Shear strength characterization of municipal solid waste at the Suzhou landfill, China

The current practice of slope stability analysis for a municipal solid waste (MSW) landfill usually overlooks the dependence of waste properties on the fill age or embedment depth. Changes in shear strength of MSW as a function of fill age were investigated by performing field and laboratory studies on the Suzhou landfill in China. The field study included sampling from five boreholes advanced to the bottom of the landfill, cone penetration tests and monitoring of pore fluid pressures. Twenty-six borehole samples representative of different fill ages (0 to 13 years) were used to perform drained triaxial compression tests. The field and laboratory study showed that the waste body in the landfill can be sub-divided into several strata corresponding to different ranges of fill age. Each of the waste strata has individual composition and shear strength characteristics. The triaxial test results showed that the MSW samples exhibited a strain-hardening and contractive behavior. As the fill age of the waste increased from 1.7 years to 11 years, the cohesion mobilized at a strain level of 10% was found to decrease from 23.3 kPa to 0 kPa, and the mobilized friction angle at the same strain level increasing from 9.9° to 26°. For a confinement stress level greater than 50 kPa, the shear strength of the recently-placed MSW seemed to be lower than that of the older MSW. This behavior was consistent with the cone penetration test results. The field measurement of pore pressures revealed a perched leachate mound above an intermediate cover of soils and a substantial leachate mound near the bottom of the landfill. The measurements of shear strength properties and pore pressures were utilized to assess the slope stability of the Suzhou landfill.     

Assessing soil erosion in Mediterranean karst landscapes of Lebanon using remote sensing and GIS

Maps showing the potential for soil erosion at 1:100,000 scale are produced in a study area within Lebanon that can be used for evaluating erosion of Mediterranean karstic terrain with two different sets of impact factors built into an erosion model. The first set of factors is: soil erodibility, morphology, land cover/use and rainfall erosivity. The second is obtained by the first adding a fifth factor, rock infiltration. High infiltration can reflect high recharge, therefore decreasing the potential of surface runoff and hence the quantity of transported materials. Infiltration is derived as a function of lithology, lineament density, karstification and drainage density, all of which can be easily extracted from satellite imagery. The influence of these factors is assessed by a weight/rate approach sharing similarities between quantitative and qualitative methods and depending on pair-wise comparison matrix.The main outcome was the production of factorial maps and erosion susceptibility maps (scale 1:100,000). Spatial and attribute comparison of erosion maps indicates that the model that includes a measure of rock infiltration better represents erosion potential. Field investigation of rills and gullies shows 87.5% precision of the model with rock infiltration. This is 17.5% greater than the precision of the model without rock infiltration. These results indicate the necessity and importance of integrating information on infiltration of rock outcrops to assess soil erosion in Mediterranean karst landscapes.     

Oxygen isotopic compositions of Allende Type C CAIs: Evidence for isotopic exchange during nebular melting and asteroidal metamorphism

In situ oxygen isotopic measurements of primary and secondary minerals in Type C CAIs from the Allende CV3 chondrite reveal that the pattern of relative enrichments and depletions of ¹⁶O in the primary minerals within each individual CAI are similar to the patterns observed in Types A and B CAIs from the same meteorite. Spinel is consistently the most ¹⁶O-rich (Δ¹⁷O = −25‰ to −15‰), followed by Al,Ti-dioside (Δ¹⁷O = −20‰ to −5‰) and anorthite (Δ¹⁷O = −15‰ to 0‰). Melilite is the most ¹⁶O-depleted primary mineral (Δ¹⁷O = −5‰ to −3‰). We conclude that the original melting event that formed Type C CAIs occurred in a ¹⁶O-rich (Δ¹⁷O  −20‰) nebular gas and they subsequently experienced oxygen isotopic exchange in a ¹⁶O-poor reservoir. At least three of these (ABC, TS26F1 and 93) experienced remelting at the time and place where chondrules were forming, trapping and partially assimilating ¹⁶O-poor chondrule fragments. The observation that the pyroxene is ¹⁶O-rich relative to the feldspar, even though the feldspar preceded it in the igneous crystallization sequence, disproves the class of CAI isotopic exchange models in which partial melting of a ¹⁶O-rich solid in a ¹⁶O-poor gas is followed by slow crystallization in that gas. For the typical (not associated with chondrule materials) Type C CAIs as well for as the Types A and B CAIs, the exchange that produced internal isotopic heterogeneity within each CAI must have occurred largely in the solid state. The secondary phases grossular, monticellite and forsterite commonly have similar oxygen isotopic compositions to the melilite and anorthite they replace, but in one case (CAI 160) grossular is ¹⁶O-enriched (Δ¹⁷O = −10‰ to −6‰) relative to melilite (Δ¹⁷O = −5‰ to −3‰), meaning that the melilite and anorthite must have exchanged its oxygen subsequent to secondary alteration. This isotopic exchange in melilite and anorthite likely occurred on the CV parent asteroid, possibly during fluid-assisted thermal metamorphism.     

