Imposex levels and concentrations of organotin compounds (TBT and its metabolites) in Nassarius nitidus from the Lagoon of Venice

Specimens of Nassarius nitidus were collected in seven stations of the Venice Lagoon to assess the levels of tributyltin (TBT) and its metabolites monobutyltin and dibutyltin in the tissues and monitor their effect on organisms, in particular the phenomenon of imposex (superimposition of male sexual characteristics on females). The following values of population indices were found: vas deferens sequence: 1.2 ± 0.7–4.0 ± 0.5; relative penis length: 6–47%. The least impacted station was situated in the northern part of the Lagoon, where females without imposex were found and Butyltin (BuTs) concentrations in the organisms (average sum of BuTs = 43 ± 14 ng Sn g⁻¹ w.) were significantly lower than in the other stations (range of average sum of BuTs: 101 ± 22–217 ± 27 ng Sn g⁻¹ d.w.). Population indices were found to be related to the TBT content in the tissues. In particular VDSI had a significant logarithmic correlation: r = 0.95, n = 8, p < 0.05.     

Long-term temporal trends (1992–2008) of imposex status associated with organotin contamination in the dogwhelk Nucella lapillus along the Icelandic coast

Using the dogwhelk Nucella lapillus as a biomonitor, we evaluated the organotin contamination along the Icelandic coast over nearly two decades. In 2008, adult dogwhelks collected from 30 locations were examined for imposex status. In 2009, tissue concentrations of six organotin species in dogwhelks from 16 of the 30 locations were analysed using gas chromatography–mass spectrometry. Tributyltin was the most predominant residue ranging from 2.07 to 70.38 μg kg⁻¹ dw, while triphenyltin was also detected at concentrations up to 22.79 μg kg⁻¹ dw. Higher total organotin concentrations and imposex indices were observed at locations near large harbours (Reykjavík and Hafnarfjörður). By comparing the current imposex results with those of previous surveys (1992–2003), we found that recovery was slow near the large harbours, but more apparent near the smaller harbours. We also observed a notable increase in imposex at several northwest sites implying incessant input of organotins.     

Assessment of tributyltin contamination in a shipyard area using a mussel transplantation approach

Mussels (Mytilus galloprovincialis) were transplanted to seven stations around a large shipyard for 126 days to evaluate tributyltin (TBT) contamination. Although the application of TBT-based paints to ships is totally banned in Korea, butyltin compounds were found to accumulate in mussels following transplantation. Concentrations of TBT and total butyltins in transplanted mussels near the shipyard were in the range of 40–350 ng Sn/g and 74–530 ng Sn/g on a dry weight basis, respectively. Obviously, low TBT concentrations (6.0–53 ng Sn/g dw) were determined in mussels at four stations outside the shipyard. A negative gradient of TBT concentrations and TBT portion to total butyltin concentrations were found in both the surface water and transplanted mussels according to distance from the shipyard. In addition, TBT concentrations in surface water and transplanted mussels showed significant correlation (r² = 0.71; p < 0.001). These results indicate that the shipyard still releases fresh TBT into surrounding waters even after TBT regulation in Korea, and mussel transplantation is useful in evaluating TBT contamination in shipyard area.     

Effects of tributyltin at concentrations below ambient levels in seawater on Caprella danilevskii (Crustacea: Amphipoda: Caprellidae)

Hatched juveniles of Caprella danilevskii (Crustacea: Amphipoda) were exposed to one of two concentrations of tributyltin (TBT) (1.1 and 10.7 ng TBT L⁻¹) for 49 d at 20 °C. These concentrations are near or below ambient levels in seawater. In both treatments and control, the survival rate was 100% at maturation, and >85% at the end of the experiments. Females reached maturation at 20 (median) to 21.5 d at instar VII, and repeated spawning 4–5 times during the experiment. The total number of juveniles per female decreased significantly from 39.5 in the control to 24.5 and 17.5 in 1.1 ng L⁻¹ and 10.7 ng L⁻¹ treatments, respectively. An earlier study reported that as the TBT concentration in seawater increased from a 0–10 ng L⁻¹ regime to a 10–20 ng L⁻¹ regime, the number of stations where Caprella spp. could be collected decreased along the coast of the Seto Inland Sea, of Japan. Thus, the present study indicates the possibility that the extremely low concentration of TBT measured in Japanese waters after 2000 lead to a reduction in reproductive success of Caprella spp.     

