The Atlantic meridional overturning circulation affects the latitudinal distribution of heat, and... more The Atlantic meridional overturning circulation affects the latitudinal distribution of heat, and is a key component of the climate system. Proxy reconstructions, based on sedimentary 231 Pa/ 230 Th ratios and the difference between surface-and deep-water radiocarbon ages, indicate that during the last glacial period, the overturning circulation was reduced during millennial-scale periods of cooling 1–5. However, much debate exists over the robustness of these proxies 6–8. Here we combine proxy reconstructions of sea surface and air temperatures and a global climate model to quantitatively estimate changes in the strength of the Atlantic meridional overturning circulation during the last glacial period. We find that, relative to the Last Glacial Maximum, the overturning circulation was reduced by approximately 14 Sv during the cold Heinrich event 1. During the Younger Dryas cold event, the overturning circulation was reduced by approximately 12 Sv, relative to the preceding warm interval. These changes are consistent with qualitative estimates of the overturning circulation from sedimentary 231 Pa/ 230 Th ratios. In addition, we find that the strength of the overturning circulation during the Last Glacial Maximum and the Holocene epoch are indistinguishable within the uncertainty of the reconstruction. The Atlantic meridional overturning circulation (AMOC) is an important feature of the Earth's climate system. It is characterized by northward-flowing water masses at the surface ocean, deep-water formation in the North Atlantic and southward-flowing water masses in the intermediate to deep ocean. This overturning cell is complemented by an underlying, generally weaker, reversed overturning cell that originates in the Southern Ocean. In the following, we use AMOC to refer only to the upper overturning cell. Owing to the large heat capacity of water, the northward-flowing near-surface waters contribute effectively to the heat transport from the tropics to the mid-and high latitudes and therefore affect the regional climate around the North Atlantic 9,10. Hence, changes of the AMOC strength can substantially influence climate in the north, especially in Europe. The depth of the southward-flowing waters and the strength of the circulation have changed in the past. During the last glacial period, abrupt warming events of several degrees within a few decades followed by slower cooling were detected in Greenland ice cores 11. As effects of the so-called Dansgaard–Oeschger events were found far beyond the Greenland ice sheet 12–14 with patterns reminiscent of varying inter-hemispheric heat distribution 15,16 , they are believed to be the result of rapid changes of the AMOC strength 17. Other examples of a reduction or even a complete shutdown of the
The present study addresses the analysis of changes in marine primary productivity derived from c... more The present study addresses the analysis of changes in marine primary productivity derived from climatic variability over the last 30,000 yr. The study area is the Alboran Sea; this is the westernmost basin of the Mediterranean Sea, and was a very sensitive area to changes in sea levels and atmospheric con®guration during the last glacial±interglacial transition. We report the results from four sediment cores recovered in both the western and eastern Alboran basins. This allowed us to monitor the W±E evolution of the hydrological structures. The study is mainly based on the diatom record, although total organic carbon (TOC), isotopes and UK H 37-SST were also used to gain further information. Paleoceanographic conditions favoured high paleoproductivity rates during the Last Glacial Maximum, although this occurred at Termination 1a and during the Younger Dryas event (YD), increasing towards the easternmost sites. During these periods, meteorological conditions, with increased westerlies, intensi®ed the¯ow to the east, driving an eastward migration of the Western Anticyclonic Gyre. A possible displacement of the North Alboran upwelling system is also considered. The major component of the diatom assemblage during the YD are the resting spores of Leptocylindrus danicus, which suggest the presence of cooler and less saline surface waters. The opposite behaviour between planktonic and benthic proxies in addition to the high TOC values allows us to infer a phase of reduced deep water renewal between 16.5 and 9 cal ky BP. Fresh-water diatoms and opal phytoliths were used as indicators of aridity and humid land-conditions, respectively. During the glacial period and until 14 cal ky BP we observed a gradual climatic deterioration, accompanied by a loss of grass belts. Climatic conditions were warmer and moister during the Bùlling±Allerùd while the YD was dry. The re-establishment of vegetation belts and replenishment of lakes was observed at 8 cal ky BP. q
ABSTRACT High-resolution proxy data analyzed on two high-sedimentation shallow water sedimentary ... more ABSTRACT High-resolution proxy data analyzed on two high-sedimentation shallow water sedimentary sequences (PO287-26B and PO287-28B) recovered off Lisbon (Portugal) provide the means for comparison to long-term instrumental time series of marine and atmospheric parameters (sea surface temperature (SST), precipitation, total river flow, and upwelling intensity computed from sea level pressure) and the possibility to do the necessary calibration for the quantification of past climate conditions. XRF Fe is used as proxy for river flow, and the upwelling-related diatom genus Chaetoceros is our upwelling proxy. SST is estimated from the coccolithophore-synthesized alkenones and U37 k' index. Comparison of the Fe record to the instrumental data reveals its similarity to a mean average run of the instrumentally measured winter (JFMA) river flow on both sites. The upwelling diatom record concurs with the upwelling indices at both sites; however, high opal dissolution, below 20-25 cm, prevents its use for quantitative reconstructions. Alkenone-derived SST at site 28B does not show interannual variation; it has a mean value around 16°C and compares quite well with the instrumental winter/spring temperature. At site 26B the mean SST is the same, but a high degree of interannual variability (up to 4°C) appears to be determined by summer upwelling conditions. Stepwise regression analyses of the instrumental and proxy data sets provided regressions that explain from 65 to 94% of the variability contained in the original data, and reflect spring and summer river flow, as well as summer and winter upwelling indices, substantiating the relevance of seasons to the interpretation of the different proxy signals. The lack of analogs and the small data set available do not allow quantitative reconstructions at this time, but this might be a powerful tool for reconstructing past North Atlantic Oscillation conditions, should we be able to find continuous high-resolution records and overcome the analog problem.
