Empirical models to predict the effect of sterilisation and storage on bisphenols migration from metallic can coatings into food simulants.

Based on response surface methodology, empirical models were built to predict the influence of can processing (heat treatment) and storage conditions (time and temperature) on the migration of bisphenol compounds from the inner lacquer of tinplate cans (4 brands) into several food simulants. Analysis using liquid chromatography revealed the presence of BADGE.2H2O and BPA in all samples. Models were significant in fitting the levels of these two bisphenols in food simulants depending on the input variables, with excellent adjusted coefficients of determination. Their prediction performance was validated through running new data sets. Further comparison of predicted values with bisphenols levels measured in canned vegetables revealed that the proposed models are conservative. By the desirability of the response output, the models are capable of proposing the range of can processing and storage conditions that limit migration for further compliance with the regulation. The proposed approach could be a convenient tool for the industries to control processing conditions in order to ensure the conformity of canned foods.

Simultaneous migration of bisphenol compounds and trace metals in canned vegetable food.

For the very first time, this study investigates the simultaneous migration of several metals and bisphenol compounds from coated tinplate cans into vegetable foods highly consumed worldwide. The role played by heat treatment, food type and brand, storage conditions, can denting and cooking food directly in cans is also assessed. Migration of bisphenol compounds (only BPA and BADGE·2H2O detected) was mainly affected by sterilization, whereas metal release was greatly influenced by storage. Based on a Principal Component Analysis different migration pattern groups were highlighted: BPA and Zn (and Pb to a lesser extent) showed similar migration trends, with dependence on food type, brand and storage temperature. Cd, Ni and Cu were similarly influenced by food type and can brand. Fe has a particular trend, with clear influence of storage time, and to a lesser extent of food type. Overall Fe and BADGE·2H2O migration were favored in acidic food.

Untargeted food contaminant detection using UHPLC-HRMS combined with multivariate analysis: Feasibility study on tea.

Powerful data pretreatment strategies inspired from the field of metabolomics were adapted to chemical food safety context to enable samples discrimination by multivariate methods based on low abundance ions. A highly automated workflow was produced. The open-source XCMS package was used and efficient data filtration strategies were set up. Data were treated using Independent Components Analysis, and data mining strategies developed to automatically detect and annotate ions of low abundance by coupling blind data exploration strategies with a broad scale database approach. Our method was efficient in discriminating tea samples based on their contamination levels (even at 10 µg.kg-1) and detecting unexpected impurities in the spiking mix. Several "tracer" contaminants were considered, covering a broad range of physicochemical properties and structural diversity with overall 66% detected and annotated blindly. The methodology was successfully applied to a data set exhibiting only 3 "tracer" contaminants (at 50 µg.kg-1) and more product diversity.

Contamination of soils by metals and organic micropollutants: case study of the Parisian conurbation.

Soils are playing a central role in the transfer and accumulation of anthropogenic pollutants in urbanized regions. Hence, this study aimed at examining the contamination levels of selected soils collected within and around the Paris conurbation (France). This also evaluated factors controlling contamination. Twenty-three trace and major elements as well as 82 organic micropollutants including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phthalates (PAEs), polybrominated diphenyl ethers (PBDEs), alkylphenols (APs), and perfluoroalkylated substances (PFASs) were analyzed. Results reinforced the concern raised by the occurrence and levels of metals such as Zn, Pb, Cu, and Hg, identified as metallic markers of anthropogenic activities, but also pointed out the ubiquitous contamination of soils by organic micropollutants in the 0.2-55,000-µg/kg dw range. For well-documented compounds like PAHs, PCBs, and to a lesser extent PBDEs, contents were in the range of background levels worldwide. The pollutant stock in tested soil was compared to the annual atmospheric input. For PAHs; Pb; and to a lesser extent Zn, Cu, Cd, Hg, Sb, PAEs, and APs, a significant stock was observed, far more important than the recent annual atmospheric fluxes. This resulted from both (i) the persistence of a fraction of pollutants in surface soils and (ii) the cumulative atmospheric inputs over several decades. Regarding PBDEs and PFASs, stronger atmospheric input contributions were observed, thereby highlighting their recent dispersal into the environment.