Assessment of TBT and organic booster biocide contamination in seawater from coastal areas of South Korea

Seawater samples from major enclosed bays, fishing ports, and harbors of Korea were analyzed to determine levels of tributyltin (TBT) and booster biocides, which are antifouling agents used as alternatives to TBT. TBT levels were in the range of not detected (nd) to 23.9 ng Sn/L. Diuron and Irgarol 1051, at concentration ranges of 35–1360 ng/L and nd to 14 ng/L, respectively, were the most common alternative biocides present in seawater, with the highest concentrations detected in fishing ports. Hot spots were identified where TBT levels exceeded environmental quality targets even 6 years after a total ban on its use in Korea. Diuron exceeded the UK environmental quality standard (EQS) value in 73% of the fishing port samples, 64% of the major bays, and 42% of the harbors. Irgarol 1051 levels were marginally below the Dutch and UK EQS values at all sites.     

Nutrients,irradiance, and mixing as factors regulating primary production in coastal waters impacted by the Mississippi River plume

Relationships among primary production, chlorophyll, nutrients, irradiance and mixing processes were examined along the salinity gradient in the Mississippi River outflow region. A series of six cruises were conducted during 1988–1992 at various times of year and stages of river discharge. Maximum values of biomass and primary production were typically observed at intermediate salinities and coincided with non-conservative decreases in nutrients along the salinity gradient. Highest values of productivity (>10 gC m⁻² d⁻¹) and biomass (>30 mg chlorophyll a m⁻³) were observed in April 1988, July–August 1990 and April–May 1992; values were lower in March and September 1991. Rates of primary production were apparently constrained by low irradiance and mixing in the more turbid, low salinity regions of the plume, and by nutrient limitation outside the plume. Highest values of primary production occurred at stations where surface nutrient concentrations exhibited large deviations from conservative mixing relationships, indicating that depletion of nutrients was related to phytoplankton uptake. Mixing and advection were important in determining the location and magnitude of primary production maxima and nutrient depletion. In addition to growth within plume surface waters, enhanced growth and/or retention of biomass may have occurred in longer residence time waters at the plume edge and/or beneath the surface plume. Vertical structure of some plume stations revealed the presence of subsurface biomass maxima in intermediate salinity water that was depleted in nutrients presumably by uptake processes. Exchange between subsurface water and the surface plume apparently contributed to the reduction in nutrients at intermediate salinities in the surface layer. DIN (=nitrate+nitrite+ammonium) : PO₄ (=phosphate) ratios in river water varied seasonally, with high values in winter and spring and low values in late summer and fall. Periods of high DIN : PO₄ ratios in river nutrients coincided with cruises when surface nutrient concentrations and their ratios indicated a high probability for P limitation. N limitation was more likely to occur at high salinities and during late summer and fall. Evidence for Si limitation was also found, particularly in spring.     

Low-degree melting of a metasomatized lithospheric mantle for the origin of Cenozoic Yulong monzogranite-porphyry,east Tibet: Geochemical and Sr–Nd–Pb–Hf isotopic constraints

