Karsten Nödler

Development of a multi-residue analytical method, based on liquid chromatography-tandem mass spectrometry, for the simultaneous determination of 46 micro-contaminants in aqueous samples

A multi-residue analytical method based on high-performance liquid chromatographic separation, electrospray ionization with tandem mass spectrometric detection (HPLC/MS-MS) was developed for the simultaneous analysis of 46 basic, neutral and acidic compounds covering a wide range of polarity (logK(OW)<0-5.9). The compound list included selected iodinated contrast media, analgesics, anti-inflammatories, stimulants, beta-blockers, antibiotics, lipid regulators, anti-histamines, psychiatric drugs, herbicides, corrosion inhibitors and the gastric acid regulator pantoprazole. The main feature of the presented method was a simultaneous solid phase extraction (SPE) of all analytes followed by simultaneous separation and detection by HPLC/MS-MS with electrospray ionization in both positive and negative polarization within the same chromatogram. Optimization of electrospray drying gas temperature resulted in using a temperature gradient on the ion source. Six different polymeric sorbents for SPE were compared with respect to recoveries, taking into account the specific surface of each sorbent. Method quantitation limits (MQL) in surface and seawater ranged from 1.2 to 28 ng/L, in wastewater from 5.0 to 160 ng/L, respectively. In order to demonstrate the applicability of the method, river water, treated wastewater and seawater were analyzed.

Polar organic micropollutants in the coastal environment of different marine systems

Polar anthropogenic organic micropollutants are frequently detected in freshwater and discharged on large scale into marine systems. In this work the results of 153 samples collected from the shorelines of the Baltic Sea (Germany), Northern Adriatic Sea (Italy), Aegean Sea and Dardanelles (Greece & Turkey), San Francisco Bay (USA), Pacific Ocean (USA), Mediterranean Sea (Israel), and Balearic Sea (Spain) are presented. The samples were analyzed for various classes of micropollutants such as pharmaceuticals, corrosion inhibitors, biocides, and stimulants. Caffeine, paraxanthine, theobromine, tolyltriazole, 1H-benzotriazole, and atrazine were detected in>50% of all samples. The detection frequencies of carbamazepine, iopamidol, diuron, sulfamethoxazole, paracetamol, theophylline, and atenolol were between 20% and 32%. As caffeine is linked to untreated wastewater, the widespread occurrence of raw sewage in marine environments and thus potentially elevated nutrient concentrations and risk for the presence of wastewater-related pathogens is remarkable.

Evidence for the microbially mediated abiotic formation of reversible and non-reversible sulfamethoxazole transformation products during denitrification.

The antibiotic sulfonamide drug sulfamethoxazole (SMX) is extensively used in both human and veterinary medicine. Since it cannot be completely eliminated by the typical state-of-the-art wastewater treatment technology, it is frequently detected in the water cycle. SMX, as aromatic amine, can undergo abiotic transformations with the under denitrifying conditions produced nitrogen species nitric oxide (NO) and nitrite (NO(2)(-)). NO and aromatic amines are commonly known to form diazonium cations. Depending on the reaction conditions the diazonium cation disintegrates under cleavage of elementary nitrogen and substitutes its diazo-group by an NO(2)-group or by hydrogen. Following this approach, two transformation products (TPs) of the persistent SMX under denitrifying conditions were hypothesized and synthesized: 4-nitro-N-(5-methylisoxazol-3-yl)-benzenesulfonamide (4-nitro-SMX) and N-(5-methylisoxazol-3-yl)-benzenesulfonamide (desamino-SMX). The synthesized compounds were identified by Nuclear Magnetic Resonance (NMR) spectroscopy and used as reference standards for their confirmation and quantification in denitrifying water/sediment batch experiments and in environmental samples. During the denitrifying degradation experiment SMX was no longer detected after 10 days whereas increasing concentrations of the two TPs were observed. However, at day 87 the SMX concentration recovered to 53 ± 16% of the initial concentration after most of the nitrate was consumed. A retransformation of 4-nitro-SMX to SMX was postulated and confirmed by another anoxic water/sediment test in the absence of nitrate as electron acceptor. Both TPs were also detected in karst spring samples, highlighting the need and benefit of focusing on transformation products in environmental studies. Furthermore, the consideration of the retransformation potential of 4-nitro-SMX can substantially improve the understanding of SMX behavior during processes such as bank filtration and artificial recharge.

