Occurrence of naphthalenesulfonates and their condensates with formaldehyde in a landfill leachate and their transport behavior in groundwater of the Upper Rhine Valley, Germany

. Naphthalenesulfonates and their condensation products with formaldehyde are manufactured in the chemical industry for broad application as tanning agents, dispersing agents, and as superplasticizers for concrete. With the disposal of waste they have found their way into the aquatic environment. Five monomeric naphthalenesulfonates and a group of dimeric sulfonated naphthalene-formaldehyde condensates (SNFC) were identified in the leachate and in groundwater observation wells downstream in the plume of the Karlsruhe-West landfill, situated in the Upper Rhine Valley in southwest Germany. For the main monomer of technical SNFC products, 2-naphthalenesulfonate (2-NS), the concentration in the leachate was 170 µg l^–1, which decreased to 9.5 µg l^–1 at a distance of about 300 m from the boundary of the landfill. In the Merdingen tracer test field, the transport of these compounds was studied under more controlled conditions in two tracer experiments with (1) two model compounds, and (2) a technical SNFC product and uranine as a reference tracer. In these experiments, the monomeric naphthalenesulfonates and the SNFC with n=2 behave as conservative tracers. Thus, the findings of the landfill study were supported by these results. Higher molecular SNFC were strongly retarded, which is attributed to adsorption to soil particles. The results of the second tracer experiment suggest a degradation of 2-NS and 2,6-naphthalenedisulfonate (2,6-NDS) after adaptation of the microorganisms in the groundwater aquifer as a consequence of the first tracer experiment.     

The BEAM-project: prediction and assessment of mixture toxicities in the aquatic environment

Freshwater and marine ecosystems are exposed to various multi-component mixtures of pollutants. Nevertheless, most ecotoxicological research and chemicals regulation focus on hazard and exposure assessment of individual substances only, the problem of chemical mixtures in the environment is ignored to a large extent. In contrast, the assessment of combination effects has a long tradition in pharmacology, where mixtures of chemicals are specifically designed to develop new products, e.g. human and veterinary drugs or agricultural and non-agricultural pesticides. In this area, two concepts are frequently used and are thought to describe fundamental relationships between single substance and mixture effects: Independent Action (Response Addition) and Concentration Addition. The question, to what extent these concepts may also be applied in an ecotoxicological and regulatory context may be considered a research topic of major importance, as the concepts would allow to make use of already existing single substance toxicity data for the predictive assessment of mixture toxicities. Two critical knowledge gaps are identified: (a) There is a lack of environmental realism, as a huge part of our current knowledge about the applicability of the concepts is restricted to artificial situations with respect to mixture composition or biological effect assessment. (b) The knowledge on what exactly is needed for using the concepts as tools for the predictive mixture toxicity assessment is insufficient. Both gaps seriously hamper the necessary, scientifically sound consideration of mixture toxicities in a regulatory context.In this paper, the two concepts will be briefly introduced, the necessity of considering the toxicities of chemical mixtures in the environment will be demonstrated and the applicability of Independent Action and Concentration Addition as tools for the prediction and assessment of mixture toxicities will be discussed. An overview of the specific aims and approaches of the BEAM project to fill in the identified knowledge gaps is given and first results are outlined.     

New palaeomagnetic data from Central Iran and a Triassic palaeoreconstruction

New pole positions for Triassic and Cretaceous times have been obtained from volcanic and sedimentary sequences in Central Iran. These new results confirm the general trend of the Apparent Polar Wander Path (APWP) of the Central-East-Iran microplate (CEIM) from the Triassic through the Tertiary as published by Soffel and Förster (1983, 1984). Two new palaeopoles for the Triassic of the CEIM have been obtained; limestones and tuffs from the Nakhlak region yield a mean direction of 094.0°/25.0°, N=12, k=4.1,α ₉₅=24.7°, after bedding correction, corresponding to a palaeopole position of 310.8°E; 3.9°S, and volcanic rocks from the Sirjan regions yield a mean direction of 114.5°/35.1°, N=44, k=45.9,α ₉₅=3.2° after bedding correction and a palaeopole position of 295.8°E; 10.3°N. Combining these with the two previously published results yields a new palaeopole position of 317.5°E; 12.7°N, for the Triassic of the CEIM, thus confirming that large counterclockwise rotations of the CEIM have occurred since the Triassic time. New results have also been obtained from Cretaceous limestones from the Saghand region of the CEIM. The mean direction of 340.7°/26.3°, N=33, k=44.3,α ₉₅=3.8°, and the corresponding palaeopole position of 283.1°E; 64.4°N, is in agreement with previously determined Cretaceous palaeopole positions of the CEIM. Furthermore, results have also been obtained from Triassic dolomite, limestone, sandstone and siltstone from the Natanz region, which is located to the west of the CEIM. A total of 161 specimens from 44 cores taken at five sites gave a mean direction of the five sites at 033.3°/25.1°, N=5, k=69.0,α ₉₅=9.3° and a palaeopole position of 167.2°E; 53.7°N. They pass the positive fold test of McElhinny (1964) on the level of 99% confidence. This pole position is in fairly good agreement with the mean Triassic pole position of the Turan Plate (149°E; 49°N). It indicates that the area of Natanz has not undergone the large counterclockwise rotation relative to the Turan plate since the Triassic, which has been shown for the CEIM. A Triassic palaeogeographic reconstruction of Iran, Arabia (Gondwana) and the Turan Plate (Eurasia) is also presented.     