SHRIMP zircon U–Pb dating, mineral chemical, element geochemical and Sr–Nd–Pb–Hf isotopic data have been determined for the Yulong monzogranite-porphyry in the eastern Tibet, China. The Yulong porphyry was emplaced into Triassic strata at about 39 Ma. The rocks are weakly peraluminous and show shoshonitic affinity, i.e., alkalis-rich, high K₂O contents with high K₂O / Na₂O ratios, enrichment in LREE and LILE. They also show some affinities with the adakite, e.g., high SiO₂ and Al₂O₃, and low MgO contents, depleted in Y and Yb, and enrichment in Sr with high Sr / Y and La / Yb ratios, and no Eu anomalies. The Yulong porphyry has radiogenic ⁸⁷Sr / ⁸⁶Sr (0.7063–0.7070) and unradiogenic ¹⁴³Nd / ¹⁴⁴Nd (ε_Nd = − 2.0 to − 3.0) ratios. The Pb isotopic compositions of feldspar phenocrysts separated from the Yulong porphyry show a narrow range of ²⁰⁶Pb / ²⁰⁴Pb ratios (18.71–18.82) and unusually radiogenic ²⁰⁷Pb / ²⁰⁴Pb (15.65–15.67) and ²⁰⁸Pb / ²⁰⁴Pb (38.87–39.00) ratios. In situ Hf isotopic composition of zircons that have been SHRIMP U–Pb dated is characterized by clearly positive initial ε_Hf values, ranging from + 3.1 to + 5.9, most between + 4 and + 5. Phenocryst clinopyroxene geothermometry of the Yulong porphyry indicates that the primary magmas had anomalously high temperature (> 1200 °C). The source depth for the Yulong porphyry is at least 100 km inferred by the metasomatic volatile phase (phlogopite–carbonate) relations. Detailed geochemical and Sr–Nd–Pb–Hf isotopic compositions not only rule out fractional crystallization or assimilation-fractional crystallization processes, but also deny the possibility of partial melting of subducted oceanic crust or basaltic lower crust. Instead, low degree (1–5%) partial melting of a metasomatized lithosphere (phlogopite–garnet clinopyroxenite) is compatible with the data. This example gives a case study that granite can be derived directly by partial melting of an enriched lithospheric mantle, which is important to understand the source and origin of diverse granites.     

Spectral attenuation of solar radiation in Patagonian fjord and coastal waters and implications for algal photobiology

The spectral attenuation of solar irradiation was measured during summer in two types of coastal waters in southern Chile, a north Patagonian fjord (Seno Reloncaví) and open coast (Valdivia). In order to relate the light availability with the light requirements of upper subtidal seaweeds, the saturating irradiance for photosynthesis (E_k) from P–I curves was measured. In addition the UV risk was assessed. Based on the z_1% of PAR, the lower limit of the euphotic zone in the studied systems averaged 21 m (K_d 0.24 m^?1) in Seno Reloncaví and 18 m (K_d 0.27 m^?1) in the coast of Valdivia. Photosynthesis of the studied seaweeds was saturated at markedly lower irradiances than found in their natural depths at the time of the study. Solar radiation penetrating into these depths at both locations largely supports the light requirements for the photosynthesis of subtidal species: 50–160 μmol m^?2 s^?1 for seaweeds from Seno Reloncaví (7 m tidal range) and 20–115 μmol m^?2 s^?1 for Valdivia assemblages (2 m tidal range). Optimal light conditions to saturate photosynthesis (E_k) were present at 10–16 m water depth. The attenuation of solar irradiation did not vary significantly between the fjord and coastal sites of this study. However, the underwater light climates to which seaweeds are exposed in these sites vary significantly because of the stronger influence of tidal range affecting the fjord system as compared with the open coastal site. The patterns of UV-B penetration in these water bodies suggest that seaweeds living in upper littoral zones such as the intertidal and shallow subtidal (<3 m) may be at risk.     

Glaciation,erosion, and landscape evolution of Iceland

Stratigraphic and sedimentological studies indicate that Iceland has experienced over 20 glaciations during the last 4–5 Myr, in reasonable agreement with the number of glaciations reconstructed from the ∂¹⁸O record in deep-sea sediment. The pattern of glacial erosion was to a large part controlled by constructive volcanic processes resulting in increased topographic relief after 2.5 Myr. Between 2.5 and 0.5 Ma valleys up to 400 m deep were excavated into the Tertiary basalts of eastern and south Iceland with an average erosion rate of 10–20 cm ka⁻¹. During the last 0.5 million years rates of erosion increased to 50–175 cm ka⁻¹, with an additional 200 to over 1000 m of valley excavation. Previous estimates of the rate of landscape erosion during the Holocene vary widely, from 5 to 70,000 cm ka⁻¹. We present new studies that define the rates of landscape denudation during the major part of the Holocene (the last 10,200 years): one based on the Iceland shelf sediment record, the other from the sediment record in the glacier-fed lake, Hvítárvatn. Both studies indicate average Holocene erosion rates of about 5 cm ka⁻¹ similar to our erosion rate estimate for 4–5 Ma old strata that has not been subjected to regional glaciation.     