Caffeine as an indicator for the quantification of untreated wastewater in karst systems.

Contamination from untreated wastewater leakage and related bacterial contamination poses a threat to drinking water quality. However, a quantification of the magnitude of leakage is difficult. The objective of this work is to provide a highly sensitive methodology for the estimation of the mass of untreated wastewater entering karst aquifers with rapid recharge. For this purpose a balance approach is adapted. It is based on the mass flow of caffeine in spring water, the load of caffeine in untreated wastewater and the daily water consumption per person in a spring catchment area. Caffeine is a source-specific indicator for wastewater, consumed and discharged in quantities allowing detection in a karst spring. The methodology was applied to estimate the amount of leaking and infiltrating wastewater to a well investigated karst aquifer on a daily basis. The calculated mean volume of untreated wastewater entering the aquifer was found to be 2.2 ± 0.5 m(3) d(-1) (undiluted wastewater). It corresponds to approximately 0.4% of the total amount of wastewater within the spring catchment.

Redox-sensitivity and mobility of selected pharmaceutical compounds in a low flow column experiment

In this study a laboratory column experiment under water saturated conditions was conducted to investigate the transport behaviour of the pharmaceutical compounds sulfamethoxazole, carbamazepine, diclofenac, and ibuprofen under varying nitrate concentrations. Organic rich sediment (f(OC)=0.01) and surface water from a formerly investigated field site were used. The water was spiked with the four compounds and the specific redox conditions in the column (0.351 m height) were varied throughout the experiment by adding nitrate in the influent water. Stepwise controlled decreasing influent nitrate concentrations between 131 and 20 mg L(-1) were applied in the course of the experiment which lasted 71 days. This established temporarily denitrifying conditions in the column during the reduction of nitrate. Sulfamethoxazole was severely influenced by this process. During denitrification sulfamethoxazole concentrations in the effluent water decreased rapidly and significantly. This experiment demonstrates the strong dependency of sulfamethoxazole transformation specifically on nitrate reducing redox conditions and therefore may help to explain the wide ranges of reported degradability for this compound. Ibuprofen was more stable under denitrifying redox conditions. Both for carbamazepine and diclofenac apparent retardation was observed. For carbamazepine this was attributed to sorption and also to degradation. For diclofenac nitrate controlled degradation seems the dominating process for the apparent retardation of this compound.

Formation of diclofenac and sulfamethoxazole reversible transformation products in aquifer material under denitrifying conditions: batch experiments.

Soil-aquifer processes have proven to work as a natural treatment for the attenuation of numerous contaminants during artificial recharge of groundwater. Nowadays, significant scientific effort is being devoted to understanding the fate of pharmaceuticals in subsurface environments, and to verify if such semipersistent organic micropollutants could also be efficiently removed from water. In this context we carried out a series of batch experiments involving aquifer material, selected drugs (initial concentration of 1 μg/L and 1 mg/L), and denitrifying conditions. Diclofenac and sulfamethoxazole exhibited an unreported and peculiar behavior. Their concentrations consistently dropped in the middle of the tests but recovered toward the end, which suggest a complex effect of denitrifying conditions on aromatic amines. The transformation products Nitro-Diclofenac and 4-Nitro-Sulfamethoxazole were detected in the biotic experiments, while nitrite was present in the water. Their concentrations developed almost opposite to those of their respective parent compounds. We conjecture that this temporal and reversible effect of denitrifying conditions on the studied aromatic amines could have significant environmental implications, and could explain at least partially the wide range of removals in subsurface environments reported in literature for DCF and SMX, as well as some apparent discrepancies on SMX behavior.