Effect of sterilisation and storage conditions on the migration of bisphenol A from tinplate cans of the Lebanese market.

The use of bisphenol A (BPA) in lacquer coating of food cans has been restricted by different authorities in many countries, such as in Europe. However, such regulation does not exist in many other countries including Lebanon. Due to the lack of data on the quality of Lebanese can production; this study investigates the migration of BPA from two types of tinplate cans manufactured in Lebanon, before and after sterilisation. Cans were analysed under different storage conditions (time and temperature) and filled with an aqueous simulant. The determination of BPA was carried out using UPLC with fluorescence detection, and further confirmed by MS detection. After sterilisation BPA levels drastically increased from an average of 0.15 to 109 µg/kg, giving a BPA migration around 10.5 µg/dm2 for both types of cans. Storage temperature and time had no significant influence on BPA levels in sterilised cans (p-value > 0.05); however, these factors significantly affected BPA levels in non-sterilised cans.

Multi-class analysis for simultaneous determination of pesticides, mycotoxins, process-induced toxicants and packaging contaminants in tea.

This study attempts at uniting the analysis of four different classes of contaminants for both liquid and solid tea samples. A total of 32 compounds, classified as pesticides, mycotoxins, process-induced toxicants or packaging contaminants, were carefully chosen for their diversity of structures and physicochemical properties. The proposed method combines a sample treatment strategy coming from metabolomics with liquid chromatography analysis using a silica bonded C18-pentafluorophenyl column coupled to high resolution mass spectrometry. For tea brew, dilute and shoot method provides good quantification (70-120% recoveries and <20% RSD) for more than 80% of compounds. For tea leaves, strong matrix effects are observed, thus, matrix-matched calibration is required to reach good performances, i.e. 63% of compounds quantified and 81% detected at 10µg/kg. Finally, method performances were evaluated against existing regulations, and it appears that 69% of contaminants are quantified and 91% detected at levels lower than their respective European regulation limits.

Endocrine disrupting compounds in gaseous and particulate outdoor air phases according to environmental factors.

This study investigated, for the first time in France, the spatial and temporal patterns of 55 endocrine disrupting chemicals (EDCs) in ambient air at three sites (urban, suburban and forest) under two climatic periods (warm/cold) for 2 successive years. All EDCs, except tetrabromobisphenol A (TBBPA), were encountered with various frequencies of up to 100%. Phthalate diesters (PAEs) were the most abundant chemicals with total concentrations as the sum of compounds, ranging from 10 to 100 ng m(-3) of total air, followed by alkylphenols (APs) and polycyclic aromatic hydrocarbons (PAHs), which were both approximately 1 ng m(-3). Polychlorinated biphenyl (PCBs) and bisphenol A (BPA) concentrations were notably lower (approximately 0.1 ng m(-3)). Air concentrations, depending on the considered compounds, were from 1.2 to 2 times higher in the urban than the suburban area and from 2 to 5 times higher in the urban than the forest site. PAH emissions were higher in the cold period, due to combustion processes. This finding is contrary to the other EDCs that are more abundant in the summer and governed by volatilisation. Most of the EDCs were largely distributed in the gaseous phase (>80% in the summer). The octanol/air partition coefficient (KOA) and vapour pressure (Vp) were relevant parameters for predicting EDC partitioning and direct relationships (p < 0.001) were observed i) between log K particle/gas partitioning (log Kp) and log KOA and ii) between EDC ratios in the gaseous phase and log vapour pressure (log Vp).

Modelling the fate of nonylphenolic compounds in the Seine River--part 2: assessing the impact of global change on daily concentrations.