Twenty century time-resolved variability of riverine deposits of polychlorobiphenyls (PCBs), DDTs... more Twenty century time-resolved variability of riverine deposits of polychlorobiphenyls (PCBs), DDTs, hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB) was studied in three (210)Pb dated sediment cores collected in a depositional shelf area adjacent to the Tagus estuary (the Tagus Prodelta). The geographic and temporal distribution patterns were consistent with discharge of these organochlorine compounds (OCs) in the area associated with the Tagus mouth. Their concentrations were not correlated with the sedimentary total organic carbon. The PCB down-core profiles were dominated by CB138 and CB153 (hexa-CBs) congeners followed by CB180 (hepta-CBs). Principal Component Analysis of the congener distributions of these compounds did not define temporal down-core trends. The ratios of DDT metabolites (p,p'-DDE/p,p'-DDT) were consistent with recent DDT inputs into the environment and/or earlier applications and long-term residence in soils/sediments until these were eroded and remobilized.
Sea Surface Temperature (SST), river discharge and biological productivity have been reconstructe... more Sea Surface Temperature (SST), river discharge and biological productivity have been reconstructed from a multi-proxy study of a high-temporal-resolution sedimentary sequence recovered from the Tagus deposition center off Lisbon (Portugal) for the last 2000 years. ...
The Ocean Anoxic Event 1 (OAE-1) in central sites of the Basque-Cantabrian Basin exhibits very re... more The Ocean Anoxic Event 1 (OAE-1) in central sites of the Basque-Cantabrian Basin exhibits very reducing depositional conditions of sedimentation. These sedimentation events have left a distinct mixture of hydrocarbons that are represented by C22-C30 n-alkanes with a predominance of the even-carbon-number homologues, high relative proportions of squalane and C16-C24 n-alkylcyclopentanes predominated by n-undecyl-, n-tridecyl- and n-pentadecylcyclopentane. Other minor compounds encompass a series of C18-C21 n-alkylcyclohexanes and C18-C24 dimethyl n-alkylcyclohexanes maximized by the even-carbon-number homologues as well as iso- and anteiso-alkanes. This unusual distribution of n-alkanes in this environment provides a new case for comparison with previously reported hypersaline and phosphorite sedimentary deposits where the occurrence of similar n-alkane distributions was reported. In the present case, these major n-alkanes and squalane are indicative of transformation under strong reducing conditions. In contrast, the occurrence of the alkylcyclopentanes, irrespective of the presence of even-carbon-number n-alkanes or squalane, suggests that reductive cyclization of fatty acids is less dependent on strong reducing conditions.
Cytochrome p450 1A (CYP1A) gene expression in fish liver increases upon exposure to a variety of ... more Cytochrome p450 1A (CYP1A) gene expression in fish liver increases upon exposure to a variety of chemical compounds, including organochlorine compounds (OCs) and polycyclic aromatic hydrocarbons (PAHs). To use this physiological response as a marker of environmental impact, we developed and validated a set of primers to quantify CYP1A expression by qRT-PCR in the brown trout, Salmo trutta. These primers were used to explore the natural variability of CYP1A expression in 8 isolated populations (65 samples) from European remote lakes, in a geographical distribution encompassing the Tyrolean Alps, Pyrenees, Rila, Tatras, and Norwegian and Scottish mountains. CYP1A expression values varied more than 2 orders of magnitude among samples, with strong variations within each population. CYP1A expression values were significantly elevated in Tatras and Pyrenees fish populations, whereas the lowest median values were found in populations from the Tyrolean Alps and Rila. These values correlated with the content of different environmentally relevant pollutants in the sediments of the lakes harboring each fish population, particularly with HCB and 4,4′-DDE contents. To our knowledge, this works represents a first report of a physiological response linked to persistent organic pollutants in fish from mountain lakes.
Aim: To determine whether prenatal exposure to hexachlorobenzene (HCB) has potential adverse effe... more Aim: To determine whether prenatal exposure to hexachlorobenzene (HCB) has potential adverse effects on child's weight and body mass index (BMI) in a general population with no local pollution sources.
A comparison of the performances of ammonia and methane as reagent gases for the analysis of trac... more A comparison of the performances of ammonia and methane as reagent gases for the analysis of trace organochlorine compounds by gas chromatography coupled to negative-ion chemical ionization mass spectrometry is performed in the present study. Examples of standard mixtures and human blood samples analyzed with both reagents in scan and selected-ion monitoring mode are shown. Important advantages are observed as a consequence of the use of ammonia. These concern detection and quantitation limits and the lower dependence of sensitivity on the degree of chlorine substitution of the compounds.
