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.     

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.     

Low-oxygen and chemical kinetic constraints on the geochemical niche of neutrophilic iron(II) oxidizing microorganisms

Neutrophilic iron oxidizing bacteria (FeOB) must actively compete with rapid abiotic processes governing Fe(II) oxidation and as a result have adapted to primarily inhabit low-O₂ environments where they can more successfully compete with abiotic Fe(II) oxidation. The spatial distribution of these microorganisms can be observed through the chemical gradients they affect, as measured using in situ voltammetric analysis for dissolved Fe(II), Fe(III), O₂, and FeS_(aq). Field and laboratory determination of the chemical environments inhabited by the FeOB were coupled with detailed kinetic competition studies for abiotic and biotic oxidation processes using a pure culture of FeOB to quantify the geochemical niche these organisms inhabit. In gradient culture tubes, the maximum oxygen levels, which were associated with growth bands of Sideroxydans lithotrophicus (ES-1, a novel FeOB), were 15-50 μM. Kinetic measurements made on S. lithotrophicus compared biotic/abiotic (killed control) Fe oxidation rates. The biotic rate can be a significant and measurable fraction of the total Fe oxidation rate below O₂ concentrations of approximately 50 μM, but biotic Fe(II) oxidation (via the biotic/abiotic rate comparison) becomes difficult to detect at higher O₂ levels. These results are further supported by observations of conditions supporting FeOB communities in field settings. Variablity in cell densities and cellular activity as well as variations in hydrous ferrous oxide mineral quantities significantly affect the laboratory kinetic rates. The microbial habitat (or geochemical niche) where FeOB are active is thus largely controlled by the competition between abiotic and biotic kinetics, which are dependent on Fe(II) concentration, P_O2, temperature and pH in addition to the surface area of hydrous ferric oxide minerals and the cell density/activity of FeOB. Additional field and lab culture observations suggest a potentially important role for the iron-sulfide aqueous molecular cluster, FeS_(aq), in the overall cycling of iron associated with the environments these microorganisms inhabit.     

Anaerobic oxidation of methane (AOM) in marine sediments from the Skagerrak (Denmark): II. Reaction-transport modeling

A steady-state reaction-transport model is applied to sediments retrieved by gravity core from two stations (S10 and S13) in the Skagerrak to determine the main kinetic and thermodynamic controls on anaerobic oxidation of methane (AOM). The model considers an extended biomass-implicit reaction network for organic carbon degradation, which includes extracellular hydrolysis of macromolecular organic matter, fermentation, sulfate reduction, methanogenesis, AOM, acetogenesis and acetotrophy. Catabolic reaction rates are determined using a modified Monod rate expression that explicitly accounts for limitation by the in situ catabolic energy yields. The fraction of total sulfate reduction due to AOM in the sulfate-methane transition zone (SMTZ) at each site is calculated. The model provides an explanation for the methane tailing phenomenon which is observed here and in other marine sediments, whereby methane diffuses up from the SMTZ to the top of the core without being consumed. The tailing is due to bioenergetic limitation of AOM in the sulfate reduction zone, because the methane concentration is too low to engender favorable thermodynamic drive. AOM is also bioenergetically inhibited below the SMTZ at both sites because of high hydrogen concentrations (∼3-6 nM). The model results imply there is no straightforward relationship between pore water concentrations and the minimum catabolic energy needed to support life because of the highly coupled nature of the reaction network. Best model fits are obtained with a minimum energy for AOM of ∼11 kJ mol⁻¹, which is within the range reported in the literature for anaerobic processes.     

The Fe-C system at 5 GPa and implications for Earth’s core

Earth’s core may contain C, and it has been suggested that C in the core could stabilize the formation of a solid inner core composed of Fe₃C. We experimentally examined the Fe-C system at a pressure of 5 GPa and determined the Fe-C phase diagram at this pressure. In addition, we measured solid metal/liquid metal partition coefficients for 17 trace elements and examined the partitioning behavior between Fe₃C and liquid metal for 14 trace elements. Solid metal/liquid metal partition coefficients are similar to those found in one atmosphere studies, indicating that the effect of pressure to 5 GPa is negligible. All measured Fe₃C/liquid metal partition coefficients investigated are less than one, such that all trace elements prefer the C-rich liquid to Fe₃C. Fe₃C/liquid metal partition coefficients tend to decrease with decreasing atomic radii within a given period. Of particular interest, our 5 GPa Fe-C phase diagram does not show any evidence that the Fe-Fe₃C eutectic composition shifts to lower C contents with increasing pressure, which is central to the previous reasoning that the inner core may be composed of Fe₃C.     

Limitations of the ferrozine method for quantitative assay of mineral systems for ferrous and total iron

The quantitative assay of clay minerals, soils, and sediments for Fe(II) and total Fe is fundamental to understanding biogeochemical cycles occurring therein. The commonly used ferrozine method was originally designed to assay extracted forms of Fe(II) from non-silicate aqueous systems. It is becoming, however, increasingly the method of choice to report the total reduced state of Fe in soils and sediments. Because Fe in soils and sediments commonly exists in the structural framework of silicates, extraction by HCl, as used in the ferrozine method, fails to dissolve all of the Fe. The phenanthroline (phen) method, on the other hand, was designed to assay silicate minerals for Fe(II) and total Fe and has been proven to be highly reliable. In the present study potential sources of error in the ferrozine method were evaluated by comparing its results to those obtained by the phen method. Both methods were used to analyze clay mineral and soil samples for Fe(II) and total Fe. Results revealed that the conventional ferrozine method under reports total Fe in samples containing Fe in silicates and gives erratic results for Fe(II). The sources of error in the ferrozine method are: (1) HCl fails to dissolve silicates and (2) if the analyte solution contains Fe³⁺, the analysis for Fe²⁺ will be photosensitive, and reported Fe(II) values will likely be greater than the actual amount in solution. Another difficulty with the ferrozine method is that it is tedious and much more labor intensive than the phen method. For these reasons, the phen method is preferred and recommended. Its procedure is simpler, takes less time, and avoids the errors found in the ferrozine method.     

