Electron ionization mass spectrometric fragmentation and multiple reaction monitoring quantification of ferulic and p-coumaric acid trimethylsilyl derivatives in deposited atmospheric particles.

RATIONALE: Ferulic and p-coumaric acids are important biological and structural components of plant cell walls and possess antioxidant and antimicrobial properties. These phenolic acids are widespread in environmental samples. However, when they are present at very low concentrations or in very complex lipid extracts, their identification and quantification can be challenging. METHODS: The electron ionization mass spectrometry (EI-MS) fragmentation pathways of ferulic and p-coumaric acid trimethylsilyl (TMS) derivatives were investigated. These pathways were deduced by (i) low-energy collision-induced dissociation (CID) gas chromatography (GC)/EI-MS/MS, (ii) accurate mass measurement, and (iii) 13 C labelling. These compounds were then characterized and quantified in multiple reaction monitoring (MRM) mode in total lipid extracts of deposited atmospheric particles using highly specific transitions based on the main fragmentation pathways elucidated. RESULTS: Low-energy CID-MS/MS analyses, accurate mass measurement and 13 C labelling enabled us to elucidate EI-MS fragmentations of ferulic and p-coumaric acid TMS derivatives. Some specific fragmentations proved useful for subsequent characterization and quantification of these compounds. As an application of some of the described fragmentations, trace amounts of these phenolic acids were characterized and quantified in MRM mode in wet- and dry-deposited atmospheric particles containing low proportions of organic matter. CONCLUSIONS: EI-MS fragmentations of ferulic and p-coumaric acid TMS derivatives exhibit specific fragment ions that can be very useful for the quantification of trace amounts of both phenolic acids in environmental samples.

Release of particles and metals into seawater following sediment resuspension of a coastal mine tailings disposal off Portmán Bay, Southern Spain.

Portmán Bay in Southern Spain is one of the most extreme cases in Europe of anthropogenic impact on the marine ecosystem by the disposal of mine tailings resulting from the processing of sulphide ores. First, the composition and extent of the surficial deposit were investigated from geochemical and metal analysis on high spatial density of sediment samples. Then, a disturbance experiment was conducted in the coastal area off Portmán Bay in order to investigate the potential impact of mining activities on marine ecosystems. Two research vessels were used for that experiment, one performing as a trawler resuspending bottom sediments while the other monitor the behaviour of turbid plumes thus generated and the evolution of their characteristics through time by using a range of acoustic and optical tools together with water and bottom sediment sampling for biogeochemical and metal analyses. The surficial part of the submarine extension of the mine tailings deposit is highly concentrated in As, Cd, Pb, Fe and Zn with peak concentrations adjacent to the present coastline, from where they decrease seawards before reaching average values for the Mediterranean Sea around 50-m water depth. The artificially triggered resuspension of the surface layer of the deposit led to the formation of resuspension plume about 100 m in width and up to 6 m in height. Resuspended plume was composed of fine particles which rapidly aggregated into flocs of 100 µm. While the biggest particles settled rapidly, the finest fraction remained in suspension during at least 3 h. Resuspended sediment and metal concentrations in particles remained at relatively high levels throughout the experiments following triggering. Fe, Pb, and As concentrations in resuspended particles showed a continuous increase while trawling before decreasing in parallel with the settling down of the resuspended sediments. Those metals have higher affinity with fine particles than with coarse ones, so that while the coarsest fraction from sediment plumes settled first, the finest fraction remained in suspension thus increasing the metals/sediments concentration ratio. On the other hand, Cd and Zn concentrations in suspended particles did not change significantly over time, which is thought to be caused by the fast dissolution of such metals in seawater. Beyond waste dumping itself, the observed increase in some metals in marine particulate material could have a significant impact on the adjacent coastal ecosystems due to their toxicity above certain thresholds. The consequences of the resuspension experiment here presented can be extrapolated to the impact of seafloor mining activities leading to the resuspension of metal-rich particle plumes into the water column. The experimental set-up presented here may be further explored for investigating metal behaviour during seafloor mining activities.

EIMS Fragmentation and MRM quantification of autoxidation products of α- and ß-amyrins in natural samples.