The enantiomeric fractions present in soil samples may provide information useful in distinguishi... more The enantiomeric fractions present in soil samples may provide information useful in distinguishing recent inputs of DDT from past DDT pollution. In this study, a chromatographic procedure for the determination of the enantiomeric fractions of o,p -DDT based on heart-cutting multidimensional gas chromatography was developed. The optimization carried out achieved low ratios of DDT degradation (<15%) in the chromatographic system. High selectivity and sensitivity in the detection of the target compounds, with a limit of detection as low as 2.1 pg L −1 , was reached. In addition, high degrees of repeatability (RSD < 2.0%) and reproducibility (RSD < 3.2%) were obtained for the enantiomeric fractions measured in analytical standards and soil samples.
Several studies have shown that some organochlorine compounds (OCs) can interfere with the thyroi... more Several studies have shown that some organochlorine compounds (OCs) can interfere with the thyroid system. As thyroid hormones (THs) are essential for normal brain development, it is important to study the association between THs and OCs during pregnancy and childhood. We have evaluated the relationship between thyroid function and OCs in preschool children. Children from a general population birth cohort in Menorca (n = 259), Spain were assessed at the age of 4 years. Concentrations of THs (free T4 and total T3), thyrotropin (TSH) and a range of OCs were measured in peripheral blood. Blood levels of dichlorodiphenyl trichloroethane (p,p&amp;amp;#39;-DDT), beta-hexachlorocylcohexane (beta-HCH), polychlorinated biphenyls (congeners PCB-138, PCB-153 and PCB-118) were related to lower total T3 levels (p&amp;amp;lt;0.05). In addition, free T4 was inversely associated with PCB-118, while no relationship was found between TSH and any of the measured OCs. This study suggests that even at background levels of exposure, OCs may affect the thyroid system, particularly total T3 levels.
BACKGROUND: Hexachlorobenzene (HCB) and other organochlorines induce porphyria cutanea tarda (PCT... more BACKGROUND: Hexachlorobenzene (HCB) and other organochlorines induce porphyria cutanea tarda (PCT) in animal studies. Evidence in humans, however, is contradictory. In neonates and adults from a population historically highly exposed to HCB (Flix, Catalonia, Spain), no relation with PCT or with porphyrin excretion was found. OBJECTIVES: We aimed to analyze the association between urinary porphyrin excretion and exposure to HCB and other organochlorinated compounds in children 4 years of age. METHODS: Our birth cohort included all newborns from Flix and the five surrounding towns (where no airborne pollution occurred). Among the 68 children with porphyrins we measured in cord blood, 52 children 4 years of age provided blood to measure organochlorine compounds, hair for methylmercury, and urine for porphyrin excretion pattern. . We found no association with methylmercury. When we fitted multiple pollutant models, p,p´-DDE had the strongest association. We found these associations in children from both Flix and other towns, and they were independent of breast-feeding and of organochlorine and porphyrin levels at birth. CONCLUSION: HCB at current levels did not induce porphyria or increase uroporphyrins. However, the increase of urinary coproporphyrins suggests an incipient toxic effect of the organochlorines, especially for p,p´-DDE, on the hepatic heme-synthesis pathway that differs from the major effects seen in PCT.
Persistent organic pollutants (POPs) comprise a large variety of toxic substances with ample dist... more Persistent organic pollutants (POPs) comprise a large variety of toxic substances with ample distribution. While exposure to these toxins occurs mainly through diet, maternal POP levels may be influenced by certain sociodemographic, environmental, or lifestyle factors. This is important given that these substances may have adverse effects on fetal development. The aim of this study is to examine the sociodemographic, environmental, lifestyle, and dietary determinants of the levels of hexachlorobenzene (HCB), b-hexachlorocyclohexane (b-HCH), 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (4,4&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;-DDT), 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (4,4&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;-DDE), and polychlorinated biphenyls (PCB congeners 118, 138, 153, 180) measured in the blood of pregnant women participating in a mother-child cohort study conducted in Valencia (Spain). The study population consisted of 541 pregnant women who formed part of the INMA (Childhood and the Environment) cohort (2004-2006). POP levels were determined in blood taken during the 12th week of pregnancy with the aid of gas chromatography with electron capture detection. Sociodemographic, environmental, and dietary information was obtained from a questionnaire. Multivariate Tobit regression models were constructed in order to assess the association between POP levels and selected covariates. The results showed that all the women had detectable levels of at least one of these compounds while in 43% of the subjects, all eight compounds were detected. The compounds found in the greatest number of women were 4,4&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;-DDE (100%) and PCBs 153 and 180 (95%). The most important determinants of high POP levels were the mother&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;s age, country of origin, increased body mass index, and number of weeks of breastfeeding after previous pregnancies. With regard to diet, 4,4&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;-DDT and 4,4&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;-DDE levels increased with the intake of meat, fruit, and cereal. PCB 153 levels increased with the intake of seafood. The levels of HCB, b-HCH, 4,4&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;-DDT, and 4,4&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;-DDE observed in this study were slightly higher than in other studies, whereas the PCB levels were similar.