Iron isotopes constrain biologic and abiologic processes in banded iron formation genesis

The voluminous 2.5 Ga banded iron formations (BIFs) from the Hamersley Basin (Australia) and Transvaal Craton (South Africa) record an extensive period of Fe redox cycling. The major Fe-bearing minerals in the Hamersley-Transvaal BIFs, magnetite and siderite, did not form in Fe isotope equilibrium, but instead reflect distinct formation pathways. The near-zero average δ⁵⁶Fe values for magnetite record a strong inheritance from Fe³⁺ oxide/hydroxide precursors that formed in the upper water column through complete or near-complete oxidation. Transformation of the Fe³⁺ oxide/hydroxide precursors to magnetite occurred through several diagenetic processes that produced a range of δ⁵⁶Fe values: (1) addition of marine hydrothermal , (2) complete reduction by bacterial dissimilatory iron reduction (DIR), and (3) interaction with excess that had low δ⁵⁶Fe values and was produced by DIR. Most siderite has slightly negative δ⁵⁶Fe values of ∼ −0.5‰ that indicate equilibrium with Late Archean seawater, although some very negative δ⁵⁶Fe values may record DIR. Support for an important role of DIR in siderite formation in BIFs comes from previously published C isotope data on siderite, which may be explained as a mixture of C from bacterial and seawater sources.Several factors likely contributed to the important role that DIR played in BIF formation, including high rates of ferric oxide/hydroxide formation in the upper water column, delivery of organic carbon produced by photosynthesis, and low clastic input. We infer that DIR-driven Fe redox cycling was much more important at this time than in modern marine systems. The low pyrite contents of magnetite- and siderite-facies BIFs suggests that bacterial sulfate reduction was minor, at least in the environments of BIF formation, and the absence of sulfide was important in preserving magnetite and siderite in the BIFs, minerals that are poorly preserved in the modern marine record. The paucity of negative δ⁵⁶Fe values in older (Early Archean) and younger (Early Proterozoic) BIFs suggests that the extensive 2.5 Ga Hamersley-Transvaal BIFs may record a period of maximum expansion of DIR in Earth’s history.     

Surface complexation of U(VI) on goethite (α-FeOOH)

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.     

Seasonal patterns of carbon chemistry and isotopes in tufa depositing groundwaters of southwestern Japan