Seasonal and vertical distributional patterns of siphonophores and medusae in the Chiloé Interior Sea,Chile

The horizontal and vertical distribution of jellyfish was assessed in the Chiloé Inland sea, in the northern area of the Chilean Patagonia. A total of 41 species of cnidarians (8 siphonophores, 31 hydromedusae, 2 scyphomedusae) were collected. Eleven jellyfish species were recorded for the first time in the area. Species richness was higher in spring than in winter (37 vs. 25 species, respectively). Species such as Muggiaea atlantica, Solmundella bitentaculata, and Clytia simplex were extremely abundant in spring. The total abundance (408,157 ind 1000 m^?3) was 18 times higher in spring than in winter (22,406 ind 1000 m^?3).The horizontal distribution of the most abundant species (four in winter, five in spring) showed decreasing abundances in the north–south direction in winter and spring. Peak abundances occurred in the northern microbasins (Reloncaví Fjord, Reloncaví and Ancud gulfs), where the water column stability, phytoplankton and zooplankton abundance were higher, compared with the southern microbasins (Corcovado Gulf, Boca del Guafo). During the spring higher jellyfish abundance season, the vertical distribution of the dominant species (except M. atlantica) showed peak values at mid-depth (30–50 m) and in the deepest sampled layer (50–200 m). This vertical distribution pattern reduced seaward transport in the shallowest layer through estuarine circulation and also limited mortality by predation in the more illuminated shallow layers. Thus, jellyfish were able to remain in the interior waters during the season of maximum biological production.     

Modeled tephra ages from lake sediments,base of Redoubt Volcano,Alaska

A 5.6-m-long lake sediment core from Bear Lake, Alaska, located 22 km southeast of Redoubt Volcano, contains 67 tephra layers deposited over the last 8750 cal yr, comprising 15% of the total thickness of recovered sediment. Using 12 AMS ¹⁴C ages, along with the ¹³⁷Cs and ²¹⁰Pb activities of recent sediment, we evaluated different models to determine the age–depth relation of the core, and to determine the age of each tephra deposit. The selected age model is based on a mixed-effect regression that was passed through the adjusted tephra-free depth of each dated layer. The estimated age uncertainty of the 67 tephras averages ±105 yr (95% confidence intervals). Tephra-fall frequency at Bear Lake was among the highest during the past 500 yr, with eight tephras deposited compared to an average of 3.7/500 yr over the last 8500 yr. Other periods of increased tephra fall occurred 2500–3500, 4500–5000, and 7000–7500 cal yr. Our record suggests that Bear Lake experienced extended periods (1000–2000 yr) of increased tephra fall separated by shorter periods (500–1000 yr) of apparent quiescence. The Bear Lake sediment core affords the most comprehensive tephrochronology from the base of the Redoubt Volcano to date, with an average tephra-fall frequency of one every 130 yr.     

Lithospheric contributions to high-MgO basanites from the Cumbre Vieja Volcano,La Palma,Canary Islands and evidence for temporal variation in plume influence

