AOX‐Bildung bei der sonolytischen Oxidation von Salicylsäure in Gegenwart von Chlorid

AOX‐formation by the Sonochemical Treatment of Salicylic Acid in Presence of Chloride Ultrasound shows great potential for improving water, wastewater and sludge treatment processes. However, a number of questions exist: for example the influence of suspended solids or salts. In this paper the influence of chloride in view of AOX‐formation should be investigated. As organic model compound salicylic acid (0.05…1 mmol/L) was used. Formation of AOX (adsorbable organically bound halogens) was measured in dependence upon chloride concentrations (1.4…141 mmol/L) and pH 2 and 9. Ultrasound irradiation was performed in glass reactor (500 mL) at 206 kHz and 353 kHz by continuous bubbling argon:oxgen (4:1) at a flow rate of 1 L/min into the solutions. The elimination of salicylic acid and the formation of hydrogen peroxide were not influenced by the presence of chloride (up to 56 mmol/L). The rate of salicylic acid elimination and the formation rate of hydrogen peroxide are at concentrations of mmol/(L min) levels but those of AOX formation of μmol/(L min) levels. The reactions leading to chlorinated by‐products can be seen as minor reaction paths. The yield of AOX depending on frequency, pH and chloride concentration lies between 10 μg/L and 900 μg/L. In acidic medium they were twice as high as in basic medium. Below the ratio chloride : salicylic acid of 2 mol/mol, AOX could not be identified.     

Arsenic fixation on iron-hydroxide-rich and plant litter-containing sediments in natural environments

Iron-hydroxide-rich and plant litter-containing sediments from natural sites contaminated with uranium mine tailing leachates were examined for their ability to adsorb arsenic. The samples with high contents of iron hydroxides (Fe_total concentration, >300 g kg⁻¹) exhibited remarkable fixation of arsenic (up to 40 g As kg⁻¹). This value corresponded approximately to the supersaturation point for natural iron hydroxides under the present conditions, and it was significantly lower than the value found for synthetic iron hydroxides. There was a strong correlation (R=0.8999) between the concentration of iron and that of arsenic at low arsenic contents, indicating adsorption on strong binding sites. Although all the samples had noticeable contents of organic carbon (plant litter), calcium, and manganese, no obvious effect of these elements on arsenic fixation could be detected. The amount of iron hydroxides was found the only fixation-controlling parameter immediately below a leaching water source.     

Advection and removal of Pb and stable Pb isotopes in the oceans: a general circulation model study

Natural Pb-isotope variability in the oceans encodes information about the sources of continental material to the oceans, about ocean circulation, and about Pb removal. In order to use this information, we must understand the natural cycle of Pb in the oceans, which is overprinted by large anthropogenic input. In this study we use ²¹⁰Pb, which has not been significantly anthropogenically perturbed, to investigate oceanic Pb. GEOSECS ²²⁶Ra and model-derived atmospheric fluxes of ²¹⁰Pb are used to input ²¹⁰Pb into an ocean general circulation model. Irreversible scavenging of this ²¹⁰Pb onto settling biogenic particles and at the seafloor are tuned so that the model replicates the observed pattern of ²¹⁰Pb in the oceans. The best-fit model run provides a map of the variability of residence time for Pb. The global average residence time of Pb in this model is 48 yr, but there is over an order of magnitude variation between areas of high and low productivity. This is expected to enhance provinciality of Pb isotope ratios in the oceans. Because stable Pb isotopes are expected to behave in seawater in a similar fashion to ²¹⁰Pb, the pattern of removal of ²¹⁰Pb derived by the model can be used to investigate the behavior of stable Pb isotopes. We use a simplified input of Pb consisting of five point sources representing major rivers and a disseminated dust input. Although this simplified input scheme does not allow precise reconstruction of Pb concentration and isotopes in the oceans, it allows us to answer some first-order questions about the behavior of Pb as an ocean tracer. With a total Pb input of 6.3 × 10⁷ mol/yr (Chow T. J. and Patterson C. C., “The occurrence and significance of Pb isotopes in pelagic sediments,” Geochim. Cosmochim. Acta26, 263-308, 1962), the model predicts natural seawater Pb concentrations averaging 2.2 pmol/kg. Even in the absence of anthropogenic input, the model ocean exhibits a near-surface maximum in Pb concentration. And the model suggests natural Pb concentrations in the Northern Hemisphere an order of magnitude higher than in the Southern Hemisphere. A point source of Pb is suggested to dominate the seawater Pb inventory close to the source but is reduced to typically less than 10% of the inventory by the time that Pb is advected out of the originating ocean. This length scale of advection for Pb isotope signals confirms their potential as tracers of ocean circulation. Assuming an 8% dissolution of dust, their input to the open ocean are seen to be a significant portion of Pb inventory throughout the oceans and make up >50% of the Pb inventory in the model’s Southern Ocean. Finally, a preliminary investigation of the response of Pb-isotope distributions to changes in boundary conditions between glacial and interglacial times illustrates that significant variation in the Pb isotopes are expected in some regions, even for reasonably small changes in climate conditions.     