Annually laminated carbonates, known as tufas, commonly develop in limestone areas and typically record seasonal patterns of oxygen- and carbon-isotope compositions. δ¹⁸O values are principally controlled by seasonal changes of water temperature, whereas δ¹³C values are the result of complex reactions among the gaseous, liquid, and solid sources of carbon in the system. We examined the processes that cause the seasonal patterns of δ¹³C in groundwater systems at three tufa-depositing sites in southwestern Japan by applying model calculations to geochemical data. Underground inorganic carbon species are exchanged with gaseous CO₂, which is mainly introduced to the underground hydrological system by natural atmospheric ventilation and by diffusion of soil air. These processes control the seasonal pattern of δ¹³C, which is low in summer and high in winter. Among the three sites we investigated, we identified two extreme cases of the degree of carbon exchange between liquid and gaseous phases. For the case with high radiocarbon composition (Δ¹⁴C) and low pCO₂, there was substantial carbon exchange because of a large contribution of atmospheric CO₂ and a small water mass. For the other extreme case, which was characterized by low Δ¹⁴C and high pCO₂, the contribution of atmospheric CO₂ was small and the water mass was relatively large. Our results suggest that at two of the three sites water residence time within the soil profile was longer than 1 year. Our results also suggested a short residence time (less than 1 year) of water in the soil profile at the site with the smallest water mass, which is consistent with large seasonal amplitude of the springwater temperature variations. The Δ¹⁴C value of tufas is closely related to the hydrological conditions in which they are deposited. If the initial Δ¹⁴C value of a tufa-depositing system is stable, ¹⁴C-chronology can be used to date paleo-tufas.     

Kinetics of Cd sorption, desorption and fixation by calcite: A long-term radiotracer study

Time-dependent sorption and desorption of Cd on calcite was studied over 210 days utilizing ¹⁰⁹Cd as a tracer to distinguish between ‘labile’ and ‘non-labile’ forms of sorbed Cd. Stabilizing the calcite suspensions for 12 months under atmospheric P_CO2 and controlled temperature was necessary to reliably follow Cd dynamics following initial sorption. Results revealed time-dependant Cd sorption and marked desorption hysteresis by calcite under environmentally relevant conditions. Data obtained were fitted to a first-order kinetic model and a concentric shell diffusion model. Both models described the progressive transfer of Cd²⁺ to a less reactive form within calcite and subsequent desorption of Cd subject to different initial contact times. The kinetic model provided a better fit to the combined sorption and desorption data (R² = 0.992). It differentiates between two ‘pools’ of sorbed Cd²⁺ on calcite, ‘labile’ and ‘non-labile’, in which labile sorbed Cd is in immediate equilibrium with the free Cd²⁺ ion activity in solution whereas non-labile Cd is kinetically restricted. For the diffusion model (R² = 0.959), the rate constants describing Cd dynamics in calcite produced a half-life for Cd desorption of ∼175 d, for release to a ‘zero-sink’ solution. Results from this study allow comment on the likely mechanisms occurring at the calcite surface following long-term Cd sorption.     

Silicon isotope fractionation in bamboo and its significance to the biogeochemical cycle of silicon

A systematic investigation on silica contents and silicon isotope compositions of bamboos was undertaken. Seven bamboo plants and related soils were collected from seven locations in China. The roots, stem, branch and leaves for each plant were sampled and their silica contents and silicon isotope compositions were determined. The silica contents and silicon isotope compositions of bulk and water-soluble fraction of soils were also measured. The silica contents of studied bamboo organs vary from 0.30% to 9.95%. Within bamboo plant the silica contents show an increasing trend from stem, through branch, to leaves. In bamboo roots the silica is exclusively in the endodermis cells, but in stem, branch and leaves, the silica is accumulated mainly in epidermal cells. The silicon isotope compositions of bamboos exhibit significant variation, from −2.3‰ to 1.8‰, and large and systematic silicon isotope fractionation was observed within each bamboo. The δ³⁰Si values decrease from roots to stem, but then increase from stem, through branch, to leaves. The ranges of δ³⁰Si values within each bamboo vary from 1.0‰ to 3.3‰. Considering the total range of silicon isotope composition in terrestrial samples is only 7‰, the observed silicon isotope variation in single bamboo is significant and remarkable. This kind of silicon isotope variation might be caused by isotope fractionation in a Rayleigh process when SiO₂ precipitated in stem, branches and leaves gradually from plant fluid. In this process the Si isotope fractionation factor between dissolved Si and precipitated Si in bamboo (α_pre-sol) is estimated to be 0.9981. However, other factors should be considered to explain the decrease of δ³⁰Si value from roots to stem, including larger ratio of dissolved H₄SiO₄ to precipitated SiO₂ in roots than in stem. There is a positive correlation between the δ³⁰Si values of water-soluble fractions in soils and those of bulk bamboos, indicating that the dissolved silicon in pore water and phytoliths in soil is the direct sources of silicon taken up by bamboo roots. A biochemical silicon isotope fractionation exists in process of silicon uptake by bamboo roots. Its silicon isotope fractionation factor (α_bam-wa) is estimated to be 0.9988. Considering the distribution patterns of SiO₂ contents and δ³⁰Si values among different bamboo organs, evapotranspiration may be the driving force for an upward flow of a silicon-bearing fluid and silica precipitation. Passive silicon uptake and transportation may be important for bamboo, although the role of active uptake of silicic acid by roots may not be neglected. The samples with relatively high δ³⁰Si values all grew in soils showing high content of organic materials. In contrast, the samples with relatively low δ³⁰Si values all grew in soil showing low content of organic materials. The silicon isotope composition of bamboo may reflect the local soil type and growth conditions. Our study suggests that bamboos may play an important role in global silicon cycle.     