New geochemical and isotopic data are presented from the oldest part of the Cumbre Vieja volcano, La Palma (Canary Islands), located near the assumed emergence of the Canary mantle plume. The volcanics comprise a suite dominated by basanite flows with subordinate amounts of phono-tephrite, tephri-phonolite and phonolite flows and intrusives. Two compositionally different basanite groups have been identified, both with HIMU (high-μ)-type incompatible trace element characteristics: Primitive high-MgO basanites (10.7–12.1% MgO), found only at the base of a stratigraphic profile near Fuencaliente on the south coast, and intermediate-MgO basanites (6.0–7.3% MgO), exposed in the upper part of the profile and widespread on the east coast of La Palma. The high-MgO basanites are interpreted as near-primary mantle melts (primary composition 14–15% MgO) derived by progressive melting (2.9% to 4.5%) of a common lithospheric mantle source. Model calculations indicate that it is not possible to generate the intermediate-MgO basanites from the high-MgO group by crystal fractionation of observed phenocrysts. Relative to intermediate-MgO basanites, the high-MgO flows have lower concentrations of LIL and HFS elements, except for Ti, which is markedly enriched in the primitive rocks (3.7–4.7% TiO₂ vs 3.4–3.9% TiO₂). Fuencaliente volcanics display limited temporal isotopic variations suggested to be a result of mixing of melts originating from the rising plume and the metazomatized lithospheric mantle. ⁸⁷Sr / ⁸⁶Sr and ¹⁴³Nd / ¹⁴⁴Nd ratios range 0.70305–0.70311 and 0.51285–0.51291, respectively, while the corresponding ranges in Pb-isotope ratios are ²⁰⁶Pb / ²⁰⁴Pb = 19.46–19.64, ²⁰⁷Pb / ²⁰⁴Pb = 15.55–15.61, and ²⁰⁸Pb / ²⁰⁴Pb = 39.16–39.53. The overall variation of the Cumbre Vieja isotopic data can be accounted for by mixtures of three mantle components in the proportions 72–79% plume source (LVC = low velocity component), 9–16% depleted mantle (DM) and up to 12% enriched mantle (EMI). Negative Δ7 / 4 Pb (− 0.6 to − 5.4) in the Cumbre Vieja volcanics suggest derivation from a young HIMU mantle source. The relative abundance of plume source material increase in younger rocks in the Fuencaliente section, suggesting waning plume–lithosphere interaction during the emplacement of this part of the Cumbre Vieja volcano. The high-MgO volcanics define regular and systematic geochemical trends, interpreted as partial melting trends, when plotted against abundances of highly incompatible elements (P, Ce). Evaluation of minor and trace element variation in consecutive melts suggests control by residual amphibole, phlogopite, garnet and a Ti-bearing phase, possibly ilmenite. The melting mode changed gradually, allowing increasing input from residual phlogopite during partial melting. The residual mineralogy constrains the source region of the high-MgO basanites to the lowermost oceanic lithospheric mantle, presumably around 100 km depths.     

Constraints on the nature of the subvolcanic reservoir at South Sister volcano,Oregon from U-series dating combined with sub-crystal trace-element analysis of plagioclase and zircon

We present sub-crystal-scale ²³⁸U–²³⁰Th zircon ages and ²³⁸U–²³⁰Th–²²⁶Ra plagioclase ages of bulk mineral separates from the Holocene (2.0–2.3 ka) eruptions of the Rock Mesa (RM) and Devil's Hills (DH) rhyolites at South Sister volcano, Oregon. We link these age data with sub-crystal trace-element analyses of zircon and plagioclase to provide insight into the subvolcanic system at South Sister, as an example of a small-volume continental arc volcano. Our results document the presence of coeval yet physically-distinct regions within the magma reservoir and constrain the timescales over which these heterogeneities existed. Zircons from the RM and DH dominantly record ages from 20 to 80 ka, with some grains recording ages > 350 ka, whereas plagioclase records ²³⁰Th–²²⁶Ra ages of 2.3–6.8 ka (RM) and 4.0–9.6 ka (DH-3) and a ²³⁸U–²³⁰Th age of 10 ± 34 ka (DH-3). We interpret zircons with ages < 350 ka as antecrysts inherited from a longer lived upper-crustal magma reservoir from which the rhyolites were generated, based on crystallization ages coeval with earlier periods of silicic volcanism at South Sister, the undersaturated nature of the RM and DH magmas with respect to zircon, and Ti-in-zircon temperatures consistent with low-temperature (< 815 °C) crystallization. In contrast, plagioclase ages are near the eruption age and dominantly preserve information about the recent (< 10 ka), higher-temperature evolution of the host magmas. Although zircon and plagioclase record different crystallization ages, each phase crystallized over the same time period in the RM compared to DH rhyolites. Linking these crystal age data with sub-crystal trace-element analyses demonstrates that zircon and plagioclase have distinct trace-element characteristics between eruptions, which require that the RM and DH crystals (and therefore magmas) were derived from distinct regions that had evolved independently for > 50 ka within a heterogeneous magmatic system and coexisted as physically-distinct, dominantly-liquid bodies prior to eruption. Thus, we favor a model where rhyolites are generated in independent batches by accumulation of evolved liquids in a heterogeneous, largely crystalline reservoir. Similarities in crystal age and chemical data to that at other young silicic systems (e.g., Mount St. Helens, Okataina Caldera Complex) suggest that this model may be more generally applicable to silicic magmas.     