Isotopic Composition of Non-Methane Hydrocarbons in Emissions from Biomass Burning

The stable carbon isotope ratios of nonmethane hydrocarbons (NMHC) and methyl chloride emitted from biomass burning were determined by analyzing seven whole air samples collected during different phases of the burning process as part of a laboratory study of wood burning. The average of the stable carbon isotope ratios of emitted alkanes, alkenes and aromatic compounds is identical to that of the burnt fuel; more than 50% of the values are within a range of ±1.5 of thecomposition of the burnt fuel wood. Thus for the majority of NMHC emitted from biomass burning stable carbon isotope ratio of the burnt fuel a good first order approximation for the isotopic composition of the emissions. Of the more than twenty compounds we studied, only methyl chloride and ethyne differed in stable carbon isotope ratios by more than a few per mil from the composition of the fuel. Ethyne is enriched in ¹³C by approximately 20–30, and most of the variability can beexplained by a dependence on flame temperature. The ¹³C values decreaseby 0.019 /K (±0.0053/K) with increasing temperature. Methyl chloride is highly depleted in ¹³C, on average by25. However the results cover a wide range of nearly 30. Specifically, in two measurements with wood from Eucalyptus (Eucalyptus delegatensis) as fuel we observed the emission of extremely light methyl chloride (–68.5and–65.5). This coincides with higher than average emission ratiosfor methyl chloride (15.5 × 10^–5 and 18 ×10^–5 mol CH₃Cl/mol CO₂). These high emission ratios are consistent with the highchlorine content of the burnt fuel, although, due to the limited number of measurements, it would be premature to generalize these findings. The limited number of observations also prevents any conclusion on a systematic dependence between chlorine content of the fuel, emission ratios and stable carbon isotope ratio of methyl chloride emissions. However, our results show that a detailed understanding of the emissions of methyl chloride from chloride rich fuels is important for understanding its global budget. It is also evident that the usefulness of stable carbon isotope ratios to constrain the global budget of methyl chloride will be complicated by the very large variability of the stable carbon isotope ratio of biomass burning emissions. Nevertheless, ultimately the large fractionation may provide additional constraints for the contribution of biomass burning emissions to the atmospheric budget of methyl chloride.     

Experimental studies to 10 kb of the bulk composition tremolite50-tschermakite50+excess H2O

Phase relations for the magnesio-hornblende bulk composition, 2 CaO·4 MgO·Al₂O₃·7 SiO₂+ excess H₂O, have been investigated to 10 kb employing hydrothermal and piston-cylinder techniques. The low-temperature limit of amphibole in this system lies at 519° C, 1,000 bars, 541° C, 2,000 bars, and 718° C, 10 kb. The low-T assemblage consists of an+chl+di+tc(+f), and is related to the adjacent high-T equilibrium assemblage, amph+an+chl+f, by the solid-solid reaction (A): 2 di+tc=tr. Small amounts of aluminum, hypothesized to be preferentially dissolved in the cpx (and in the tc) relative to amph, may account for the broad P-T stability range of the di+tc assemblage in the synthetic work relative to systems involving stoichiometric tr, Ca₂Mg₅Si₈O₂₂(OH)₂, such as are common in natural, Al-poor calc-silicate parageneses. Alternatively, the low-temperature assemblage produced in the experiments may be metastable. For the investigated bulk composition, synthetic tremolitic-cummingtonitic amphibole contains relatively modest amounts of ts, Ca₂Mg₃Al₂ ^IVSi₆-Al₂ ^IVO₂₂(OH)₂; at pressures of 1,000–3,000 bars, solid solution extends from near tremolite only to about cu₁₁tr₆₉ts₂₀, analogous to most analyzed natural magnesio-hornblendic specimens. At 10 kb fluid pressure, the solid solution reaches approximately cu₀₆tr₅₃ts₄₁ for the investigated bulk composition, and appears to be virtually independent of temperature. Amphibole and 14 Å chl react within the amphibole stability field, along curve (B), at about 704° C and 2,000 bars, to produce an, en, fo and f (H=40.9 kcal/ mole); at pressures greater than approximately 7kb, due to the incompatibility of an and fo, the higher temperature assemblage consists of amph, an, en, sp and f. Above P _fluid– T curve (B), the amphibole coexists with an+en+fo+f at low pressures; at higher pressures, the amphibole, which is in equilibrium with an+en+sp+f, is relatively more aluminous. The high-T stability limit of aluminous tr+fo lies approximately 20–25° C below the dehydration curve for stoichiometric tremolite on its own bulk composition. Reaction (C), tr+fo=2 di+5 en+f (H = 39.4 kcal/mole), produces an+di+en+f, the highest temperature subsolidus assemblage investigated for the tr₅₀ts₅₀ bulk composition. Hydrous melt is encountered at temperatures at least as low as 900° C at 10 kb, and at that fluid pressure coexists with amphibole over an interval of more than 60° C. Limited solid solution observed between tr and ts in nature (tr_100-70) is accounted for by the restricted range of amphibole compositions produced in the present study. Such amphiboles, moreover, appear to have both high- and low-temperature stability limits, as demonstrated by the experimental results.Institute of Geophysics and Planetary Physics Publication No. 2811     