Several microcosm experiments were run in parallel to evaluate the efficiency of microbial mats f... more Several microcosm experiments were run in parallel to evaluate the efficiency of microbial mats for crude oil degradation as compared with physico-chemical weathering. The oils used in the experiments constituted representative examples of those currently used for commercial purposes. One was aliphatic and of low viscosity (33.4 American Petroleum Institute degrees, 8 API) and the other was predominantly aromatic, with high sulphur content (ca. 2.7%) and viscosity (16.68 API). After crude oil introduction, the microcosms were kept under cyclic changes in water level to mimic coastal tidal movements.
. Some applications in the use of compound-specific isotopic analyses CSIA for biomarker source e... more . Some applications in the use of compound-specific isotopic analyses CSIA for biomarker source elucidation in the marine environment and its potential applications to paleoclimatology are evaluated in the present study. The potential use of the carbon isotope ratios of marine biomarkers as recorders of CO levels has been considered. A 2 significant correlation between ␦ 13 C cholesterol of suspended particulates and seawater CO concentrations from the 2 south Indian Ocean has been found. ␦ 13 C composition in biomarkers of different functionalities from three photosynthetic organisms has been examined. Small variations within and between biosynthetically related compound classes have been observed in cyanobacteria. In algae, e.g. diatoms and dinoflagellates, significant differences 13 Ž . between the average ␦ C composition of fatty acids and sterols were observed 7.5‰ and 2‰, respectively . These differences can be attributed to diverse isotope effects associated with different biosynthetic reactions. Isotopic variations among homologues of the same lipid class have also been observed. In diatoms, variations were up to 5‰ within each class of fatty acids and sterols and in the dinoflagellate species, these variations were lower than 3‰. U Corresponding author. Tel.: q377-97977241; fax: q377-97977276. Ž . E-mail address: [email protected] I. Tolosa 1 Ž . Present address: Institut des Sciences de l'Evolution UMR CNRS 5554 Universite Montpellier II ᎏ pl. E. Bataillon, case postalé 64, 34095 Montpellier cedex 05, France. 0048-9697r99r$ -see front matter ᮊ 1999 Elsevier Science B.V. All rights reserved. Ž . PII: S 0 0 4 8 -9 6 9 7 9 9 0 0 1 5 9 -X ( ) I. Tolosa et al. r The Science of the Total En¨ironment 237 r 238 1999 473᎐481 474
Massive amounts of acidic waters and mud (pH approximately 3) containing toxic metals such as zin... more Massive amounts of acidic waters and mud (pH approximately 3) containing toxic metals such as zinc, lead, arsenic, copper, antimony, cobalt, thallium, bismuth, cadmium, silver, mercury and selenium were released in the surroundings of Doñana Park as a consequence of the mine tailings spill accident in Aznalcollar (SW Spain). This introductory paper describes the main characteristics of Doñana Park, the mine activities developed in Aznalcollar and their related environmental risks. The tailing spill accident and the first package of urgent actions undertaken for preventive and mitigation purposes are also summarized.
. The dissolved-particulate phase distribution of polychlorobiphenyls PCBs in the waters of a hig... more . The dissolved-particulate phase distribution of polychlorobiphenyls PCBs in the waters of a high mountain lake Ž . Redo Lake, Pyrenees has been studied. The lake is oligotrophic and its water hydrology is dominated bý atmospheric precipitation; inputs from catchment or other sources are not significant. Samples were collected in several periods encompassing the summer and winter seasons. The PCB congener concentrations were rather uniform both in terms of water depth and seasonality showing steady state conditions. Seventy percent of the Ž . variation of the PCB particulate-dissolved phase coefficient K was correlated with temperature and log d Ž . octanol᎐water K . Lower temperatures and hydrophobicity involved a higher association with the particulate ow phase. This behavior is consistent with the predominance of plankton among suspended particles following a two compartment model. Thus, temperature dependence seems mainly related to a rapid phase transfer mechanism such as surface adsorption to the cell membranes and log K influence could reflect steric restrictions for the uptake of ow these compounds upon algal ingestion. ᮊ
A consortium of microorganisms with the capacity to degrade crude oil has been characterized by m... more A consortium of microorganisms with the capacity to degrade crude oil has been characterized by means of confocal laser scanning microscopy (CLSM), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The analysis using CLSM shows that Microcoleus chthonoplastes is the dominant organism in the consortium. This cyanobacterium forms long filaments that group together in bundles inside a mucopolysaccharide sheath. Scanning electron microscopy and transmission electron microscopy have allowed us to demonstrate that this cyanobacterium forms a consortium primarily with three morphotypes of the heterotrophic microorganisms found in the Microcoleus chthonoplastes sheath. The optimal growth of Microcoleus consortium was obtained in presence of light and crude oil, and under anaerobic conditions. When grown in agar plate, only one type of colony (green and filamentous) was observed.