This study aims at modelling the daily concentrations of nonylphenolic compounds such as 4-nonylphenol (4-NP), nonylphenol monoethoxylate (NP1EO) and nonylphenoxy acetic acid (NP1EC) within the Seine River downstream of Paris City for over a year, firstly in the present state (year 2010) and for years 2050 and 2100 in order to assess the consequences of global change on the fate of nonylphenolic compounds in the Seine river. Concentrations were first simulated for the year 2010 and compared to monthly measured values downstream of Paris. To achieve this goal, the hydrodynamic and biogeochemical model, ProSe, was updated to simulate the fate of 4-NP, NP1EO and NP1EC. The Seine upstream and Oise River (tributaries of the Seine River) concentrations are estimated according to concentrations-flow relationships. For Seine Aval wastewater treatment plant (SA-WWTP), the concentrations are considered constant and the median values of 11 campaigns are used. The biodegradation kinetics of 4-NP, NP1EO and NP1EC in the Seine River were deduced from the results of the companion paper. The Nash-Sutcliffe coefficient indicates a good efficiency to simulate the concentrations of 4-NP, NP1EC and NP1EO over an entire year. Eight scenarios were built to forecast the impacts of global warming (flow decrease), population growth (SA-WWTP flow increase) and optimisation of wastewater treatment (improvement of the quality of effluents) on annual concentrations of 4-NP, NP1EO and NP1EC at Meulan by 2050 and 2100. As a result, global warming and population growth may increase the concentrations of 4-NP, NP1EC and NP1EO, especially during low-flow conditions, while the optimisation of wastewater treatment is an efficient solution to balance the global change by reducing WWTP outflows.

Modelling the fate of nonylphenolic compounds in the Seine River--part 1: determination of in-situ attenuation rate constants.

Assessing the fate of endocrine disrupting compounds (EDCs) in the environment is currently a key issue for determining their impacts on aquatic ecosystems. The 4-nonylphenol (4-NP) is a well known EDC and results from the biodegradation of surfactant nonylphenol ethoxylates (NPnEOs). Fate mechanisms of NPnEO are well documented but their rate constants have been mainly determined through laboratory experiments. This study aims at evaluating the in-situ fate of 4-NP, nonylphenol monoethoxylate (NP1EO) and nonylphenolic acetic acid (NP1EC). Two sampling campaigns were carried out on the Seine River in July and September 2011, along a 28km-transect downstream Paris City. The field measurements are used for the calibration of a sub-model of NPnEO fate, included into a hydro-ecological model of the Seine River (ProSe). The timing of the sampling is based on the Seine River velocity in order to follow a volume of water. Based on our results, in-situ attenuation rate constants of 4-NP, NP1EO and NP1EC for both campaigns are evaluated. These rate constants vary greatly. Although the attenuation rate constants in July are especially high (higher than 1d(-1)), those obtained in September are lower and consistent with the literature. This is probably due to the biogeochemical conditions in the Seine River. Indeed, the July sampling campaign took place at the end of an algal bloom leading to an unusual bacterial biomass while the September campaign was carried out during common biogeochemical status. Finally, the uncertainties on measurements and on the calibration parameters are estimated through a sensitivity analysis. This study provides relevant information regarding the fate of biodegradable pollutants in an aquatic environment by coupling field measurements and a biogeochemical model. Such data may be very helpful in the future to better understand the fate of nonylphenolic compounds or any other pollutants at the basin scale.

Meta-analysis of environmental contamination by phthalates.

Phthalate acid esters (PAE), commonly named phthalates, are toxics classified as endocrine-disrupting compounds; they are primarily used as additives to improve the flexibility in polyvinyl chloride. Many studies have reported the occurrence of phthalates in different environmental matrices; however, none of these studies has yet established a complete overview for those compounds in the water cycle within an urban environment. This review summarizes PAE concentrations for all environmental media throughout the water cycle, from atmosphere to receiving waters. Once the occurrences of compounds have been evaluated for each environmental compartment (urban wastewater, wastewater treatment plants, atmosphere, and the natural environment), we reviewed data in order to identify the fate of PAE in the environment and establish whether geographical and historical trends exist. Indeed, geographical and historical trends appear between Europe and other countries such as USA/Canada and China, however they remain location dependent. This study aimed at identifying both the correlations existing between environmental compartments and the processes influencing the fate and transport of these contaminants into the environment. In Europe, the concentrations measured in waterways today represent the background level of contamination, which provides evidence of a past diffuse pollution. In contrast, an increasing trend has actually been observed for developing countries, especially for China.

Alkylphenolic compounds and bisphenol A contamination within a heavily urbanized area: case study of Paris.