Elasticity of antigorite,seismic detection of serpentinites,and anisotropy in subduction zones

Serpentinization of the mantle wedge is an important process that influences the seismic and mechanical properties in subduction zones. Seismic detection of serpentines relies on the knowledge of elastic properties of serpentinites, which thus far has not been possible in the absence of single-crystal elastic properties of antigorite. The elastic constants of antigorite, the dominant serpentine at high-pressure in subduction zones, were measured using Brillouin spectroscopy under ambient conditions. In addition, antigorite lattice preferred orientations (LPO) were determined using an electron back-scattering diffraction (EBSD) technique. Isotropic aggregate velocities are significantly lower than those of peridotites to allow seismic detection of serpentinites from tomography. The isotropic V_P/V_S ratio is 1.76 in the Voigt–Reuss–Hill average, not very different from that of 1.73 in peridotite, but may vary between 1.70 and 1.86 between the Voigt and Reuss bonds. Antigorite and deformed serpentinites have a very high seismic anisotropy and remarkably low velocities along particular directions. V_P varies between 8.9 km s^? 1 and 5.6 km s^? 1 (46% anisotropy), and 8.3 km s^? 1 and 5.8 km s^? 1 (37%), and V_S between 5.1 km s^? 1 and 2.5 km s^? 1 (66%), and 4.7 km s^? 1 and 2.9 km s^? 1 (50%) for the single-crystal and aggregate, respectively. The V_P/V_S ratio and shear wave splitting also vary with orientation between 1.2 and 3.4, and 1.3 and 2.8 for the single-crystal and aggregate, respectively. Thus deformed serpentinites can present seismic velocities similar to peridotites for wave propagation parallel to the foliation or lower than crustal rocks for wave propagation perpendicular to the foliation. These properties can be used to detect serpentinite, quantify the amount of serpentinization, and to discuss relationships between seismic anisotropy and deformation in the mantle wedge. Regions of high V_P/V_S ratios and extremely low velocities in the mantle wedge of subduction zones (down to about 6 and 3 km.s^?1 for V_P and V_S, respectively) are difficult to explain without strong preferred orientation of serpentine. Local variations of anisotropy may result from kilometer-scale folding of serpentinites. Shear wave splittings up to 1–1.5 s can be explained with moderately thick (10–20 km) serpentinite bodies.     

Active segment of the 12 November 2003 Mw 5.6 earthquake at Salsipuedes oceanic basin,Gulf of California. Mexico

We analyzed records of eight seismic stations of the autonomous broadband seismograph network of a joint project between Utrecht University (the Netherlands), California Institute of Technology, and Centro de Investigación Científica y de Estudios Superiores de Ensenada (CICESE). These stations recorded the Mw 5.6 earthquake that occurred on 12 November 2003 at Salsipuedes basin in the middle of the Gulf of California 2 km west of the island Angel de la Guarda. This event was located at 29.16º N and 113.37º W, 30 km northeast of Bahia de los Angeles. A foreshock and hundreds of aftershocks were recorded in the 48 hours after its origin time. With the location of 29 earthquakes we identified the active segment, perpendicular to the main transform fault NW–SE of Canal de Ballenas, representing the transtensional boundary between the Pacific and North American plates. The direction of the active fault described is consistent with the normal fault mechanism reported by the National Earthquake Information Center (strike=39º, dip=34º, slip=–44º).From the duration magnitude of 456 aftershocks, we calculated a b-value of 1.14±0.28; furthermore, we calculated a seismic moment of (3.5 ±3.3) X10¹⁷Nm, a source radius of 3.7 ± 2.63 km, and a static stress drop of 3.94 ± 1.15 MPa (39.4 ± 11.5 bar.).     

