Mercury concentrations in lean fish from the Western Mediterranean Sea: Dietary exposure and risk assessment in the population of the Balearic Islands

The present study reports total mercury (THg) and methylmercury (MeHg) concentrations in 32 different lean fish species from the Western Mediterranean Sea, with a special focus on the Balearic Islands. The concentrations of THg ranged between 0.05mg/kg ww and 3.1mg/kg ww (mean 0.41mg/kg ww). A considerable number of the most frequently fish species consumed by the Spanish population exceed the maximum levels proposed by the European legislation when they originate from the Mediterranean Sea, such as dusky grouper (100% of the examined specimens), common dentex (65%), conger (45%), common sole (38%), hake (26%) and angler (15%), among others. The estimated weekly intakes (EWI) in children (7-12 years of age) and adults from the Spanish population (2.7µg/kg bw and 2.1µg/kg bw, respectively) for population only consuming Mediterranean fish were below the provisional tolerable weekly intake (PTWI) of THg established by EFSA in 2012, 4µg/kg bw. However, the equivalent estimations for methylmercury, involving PTWI of 1.3µg/kg bw, were two times higher in children and above 50% in adults. For hake, sole, angler and dusky grouper, the most frequently consumed fish, the estimated weekly intakes in both children and adults were below the maximum levels accepted. These intakes correspond to maximum potential estimations because fish from non-Mediterranean origin is often consumed by the Spanish population including the one from the Balearic Islands

27. meeting of the Spanish Chromatography Group (GCTA) of the Royal Society of Chemistry

Centro de Informacion y Documentacion Cientifica (CINDOC). C/Joaquin Costa, 22. 28002 Madrid. SPAIN / CINDOC - Centro de Informaciòn y Documentaciòn CientìficaSIGLEESSpai

Chemical and carbon isotopic evolution of hydrocarbons during prograde metamorphism from 100°C to 550°C: Case study in the Liassic black shale formation of Central Swiss Alps

Hydrocarbon distributions and stable isotope ratios of carbonates (delta(13)C(car), delta(18)O(car)), kerogen (delta(13)C(ker)), extractable organic matter (delta(13)C(EOM)) and individual hydrocarbons of Liassic black shale samples from a prograde metamorphic sequence in the Swiss Alps were used to identify the major organic reactions with increasing metamorphic grade. The studied samples range from the diagenetic zone (< 100 degrees C) to amphibolite facies (similar to 550 degrees C). The samples within the diagenetic zones (< 100 and 150 degrees C) are characterized by the dominance of C-< 20 n-alkanes, suggesting an origin related with marine and/or bacterial inputs. The metamorphic samples (200 to 550 degrees C) have distributions significantly dominated by C-12 and C-13 n-alkanes, C-14, C-16 and C-18 n-alkylcyclopentanes and to a lesser extend C-15, C-17 and C-21 n-alkylcyclohexanes. The progressive C-13-enrichment (up to 3.9 parts per thousand) with metamorphism of the C-> 17 n-alkanes suggests the occurrence of cracking reactions of high molecular weight compounds. The isotopically heavier (up to 5.6 parts per thousand) C-< 17 n-alkanes in metamorphic samples are likely originated by thermal degradation of long-chain homologous with preferential release of isotopically light C-1 and C-2 radicals. The dominance of specific even C-number n-alkylcyclopentanes suggests an origin related to direct cyclization mechanism (without decarboxylation step) of algal or bacterial fatty acids occurring in reducing aqueous metamorphic fluid conditions. The regular increase of the concentrations of n-alkylcycloalkanes vs. C-> 13 n-alkanes with metamorphism suggests progressive thermal release of kerogen-linked fatty acid precursors and degradation of n-alkanes. Changes of the steroid and terpenoid distributions are clearly related to increasing metamorphic temperatures. The absence of 18 alpha(H)-22,29,30-trisnorneohopane (Ts), the occurrence of 17 beta(H)-trisnorhopane, 17 beta(H), 21 alpha(H)-hopanes in the C-29 to C-31 range and 5 alpha(H),14 alpha(H),17 alpha(H)-20R C-27, C-29 steranes in the low diagenetic samples (< 100 degrees C) are characteristic of immature bitumens. The higher thermal stress within the upper diagenetic zone (150 degrees C) is marked by the presence of Ts, the disappearance of 17 beta(H)-trisnorhopane and thermodynamic equilibrium of the 22S/(22S + 22R) homohopane ratios. The increase of the alpha alpha alpha-sterane 20S/(20S + 20R) and 20R beta beta/(beta beta + alpha alpha) ratios (from 0.0 to 0.55 and from 0.0 to 0.40, respectively) in the upper diagenetic zone indicates the occurrence of isomerization reactions already at < 150 degrees C. However, the isomerization at C-20 (R -> S) reaches thermodynamic equilibrium values already at the upper diagenesis (similar to 150 degrees C) whereas the epimerisation at C-14 and C-17 (alpha alpha ->beta beta) arrives to constant values in the lower anchizone (similar to 200 degrees C). The ratios Ts vs. 17 alpha(H)-22,29,30-trisnorneohopane [(Ts/(Ts + Tm)] and 18 alpha(H)-30-norneohopane (C29Ts) vs. 17 alpha(H),21 beta(H)-30-norhopane [C29Ts/(C29Ts + C-29)] increase until the medium anchizone (200 to 250 degrees C) from 0.0 to 0.96 and from 0.0 to 0.44, respectively. An opposite trend owards lower values is observed in the higher metamorphic samples. The occurrence of specific hydrocarbons (e.g., n-alkylcyclopentanes, cadalene, hydrogenated aromatic compounds) in metamorphic samples points to kerogen degradation reactions most probably occurring in the presence of water and under reducing conditions. The changes of hydrocarbon distributions and carbon isotopic compositions of n-alkanes related to metamorphism suggest that the organic geochemistry may help to evaluate the lowest grades of prograde metamorphism. Copyright (c) 2005 Elsevier Ltd