Cr-spinel/olivine and Cr-spinel/liquid nickel partition coefficients from natural samples

The Nernst partition coefficient of nickel (D^Ni) between Cr-spinel and silicate melt in natural systems has been investigated using mid-ocean ridge basalts (MORB) and other volcanic rocks. The Cr-spinel/olivine D^Ni values in volcanic rocks are between 1.2 and 0.3, indicating that the Cr-spinel/liquid D^Ni values vary from slightly higher to significantly lower than the olivine/liquid D^Ni values in natural systems. The Cr-spinel/liquid D^Ni values from the MORB samples vary between 6 and 11, slightly higher than those from the S-bearing experiments of Satari et al. [Satari P., Brenan J. M., Horn I. and McDonough W. F. (2002) Experimental constraints on the sulfide- and chromite-silicate melt partitioning behavior of rhenium and platinum-group elements. Economic Geology97, 385-398]. The results of the MORB samples and the experiments of Satari et al. (2002) indicate a negative correlation between the Cr-spinel/liquid D^Ni and the X_Cr values in Cr-spinels (Cr cation number on the basis of 3 total cations in the spinel structure). Variations of Cr-spinel/liquid D^Ni values with Cr-spinel compositions can be estimated from an empirical equation based on the results of the MORB samples and the experiments by Satari et al. (2002). The choice of Cr-spinel/liquid D^Ni = 10 for numerical modeling by Righter et al. [Righter K., Leeman W. P. and Hervig R. L. (2006) Partitioning of Ni, Co, and V between spinel-structured oxides and silicate melts: importance of spinel composition. Chemical Geology227, 1-25] is reasonable for basaltic systems. For picritic and komatiitic systems a lower value of ∼5 is more appropriate.     

Evidence for crustal degassing of CF4 and SF6 in Mojave Desert groundwaters

Dissolved tetrafluoromethane (CF₄) and sulfur hexafluoride (SF₆) concentrations were measured in groundwater samples from the Eastern Morongo Basin (EMB) and Mojave River Basin (MRB) located in the southern Mojave Desert, California. Both CF₄ and SF₆ are supersaturated with respect to equilibrium with the preindustrial atmosphere at the recharge temperatures and elevations of the Mojave Desert. These observations provide the first in situ evidence for a flux of CF₄ from the lithosphere. A gradual basin-wide enhancement in dissolved CF₄ and SF₆ concentrations with groundwater age is consistent with release of these gases during weathering of the surrounding granitic alluvium. Dissolved CF₄ and SF₆ concentrations in these groundwaters also contain a deeper crustal component associated with a lithospheric flux entering the EMB and MRB through the underlying basement. The crustal flux of CF₄, but not of SF₆, is enhanced in the vicinity of local active fault systems due to release of crustal fluids during episodic fracture events driven by local tectonic activity. When fluxes of CF₄ and SF₆ into Mojave Desert groundwaters are extrapolated to the global scale they are consistent, within large uncertainties, with the fluxes required to sustain the preindustrial atmospheric abundances of CF₄ and SF₆.