Assessment of the contamination by 2,4,6-tribromophenol of marine waters and organisms exposed to chlorination discharges.

2,4,6-tribromophenol (TBP) is implied in the production of brominated flame retardants but is also a major chlorination by-product in seawater. A growing number of studies indicate that TBP is highly toxic to the marine biota, but the contribution of anthropogenic sources among natural production is still under question concerning its bioaccumulation in marine organisms. Here, several water sampling campaigns were carried out in the industrialized Gulf of Fos (northwestern Mediterranean Sea, France) and clearly showed the predominant incidence of industrial chlorination discharges on the TBP levels in water, at the 1-10 ng L-1 level in average and reaching up to 580 ng L-1 near the outlets. The bioaccumulation of TBP was measured in 90 biota samples from the Gulf of Fos. The concentrations found in European conger muscle tissues (140-1000 ng g-1 lipid weight, in average), purple sea urchin gonads (830-880 ng g-1 lipid weight, in average), and Mediterranean mussel body (1500-2000 ng g-1 lipid weight, in average) were above all published references. Significant correlations with fish length (European conger) and gonad somatic index (purple sea urchin) were also identified. Comparatively, fish, urchins and mussels from other Mediterranean sites analyzed within this study showed a lower bioaccumulation level of TBP, consistently with what found elsewhere. Industrial outflows were thus identified as hotspots for TBP in seawater and marine organisms. The environmental risk assessment indicated a high potential toxicity in the industrial Gulf of Fos, in particular near the outlets, and a limited threat to human but toxicological references are lacking.

Influence of environmental and dietary exposures on metals accumulation among the residents of a major industrial harbour (Fos-sur-Mer, France).

OBJECTIVES: We sought to determine whether the residents living closer to the core industrial zone (Fos-sur-Mer) had higher trace metals blood and urinary levels than residents who lived further away (Saint-Martin-de-Crau). MATERIALS AND METHODS: As part of The INDEX study, we measured the following trace metals into blood and urine samples of 138 participants (80 in the core industrial zone and 58 in the reference area): Antimony, Arsenic, Cadmium, Chromium, Cobalt, Mercury, Nickel, Lead and Vanadium. Participants were recruited using a stratified random sampling method and had to meet the following inclusion criteria: 30-65 years old, living in the area since at least 3 years, not working in the industrial sector, non-smoker. We used single-pollutant multivariate linear regression models, using substitution when censored data were under 15 % and Tobit models alternatively, adjusting for personal physiological, social, dietary, housing characteristics and leisure activities. We also measured these trace metals in samples of lichens (Xanthoria parietina) and atmospheric particles (PM2.5). RESULTS: We showed higher lichen and air levels of several metals (Cd, Cr, Co, Ni and Pb) in the exposed area. Living close to the core industrial zone was significantly associated with an increase in blood levels of lead (adjusted geometric mean = 17.2 [15.8-18.7] vs 15.1 [13.7-16.7] µg.L-1, p < 0.05). We report significant increase of some metals urinary levels among residents of the industrial port zone, as the result of the use of the environment, itself contaminated by industrial activities: dietary history of self-consumption of vegetables (Cadmium), eggs and poultries (Vanadium). However, Vanadium levels were greater among self-consumers of poultry in the reference area and gardeners had circulatory levels of Lead greater than non-gardeners only in the reference area. Consumption of non-local sea-products increased the level of Cadmium. CONCLUSIONS: These results brought interesting clues, in complement to national programs, regarding the exposure to trace metals of residents living in a major industrial harbor.

Underestimation of Anthropogenic Bromoform Released into the Environment?

Bromoform (CHBr3) belongs to very-short-lived substances (VSLSs), which are important precursors of reactive bromine species (BrOx) contributing to tropospheric and stratospheric chemistry. To date, most models calculating bromine product emissions to the atmosphere only consider the natural production of CHBr3 from marine organisms such as macroalgae and phytoplankton. However, CHBr3 has many other anthropogenic sources (coastal industrial sites, desalination and wastewater plants, ballast waters, and seawater toilets) that may drastically increase the amounts emitted in the atmosphere. Here, we report the levels of CHBr3 released in water and air (according to real-time and offline measurements by proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) and gas chromatography with electron capture detection (GC-ECD)) in a highly industrialized area where 3 million cubic meters of chlorinated seawater is released each day, which were measured during six field campaigns (at sea and on land) distributed over 3 years. The highest levels found during this survey (which were correlated to the physical-chemical characteristics of the water, meteorological and hydrological conditions, salinity, and temperature gradients along the water column) reached 34.6 µg L-1 in water (100-10 000 times higher than reported natural levels) and 3.9 ppbv in the air (100 times higher than the maximum reported value to date). These findings suggest the need to undertake sampling and analysis campaigns as close as possible to chlorinated discharges, as anthropogenic CHBr3 sources from industrial discharges may be a missing factor in global flux estimates or organic bromine to the atmosphere.

