Heinrich Taubald

Carbon and hydrogen isotope effects during sorption of organic contaminants on carbonaceous materials.

Stable carbon and hydrogen isotopes can be an efficient means to validate biodegradation of organic contaminants in groundwater since it results in an isotopic fractionation. A prerequisite in applying this method in the field is the proof that other processes decreasing the contaminant concentration are conservative with respect to isotope effects. In this paper we show for carbon isotopes of halogenated hydrocarbon compounds [trichloroethene (TCE), cis-dichloroethene (c-DCE), vinylchloride (VC)] and carbon and hydrogen isotopes of BTEX compounds (benzene, toluene, p-xylene) that no significant fractionation occurs during equilibrium sorption onto activated carbon, lignite coke and lignite. In general, effects were in the range of the reproducibility limit of the analytical instrument (0.5 per thousand for delta13C, and 8 per thousand for delta2H). This observation was made for fractions sorbed of less than 5% to more than 95%. Also for rate-limited sorption of TCE onto activated carbon, no significant fractionation in carbon isotopes could be observed. These findings support the assumption that for these classes of compounds, sorption processes in aquifer systems are conservative with respect to isotope effects.

Modelling of geochemical and isotopic changes in a column experiment for degradation of TCE by zero-valent iron

Zero-valent iron (ZVI) permeable-reactive barriers have become an increasingly used remediation option for the in situ removal of various organic and inorganic chemicals from contaminated groundwater. In the present study a process-based numerical model for the transport and reactions of chlorinated hydrocarbon in the presence of ZVI has been developed and applied to analyse a comprehensive data set from laboratory-scale flow-through experiments. The model formulation includes a reaction network for the individual sequential and/or parallel transformation of chlorinated hydrocarbons by ZVI, for the resulting geochemical changes such as mineral precipitation, and for the carbon isotope fractionation that occurs during each of the transformation reactions of the organic compounds. The isotopic fractionation was modelled by formulating separate reaction networks for lighter ((12)C) and heavier ((13)C) isotopes. The simulation of a column experiment involving the parallel degradation of TCE by hydrogenolysis and beta-elimination can conclusively reproduce the observed concentration profiles of all collected organic and inorganic data as well as the observed carbon isotope ratios of TCE and its daughter products.

MINERALOGY AND GEOCHEMISTRY OF THE SEDIMENTARY KAOLIN DEPOSITS FROM SINAI, EGYPT: IMPLICATIONS FOR CONTROL BY THE SOURCE ROCKS

Mineralogical and geochemical variations among the Carboniferous and Cretaceous sedimentary kaolin deposits from Sinai provided an opportunity to examine the effect of the source area on compositions of the deposits. The Carboniferous kaolin deposits are mineralogically and geochemically heterogeneous. The Khaboba and Hasbar deposits consist of kaolinite, quartz, anatase, illite, chlorite, zircon, and leucoxene. The shale-normalized rare earth element (REE) patterns of the Khaboba deposit showed a slight LREE over HREE enrichment ((La/Yb)SN = 1.19–1.51) with a MREE depletion (Gd/Gd*SN = 0.51–0.75), while the Hasbar kaolin had a MREE enrichment. The Abu Natash kaolin deposit consisted of kaolinite, anatase, and a little quartz with larger TiO2, Cr, and V and smaller Zr and Nb contents compared to other Carboniferous deposits. The shale-normalized REE patterns of the Abu Natash deposit exhibited a positive Eu anomaly (Eu/Eu*SN = 1.28–1.40) and a MREE enrichment (Gd/Gd*SN = 1.41–2.05). The Cretaceous deposits were relatively homogeneous in terms of mineralogical composition and geochemistry and are composed of kaolinite, quartz, anatase, rutile, zircon, and leucoxene. The Cretaceous kaolin deposits showed mostly flat shale-normalized REE patterns with a variable LREE depletion.The presence of illite and chlorite, the absence of rutile, large Zr and Nb contents, and the REE patterns suggested a component of weathered low-grade metasediments as a source for the Carboniferous deposits in the Khaboba and Hasbar areas, while the large Ti, Cr, and V, and small quartz contents indicated mafic source rocks for the Abu Natash deposit. The abundance of high-Cr rutile and the absence of illite and chlorite, and large Zr, Ti, Cr, and V contents suggested a mixture of medium- to high-grade metamafic and granitic rocks as source rocks for the Cretaceous kaolin deposits. The occurrence of alkaline rocks in the source of the deposits studied was identified by high-Nb contents and the presence of bastnaesite. The mineralogical and geochemical heterogeneity and lesser maturity of the Carboniferous deposits suggested local sources for each deposit and their deposition in basins close to the sources. The mineralogical and geochemical homogeneity and maturity of the Cretaceous deposits, on the other hand, indicated common sources for all deposits and their deposition in relatively remote basins.