The Atlantic meridional overturning circulation affects the latitudinal distribution of heat, and... more The Atlantic meridional overturning circulation affects the latitudinal distribution of heat, and is a key component of the climate system. Proxy reconstructions, based on sedimentary 231 Pa/ 230 Th ratios and the difference between surface-and deep-water radiocarbon ages, indicate that during the last glacial period, the overturning circulation was reduced during millennial-scale periods of cooling 1–5. However, much debate exists over the robustness of these proxies 6–8. Here we combine proxy reconstructions of sea surface and air temperatures and a global climate model to quantitatively estimate changes in the strength of the Atlantic meridional overturning circulation during the last glacial period. We find that, relative to the Last Glacial Maximum, the overturning circulation was reduced by approximately 14 Sv during the cold Heinrich event 1. During the Younger Dryas cold event, the overturning circulation was reduced by approximately 12 Sv, relative to the preceding warm interval. These changes are consistent with qualitative estimates of the overturning circulation from sedimentary 231 Pa/ 230 Th ratios. In addition, we find that the strength of the overturning circulation during the Last Glacial Maximum and the Holocene epoch are indistinguishable within the uncertainty of the reconstruction. The Atlantic meridional overturning circulation (AMOC) is an important feature of the Earth's climate system. It is characterized by northward-flowing water masses at the surface ocean, deep-water formation in the North Atlantic and southward-flowing water masses in the intermediate to deep ocean. This overturning cell is complemented by an underlying, generally weaker, reversed overturning cell that originates in the Southern Ocean. In the following, we use AMOC to refer only to the upper overturning cell. Owing to the large heat capacity of water, the northward-flowing near-surface waters contribute effectively to the heat transport from the tropics to the mid-and high latitudes and therefore affect the regional climate around the North Atlantic 9,10. Hence, changes of the AMOC strength can substantially influence climate in the north, especially in Europe. The depth of the southward-flowing waters and the strength of the circulation have changed in the past. During the last glacial period, abrupt warming events of several degrees within a few decades followed by slower cooling were detected in Greenland ice cores 11. As effects of the so-called Dansgaard–Oeschger events were found far beyond the Greenland ice sheet 12–14 with patterns reminiscent of varying inter-hemispheric heat distribution 15,16 , they are believed to be the result of rapid changes of the AMOC strength 17. Other examples of a reduction or even a complete shutdown of the
The present study addresses the analysis of changes in marine primary productivity derived from c... more The present study addresses the analysis of changes in marine primary productivity derived from climatic variability over the last 30,000 yr. The study area is the Alboran Sea; this is the westernmost basin of the Mediterranean Sea, and was a very sensitive area to changes in sea levels and atmospheric con®guration during the last glacial±interglacial transition. We report the results from four sediment cores recovered in both the western and eastern Alboran basins. This allowed us to monitor the W±E evolution of the hydrological structures. The study is mainly based on the diatom record, although total organic carbon (TOC), isotopes and UK H 37-SST were also used to gain further information. Paleoceanographic conditions favoured high paleoproductivity rates during the Last Glacial Maximum, although this occurred at Termination 1a and during the Younger Dryas event (YD), increasing towards the easternmost sites. During these periods, meteorological conditions, with increased westerlies, intensi®ed the¯ow to the east, driving an eastward migration of the Western Anticyclonic Gyre. A possible displacement of the North Alboran upwelling system is also considered. The major component of the diatom assemblage during the YD are the resting spores of Leptocylindrus danicus, which suggest the presence of cooler and less saline surface waters. The opposite behaviour between planktonic and benthic proxies in addition to the high TOC values allows us to infer a phase of reduced deep water renewal between 16.5 and 9 cal ky BP. Fresh-water diatoms and opal phytoliths were used as indicators of aridity and humid land-conditions, respectively. During the glacial period and until 14 cal ky BP we observed a gradual climatic deterioration, accompanied by a loss of grass belts. Climatic conditions were warmer and moister during the Bùlling±Allerùd while the YD was dry. The re-establishment of vegetation belts and replenishment of lakes was observed at 8 cal ky BP. q
ABSTRACT High-resolution proxy data analyzed on two high-sedimentation shallow water sedimentary ... more ABSTRACT High-resolution proxy data analyzed on two high-sedimentation shallow water sedimentary sequences (PO287-26B and PO287-28B) recovered off Lisbon (Portugal) provide the means for comparison to long-term instrumental time series of marine and atmospheric parameters (sea surface temperature (SST), precipitation, total river flow, and upwelling intensity computed from sea level pressure) and the possibility to do the necessary calibration for the quantification of past climate conditions. XRF Fe is used as proxy for river flow, and the upwelling-related diatom genus Chaetoceros is our upwelling proxy. SST is estimated from the coccolithophore-synthesized alkenones and U37 k&#39; index. Comparison of the Fe record to the instrumental data reveals its similarity to a mean average run of the instrumentally measured winter (JFMA) river flow on both sites. The upwelling diatom record concurs with the upwelling indices at both sites; however, high opal dissolution, below 20-25 cm, prevents its use for quantitative reconstructions. Alkenone-derived SST at site 28B does not show interannual variation; it has a mean value around 16°C and compares quite well with the instrumental winter/spring temperature. At site 26B the mean SST is the same, but a high degree of interannual variability (up to 4°C) appears to be determined by summer upwelling conditions. Stepwise regression analyses of the instrumental and proxy data sets provided regressions that explain from 65 to 94% of the variability contained in the original data, and reflect spring and summer river flow, as well as summer and winter upwelling indices, substantiating the relevance of seasons to the interpretation of the different proxy signals. The lack of analogs and the small data set available do not allow quantitative reconstructions at this time, but this might be a powerful tool for reconstructing past North Atlantic Oscillation conditions, should we be able to find continuous high-resolution records and overcome the analog problem.