Effects of meteorological conditions and topography on the bioaccumulation of PAHs and metal elements by native lichen (Xanthoria parietina).

The bioaccumulation of PAHs and metal elements in the indigenous lichens Xanthoria parietina was monitored during two years at a quarterly frequency, in 3 sites of contrasted anthropic influence. The impact of the meteorological factors (temperature, relative humidity, rainfall, wind speed) was first estimated through principal component analysis, and then by stepwise multilinear regressions to include wind directions. The pollutants levels reflected the proximity of atmospheric emissions, in particular from a large industrial harbor. High humidity and mild temperatures, and in a lower extent low wind speed and rainfall, also favored higher concentration levels. The contributions of these meteorological aspects became minor when including wind direction, especially when approaching major emission sources. The bioaccumulation integration time towards meteorological variations was on a seasonal basis (1-2 months) but the wind direction and thus local emissions also relied on a longer time scale (12 months). This showed that the contribution of meteorological conditions may be prevalent in remote places, while secondary in polluted areas, and should be definitely taken into account regarding long-term lichen biomonitoring and inter-annual comparisons. In the same time, a quadruple sampling in each site revealed a high homogeneity among supporting tree species and topography. The resulting uncertainty, including sampling, preparation and analysis was below 30% when comfortable analytical conditions were achieved. Finally, the occurrence of unexpected events such as a major forest fire, permitted to evaluate that this type of short, although intense, events did not have a strong influence on PAH and metals bioaccumulation by lichen.

Occurrence and speciation of chlorination byproducts in marine waters and sediments of a semi-enclosed bay exposed to industrial chlorinated effluents.

Chlorination of seawater is one of the most effective technologies for industrial biofouling control. However, chlorination leads to the formation of halogenated chlorination byproducts (CBPs) associated with potential risks to environmental and human health. The present study investigated the occurrence and distribution of CBPs in the Gulf of Fos, a semi-enclosed bay where chlorinated effluents of multiple industrial plants are discharged. Seawater samples (surface and bottom) were collected at 24 sampling stations, with some near industrial outlets and others dispersed throughout the bay. Sediment samples were also collected at 10 sampling stations. Physicochemical parameters including water temperature, pH, salinity, bromide content, and free and total residual oxidant were determined. Several chemical classes of CBPs including trihalomethanes, haloacetic acids, haloacetonitriles, trihaloacetaldehydes, and halophenols were analyzed. Bromoform was the most abundant CBP in seawater, and it was detected at most of the sampling stations of the bay with highest concentrations occurring near the industrial effluent outlets. Dibromoacetic acid was the second most abundant CBP at most of the sites followed by dibromoacetonitrile. Other detected CBPs included tribromoacetic acid, bromochloroacetonitrile, and bromal hydrate. To our knowledge, the concentration of the latter CBP was reported here for the first time in the context of industrial seawater chlorination. In sediments, two bromine-containing halophenols (2-chloro-4-bromophenol and 2,4,6-tribromophenol) were detected at two sampling stations. Ecotoxicological assays and risk assessment studies based on the detected environmental concentrations are warranted to elucidate the impacts of marine CBP contamination.

Characterization of atmospheric emission sources in lichen from metal and organic contaminant patterns.

Lichen samples from contrasted environments, influenced by various anthropic activities, were investigated focusing on the contaminant signatures according to the atmospheric exposure typologies. Most of the contaminant concentrations measured in the 27 lichen samples, collected around the industrial harbor of Fos-sur-Mer (France), were moderate in rural and urban environments, and reached extreme levels in industrial areas and neighboring cities (Al up to 6567 mg kg-1, Fe 42,398 mg kg-1, or ΣPAH 1417 µg kg-1 for example). At the same time, a strong heterogeneity was noticed in industrial samples while urban and rural ones were relatively homogeneous. Several metals could be associated to steel industry (Fe, Mn, Cd), road traffic, and agriculture (Sb, Cu, Sn), or to a distinct chemical installation (Mo). As well, PCDFs dominated in industrial samples while PCDDs prevailed in urban areas. The particularities observed supported the purpose of this work and discriminated the contributions of various atmospheric pollution emission sources in lichen samples. A statistical approach based on principal component analysis (PCA) was applied and resolved these potential singularities into specific component factors. Even if a certain degree of mixing of the factors is pointed out, relevant relationships were observed with several atmospheric emission sources. By this methodology, the contribution of industrial emissions to the atmospheric metal, PAH, PCB, and PCDD/F levels was roughly estimated to be 60.2%, before biomass burning (10.2%) and road traffic (3.8%). These results demonstrate that lichen biomonitoring offers an encouraging perspective of spatially resolved source apportionment studies.