Planetesimal sulfate and aqueous alteration in CM and CI carbonaceous chondrites

Water-soluble sulfate salts extracted from six CM chondrites have oxygen isotope compositions that are consistent with an extraterrestrial origin. The Δ¹⁷O of sulfate are correlated with previously reported whole rock δ¹⁸O and with an index of meteorite alteration, and may display a correlation with the date of the fall. The enrichments and depletions for Δ¹⁷O of water-soluble sulfate from the CM chondrites relative to the terrestrial mass dependent fractionation line are consistent with sulfate formation in a rock dominated asteroidal environment, and from aqueous fluids that had undergone relatively low amounts of oxygen isotope exchange and little reaction with anhydrous components of the meteorites. It is unresolved how the oxidation of sulfide to sulfate can be reconciled with the inferred low oxidation state during the extraterrestrial alteration process. Oxygen isotope data for two CI chondrites, Orgueil and Ivuna, as well as the ungrouped C2 chondrite Essebi are indistinguishable from sulfate of terrestrial origin and may be terrestrial weathering products, consistent with previous assertions. Our oxygen isotope data, however, can not rule out a preterrestrial origin either.     

Flowers in the bathtub: boundary crossings at the public-private divide

Legal spaces are said to be a crucial materialization of law, serving to communicate legal meaning and, in so doing, helping to produce a liberal-legal consciousness. Given its centrality to legal ordering and liberal ideology, the spatial manifestation of the public-private divide, especially when related to property, would appear to be particularly important in this regard. Public and private are assumed to be both mutually exclusive and exhaustive. Drawing upon empirical research conducted in a neighbourhood in Vancouver, Canada, I argue that spatial and legal categories such as public and private may be more fluid than one might suppose. While the public/private divide is clearly powerful, and informs much policy and governmental action, it is not necessarily the case that it has the purchase on everyday life that some scholars have suggested. People may live in more complicated and overlapping worlds when it comes to supposedly determinate categories such as property.     

Zircon M127 – A Homogeneous Reference Material for SIMS U–Pb Geochronology Combined with Hafnium,Oxygen and,Potentially, Lithium Isotope Analysis

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS‐determined mean U–Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for ²⁰⁶Pb/²³⁸U and 0.67676 ± 0.00023 for ²⁰⁷Pb/²³⁵U (weighted means, 2s uncertainties). Its ²⁰⁶Pb/²³⁸U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The δ¹⁸O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio (determined by solution ICP‐MS) is 0.282396 ± 0.000004 (2s). The SIMS‐determined δ⁷Li value is ?0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 μg g^?1 Li (2s). Zircon M127 contains ~ 923 μg g^?1 U. The moderate degree of radiation damage corresponds well with the time‐integrated self‐irradiation dose of 1.82 × 10¹⁸ alpha events per gram. This observation, and the (U–Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U–Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.     

Mineralogical and geochemical characterization of precipitates on stream receiving acid mine water, Korea

Seasonal variations of water chemistry occurred in acid mine drainage receiving mine and leachate water. Sulfate and metal concentrations were low in winter but high in spring and summer. Mine waters were highly acidic (up to pH 3.4) in nature with high concentrations of manganese, copper and zinc but high electrical conductivity and sulfate in leachate. The blue and brownish yellow precipitates were formed under different chemical environments of acid mine drainage. Brownish yellow (Munsell color 7.5YR 8/12), blue (Munsell color 2.5B 9/7) and light blue (Munsell color 2.5B 9/3) precipitates deposited on the stream bottom receiving acid mine water. The brownish yellow precipitates formed in the acid mine water, whereas the blue and light blue precipitates formed in the leachate water. The brownish yellow precipitates consisted mainly of ferrihydrite, whereas the blue and light blue precipitates consisted of glaucocerinite and/or woodwardite.     

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.     

Cu(II) adsorption at the calcite-water interface in the presence of natural organic matter: Kinetic studies and molecular-scale characterization

We have characterized the adsorption of Suwannee River humic acid (SRHA) and Cu(II) on calcite from preequilibrated solutions at pH 8.25. Sorption isotherms of SRHA on calcite follow Langmuir-type behavior at SRHA concentrations less than 15 mg C L⁻¹, whereas non-Langmuirian uptake becomes evident at concentrations greater than 15 mg C L⁻¹. The adsorption of SRHA on calcite is rapid and mostly irreversible, with corresponding changes in electrostatic properties. At pH 8.25, Cu(II) uptake by calcite in the presence of dissolved SRHA decreases with increasing dissolved SRHA concentration, suggesting that formation of Cu-SRHA aqueous complexes is the primary factor controlling Cu(II) sorption at the calcite surface under the conditions of our experiments. We also observed that surface-bound SRHA has little influence on Cu(II) uptake by calcite, suggesting that Cu(II) coordinates to calcite surface sites rather than to surface-bound SRHA.Cu K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectroscopic results show that the local coordination of Cu adsorbed at the calcite surface is very similar in the presence and absence of SRHA. Ca backscatterers at ∼3.90 Å indicate that Cu(II) forms tetragonally distorted inner-sphere adsorption complexes in both binary and ternary systems. Subtle differences in the XANES and EXAFS between binary sorption samples and ternary sorption samples, however, prevent us from ruling out the formation of ternary Cu-SRHA surface complexes. Our findings demonstrate that SRHA plays an important role in controlling the fate and transport of Cu(II) in calcite-bearing systems.     