Content and distribution of trace metals in surface sediments from the northern Bering Sea,Chukchi Sea and adjacent Arctic areas

Concentrations of trace metals (Zn, Cr, Cu, V, Cd and Pb), total organic carbon (TOC), black carbon (BC) and their granulometry were examined in 25 surface sediment samples from the northern Bering Sea, Chukchi Sea and adjacent areas. Trace metal concentrations in the sediments varied from 21.06–168.21 mg kg⁻¹ for Zn, 8.91–46.94 mg kg⁻¹ for Cr, 2.69–49.39 mg kg⁻¹ for Cu, 32.46–185.54 mg kg⁻¹ for V, 0.09–0.92 mg kg⁻¹ for Cd, and 0.95–15.25 mg kg⁻¹ for Pb. The geoaccumulation index (I_geo) indicated that trace metal contamination (Zn and Cd) existed in some stations of the study area. The distribution of grain size plays an important role in influencing the distribution of trace metals (Zn, Cr, Cu, V, and Pb) in sediments from the Chukchi Sea and adjacent areas.     

Spatial and temporal changes of TBT pollution along the Portuguese coast: inefficacy of the EEC directive 89/677

Nucella lapillus imposex (superimposition of male characters onto prosobranch females) and organotin body burden were surveyed in the Portuguese coast in 1997 and 2000. Time comparisons of the available data on Nucella lapillus imposex in the Portuguese coast indicate a global increase of TBT pollution in recent years, revealing the inefficacy of the 1993 legislation that bans the use of TBT paints on small boats (<25 m). The absence or scarcity of the species inside harbours, which are the most polluted sites in Portugal, is probably a consequence of extinction due to female sterilisation by TBT.     

The origins and concentrations of water,carbon, nitrogen and noble gases on Earth

The isotopic compositions of terrestrial hydrogen and nitrogen are clearly different from those of the nebular gas from which the solar system formed, and also differ from most of cometary values. Terrestrial N and H isotopic compositions are in the range of values characterizing primitive meteorites, which suggests that water, nitrogen, and other volatile elements on Earth originated from a cosmochemical reservoir that also sourced the parent bodies of primitive meteorites. Remnants of the proto-solar nebula (PSN) are still present in the mantle, presumably signing the sequestration of PSN gas at an early stage of planetary growth. The contribution of cometary volatiles appears limited to a few percents at most of the total volatile inventory of the Earth. The isotope signatures of H, N, Ne and Ar can be explained by mixing between two end-members of solar and chondritic compositions, respectively, and do not require isotopic fractionation during hydrodynamic escape of an early atmosphere.The terrestrial inventory of ⁴⁰Ar (produced by the decay of ⁴⁰K throughout the Earth's history) suggests that a significant fraction of radiogenic argon may be still trapped in the silicate Earth. By normalizing other volatile element abundances to this isotope, it is proposed that the Earth is not as volatile-poor as previously thought. Our planet may indeed contain up to ~ 3000 ppm water (preferred range: 1000–3000 ppm), and up to ~ 500 ppm C, both largely sequestrated in the solid Earth. This volatile content is equivalent to an ~ 2 (± 1) % contribution of carbonaceous chondrite (CI-CM) material to a dry proto-Earth, which is higher than the contribution of chondritic material advocated to account for the platinum group element budget of the mantle. Such a (relatively) high contribution of volatile-rich matter is consistent with the accretion of a few wet planetesimals during Earth accretion, as proposed by recent dynamical models.The abundance pattern of major volatile elements and of noble gases is also chondritic, with two notable exceptions. Nitrogen is depleted by one order of magnitude relative to water, carbon and most noble gases, which is consistent with either N retention in a mantle phase during magma generation, or trapping of N in the core. Xenon is also depleted by one order of magnitude, and enriched in heavy isotopes relative to chondritic or solar Xe (the so-called “xenon paradox”). This depletion and isotope fractionation might have taken place due to preferential ionization of xenon by UV light from the early Sun, either before Earth's formation on parent material, or during irradiation of the ancient atmosphere. The second possibility is consistent with a recent report of chondritic-like Xe in Archean sedimentary rocks that suggests that this process was still ongoing during the Archean eon (Pujol et al., 2011). If the depletion of Xe in the atmosphere was a long-term process that took place after the Earth-building events, then the amounts of atmospheric ¹²⁹Xe and ^131–136Xe, produced by the short-lived radioactivities of ¹²⁹I (T_1/2 = 16 Ma) and ²⁴⁴Pu (T_1/2 = 82 Ma), respectively, need to be corrected for subsequent loss. Doing so, the I–Pu–Xe age of the Earth becomes ≤ 50 Ma after start of solar system formation, instead of ~ 120 Ma as computed with the present-day atmospheric Xe inventory.     