Twenty century time-resolved variability of riverine deposits of polychlorobiphenyls (PCBs), DDTs... more Twenty century time-resolved variability of riverine deposits of polychlorobiphenyls (PCBs), DDTs, hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB) was studied in three (210)Pb dated sediment cores collected in a depositional shelf area adjacent to the Tagus estuary (the Tagus Prodelta). The geographic and temporal distribution patterns were consistent with discharge of these organochlorine compounds (OCs) in the area associated with the Tagus mouth. Their concentrations were not correlated with the sedimentary total organic carbon. The PCB down-core profiles were dominated by CB138 and CB153 (hexa-CBs) congeners followed by CB180 (hepta-CBs). Principal Component Analysis of the congener distributions of these compounds did not define temporal down-core trends. The ratios of DDT metabolites (p,p&amp;amp;#39;-DDE/p,p&amp;amp;#39;-DDT) were consistent with recent DDT inputs into the environment and/or earlier applications and long-term residence in soils/sediments until these were eroded and remobilized.
Sea Surface Temperature (SST), river discharge and biological productivity have been reconstructe... more Sea Surface Temperature (SST), river discharge and biological productivity have been reconstructed from a multi-proxy study of a high-temporal-resolution sedimentary sequence recovered from the Tagus deposition center off Lisbon (Portugal) for the last 2000 years. ...
The Ocean Anoxic Event 1 (OAE-1) in central sites of the Basque-Cantabrian Basin exhibits very re... more The Ocean Anoxic Event 1 (OAE-1) in central sites of the Basque-Cantabrian Basin exhibits very reducing depositional conditions of sedimentation. These sedimentation events have left a distinct mixture of hydrocarbons that are represented by C22-C30 n-alkanes with a predominance of the even-carbon-number homologues, high relative proportions of squalane and C16-C24 n-alkylcyclopentanes predominated by n-undecyl-, n-tridecyl- and n-pentadecylcyclopentane. Other minor compounds encompass a series of C18-C21 n-alkylcyclohexanes and C18-C24 dimethyl n-alkylcyclohexanes maximized by the even-carbon-number homologues as well as iso- and anteiso-alkanes. This unusual distribution of n-alkanes in this environment provides a new case for comparison with previously reported hypersaline and phosphorite sedimentary deposits where the occurrence of similar n-alkane distributions was reported. In the present case, these major n-alkanes and squalane are indicative of transformation under strong reducing conditions. In contrast, the occurrence of the alkylcyclopentanes, irrespective of the presence of even-carbon-number n-alkanes or squalane, suggests that reductive cyclization of fatty acids is less dependent on strong reducing conditions.
Cytochrome p450 1A (CYP1A) gene expression in fish liver increases upon exposure to a variety of ... more Cytochrome p450 1A (CYP1A) gene expression in fish liver increases upon exposure to a variety of chemical compounds, including organochlorine compounds (OCs) and polycyclic aromatic hydrocarbons (PAHs). To use this physiological response as a marker of environmental impact, we developed and validated a set of primers to quantify CYP1A expression by qRT-PCR in the brown trout, Salmo trutta. These primers were used to explore the natural variability of CYP1A expression in 8 isolated populations (65 samples) from European remote lakes, in a geographical distribution encompassing the Tyrolean Alps, Pyrenees, Rila, Tatras, and Norwegian and Scottish mountains. CYP1A expression values varied more than 2 orders of magnitude among samples, with strong variations within each population. CYP1A expression values were significantly elevated in Tatras and Pyrenees fish populations, whereas the lowest median values were found in populations from the Tyrolean Alps and Rila. These values correlated with the content of different environmentally relevant pollutants in the sediments of the lakes harboring each fish population, particularly with HCB and 4,4′-DDE contents. To our knowledge, this works represents a first report of a physiological response linked to persistent organic pollutants in fish from mountain lakes.
Aim: To determine whether prenatal exposure to hexachlorobenzene (HCB) has potential adverse effe... more Aim: To determine whether prenatal exposure to hexachlorobenzene (HCB) has potential adverse effects on child's weight and body mass index (BMI) in a general population with no local pollution sources.
A comparison of the performances of ammonia and methane as reagent gases for the analysis of trac... more A comparison of the performances of ammonia and methane as reagent gases for the analysis of trace organochlorine compounds by gas chromatography coupled to negative-ion chemical ionization mass spectrometry is performed in the present study. Examples of standard mixtures and human blood samples analyzed with both reagents in scan and selected-ion monitoring mode are shown. Important advantages are observed as a consequence of the use of ammonia. These concern detection and quantitation limits and the lower dependence of sensitivity on the degree of chlorine substitution of the compounds.