Occurrence and spatial distribution of organic micro-pollutants in a complex hydrogeological karst system during low flow and high flow periods, results of a two-year study

Fifty-four different organic micro-pollutants (OMPs) including pharmaceuticals, pesticides, corrosion inhibitors and other typical wastewater compounds such as caffeine are repeatedly analyzed in approximately fifty groundwater observation points in a complex faulted and fractured carbonate aquifer system consisting of three spring catchment areas. With the applied HPLC-MS/MS method, achieving method quantification limits (MQL) of 1.2-28 ng L(-1), forty-four of the OMPs are detected in groundwater. Regarding the vertical distribution in the aquifer system the highest variety of OMPs occurs in the shallow aquifer. Most frequently detected compounds are atrazine together with the metabolites of several triazines, desethylatrazine (DEA) and desisopropylatrazine (DIA), the corrosion inhibitors 1H-benzotriazole and tolytriazoles and as pharmaceutical residues the anti-epileptic drug carbamazepine as well as the analgesic drug phenazone. Median OMP concentrations are in the range of 20-40 ng L(-1) with occasionally and locally higher concentrations of up to 6000 ng L(-1). Defined combinations of OMPs occur repeatedly in the same observation wells and allow to distinguish different input functions. The comparison of detection frequency with the number of prescribed doses gives information about the specific persistence of pharmaceuticals. The analgesic phenazone exhibits a peculiar high detection frequency, although it is recently not prescribed in significant amounts. The detection of the estrogen antagonist tamoxifen (6-17 ng L(-1)) in a groundwater flow system is reported for the first time.

Twenty years later--atrazine concentrations in selected coastal waters of the Mediterranean and the Baltic Sea.

Despite its EU-wide ban in 2004 the triazine herbicide atrazine (ATR) and its transformation products (TPs) are frequently detected in the aqueous environment. In this study, concentrations of ATR, two of its TPs, and terbuthylazine (TERB) are presented and discussed in coastal waters of the Northern Aegean Sea, the Dardanelles, the Baltic Sea (Germany), the Northern Adriatic Sea (Italy), and the coastline close to Barcelona (Spain). The water samples (n=132) were taken in 2009-2011. Sediment samples (n=7) were taken from Baltic Sea (Germany) and Thermaikos Gulf (Greece). Maximum ATR concentrations (31-41 ng L⁻¹) were detected in Istanbul and the Dardanelles. A concentration gradient from East to West in the Aegean Sea was observed, indicating ongoing ATR contamination via the Dardanelles. Low concentrations and detection frequencies were observed at the other locations, indicating the success of the prohibition. However, the presence of TERB in the Northern Adriatic Sea raises concern.

Fate of β-blockers in aquifer material under nitrate reducing conditions: Batch experiments

The fate of the three environmentally relevant β-blockers atenolol, metoprolol and propranolol has been studied in batch experiments involving aquifer material and nitrate reducing conditions. Results from the about 90 d long tests indicate that abiotic processes, most likely sorption, jointly with biotransformation to atenololic acid were responsible for the 65% overall removal observed for atenolol. Zero order kinetics, typical of enzyme-limited reactions, controlled the transformation of this beta blocker to its corresponding carboxylic acid. The mass balance evidences that no mineralization of atenolol occurs in the biotic experiment and that atenololic acid is more stable than its parent compound under the studied conditions. This finding stresses the importance of considering atenololic acid as target compound in the environmental studies on the fate of atenolol. For metoprolol and propranolol the results from the experiment suggest a slower sorption to be the dominant removal process, which led to final decreases in concentrations of 25-30% and 40-45%, respectively. Overall, the removals observed in the experiments suggest that subsurface processes potentially constitute an alternative water treatment for the target beta-blockers, when compared to the removals reported for conventional wastewater treatment plants.

The challenge of sample-stabilisation in the era of multi-residue analytical methods: a practical guideline for the stabilisation of 46 organic micropollutants in aqueous samples.

Water sample storage and stabilisation may affect data quality, if samples are managed improperly. In this study three stabilising strategies are evaluated for 46 relevant organic micro-pollutants: addition of the biocides (i) copper sulphate and (ii) sodium azide to water samples directly after sampling with subsequent sample storage as liquid phase and (iii) direct solid phase extraction (SPE), stabilising the samples by reducing the activity of water. River water and treated effluent were chosen as commonly investigated matrices with a high potential of biotransformation activity. Analyses were carried out for sample storage temperatures of 4 and 28°C for water samples stored as liquid phase and for sample storage temperatures of 4, 20 and 40°C for SPE cartridges. Cooling of water samples alone was not sufficient for longer storage times (>24h). While copper sulphate caused detrimental interferences with nitrogen containing heterocyclic compounds, sodium azide proved to be a suitable stabilising agent. The best results could be obtained for SPE cartridges stored cool. Recommendations for samples preservation are provided.