A molecular isotopic study of 13C-enriched organic matter in evaporitic deposits: Recognition of CO2-limited ecosystems

Biomarkers were analysed in a surface sediment from La Trinitat saltern ponds and a Miocene marl from the Northern Appenines. Both are characterised by enriched 13C values for bulk organic matter and for biomarkers, i.e. heavier than −20 . Exceptions are long-chain C22 C34 n-alkanes and C16 C20 fatty acids which have values typically lighter than −20 , suggesting that they are not derived from aquatic organisms but from surrounding terrestrial vegetation. The enriched 13C values for biomarkers of different algae and bacteria suggest that the local (microbial mat) ecosystem may have been CO2-limited

13C-contents of bacterial lipids in a shallow sulfidic monomictic lake (Lake Ciso, Spain)

Stable carbon isotopic analysis was performed on sedimentary biomarkers of a shallow sulfide-rich monomictic lake, Lake Cisó (NE Spain). Specific biomarkers derived from phototrophic sulfur bacteria in Lake Cisó were considerably depleted in 13C, most likely due to the depleted 13C-content of the dissolved inorganic carbon that was photosynthetically fixed. Recycling of respired CO2, a well-known phenomenon in monomictic lakes, probably caused this depletion. The stable carbon isotopic composition of terrestrial markers, such as C25 33 odd-carbon-numbered n-alkanes and C22 30 even-carbon-numbered n-alkan-1-ols and fatty acids, were rather similar to each other and their 13C depleted values (c. −31 to −35 ) indicated that they were derived from the surrounding vegetation. Phytol was predominantly derived from the bacteriochlorophylls of phototrophic purple sulfur bacteria as were specific fatty acids

Cambios en las concentraciones de compuestos organoclorados en las mujeres de Flix, Tarragona

La población de Flix (comarca de la Ribera del Ebro, Tarragona) se encuentra altamente expuesta a hexaclorobenceno (HCB) debido a la proximidad de una empresa electroquímica. Aunque los niveles de contaminación por HCB en esta población continúan siendo elevados, se ha observado que las concentraciones en sangre venosa de las mujeres de 18-40 años en 1997-1999 fueron un 61% más bajos que en 1994 (4,1 ng/ml frente a 10,6 ng/ml). Las concentraciones de diclorodifenil dicloroetano (p,p'-DDE) y betahexaclorociclohexano (ß-HCH) tambiιn mostraron esta tendencia a la baja, aunque su disminuciσn no fue estadνsticamente significativa. Por el contrario, los niveles de bifenilos policlorados (PCB) en 1997-1999 aumentaron con relaciσn a 1994, aunque la diferencia no fue estadísticamente significativa

13C-contents of bacterial lipids in a shallow sulfidic monomictic lake (Lake Ciso, Spain)

Stable carbon isotopic analysis was performed on sedimentary biomarkers of a shallow sulfide-rich monomictic lake, Lake Cisó (NE Spain). Specific biomarkers derived from phototrophic sulfur bacteria in Lake Cisó were considerably depleted in 13C, most likely due to the depleted 13C-content of the dissolved inorganic carbon that was photosynthetically fixed. Recycling of respired CO2, a well-known phenomenon in monomictic lakes, probably caused this depletion. The stable carbon isotopic composition of terrestrial markers, such as C25 33 odd-carbon-numbered n-alkanes and C22 30 even-carbon-numbered n-alkan-1-ols and fatty acids, were rather similar to each other and their 13C depleted values (c. −31 to −35 ) indicated that they were derived from the surrounding vegetation. Phytol was predominantly derived from the bacteriochlorophylls of phototrophic purple sulfur bacteria as were specific fatty acids