The enantiomeric fractions present in soil samples may provide information useful in distinguishi... more The enantiomeric fractions present in soil samples may provide information useful in distinguishing recent inputs of DDT from past DDT pollution. In this study, a chromatographic procedure for the determination of the enantiomeric fractions of o,p -DDT based on heart-cutting multidimensional gas chromatography was developed. The optimization carried out achieved low ratios of DDT degradation (<15%) in the chromatographic system. High selectivity and sensitivity in the detection of the target compounds, with a limit of detection as low as 2.1 pg L −1 , was reached. In addition, high degrees of repeatability (RSD < 2.0%) and reproducibility (RSD < 3.2%) were obtained for the enantiomeric fractions measured in analytical standards and soil samples.
Several studies have shown that some organochlorine compounds (OCs) can interfere with the thyroi... more Several studies have shown that some organochlorine compounds (OCs) can interfere with the thyroid system. As thyroid hormones (THs) are essential for normal brain development, it is important to study the association between THs and OCs during pregnancy and childhood. We have evaluated the relationship between thyroid function and OCs in preschool children. Children from a general population birth cohort in Menorca (n = 259), Spain were assessed at the age of 4 years. Concentrations of THs (free T4 and total T3), thyrotropin (TSH) and a range of OCs were measured in peripheral blood. Blood levels of dichlorodiphenyl trichloroethane (p,p&amp;amp;#39;-DDT), beta-hexachlorocylcohexane (beta-HCH), polychlorinated biphenyls (congeners PCB-138, PCB-153 and PCB-118) were related to lower total T3 levels (p&amp;amp;lt;0.05). In addition, free T4 was inversely associated with PCB-118, while no relationship was found between TSH and any of the measured OCs. This study suggests that even at background levels of exposure, OCs may affect the thyroid system, particularly total T3 levels.
BACKGROUND: Hexachlorobenzene (HCB) and other organochlorines induce porphyria cutanea tarda (PCT... more BACKGROUND: Hexachlorobenzene (HCB) and other organochlorines induce porphyria cutanea tarda (PCT) in animal studies. Evidence in humans, however, is contradictory. In neonates and adults from a population historically highly exposed to HCB (Flix, Catalonia, Spain), no relation with PCT or with porphyrin excretion was found. OBJECTIVES: We aimed to analyze the association between urinary porphyrin excretion and exposure to HCB and other organochlorinated compounds in children 4 years of age. METHODS: Our birth cohort included all newborns from Flix and the five surrounding towns (where no airborne pollution occurred). Among the 68 children with porphyrins we measured in cord blood, 52 children 4 years of age provided blood to measure organochlorine compounds, hair for methylmercury, and urine for porphyrin excretion pattern. . We found no association with methylmercury. When we fitted multiple pollutant models, p,p´-DDE had the strongest association. We found these associations in children from both Flix and other towns, and they were independent of breast-feeding and of organochlorine and porphyrin levels at birth. CONCLUSION: HCB at current levels did not induce porphyria or increase uroporphyrins. However, the increase of urinary coproporphyrins suggests an incipient toxic effect of the organochlorines, especially for p,p´-DDE, on the hepatic heme-synthesis pathway that differs from the major effects seen in PCT.
Persistent organic pollutants (POPs) comprise a large variety of toxic substances with ample dist... more Persistent organic pollutants (POPs) comprise a large variety of toxic substances with ample distribution. While exposure to these toxins occurs mainly through diet, maternal POP levels may be influenced by certain sociodemographic, environmental, or lifestyle factors. This is important given that these substances may have adverse effects on fetal development. The aim of this study is to examine the sociodemographic, environmental, lifestyle, and dietary determinants of the levels of hexachlorobenzene (HCB), b-hexachlorocyclohexane (b-HCH), 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (4,4&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;-DDT), 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (4,4&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;-DDE), and polychlorinated biphenyls (PCB congeners 118, 138, 153, 180) measured in the blood of pregnant women participating in a mother-child cohort study conducted in Valencia (Spain). The study population consisted of 541 pregnant women who formed part of the INMA (Childhood and the Environment) cohort (2004-2006). POP levels were determined in blood taken during the 12th week of pregnancy with the aid of gas chromatography with electron capture detection. Sociodemographic, environmental, and dietary information was obtained from a questionnaire. Multivariate Tobit regression models were constructed in order to assess the association between POP levels and selected covariates. The results showed that all the women had detectable levels of at least one of these compounds while in 43% of the subjects, all eight compounds were detected. The compounds found in the greatest number of women were 4,4&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;-DDE (100%) and PCBs 153 and 180 (95%). The most important determinants of high POP levels were the mother&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;s age, country of origin, increased body mass index, and number of weeks of breastfeeding after previous pregnancies. With regard to diet, 4,4&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;-DDT and 4,4&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;-DDE levels increased with the intake of meat, fruit, and cereal. PCB 153 levels increased with the intake of seafood. The levels of HCB, b-HCH, 4,4&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;-DDT, and 4,4&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39;-DDE observed in this study were slightly higher than in other studies, whereas the PCB levels were similar.