Stable water isotope patterns in a climate change hotspot: the isotope hydrology framework of Corsica (western Mediterranean)

The Mediterranean is regarded as a region of intense climate change. To better understand future climate change, this area has been the target of several palaeoclimate studies which also studied stable isotope proxies that are directly linked to the stable isotope composition of water, such as tree rings, tooth enamel or speleothems. For such work, it is also essential to establish an isotope hydrology framework of the region of interest. Surface waters from streams and lakes as well as groundwater from springs on the island of Corsica were sampled between 2003 and 2009 for their oxygen and hydrogen isotope compositions. Isotope values from lake waters were enriched in heavier isotopes and define a local evaporation line (LEL). On the other hand, stream and spring waters reflect the isotope composition of local precipitation in the catchment. The intersection of the LEL and the linear fit of the spring and stream waters reflect the mean isotope composition of the annual precipitation (δP) with values of−8.6(±0.2) ‰ for δ18O and−58(±2) ‰ for δ2H. This value is also a good indicator of the average isotope composition of the local groundwater in the island. Surface water samples reflect the altitude isotope effect with a value of−0.17(±0.02) ‰ per 100 m elevation for oxygen isotopes. At Vizzavona Pass in central Corsica, water samples from two catchments within a lateral distance of only a few hundred metres showed unexpected but systematic differences in their stable isotope composition. At this specific location, the direction of exposure seems to be an important factor. The differences were likely caused by isotopic enrichment during recharge in warm weather conditions in south-exposed valley flanks compared to the opposite, north-exposed valley flanks.

Assessing the use of δ18O in phosphate as a tracer for catchment phosphorus sources

Procedures for source apportionment of nutrients transported in rivers and streams are often uncertain and difficult to validate. In this study, we investigated if the oxygen isotope ratios in stream dissolved phosphate (δ18OP) can be used to distinguish between the phosphorus (P) originating from agricultural runoff and from rural sewage, at different periods of the year. Water was collected from septic tanks, drainage wells and the stream outlet in a small (7.3 km2) agricultural catchment to capture variations in the isotope signature at different flow events. The δ18OP signature in septic tank effluent (+13.2 to +14.5‰) was significantly different from that in drainage water (+9.0 to +15.7‰). Four different septic tanks had surprisingly similar isotope signature when 24 h composite samples were collected. Most of the water samples were not in oxygen isotope equilibrium. In three drainage wells, the δ18OP signature varied from +7.8 up to +15.7‰ with higher values in periods with a larger contribution of superficial streamflow generation. A rainfall soon after manure had been spread resulted in a δ18OP of 15.7‰ in a drainage well, and was also reflected in a similar value at the catchment outlet. This implies that the source isotope signal may be conserved during moderate or high flows. A three end-member model including the geological background would be a useful start to quantify the P contribution from diverse sources. Temporal differences in biological activity and the predominant transport pathways through soil profiles must be considered along with information about fertilisation. In combination with hydrological modelling of water pathways, this may considerably improve our understanding of catchment P losses.

Dynamic Metasomatism: Stable Isotopes, Fluid Evolution, and Deformation of Albitite and Scapolite Metagabbro (Bamble Lithotectonic Domain, South Norway)

New stable isotopic data from mineral separates of albite, scapolite, amphibole, quartz, and calcite of metasomatic rocks (Bamble lithotectonic domain) give increased knowledge on fluid type, source, and evolution duringmetamorphism. Albite from a variety of albitites givesδ18OSMOW values of 5.1–11.1‰,while quartz fromclinopyroxene-bearing albitite gives 11.5–11.6‰. δ 18OSMOW values for calcite samples varies between 3.4 and 12.4‰ and shows more consistent δC values of −4.6 to −6.0‰. Amphibole from scapolite metagabbro yields a δ18OSMOW value of 4.3 to 6.7‰and δDSMOW value of−84 to−50‰,while the scapolite gives δ 18OSMOW values in the range of 7.4 to 10.6‰.These results support the interpretation that the originalmagmatic rocks weremetasomatised by seawater solutions with a possible involvement from magmatic fluids. Scapolitisation and albitisation led to contrasting chemical evolution with respect to elements like P, Ti, V, Fe, and halogens. The halogens deposited as Cl-scapolite were dissolved by albitisation fluid and reused as a ligand for metal transport. Many of the metal deposits in the Bamble lithotectonic domain, including Fe-ores, rutile, and apatite deposits formed during metasomatism. Brittle to ductile deformation concurrent with metasomatic infiltration illustrates the dynamics and importance of metasomatic processes during crustal evolution.