Influence of nitrate and dissolved organic carbon loading on the interaction of Microcystis aeruginosa and heterotrophic bacteria from hyper-eutrophic lake (Taihu Lake,China)

To investigate the interaction between cyanobacteria and heterotrophic bacteria under gradients of glucose and nitrate, a cyanobacterial strain of Microcystis aeruginosa was grown in microcosms with and without a freshwater bacterial mixture, which was collected from Lake Taihu. Concentrations of glucose (1350, 975, 600, 300, 150, and 37.5 μmol C L⁻¹) and nitrate (150, 300, and 9000 μmol N L⁻¹) were used in a range of combinations giving 9 different treatments of glucose:nitrate. In the microcosm without the bacterial mixture, M. aeruginosa abundance gradually increased with days in all treatments. However, M. aeruginosa had much lower density in some treatments with the bacterial mixture. The difference in M. aeruginosa growth could be explained by competition with bacteria in the cultures in which these were added. The abundance of M. aeruginosa and bacteria when grown together was nearly equal and the number of the bacterial species was highest in the treatment with 300 μmol C L⁻¹ and 150 μmol N L⁻¹. Our results suggest that at this glucose:nitrate ratio M. aeruginosa and the bacterial mixture maintain a balance, and bacteria maintain diversity. In conclusion, we propose that dissolved organic carbon and nitrate availability fundamentally affects the structure as well as stoichiometry of pelagic associations.     

Determination of selected persistent organic pollutants in wastewater from landfill leachates,using an amperometric biosensor

Landfill leachates that contain persistent organic pollutants (POPs) are a big threat to groundwater systems and are projected to have hazardous effects in the long term if proper management strategies of the landfills are not put in place by those responsible. Monitoring the levels of POPs in landfill leachates is very crucial. This work presents an amperometric biosensor for determination of selected POPs in landfill leachates. The biosensor is based on kinetic inhibition of horseradish peroxidase (HRP). The enzyme was immobilised by electrostatic attachment on a polyaniline-modified Pt electrode surface. Selected POPs inhibited HRP enzyme activity and the decrease in the enzyme activity was used to determine these environmental pollutants. Selected polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and polychlorinated biphenyls (PCBs) were the analytes of choice because they are commonly found in South Africa water systems. Limits of detection for the amperometric biosensor were established as 0.014, 0.018, 0.022, 0.016 and 0.019 μg l⁻¹ for BDE-100, PBB-1, PCB-1, PCB-28 and PCB-101, respectively. The HRP biosensor system gave different linear ranges for; BDE-100 (0.424–25.8 μg l⁻¹), PBB-1 (0.862–13.4 μg l⁻¹), PCB-1 (0.930–18.1 μg l⁻¹), PCB-28 (0.730–15.7 μg l⁻¹) and PCB-101 (0.930–27.1 μg l⁻¹). Inhibition studies on HRP biosensor response toward the reduction of H₂O₂ in the absence and presence of the selected POPs were carried out to investigate the inhibition kinetics and its mechanism. The results obtained indicated that the inhibition mechanism was competitive for PBDEs and non-competitive for biphenyls (PCBs and PBBs). The application of the biosensor was tested on wastewater samples obtained from landfill leachate for determination of selected POPs. The leachate samples were found to contain PCB-28 (0.28 ± 0.03 μg l⁻¹) and PCB-101 (0.31 ± 0.02 μg l⁻¹). The samples were also analysed by GC–MS as a cross-check method and the two sets of results were in close agreement.