A Closure Study of Aerosol Hygroscopic Growth Factor during the 2006 Pearl River Delta Campaign

Measurements of aerosol physical, chemical and optical parameters were carried out in Guangzhou, China from 1 July to 31 July 2006 during the Pearl River Delta Campaign. The dry aerosol scattering coefficient was measured using an integrating nephelometer and the aerosol scattering coefficient for wet conditions was determined by subtracting the sum of the aerosol absorption coefficient, gas scattering coefficient and gas absorption coefficient from the atmospheric extinction coefficient. Following this, the aerosol hygroscopic growth factor, f(RH), was calculated as the ratio of wet and dry aerosol scattering coefficients. Measurements of size-resolved chemical composition, relative humidity (RH), and published functional relationships between particle chemical composition and water uptake were likewise used to find the aerosol scattering coefficients in wet and dry conditions using Mie theory for internally- or externally-mixed particle species [(NH₄)₂SO₄, NH₄NO₃, NaCl, POM, EC and residue]. Closure was obtained by comparing the measured f(RH) values from the nephelometer and other in situ optical instruments with those computed from chemical composition and thermodynamics. Results show that the model can represent the observed f(RH) and is appropriate for use as a component in other higher-order models.     

Source identification of PM2.5 particles measured in Gwangju, Korea

The UNMIX and Chemical Mass Balance (CMB) receptor models were used to investigate sources of PM_2.5 aerosols measured between March 2001 and February 2002 in Gwangju, Korea. Measurements of PM_2.5 particles were used for the analysis of carbonaceous species (organic (OC) and elemental carbon (EC)) using the thermal manganese dioxide oxidation (TMO) method, the investigation of seven ionic species using ion chromatography (IC), and the analysis of twenty-four metal species using Inductively Coupled Plasma (ICP)-Atomic Emission Spectrometry (AES)/ICP-Mass Spectrometry (MS). According to annual average PM_2.5 source apportionment results obtained from CMB calculations, diesel vehicle exhaust was the major contributor, accounting for 33.4% of the measured PM_2.5 mass (21.5 μg m^− 3), followed by secondary sulfate (14.6%), meat cooking (11.7%), secondary organic carbon (8.9%), secondary nitrate (7.6%), urban dust (5.5%), Asian dust (4.4%), biomass burning (2.8%), sea salt (2.7%), residual oil combustion (2.6%), gasoline vehicle exhaust (1.9%), automobile lead (0.5%), and components of unknown sources (3.4%). Seven PM_2.5 sources including diesel vehicles (29.6%), secondary sulfate (17.4%), biomass burning (14.7%), secondary nitrate (12.6%), gasoline vehicles (12.4%), secondary organic carbon (5.8%) and Asian dust (1.9%) were identified from the UNMIX analysis. The annual average source apportionment results from the two models are compared and the reasons for differences are qualitatively discussed for better understanding of PM_2.5 sources.Additionally, the impact of air mass pathways on the PM_2.5 mass was evaluated using air mass trajectories calculated with the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) backward trajectory model. Source contributions to PM_2.5 collected during the four air mass patterns and two event periods were calculated with the CMB model and analyzed. Results of source apportionment revealed that the contribution of diesel traffic exhaust (47.0%) in stagnant conditions (S) was much higher than the average contribution of diesel vehicle exhaust (33.4%) during the sampling period. During Asian dust (AD) periods when the air mass passed over the Korean peninsula, Asian dust and secondary organic carbon accounted for 25.2 and 23.0% of the PM_2.5 mass, respectively, whereas Asian dust contributed only 10.8% to the PM_2.5 mass during the AD event when the air mass passed over the Yellow Sea. The contribution of biomass burning to the PM_2.5 mass during the biomass burning (BB) event equaled 63.8%.     

Observations of boundary-layer convection cells measured by dual-Doppler radar and echosonde,and by microbarograph array

Three-dimensional air motion, observed with radar in a convective planetary boundary layer under light wind conditions, is organized in cellular structures scaled from 2 to 5 km; simultaneous acoustic echosonde measurements indicate that near the ground there are smaller cells than those observable by the radar. At heights of 400 m, cell scales become as large as those observable by the radar. Pressure fluctuations at the ground measured with spatial pressure transducers, at the same time as the radar and echosonde observations, traveled at the same speed and direction as the radar volume-averaged wind. The length scale determined at the ground with pressure fluctuation data was between 1.2 and 2.4 km, smaller than the largest radar-measured motion scales.