Dye residues in aquaculture products: Targeted and metabolomics mass spectrometric approaches to track their abuse.

The aim of the study was to initiate an exhaustive strategy of control by implementing both targeted and non-targeted metabolomics approaches. A LC-MS/MS method including an oxidative step for most of dyes was developed and validated to target the analysis of 14 residues belonging to different families of dyes. The method was suitable for the quantitative confirmation of 13 dyes at low ppb levels. The metabolomics approach objective was to compare fingerprints between farmed fish treated with malachite green and farmed fish treated with victoria pure blue bo. Analytical information on modifications in the metabolome of muscle, liver and plasma was exploited by HRMS following by multivariate statistics and revealed some direct or endogenous metabolites among relevant mass features contributing to the constructed models. These two approaches, either appropriate biomarkers either enlarged targeted dyes are explored concomitantly to help improving the strategy for tracking new illegal practices in aquaculture.

Storage of natural water samples and preservation techniques for pharmaceutical quantification.

In order to perform a human and ecological risk assessment of pharmaceutical products (PPs) in natural waters, it is necessary to accurately quantify a broad variety of PPs at low concentrations. Although numerous currently implemented analytical methodologies, less is known about the preservation of PPs in natural water samples within the period before analysis (holding time, storage conditions). This paper is the first literature review about the stability of PPs in natural waters (surface and groundwaters) during sample storage. The current work focuses on a comparison of the performances of the available preservation techniques (filtration, container materials, storage temperature, preservative agents, etc.) for PPs in samples. All 58 reviewed PPs may be successfully stabilized during 7 days in surface waters by at least one appropriate methodology regarding temperature, acidic and non-acidic preservatives. When temperature is not a sufficient preservation parameter for some PPs (hormones and fluoxetine) its combination with the addition of chemical agents into the samples may prolong the integrity of the PPs during storage in surface water. There is a strong need to use standard protocols to assess and compare the stability of PPs in environmental water matrices during storage as well as during analytical preparation or analysis (European criteria 2002/657/EC). Since the stability of PPs during sample storage is a critical parameter that could call into question the quality of the data provided for the concentrations, the design of stability studies should rigorously take into account all critical parameters that could impact the concentrations of the PPs with time.

Inter-laboratory exercise on antibiotic drugs analysis in aqueous samples.

An inter-laboratory exercise was organized under the PHARMAS EU project, by the Advanced School of Public Health (EHESP), in order to evaluate the performances of analytical methods for the measurement of antibiotics in waters (surface and tap). This is the first time such an exercise on antibiotics has been organized in Europe, using different kinds of analytical methods and devices. In this exercise thirteen laboratories from five countries (Canada, France, Italy, the Netherlands and Portugal) participated, and a total number of 78 samples were distributed. During the exercise, 2 testing samples (3 bottles of each) prepared from tap water and river water, respectively, spiked with antibiotics, were sent to participants and analyzed over a period of one month. A final number of 77 (98.7%) testing samples were considered. Depending on substances studied by each participant, 305 values in duplicate were collected, with the results for each sample being expressed as the target concentration. A statistical study was initiated using 611 results. The mean value, standard deviation, coefficient of variation, standard uncertainty of the mean, median, the minimum and maximum values of each series as well as the 95% confidence interval were obtained from each participant laboratory. In this exercise, 36 results (6% of accounted values) were outliers according to the distribution over the median (box plot). The outlier results were excluded. In order to establish the stability of testing samples in the course of the exercise, differences between variances obtained for every type of sample at different intervals were evaluated. The results showed no representative variations and it can be considered that all samples were stable during the exercise. The goals of this inter-laboratory study were to assess results variability when analysis is conducted by different laboratories, to evaluate the influence of different matrix samples, and to determine the rate at which participating laboratories successfully completed the tests initiated.

Contamination levels of human pharmaceutical compounds in French surface and drinking water.

The occurrence of 20 human pharmaceutical compounds and metabolites from 10 representative therapeutic classes was analysed from resource and drinking water in two catchment basins located in north-west France. 98 samples were analysed from 63 stations (surface water and drinking water produced from surface water). Of the 20 human pharmaceutical compounds selected, 16 were quantified in both the surface water and drinking water, with 22% of the values above the limit of quantification for surface water and 14% for drinking water). Psychostimulants, non-steroidal anti-inflammatory drugs, iodinated contrast media and anxiolytic drugs were the main therapeutic classes of human pharmaceutical compounds detected in the surface water and drinking water. The results for surface water were close to results from previous studies in spite of differences in prescription rates of human pharmaceutical compounds in different countries. The removal rate of human pharmaceutical compounds at 11 water treatment units was also determined. Only caffeine proved to be resistant to drinking water treatment processes (with a minimum rate of 5%). Other human pharmaceutical compounds seemed to be removed more efficiently (average elimination rate of over 50%) by adsorption onto activated carbon and oxidation/disinfection with ozone or chlorine (not taking account of the disinfection by-products). These results add to the increasing evidence of the occurrence of human pharmaceutical compounds in drinking water that may represent a threat to human beings exposed to a cocktail of human pharmaceutical compounds and related metabolites and by-products in drinking water.

Occurrence and fate of pharmaceutical products and by-products, from resource to drinking water.

Among all emerging substances in water, pharmaceutical products (PPs) and residues are a lot of concern. These last two years, the number of studies has increased drastically, however much less for water resources and drinking water than for wastewater. This literature review based on recent works, deals with water resources (surface or groundwater), focusing on characteristics, occurrence and fate of numerous PPs studied, and drinking water including water quality. Through this review, it appears that the pharmaceutical risk must be considered even in drinking water where concentrations are very low. Moreover, there is a lack of research for by-products (metabolites and transformation products) characterization, occurrence and fate in all water types and especially in drinking water.