a minor decrease. The estrogenic/androgenic removal of the same WWTP was also evaluated with estrogen receptor (androgen receptor) (ER (AR))‐binding assays, in which the removal efficiencies for E2 equivalents (EEQ) or testosterone equivalents (TEQ) were 68.5 and 72.2%. In addition, the chemically calculated EEQ from natural estrogens were about 20.6–39.3% that of the ER‐binding assay, in which E3 contributed the biggest proportion in both the influent and PS, while the calculated value of E1 increased from only 6.7% in the influent to as high as 20.6% in the effluent.     

Concurrent Treatment of 1,4‐Dioxane and Chlorinated Aliphatics in a Groundwater Recirculation System Via Aerobic Cometabolism

This research demonstrates that groundwater contaminated by a relatively dilute but persistent concentration of 1,4‐dioxane (1,4‐D), approximately 60 μg/L, and chlorinated aliphatic co‐contaminants (1.4 to 10 μg/L) can be efficiently and reliably treated by in situ aerobic cometabolic biodegradation (ACB). A field trial lasting 265 days was conducted at Operable Unit D at the former McClellan Air Force Base and involved establishing an in situ ACB reactor through amending recirculated groundwater with propane and oxygen. The stimulated indigenous microbial population was able to consistently degrade 1,4‐D to below 3 μg/L while the co‐contaminants trichloroethene (TCE) and 1,2‐dichloroethane (1,2‐DCA) were decreased to below 1 μg/L and 0.18 μg/L, respectively. A stable treatment efficiency of more than 95% removal for 1,4‐D and 1,2‐DCA and of more than 90% removal for TCE was achieved. High treatment efficiencies for 1,4‐D and all co‐contaminants were sustained even without propane and oxygen addition for a 2‐week period.     

Zielvorgaben für Pflanzenschutzmittelwirkstoffe und andere Schadstoffe in Oberflächengewässern

Quality Targets for Pesticides and Other Pollutants in Surface Waters Surface waters are not only adversely affected by industrial and municipal wastewaters but also by diffuse sources. For the control of the ecological water quality, so‐called quality targets are set. The quality targets are threshold concentrations for hazardous substances related to the protected goods like water ecosystems, drinking water supply, sediments, or fishing. In this paper, quality targets for the protection of aquatic life in surface waters were derived on the basis of a concept developed by the International Commission for the Protection of the Rhine (Internationale Kommission zum Schutze des Rheins – IKSR). The quality targets for the selected hazardous substances, which mainly belong to the chemical class of pesticides, were calculated using ecotoxicological results for species of bacteria, algae, fish, and small crustaceans, as the four trophic standards of the water ecosystem. In cooperation with the Federal Environmental Agency (Umweltbundesamt – UBA) the effect data were taken from ecotoxicological data bases. According to the concept of the IKSR, the lowest test result for the most sensitive species was multiplied by an assessment factor. This proceeding concerns the difficulty in describing the complex interactions in water ecosystems with toxicity data of single laboratory experiments for a few organisms. For seven pesticides quality targets below 0.1 μg/L were proposed. These results show that the ecotoxicologically based quality targets might be even lower than the limit values for pesticides in drinking water of 0.1 μg/L. But for most of the substances the determined values are significantly higher. The great concentration range of quality targets demonstrates distinctly that one standard concentration for all pesticides could not be given with regard to the different effects on aquatic organisms.