Quaternary minettes and associated volcanic rocks of Mascota,western Mexico: a consequence of plate extension above a subduction modified mantle wedge

 Pleistocene-Holocene volcanism in the Jalisco block of western Mexico is confined to two conspicuous grabens, where potassic eruptives range from absarokites (48–52% SiO₂) and minettes (49–54% SiO₂) through basaltic andesites (53–57% SiO₂), the most voluminous type, to andesites and their lamprophyric equivalent spessartite (58–62% SiO₂); there are no contemporary rhyolitic rocks. This suite has high concentrations of Mg, Cr (<550 ppm) and Ni (<450 ppm) accompanied by large concentrations of K, P, Ba (<4000 ppm) and Sr (<5000 ppm) and elements such as LREE and Zr (<600 ppm). No combination of crystal fractionation and/or crustal contamination can reproduce the compositional range of these magmas, which nevertheless are believed to be genetically related because of their proximity in time and space. Hydrous minerals in the lamprophyres and the typical absence of plagioclase phenocrysts in both basaltic andesites and andesites reflect the relatively high concentrations of water in the magmas, which suppressed the crystallisation of feldspar. Experimental verification of the minimal amounts of water required to reproduce the phenocryst assemblages in selected rocks range from 3.5 to 6%. During ascent in a volcanic conduit, andesitic magma may lose water and consequently precipitate plagioclase, or it may ascend more rapidly, retaining more of its initial water, which stabilises phenocrysts of hornblende at the expense of plagioclase. Our estimates of water concentrations, which are consistent with the various low pressure phenocryst assemblages, will be minimal for the magmas in their source regions, and the process of magmatic dewatering on ascent may be typical in well established volcanic conduits. In accord with the compositions of phenocrystic olivine in the basaltic andesites and the minettes, the values of FeO and Fe₂O₃ of the bulk lavas and scoriae are demonstrably pristine. As a consequence, there are two characteristic features of the Mascota suite: the high range of relative oxygen fugacities (ΔNNO=1–5) and the high Mg# (MgO/MgO+FeO) that ranges from 0.70 to 0.91 (with only one andesite as low as 0.66). From the evidence of phlogopite phenocrysts, a partial melt involving phlogopite would have a higher Mg# than one from olivine (Fo₉₀) and pyroxene alone. As the Mascota series shows a correlation between K₂O and Mg#, we conclude that it was generated by partial fusion of the mantle wedge, with a variable contribution of phlogopite and apatite from veins throughout the lherzolitic assemblage. In conformity with an origin by varying increments of partial fusion of a phlogopite-bearing mantle, all incompatible elements vary linearly with Ti (or K) as if phlogopite (+apatite) in the source dominated their contribution to the partial melts. Fluids from dehydration of the subducting slab presumably deposit hydrous and other minerals in veins in the mantle wedge and also increase its redox state. As the Mascota volcanism occurs in grabens closer to the trench than the main andesite arc, it is concluded that the eruption of these small volumes of hydrous magmas require the tectonically favored ascent paths offered by the extensional grabens to reach the surface from their mantle sources. Received: 24 January 1995 / Accepted: 21 February 1996     

Role of the subducted slab,mantle wedge and continental crust in the generation of adakites from the Andean Austral Volcanic Zone

