Effects of natural attenuation processes on groundwater contamination caused by abandoned waste sites in Berlin

The aim of this research project is to identify, characterize and quantify natural attenuation (NA) processes in groundwater affected by emissions of abandoned waste disposal sites in Berlin-Kladow/Gatow, Germany. It is part of the funding priority called KORA established by the Federal Ministry for Education and Research (BMBF) to explore the extent to which NA can be used for remedial purposes for varied forms of soil and groundwater contamination. Information on the emission behaviour of individual parameters is generated on the basis of hydrogeochemical comparison of 20 years old and new data. Using groundwater-modelling and CFC-analysis, information on the transport and retention of pollutants in groundwater is compiled. The microbial colonization of contaminated aquifers is characterized by molecular biological methods [polymerase chain reaction (PCR) and denaturing gradient gel electrophoresis (DGGE)] to differentiate between contaminated and not contaminated zones.     

Sequential extraction and leaching characteristics of heavy metals in abandoned tungsten mine tailings sediments

The chemical speciation of potentially toxic elements (As, Cd, Cu, Pb, and Zn) in the contaminated soils and sulfides-rich tailings sediments of an abandoned tungsten mine in Korea was evaluated by conducting modified BCR sequential extraction tests. Kinetic and static batch leaching tests were also conducted to evaluate the potential release of As and other heavy metals by acidic rain water and the leaching behaviors of these heavy metals. The major sources of the elements were As-, Zn- and Pb-bearing sulfides, Pb carbonates (i.e., cerussite), and Pb sulfates (i.e., anglesite). The biggest pollutant fraction in these soil and tailing samples consists of metals bound to the oxidizable host phase, which can be released into the environment if conditions become oxidative, and/or to residual fractions. No significant difference in total element concentrations was observed between the tailings sediments and contaminated soils. For both sample types, almost no changes occurred in the mobility of As and the other heavy metals at 7 days, but the mobility increased afterwards until the end of the tests at 30 days, regardless of the initial pH. However, the mobility was approximately 5–10 times higher at initial pH 1.0 than at initial pHs of 3.0 and 5.0. The leached amounts of all the heavy metal contents were higher from tailings sediments than from contaminated soils at pH > 3.0, but were lower at pH < 3.0 except for As. Results of this study suggest that further dissolution of heavy metals from soil and tailing samples may occur during extended rainfall, resulting in a serious threat to surface and groundwater in the mine area.     

Iron isotopic analyses of geological reference materials on MC-ICP-MS with instrumental mass bias corrected by three independent methods

Here we report iron (Fe) isotopic data of three pure Fe solution standards (IRMM-014, GSB Fe, and NIST 3126a) and five widely used geological reference materials (RMs) from the United States Geological Survey and Geological Survey of Japan obtained on a Neptune Plus multi-collector–inductively coupled plasma–mass spectrometer (MC-ICP-MS) in our laboratory over the past 3 years. The instrumental mass bias was corrected by three independent methods: sample-standard bracketing (SSB), Ni doping?+?SSB, and ⁵⁷Fe–⁵⁸Fe double spike?+?SSB. Measurements reveal that both the Ni doping and double spike methods helped calibrate short-term fluctuations in mass bias. Collectively, almost all measurements of RMs yielded δ⁵⁶Fe within?±?0.05 of recommended values, provided that each sample was measured four times on MC-ICP-MS. For the first time, new recommended values for NIST SRM3126a are reported (δ⁵⁶Fe?=?0.363?±?0.006, 2SE, 95% CI; and δ⁵⁷Fe?=?0.534?±?0.010, 2SE).     

The effect of annealing on the luminescence decay-time of synthetic calcite:Mn

Calcite was synthesized by four methods, and the luminescence decay-time was measured for nine samples before and after heating hydrothermally in the temperature range 200–400°C. Decay-time data were collected between room temperature and approximately 15 K. The decay time at room temperature is approximately 50 ms, with little difference between a given calcite before and after hydrothermal treatment. The decay time at 15 K is always greater than at room temperature as the effect of thermal quenching diminishes. Differences in decay time before and after heating are more apparent at low temperature owing to this reduction in thermal quenching. The decay time decreased significantly in two samples, and an increase in decay time was observed in the remaining seven samples following heating. Among the latter group, the change in decay time was insignificant in three samples. The results are compared with previous data in which it was shown that the effect of heating is to increase the intensity of luminescence.     

