Needs for reliable analytical methods for monitoring chemical pollutants in surface water under the European Water Framework Directive

The state of the art in monitoring chemical pollutants to assess water quality status according to Water Framework Directive (WFD) and the challenges associated with it have been reviewed. The article includes information on environmental quality standards (EQSs) proposed to protect the aquatic environment and humans against hazardous substances and the resulting monitoring requirements. Furthermore, minimum performance criteria for analytical methods and quality assurance issues have been discussed. The result of a survey of existing standard methods with a focus on European (EN) and international standards (ISO) for the analysis of chemical pollutants in water is reported and the applicability of those methods for the purpose of compliance checking with EQSs is examined. Approximately 75% of the 41 hazardous substances for which Europe-wide EQSs have been proposed can be reliably monitored in water with acceptable uncertainty when applying existing standardised methods. Monitoring in water encounters difficulties for some substances, e.g., short-chain chlorinated paraffins (SCCPs), polybrominated diphenyl ethers (PBDEs), tributyltin compounds, certain organochlorine pesticides and six-ring PAHs, mainly due to a lack of validated, sufficiently sensitive methods that are applicable in routine laboratory conditions. As WFD requires monitoring of unfiltered samples for organic contaminants more attention needs to be paid to the distribution of chemical pollutants between suspended particulate matter and the liquid phase. Methods allowing complete extraction of organic contaminants from whole water samples are required. From a quality assurance point of view, there is a need to organise interlaboratory comparisons specifically designed to the requirements of WFD (concentrations around EQSs, representative water samples) as well as field trials to compare sampling methodologies. Additional analytical challenges may arise when Member States have identified their river basin specific pollutants and after revision of the list of priority substances.     

Multi-residue analysis and ultra-trace quantification of 36 priority substances from the European Water Framework Directive by GC-MS and LC-FLD-MS/MS in surface waters

A multi residue analysis was developed for screening, quantification and confirmation of 36 priority organic compounds included in the 2000/60/EC European Water Framework Directive. The compounds analyzed included 19 pesticides, 8 PAH, 5 endocrine-disruptors and 4 organochlorine compounds. The method was developed in three steps. First, automated off-line solid-phase extraction using Strata X cartridges was optimized to trap simultaneously the 36 studied compounds. Second, the more volatile compounds were analysed by gas chromatography coupled to mass spectrometry with electron impact ionisation in selected ion monitoring mode (SIM). Third, the last 20 compounds were detected and quantified, in one run, by liquid chromatography coupled to fluorescence detector and tandem mass spectrometry. The excellent selectivity and sensitivity allowed us satisfactory quantification and confirmation at levels as low as 0.2-67 ng L⁻¹ with recoveries between 59 and 105%. Such methodology was then applied to French surface waters: all the waters present organic contaminants, and their concentration varied according to the origin and nature of substances.     

Recent applications of surface plasmon resonance biosensors for analyzing residues and contaminants in food

Abstract  Optical biosensors based on surface plasmon resonance are increasingly used to detect and (semi)quantify residues and contaminants in food. This review provides an overview of the methods published in this field since the year 2003. Such biosensors have mostly been applied to veterinary drug residues, like aminoglycosides, beta-agonists, cephalexin, chloramphenicol, fluoroquinolones, levamisole, nicarbazin, nitroimidazoles, penicillins, ractopamine, sulfonamides, tetracyclines, and tylosin in milk, egg, honey, prawn, muscle, liver and kidney. Only a few methods have been published on pesticide residues, mycotoxins, phycotoxins, polychlorinated biphenyls and surfactants. These procedures are described with regard to biological recognition element, type of sensor chip, immobilisation procedure, sample extraction and clean-up, crossreactivity, nonspecific binding, matrix interference, chip regeneration, assay formats, calibration, validation and instrumentation. Graphical Abstract        

Environmental monitoring approaches for the detection of organic contaminants in marine environments: A critical review

This review reports different approaches for monitoring the presence of organic contaminants in marine environments. From the traditional standard chromatographic methodologies coupled to different detectors to the recent advances in sensor technology, different strategies have been adopted by researchers aiming to provide more comprehensive, realistic and accurate environmental monitoring data sets. Reports on chemical analysis by different techniques of marine water and sediments, using grab and passive sampling techniques, are the most abundant in literature, showing relevant developments. Analysis of the marine biota (biomonitoring) has also been widely used as a proxy for the detection of organic chemicals in seawater, with bivalves being the most used as sentinel specie. Such biomonitoring can provide insights on bioavailability and bioaccumulation of organic pollutants, which is not possible to obtain by water and sediment analysis solely. Furthermore, effect-based methods are also presented as an important approach when it comes to obtain environmental meaningful data, such as potential toxicity and hazards posed by the complex chemical mixtures to local biota. This approach is reported to be a useful tool for screening areas without any previous knowledge on chemical composition, with subsequential qualitative and quantitative characterization being performed by chemical analysis. Finally, some of the most recent developments in sensor and biosensor technology for environmental purposes are also discussed, with some proof-of-concept studies showing promising results. However, further development and validations work is strongly advised prior to the use of those sensing platforms in real field trials.     