This study evaluates the influence of a heavily urbanized area (Paris Metropolitan area), on receiving water contamination by both bisphenol A (BPA) and alkylphenol ethoxylate (APE) biodegradation product. The study began by investigating concentrations within urban sources. In addition to the more commonly studied wastewater treatment plant effluent, wet weather urban sources (including combined sewer overflows, urban runoff, and total atmospheric fallout) were considered. The initial results highlight a significant contamination of all urban sources (from a few nanograms per liter in atmospheric fallout to several micrograms per liter in the other sources) with clearly distinguishable distribution patterns. Secondly, concentration changes along the Seine River from upstream of the Paris Metropolitan area to downstream were investigated. While the concentrations of BPA and nonylphenoxy acetic acid (NP1EC) increase substantially due to urban sources, the 4-nonylphenol concentrations remain homogeneous along the Seine. These results suggest a broad dissemination of 4-nonylphenol at the scale of the Seine River basin. Moreover, the relationship between pollutant concentrations and Seine River flow was assessed both upstream and downstream of the Paris conurbation. Consequently, a sharp decrease in dissolved NP1EC concentrations relative to Seine River flow underscores the influence of single-point urban pollution on Seine River contamination. Conversely, dissolved 4-nonylphenol concentrations serve to reinforce the hypothesis of its widespread presence at the Seine River basin scale.

Meta-analysis of environmental contamination by alkylphenols.

Alkylphenols and alkylphenol ethoxylates (APE) are toxics classified as endocrine-disrupting compounds; they are used in detergents, paints, herbicides, pesticides, emulsifiers, wetting and dispersing agents, antistatic agents, demulsifiers, and solubilizers. Many studies have reported the occurrence of alkylphenols in different environmental matrices, though none of these studies have yet to establish a comprehensive overview of such compounds in the water cycle within an urban environment. This review summarizes APE concentrations for all environmental media throughout the water cycle, from the atmosphere to receiving waters. Once the occurrence of compounds has been assessed for each environmental compartment (urban wastewater, wastewater treatment plants [WWTP], atmosphere, and the natural environment), data are examined in order to understand the fate of APE in the environment and establish their geographical and historical trends. From this database, it is clear that the environment in Europe is much more contaminated by APE compared to North America and developing countries, although these APE levels have been decreasing in the last decade. APE concentrations in the WWTP effluent of developed countries have decreased by a factor of 100 over the past 30 years. This study is aimed at identifying both the correlations existing between environmental compartments and the processes that influence the fate and transport of these contaminants in the environment. In industrial countries, the concentrations observed in waterways now represent the background level of contamination, which provides evidence of a past diffuse pollution in these countries, whereas sediment analyses conducted in developing countries show an increase in APE content over the last several years. Finally, similar trends have been observed in samples drawn from Europe and North America.

Priority pollutants in urban stormwater: part 2 - case of combined sewers.

This study has evaluated the quality of combined sewer overflows (CSOs) in an urban watershed, such as Paris, by providing accurate data on the occurrence of priority pollutants (PPs) and additional substances, as well as on the significance of their concentrations in comparison with wastewater and stormwater. Of the 88 substances monitored, 49 PPs were detected, with most of these also being frequently encountered in wastewater and stormwater, thus confirming their ubiquity in urban settings. For the majority of organic substances, concentrations range between 0.01 and 1 µgl(-1), while metals tend to display concentrations above 10 µgl(-1). Despite this ubiquity, CSO, wastewater and stormwater feature a number of differences in both their concentration ranges and pollutant patterns. For most hydrophobic organic pollutants and some particulate-bound metals, CSOs exhibit higher concentrations than those found in stormwater and wastewater, due to the contribution of in-sewer deposit erosion. For pesticides and Zn, CSOs have shown concentrations close to those of stormwater, suggesting runoff as the major contributor, while wastewater appears to be the main source of volatile organic compounds. Surprisingly, similar concentration ranges have been found for DEHP and tributyltin compounds in CSOs, wastewater and stormwater. The last section of this article identifies substances for which CSO discharges might constitute a major risk of exceeding Environmental Quality Standards in receiving waters and moreover indicates a significant risk for PAHs, tributyltin compounds and chloroalkanes. The data generated during this survey can subsequently be used to identify PPs of potential significance that merit further investigation.