Adsorption of antimony(V) on kaolinite as a function of pH,ionic strength and humic acid

The present work investigated the adsorption and mobility (desorption) of Sb(V) on kaolinite using batch experiments. The adsorption of Sb(V) on kaolinite was studied as a function of contact time, pH, ionic strength, humic acid (HA), initial Sb(V) concentration and temperature. Kinetic studies suggest that the equilibrium is achieved within 24 h. The adsorption of Sb(V) was strongly affected by changes in I at low ionic strength and unaffected at high ionic strength. The adsorption is weakly dependent on the presence of humic acid, but is strongly dependent on pH. Within the range tested, the optimal pH for Sb(V) adsorption is 3.6, and close to 75% removal can be achieved. Desorption is dependent on the original suspension pH. The addition sequence of Sb(V)/HA do not influence the adsorption of Sb(V) on kaolinite. The adsorption data fit both the Freundlich and Langmuir isotherm. The thermodynamic parameters (ΔH ⁰, ΔS ⁰ and ΔG ⁰) were calculated from the temperature dependence, and the results suggest the endothermic and spontaneous nature of the process.     

Ionic conductivity in gem-quality single-crystal alkali feldspar from the Eifel: temperature,orientation and composition dependence

We measured the ion conductivity of single-crystal alkali feldspar originating from two different locations in the Eifel/Germany, named Volkesfeld and Rockeskyller sanidine and having potassium site fractions \(C_\mathrm{K}\) of 0.83 and 0.71, respectively. The dc conductivities resulting from electrochemical impedance spectroscopy over the temperature range of 300–900 \(^{\circ }\hbox {C}\) show a weak composition dependence but pronounced differences between the b-direction [\(\perp (010)\)] and \(c^{*}\)-direction [\(\perp (001)\)] of the monoclinic feldspar structure. Conductivity activation energies obtained from the observed linear Arrhenius plots are close to 1.2 eV in all cases, which is closely similar to the activation energies of the \(^{22}\mathrm{Na}\) tracer diffusivity in the same crystals. Taking into account literature data on K tracer diffusion and diffusion correlation effects, the present results point to a predominance of the interstitialcy mechanism over the vacancy mechanism in mass and charge transport on the alkali sublattice in potassium-rich alkali feldspar.     

Petrography and geochemistry of Jurassic sandstones from the Jhuran Formation of Jara dome,Kachchh basin,India: Implications for provenance and tectonic setting

Sandstones of Jhuran Formation from Jara dome, western Kachchh, Gujarat, India were studied for major, trace and rare earth element (REE) geochemistry to deduce their paleo-weathering, tectonic setting, source rock characteristics and provenance. Petrographic analysis shows that sandstones are having quartz grains with minor amount of K-feldspar and lithic fragments in the modal ratio of Q ₈₉:F ₇:L ₄. On the basis of geochemical results, sandstones are classified into arkose, sub-litharenite, wacke and quartz arenite. The corrected CIA values indicate that the weathering at source region was moderate to intense. The distribution of major and REE elements in the samples normalized to upper continental crust (UCC) and chondrite values indicate similar pattern of UCC. The tectonic discrimination diagram based on the elemental concentrations and elemental ratios of Fe₂O₃ + MgOvs. TiO₂, SiO₂ vs. log(K₂O/Na₂O), Sc/Cr vs. La/Y, Th–Sc–Zr/10, La–Th–Sc plots Jhuran Formation samples in continental rift and collision settings. The plots of Ni against TiO₂, La/Sc vs. Th/Co and V–Ni–Th ?10 reveals that the sediments of Jhuran Formation were derived from felsic rock sources. Additionally, the diagram of (Gd/Yb) _N against Eu/Eu ^? suggest the post-Archean provenance as source possibly Nagar Parkar complex for the studied samples.     

Proximal and distal styles of pegmatite-related metasomatic emerald mineralization at Ianapera,southern Madagascar

The Ianapera emerald deposit is located in the Neoproterozoic Vohibory Block of southern Madagascar. The local geology consists of intercalated migmatitic gneissic units and calcareous metasedimentary rocks, containing boudinaged metamorphosed mafic/ultramafic lenses, all intruded by pegmatite veins. These units occur near the hinge of the tightly folded Ianapera antiform, within a few kilometers of the Ampanihy shear zone. Emerald mineralization is hosted by metasomatic phlogopite veins, and bodies developed within the mafic/ultramafic rocks. Based on field and textural relationships, we distinguish proximal and distal styles of mineralization. Proximal mineralization occurs at the contact of pegmatite veins with mafic/ultramafic units; in the distal style, pegmatites are not observed. Three types of emeralds could be distinguished, mainly on the basis of color and mineral zoning. Some of these emeralds have the most Al-depleted and Cr-rich composition ever recorded. Another characteristic feature to the Ianapera deposit and, to our knowledge, yet unreported, is the association of some emeralds with scapolite in metasomatised mafic rocks. Mineral inclusions are common in most emeralds and include phlogopite, carbonates, barite, K-feldspar, quartz, pyrite, zircon, monazite, bastnaesite, phenakite, plus Fe and Cr oxides. However, feldspar and rare earth element-bearing minerals occur predominantly in proximal emeralds, which also have a more incompatible trace-element signature than distal emeralds. We propose a model related to syn- to post-tectonic magmatic-hydrothermal activity. Pegmatitic bodies intruded units of the Ianapera antiform probably during tectonic relaxation. Exsolution of fluids rich in halogens and incompatible elements from the cooling pegmatites caused hydrothermal metasomatism of Cr-bearing mafic/ultramafic rocks in direct contact with the pegmatites. Local fracturing favored fluid infiltration, permitting the formation of distal mineralization. Emerald composition was controlled by the chemistry of the host rock. The presence of carbonate mineral inclusions in the emeralds and the high F-activity indicated by elevated F-contents in newly formed minerals suggest transport of Be as a fluoride-carbonate complex. It seems likely that beryl formation was triggered by precipitation of F-rich phlogopite, which removed the complexing ligand from the fluid.     