RATIONALE: Riverine particulate organic matter is generally considered to be refractory with respect to further decomposition in the ocean. In order to check the validity of this paradigm, there is a real need for tracers sufficiently stable and specific to monitor the degradation of terrestrial higher plant material in the environment. 3ß-hydroxy-urs-12-en-11-one and 3ß-hydroxy-olean-12-en-11-one (autoxidation products of α- and ß-amyrin) were previously proposed for such use. METHODS: EIMS fragmentation pathways of 3ß-hydroxy-urs-12-en-11-one and 3ß-hydroxy-olean-12-en-11-one TMS derivatives were investigated. These pathways were deduced by: (i) low energy CID-GC/MS/MS, (ii) accurate mass measurement and (iii) deuterium labelling. Quantification of these compounds in total lipid extracts of natural samples was then carried out in MRM mode. RESULTS: CID-MS/MS analyses, accurate mass measurement and deuterium labelling experiments allowed us to elucidate EIMS fragmentations of 3ß-hydroxy-urs-12-en-11-one and 3ß-hydroxy-olean-12-en-11-one TMS derivatives. Some specific fragmentation pathways, useful in addition to chromatographic retention times for further characterization, could be selected. As an application of some of the described fragmentations, TMS derivatives of these oxidation products were characterized and quantified in MRM mode in different natural samples. CONCLUSIONS: EIMS fragmentations of 3ß-hydroxy-urs-12-en-11-one and 3ß-hydroxy-olean-12-en-11-one TMS derivatives exhibit specific fragment ions, which appear to be very useful for the quantification of these oxidation products in natural samples (riverine particulate matter, wet and dry deposited atmospheric particles).

Multicontamination phenomena occur more often than expected in Mediterranean coastal watercourses: Study case of the Têt River (France).

Contaminants found in watercourses are not only the result of anthropogenic activities but also depend on river's seasonal hydrodynamics. This is particularly true in Mediterranean climate regions where long dry periods are interrupted by strong rainfalls. Storm events remobilize particles from soils and sediments and, as a consequence, the load of particulate matter in rivers can be quite considerable, severely affecting water quality. Nevertheless, an absence of fieldwork studies exists concerning the simultaneous dynamics of mixtures of pollutants in river waters, particularly during strong rainfalls and floods. Our study assessed the concentrations of six families of pollutants, including pesticides, at these events, and compared them to those observed at drought sampling periods. We have used as model a typical Mediterranean coastal river from Southeast France, the Têt River, whose hydrodynamics and major elements fluxes have been fairly investigated. As expected, our results show that chemical mixtures due to human activities occur and that they are particularly relevant during storm events. But the results of our study argue that exceptional multicontamination phenomena actually happen more often than expected because they are linked to recurrent sudden intense rainfall events in the Mediterranean. In particular, combined sewer overflows are responsible for this major issue in urbanized areas, whereas runoff and leaching will be the most important sources of pollutant mixtures occurring at flood flow peak. After an overview of the sources responsible for chronic multiple stressors events in regions under a Mediterranean climate regime worldwide, we revisit best management measures to reduce risks from the presence of chemical mixtures in the environment.

Unexpected biotic resilience on the Japanese seafloor caused by the 2011 Tohoku-Oki tsunami.

On March 11(th), 2011 the Mw 9.0 2011 Tohoku-Oki earthquake resulted in a tsunami which caused major devastation in coastal areas. Along the Japanese NE coast, tsunami waves reached maximum run-ups of 40 m, and travelled kilometers inland. Whereas devastation was clearly visible on land, underwater impact is much more difficult to assess. Here, we report unexpected results obtained during a research cruise targeting the seafloor off Shimokita (NE Japan), shortly (five months) after the disaster. The geography of the studied area is characterized by smooth coastline and a gradually descending shelf slope. Although high-energy tsunami waves caused major sediment reworking in shallow-water environments, investigated shelf ecosystems were characterized by surprisingly high benthic diversity and showed no evidence of mass mortality. Conversely, just beyond the shelf break, the benthic ecosystem was dominated by a low-diversity, opportunistic fauna indicating ongoing colonization of massive sand-bed deposits.

Marine natural meroterpenes: synthesis and antiproliferative activity.

Meroterpenes are compounds of mixed biogenesis, isolated from plants, microorganisms and marine invertebrates. We have previously isolated and determined the structure for a series of meroterpenes extracted from the ascidian Aplidium aff. densum. Here, we demonstrate the chemical synthesis of three of them and their derivatives, and evaluate their biological activity on two bacterial strains, on sea urchin eggs, and on cancerous and healthy human cells.

Soil transformation of prosulfuron.

The transformation of prosulfuron [1-(4-methoxy-6-methyltriazine-2-yl)-3-[2-(3,3,3-trifluropropyl)phenylsulfonyl]urea] in three soils at different pH values (sterilized and unsterilized) was studied, and it was shown that the rate of transformation was high in acidic soil. From the results obtained in sterile soils, it is shown that the mechanism of dissipation was mainly chemical in acidic soils. A new metabolite, 2-(3,3,3-trifluoropropyl)phenylsulfonic acid, was identified.