 All six Holocene volcanic centers of the Andean Austral Volcanic Zone (AVZ; 49–54°S) have erupted exclusively adakitic andesites and dacites characterized by low Yb and Y concentrations and high Sr/Y ratios, suggesting a source with residual garnet, amphibole and pyroxene, but little or no olivine and plagioclase. Melting of mafic lower crust may be the source for adakites in some arcs, but such a source is inconsistent with the high Mg# of AVZ adakites. Also, the AVZ occurs in a region of relatively thin crust (<35 km) within which plagioclase rather than garnet is stable. The source for AVZ adakites is more likely to be subducted oceanic basalt, recrystallized to garnet-amphibolite or eclogite. Geothermal models indicate that partial melting of the subducted oceanic crust is probable below the Austral Andes due to the slow subduction rate (2 cm/year) and the young age (<24 Ma) of the subducted oceanic lithosphere. Geochemical models for AVZ adakites are also consistent with a large material contribution from subducted oceanic crust (35–90% slab-derived mass), including sediment (up to 4% sediment-derived mass, representing approximately 15% of all sediment subducted). Variable isotopic and trace-element ratios observed for AVZ adakites, which span the range reported for adakites world-wide, require multistage models involving melting of different proportions of subducted basalt and sediment, as well as an important material contribution from both the overlying mantle wedge (10–50% mass contribution) and continental crust (0–30% mass contribution). Andesites from Cook Island volcano, located in the southernmost AVZ (54°S) where subduction is more oblique, have MORB-like Sr, Nd, Pb and O isotopic composition and trace-element ratios. These can be modeled by small degrees (2–4%) of partial melting of eclogitic MORB, yielding a tonalitic parent (intermediate SiO₂, CaO/Na₂O>1), followed by limited interaction of this melt with the overlying mantle (≥90% MORB melt, ≤10% mantle), but only very little (≤1%) or no participation of either subducted sediment or crust. In contrast, models for the magmatic evolution of Burney (52°S), Reclus (51°S) and northernmost AVZ (49–50°S) andesites and dacites require melting of a mixture of MORB and subducted sediment, followed by interaction of this melt not only with the overlying mantle, but the crust as well. Crustal assimilation and fractional crystallization (AFC) processes and the mass contribution from the crust become more significant northwards in the AVZ as the angle of convergence becomes more orthogonal. Received: 1 March 1995 / Accepted: 13 September 1995     

Self-sedimentation of phytoplankton blooms in the geologic record

Understanding the formation of laminated, organic-rich sediments is an essential topic for researchers interested in fossil fuels, biogeochemical cycles, Earth's environmental history and global change. Biologists have very recently demonstrated that some marine phytoplankton blooms actively govern their own sedimentation by the formation of sticky transparent gels that facilitate rapid aggregation, accelerated sinking and efficient export flux. Here we present fossil evidence of unfragmented, low-diversity phytoplankton assemblages preserved as sedimentary laminae and irregular flocs that are attributable to a similar phytoplankton-driven sedimentary mechanism we term ‘self-sedimentation’. The geological evidence suggests that self-sedimentation precludes significant heterotrophic grazing, propels the formation of some conspicuous hemipelagic sedimentary laminae and results in efficient carbon and opal flux to the sediments. We suggest that the self-sedimentation phenomenon may have broad implications for the geological history of biogeochemical cycling, oceanic ecological dynamics, and abrupt atmospheric/environmental change. Broader recognition of the self-sedimentation phenomenon as explicitly defined here is a prerequisite to testing these unconventional hypotheses.     

Zircon fission‐track ages from Newfoundland—A proxy for high geothermal gradients and exhumation before opening of the Central Atlantic Ocean

Following Appalachian orogenesis, metamorphic rocks in central Newfoundland were exhumed and reburied under Tournaisian strata. New zircon fission‐track (ZFT) ages of metamorphic rocks below the Tournaisian unconformity yield post‐depositionally reset ages of 212–235 Ma indicating regional fluid‐absent reheating to at least ≥220°C. Post‐Tournaisian sedimentary thicknesses in surrounding basins show that burial alone cannot explain such temperatures, thus requiring that palaeo‐geothermal gradients increased to ≥30–40°C/km before final late Triassic accelerated cooling. We attribute these elevated palaeo‐geothermal gradients to localized thermal blanketing by insulating sediments overlying radiogenic high‐heat‐producing granitoids. Late Triassic rifting and magmatism before break up of Pangaea likely also contributed to elevated heat flow, as well as uplift, triggering late Triassic accelerated cooling and exhumation. Thermochronological ages of 240–200 Ma are seen throughout Atlantic Canada, and record rifting and basaltic magmatism on the conjugate margins of the Central Atlantic Ocean preceding the onset of oceanic spreading at ~190 Ma.     

Microbially influenced formation of Mg‐calcite and Ca‐dolomite in the presence of exopolymeric substances produced by sulphate‐reducing bacteria

Some species of sulphate‐reducing bacteria (SRB) are known to mediate the formation of dolomite and Mg‐calcite. However, their exact role in the mineralization process remains elusive. Here, we present the result of a laboratory experiment that was designed to test whether formation of carbonate minerals by SRB can occur in the absence of living cells, through passive mineralization of their exopolymeric substances (EPS). SRB capable of mediating dolomite were cultivated in the laboratory, allowing them to secrete EPS. Microbial activity within the cultures was subsequently inhibited with antibiotics. Only after this step, Ca²⁺ and Mg²⁺ were added to the solution and carbonate minerals could form. Mg‐calcite and disordered Ca‐dolomite precipitated in association with EPS. The mol.% of Mg²⁺ in the crystals increased with longer incubation times. This result demonstrates that organic compounds produced by SRB can mediate the formation of Ca‐Mg carbonates in the absence of an active metabolism.