Coupled and complex: Human-environment interaction in the Greater Yellowstone Ecosystem, USA

Complexity theory has received considerable attention over the past decade from a wide variety of disciplines. Some who write on this topic suggest that complexity theory will lead to a unifying understanding of complex phenomena; others dismiss it as a passing and disruptive fad. We suggest that for the analysis of coupled natural/human systems, the truth emerges from the middle ground. As an approach focused as much on the connections among system elements as the elements themselves, we argue that complexity theory provides a useful conceptual framework for the study of coupled natural/human systems. It is, if nothing else, a framework that leads us to ask interesting questions about, for example, sustainability, resilience, threshold events, and predictability.In this paper we attempt to demystify the ongoing discussions on complexity theory by linking its evocative and overloaded terminology to real-world processes. We illustrate how a shift in focus from system elements to connections among elements can lead to meaningful insight into human-environment interactions that might otherwise be overlooked. We ground our discussion in ongoing interdisciplinary research surrounding Yellowstone National Park’s northern elk winter range; a tightly coupled natural/human system that has been the center of debate, conflict, and compromise for more than 135 years.     

Phase Relations and Melting of Anhydrous K-bearing Eclogite from 1200 to 1600{degrees}C and 3 to 5 GPa

To investigate eclogite melting under mantle conditions, wehave performed a series of piston-cylinder experiments usinga homogeneous synthetic starting material (GA2) that is representativeof altered mid-ocean ridge basalt. Experiments were conductedat pressures of 3·0, 4·0 and 5·0 GPa andover a temperature range of 1200–1600°C. The subsolidusmineralogy of GA2 consists of garnet and clinopyroxene withminor quartz–coesite, rutile and feldspar. Solidus temperaturesare located at 1230°C at 3·0 GPa and 1300°C at5·0 GPa, giving a steep solidus slope of 30–40°C/GPa.Melting intervals are in excess of 200°C and increase withpressure up to 5·0 GPa. At 3·0 GPa feldspar, rutileand quartz are residual phases up to 40°C above the solidus,whereas at higher pressures feldspar and rutile are rapidlymelted out above the solidus. Garnet and clinopyroxene are theonly residual phases once melt fractions exceed 20% and garnetis the sole liquidus phase over the investigated pressure range.With increasing melt fraction garnet and clinopyroxene becomeprogressively more Mg-rich, whereas coexisting melts vary fromK-rich dacites at low degrees of melting to basaltic andesitesat high melt fractions. Increasing pressure tends to increasethe jadeite and Ca-eskolaite components in clinopyroxene andenhance the modal proportion of garnet at low melt fractions,which effects a marked reduction in the Al₂O₃ and Na₂O contentof the melt with pressure. In contrast, the TiO₂ and K₂O contentsof the low-degree melts increase with increasing pressure; thusNa₂O and K₂O behave in a contrasted manner as a function ofpressure. Altered oceanic basalt is an important component ofcrust returned to the mantle via plate subduction, so GA2 maybe representative of one of many different mafic lithologiespresent in the upper mantle. During upwelling of heterogeneousmantle domains, these mafic rock-types may undergo extensivemelting at great depths, because of their low solidus temperaturescompared with mantle peridotite. Melt batches may be highlyvariable in composition depending on the composition and degreeof melting of the source, the depth of melting, and the degreeof magma mixing. Some of the eclogite-derived melts may alsoreact with and refertilize surrounding peridotite, which itselfmay partially melt with further upwelling. Such complex magma-genesisconditions may partly explain the wide spectrum of primitivemagma compositions found within oceanic basalt suites. KEY WORDS: eclogite; experimental petrology; mafic magmatism; mantle melting; oceanic basalts     

Characterization and cycling of atmospheric mercury along the central US Gulf Coast

Concentrations of atmospheric Hg species, elemental Hg (Hg^°), reactive gaseous Hg (RGM), and fine particulate Hg (Hg-PM_2.5) were measured at a coastal site near Weeks Bay, Alabama from April to August, 2005 and January to May, 2006. Mean concentrations of the species were 1.6 ± 0.3 ng m⁻³, 4.0 ± 7.5 pg m⁻³ and 2.7 ± 3.4 pg m⁻³, respectively. A strong diel pattern was observed for RGM (midday maximum concentrations were up to 92.7 pg m⁻³), but not for Hg^° or Hg-PM_2.5. Elevated RGM concentrations (>25 pg m⁻³) in April and May of 2005 correlated with elevated average daytime O₃ concentrations (>55 ppbv) and high light intensity (>500 W m⁻²). These conditions generally corresponded with mixed continental-Gulf and exclusively continental air mass trajectories. Generally lower, but still elevated, RGM peaks observed in August, 2005 and January–March, 2006 correlated significantly (p < 0.05) with peaks in SO₂ concentration and corresponded to periods of high light intensity and lower average daytime O₃ concentrations. During these times air masses were dominated by trajectories that originated over the continent. Elevated RGM concentrations likely resulted from photochemical oxidation of Hg^° by atmospheric oxidants. This process may have been enhanced in and by the near-shore environment relative to inland sites. The marine boundary layer itself was not found to be a significant source of RGM.