The heat transfer in the region of the Mauna Kea (Hawaii)—constraints from borehole temperature measurements and coupled thermo-hydraulic modeling

The objectives of this paper are an understanding of the thermal and hydraulic field because of a negative temperature gradient and cold temperatures in the 1-km-deep borehole of the Hawaiian Scientific Drilling Project (HSDP), located near the coast line. The temperature pattern is attributed to a superposition of thermal and hydraulic processes. In the deeper borehole (HSDP-2, depth 3.1 km) detailed temperature monitoring was performed. Temperature measurements reveal two different thermal regimes. The upper part is characterised by cold temperatures and a negative temperature gradient similar to those observed in the shallow pilot borehole. Below 1100 m, increasing temperatures are observed. Different processes, such as topographically driven groundwater flow, ingress of salt water and conductive heat flow are investigated by numerical modeling. A pure conductive scenario fails to match the temperature measurements, implying that both borehole sections are overprinted by advective conditions. Coupled fluid and heat flow modeling with solute transport yield results that agree with observed temperatures. The results of these simulations suggest that meteoric water flow from the mountain range controls the thermal conditions in the upper part of the borehole. Below this level, the thermal regime is additionally affected by circulation of salt water from the nearby ocean. Each of these flow systems has been observed at other locations: topographically driven fresh water at locations with pronounced topography and ingress of salt water is typical for islands or coastal areas. At Hawaii, they coincide and influence each other, resulting in a salt water interface occurring at greater depth than expected.     

A plagioclase-olivine-spinel-magnetite inclusion from Maralinga (CK): evidence for sequential condensation and solid-gas exchange

We report a detailed petrography, mineral chemistry, and trace element study of MaTroc, a large calcium-aluminum-rich inclusion (CAI) (5 × 2.5 mm) of irregular triangular shape. The inclusion has a zonal structure: The core consists of a porous plagioclase-olivine-Ca-rich pyroxene intergrowth with subordinate apatite. Its texture is meta-gabbro-like, similar to other plagioclase-olivine inclusions (POIs). The mantle has variable thickness (0.1-1.5 mm) and consists of a compact symplectitic intergrowth of spinel (hercynite) and plagioclase with abundant dispersed magnetite, subordinate Ca-rich pyroxene, and traces of sulfides. The thin (5-50 μm) discontinuous crust of MaTroc consists mainly of plagioclase with some olivine and magnetite.The Mg-Fe phases of MaTroc are Fe-rich: olivine has Fa33.2 and high NiO content, similar to that in the host rock, Ca-rich pyroxene has much lower TiO₂ and Cr₂O₃ contents than that of the host chondrite, and plagioclase is An55-An74. Magnetites have variable compositions, are poorer in Al₂O₃ and Cr₂O₃ and richer in NiO than those in the host. Spinels have also variable compositions, rich in FeO, NiO, and ZnO.Despite their different mineralogy, both core and mantle have bulk trace element abundances similar to those in average group II CAIs. However, the mantle is richer in Nb and U and poorer in Eu, Be, B, Sr, and Li than the core. All minerals have high trace element contents. Minerals in the core show signs of incomplete equilibration of trace elements within and between them. Mantle minerals are far from equilibrium with each other and the bulk system. Spinel and anorthite carry the trace element signature of their precursor melilite (or hibonite), and magnetite contains large amounts of a heterogeneously distributed remnant extremely rich in trace elements (“obscurite”), possibly of a former perovskite.Inclusion MaTroc has a complex history. The POI core probably formed by reaction of an unknown precursor(s) of condensation origin with a vapor to form olivine, plagioclase, clinopyroxene, apatite, and (an) unknown phase(s) that vanished, leaving abundant void space. The spinel-rich mantle is also a secondary mineral assemblage that formed by breakdown of and solid-vapor reactions with a precursor or precursors, possibly melilite (or hibonite). The abundant magnetite formed by reaction of perovskite with an oxidizing vapor and by precipitation from such a vapor. All phases of the inclusion experienced the metasomatic addition of Fe, Ni, and moderately volatile elements such as V, Be, Li, Cr, and Mn—similar to all other constituents of the Maralinga CK chondrite. Phases in MaTroc and in the host rock are close to equilibrium in the distribution of Fe, Mg, Ni, and Mn but far from equilibrium in the distribution of M⁺³ and M⁺⁴ ions. The minor and trace element abundances in the magnetite of the host rock and of MaTroc preclude an origin by oxidation of a metal precursor.