Validation of stir bar sorptive extraction for the determination of 24 priority substances from the European Water Framework Directive in estuarine and sea water

This paper describes the validation of a method for the determination of 24 priority substances from the European Framework Directive in estuarine and sea water using the new extraction technique known as stir bar sorptive extraction (SBSE), followed by thermal desorption using capillary gas chromatography-mass spectrometry. We studied linearity, detection and quantitation limits and accuracy (which includes determination of trueness and precision). Using the lack-of-fit method we tested linearity in the 0-200 ng L⁻¹ range for all the priority substances. The detection and quantification limits were less than 5 and 10 ng L⁻¹, respectively, for most of the compounds studied. Precision was assessed by variance analysis (ANOVA) and relative standard values of less than 10% were obtained for repeatability and less than 15% for intermediate precision. The recovery percentages in spiked estuarine and sea water were close to 100%. Finally, for quality control of the method (stability of precision and accuracy through time), we developed a method for calculating Shewhart control charts based on the information obtained in the validation process.     

Optimal conditions and sample storage for the determination of H2O2 in marine waters by the scopoletin-horseradish peroxidase fluorometric method

The conditions presently in use for the fluorometric determination of H₂O₂ in marine waters, by reacting H₂O₂ with scopoletin in the presence of horseradish peroxidase (HRP) and measuring the quenching of the fluorescence intensity of scopoletin, are not the optimal conditions. Under the optimized conditions of a pH of 8.5–9.5, an excitation wavelength of 390 nm and an emission wavelength of 460, the sensitivity of the method can be increased significantly, by up to more than a factor of 3 and the variations in the sensitivity from sample to sample can be significantly reduced. Furthermore, the samples need not be analyzed immediately after sample collection as presently prescribed. After scopoletin and HRP have been added to a sample immediately after sample collection, the sample may be stored at room temperature in the dark for up to four days before the quenched fluorescence intensity of scopoletin is read.     

Application of EU Water Framework Directive for monitoring of small water catchment areas in Hungary, II. Preliminary study for establishment of surveillance monitoring system for moderately loaded (rural) and heavily loaded (urban) catchment areas

For the elaboration of a monitoring guidance corresponding to the EU Water Framework Directives, a comprehensive monitoring network on small water catchment areas was developed on three investigated areas in Hungary. In the present study the experience of monitoring of the Galga and Rákos streams are presented, which represent a moderately loaded rural and a heavily impacted urbanic catchment area, respectively. Hydrological, biological and chemical parameters were monitored during one year. The influence of human impact on the spatial and temporal variability of parameters and the appropriate frequency of sampling were compared. Necessary actions to improve the ecological status can be suggested on the basis of the above monitoring programme.     

Collaborative sampling trial in the context of quality assurance in the German marine monitoring programme for the North Sea and the Baltic Sea

This paper presents the assessment of a collaborative trial in sampling in the Baltic Sea in the framework of quality assurance in the German marine monitoring programme for the North Sea and the Baltic Sea. The objective of investigations was to determine the influence of sampling on analytical results for selected monitoring parameters and to harmonize the procedure for sampling of sea water to a large extent. In these studies the staff of three vessels took replicate sea water samples, 1 m below the surface and below the halocline, at two monitoring stations. Mass concentration mean values for different nutrient parameters were obtained from each sample, all in one laboratory. Data produced from the hierarchical design were treated with robust analysis of variance (ANOVA) to generate uncertainty estimates, as standard uncertainties (“u” expressed as standard deviation), for geochemical variation (s _geochem), primary sampling (s _sampling), and chemical analysis (s _analysis). Geochemical variation dominated the total variance in all cases. Sampling and analytical uncertainties contributed together up to 15% of the total variance and had a relative measurement uncertainty (u%) of less than 2% for all the parameters investigated. Thus for this study the sampling protocol and the analytical method could be regarded as fit-for-purpose. M. Gluschke was formerly affiliated to the Federal Environmental Agency, P.O. Box 33 00 22, 14191 Berlin, Germany.