Several microcosm experiments were run in parallel to evaluate the efficiency of microbial mats f... more Several microcosm experiments were run in parallel to evaluate the efficiency of microbial mats for crude oil degradation as compared with physico-chemical weathering. The oils used in the experiments constituted representative examples of those currently used for commercial purposes. One was aliphatic and of low viscosity (33.4 American Petroleum Institute degrees, 8 API) and the other was predominantly aromatic, with high sulphur content (ca. 2.7%) and viscosity (16.68 API). After crude oil introduction, the microcosms were kept under cyclic changes in water level to mimic coastal tidal movements.
. Some applications in the use of compound-specific isotopic analyses CSIA for biomarker source e... more . Some applications in the use of compound-specific isotopic analyses CSIA for biomarker source elucidation in the marine environment and its potential applications to paleoclimatology are evaluated in the present study. The potential use of the carbon isotope ratios of marine biomarkers as recorders of CO levels has been considered. A 2 significant correlation between ␦ 13 C cholesterol of suspended particulates and seawater CO concentrations from the 2 south Indian Ocean has been found. ␦ 13 C composition in biomarkers of different functionalities from three photosynthetic organisms has been examined. Small variations within and between biosynthetically related compound classes have been observed in cyanobacteria. In algae, e.g. diatoms and dinoflagellates, significant differences 13 Ž . between the average ␦ C composition of fatty acids and sterols were observed 7.5‰ and 2‰, respectively . These differences can be attributed to diverse isotope effects associated with different biosynthetic reactions. Isotopic variations among homologues of the same lipid class have also been observed. In diatoms, variations were up to 5‰ within each class of fatty acids and sterols and in the dinoflagellate species, these variations were lower than 3‰. U Corresponding author. Tel.: q377-97977241; fax: q377-97977276. Ž . E-mail address: [email protected] I. Tolosa 1 Ž . Present address: Institut des Sciences de l'Evolution UMR CNRS 5554 Universite Montpellier II ᎏ pl. E. Bataillon, case postalé 64, 34095 Montpellier cedex 05, France. 0048-9697r99r$ -see front matter ᮊ 1999 Elsevier Science B.V. All rights reserved. Ž . PII: S 0 0 4 8 -9 6 9 7 9 9 0 0 1 5 9 -X ( ) I. Tolosa et al. r The Science of the Total En¨ironment 237 r 238 1999 473᎐481 474
Massive amounts of acidic waters and mud (pH approximately 3) containing toxic metals such as zin... more Massive amounts of acidic waters and mud (pH approximately 3) containing toxic metals such as zinc, lead, arsenic, copper, antimony, cobalt, thallium, bismuth, cadmium, silver, mercury and selenium were released in the surroundings of Doñana Park as a consequence of the mine tailings spill accident in Aznalcollar (SW Spain). This introductory paper describes the main characteristics of Doñana Park, the mine activities developed in Aznalcollar and their related environmental risks. The tailing spill accident and the first package of urgent actions undertaken for preventive and mitigation purposes are also summarized.
. The dissolved-particulate phase distribution of polychlorobiphenyls PCBs in the waters of a hig... more . The dissolved-particulate phase distribution of polychlorobiphenyls PCBs in the waters of a high mountain lake Ž . Redo Lake, Pyrenees has been studied. The lake is oligotrophic and its water hydrology is dominated bý atmospheric precipitation; inputs from catchment or other sources are not significant. Samples were collected in several periods encompassing the summer and winter seasons. The PCB congener concentrations were rather uniform both in terms of water depth and seasonality showing steady state conditions. Seventy percent of the Ž . variation of the PCB particulate-dissolved phase coefficient K was correlated with temperature and log d Ž . octanol᎐water K . Lower temperatures and hydrophobicity involved a higher association with the particulate ow phase. This behavior is consistent with the predominance of plankton among suspended particles following a two compartment model. Thus, temperature dependence seems mainly related to a rapid phase transfer mechanism such as surface adsorption to the cell membranes and log K influence could reflect steric restrictions for the uptake of ow these compounds upon algal ingestion. ᮊ
A consortium of microorganisms with the capacity to degrade crude oil has been characterized by m... more A consortium of microorganisms with the capacity to degrade crude oil has been characterized by means of confocal laser scanning microscopy (CLSM), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The analysis using CLSM shows that Microcoleus chthonoplastes is the dominant organism in the consortium. This cyanobacterium forms long filaments that group together in bundles inside a mucopolysaccharide sheath. Scanning electron microscopy and transmission electron microscopy have allowed us to demonstrate that this cyanobacterium forms a consortium primarily with three morphotypes of the heterotrophic microorganisms found in the Microcoleus chthonoplastes sheath. The optimal growth of Microcoleus consortium was obtained in presence of light and crude oil, and under anaerobic conditions. When grown in agar plate, only one type of colony (green and filamentous) was observed.
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