Tin partition behavior and implications for the Furong tin ore formation associated with peralkaline intrusive granite in Hunan Province,China

Tin deposits are often closely associated with granitic intrusions. In this study, we analyzed tin partition coefficients between different fluids and melts (\({\text{D}}_{Sn}^{aq.fl./melt}\)) as well as various crystals and melts \({\text{D}}_{Sn}^{aq.fl./melt}\)(\({\text{D}}_{Sn}^{crystal/melt}\)) from the Furong tin deposit associated with the Qitianling A-type granite. Our experimental results indicate that tin partition behavior is affected by the chemical compositions of fluids, melts, and minerals. Tin is prone to partitioning into the residual magma in fractional crystallization or other differential magmatic processes if the magma originated from crustal sources with high alkali content, high volatile content, and low oxygen fugacity. Highly evolved residual peralkaline granitic magma enriched in tin can lead to tin mineralization in a later stage. Furthermore, the volatiles F and Cl in the magma play important roles in tin partitioning behavior. Low F contents in the melt phase and high Cl content in the aqueous fluid phase are favorable factors for tin partitioning in the aqueous fluid phase. High Cl content in the aqueous fluid catalyzes water–rock interaction and leads to the extraction of tin from tin-bearing minerals. All these findings support a hydrothermal origin for the tin deposits. In light of the geotectonic setting, petrochemical characteristics, and mineralizing physicochemical conditions of the Furong tin deposit, it is inferred that the ore-forming fluid of the Furong tin ore deposit could have derived from the Qitianling peralkaline intrusion.     

Spatio-temporal trends of heavy metals and source apportionment in Tolo Harbour,Hong Kong

This study provided a picture of the spatial and temporal distributions of Cr, Co, Ni Cu, Zn, As, Cd and Pb in bottom sediments of Tolo Harbour. The concentrations of the eight heavy metals differed significantly between sites due to the poor tidal flushing in Tolo Harbour. The levels of Cu, Zn, Cd and Pb were generally enriched in sediments from inner Tolo Harbour, while sediments from outer Tolo Harbour (Tolo Channel) had higher levels of Cr, Co and Ni. The redox sensitive element arsenic showed no distinct spatial pattern in Tolo Harbour. The decreasing levels of Cu, Zn, Pb and Cd in sediments with increasing distance from land demonstrated a typical diffusion pattern from land to the direction of sea. Two hot spots of Cu, Zn, Pb and Cd in sediments were located near Tai Po and Sha Tin new town, indicating that Cu, Zn, Pb and Zn were from land-derived sources. The sites with relatively high levels of Cr, Co and Ni in sediments were located in areas close to waste spoil in sea floor. The natural and anthropogenic inputs from Sha Tin and Tai Po to Tolo Harbour were mostly responsible for Cu, Zn, Cd and Pb enrichment in sediments from inner Tolo Harbour. The waste spoil in sea floor was believed to contribute to the Cr, Co and Ni in outer Tolo Harbour. The results of correlation coefficient between the eight heavy metals showed that Cu, Zn, Cd and Pb were strongly positively correlated, and Cr, Co and Ni were also significantly correlated with each other. The best explanation of strong correlation was their similar source. As, however, is not well correlated with the other seven heavy metals. The average concentrations of Cu and Zn displayed general increasing trends from 1978 to 2006 in Tolo Harbour, while the mean levels of Cr and Pb displayed a substantial decrease from 1978 to 1987, then a slight increase after 1987. No distinct temporal trends of the concentrations of Ni and As were observed from 1978 due to the inconsecutive data. On the other hand, the increasing trends of Cr, Cu, Zn, Cd and Pb were observed since 1996.