Solubility and dissimilatory reduction kinetics of iron(III) oxyhydroxides: A linear free energy relationship

Rates of reduction of Fe(III) oxyhydroxides by the bacterium Shewanella putrefaciens were measured as a function of the bacterial density and the Fe(III) substrate concentration. The results show that an earlier reported positive correlation between the solubility products (^*K_so) and the maximum cell-specific reduction rates (v_max) of predominantly poorly crystalline Fe(III) oxyhydroxides also applies to insoluble and crystalline Fe(III) oxyhydroxides. The mineral solubilities were measured by a dialysis bag technique under acidic conditions (pH 1 up to 2.5) at 25 °C. Initial iron reduction rates by S. putrefaciens were determined in the presence of excess lactate as electron donor. In all cases, the microbial reduction rate exhibited saturation behavior with respect to the Fe(III) oxyhydroxide concentration. On a double logarithmic scale, the maximum rates v_max and the solubility products defined a single linear free energy relationship (LFER) for all the Fe(III) oxyhydroxides considered. The solubility provided a better predictor of v_max than the specific surface area of the mineral phase. A rate limitation by the electron transfer between an iron reductase and a Fe(III) center, or by the subsequent desorption of Fe²⁺ from the iron oxide mineral surface, are both consistent with the observed LFER.     

Biogeochemistry of mineral-organic associations across a long-term mineralogical soil gradient (0.3-4100 kyr), Hawaiian Islands

Organic matter (OM) in mineral-organic associations (MOAs) represents a large fraction of carbon in terrestrial ecosystems which is considered stable against biodegradation. To assess the role of MOAs in carbon cycling, there is a need to better understand (i) the time-dependent biogeochemical evolution of MOAs in soil, (ii) the effect of the mineral composition on the physico-chemical properties of attached OM, and (iii) the resulting consequences for the stabilization of OM. We studied the development of MOAs across a mineralogical soil gradient (0.3-4100 kyr) at the Hawaiian Islands that derived from basaltic tephra under comparable climatic and hydrological regimes. Mineral-organic associations were characterized using biomarker analyses of OM with chemolytic methods (lignin phenols, non-cellulosic carbohydrates) and wet chemical extractions, surface area/porosity measurements (N₂ at 77 K and CO₂ at 273 K), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The results show that in the initial weathering stage (0.3 kyr), MOAs are mainly composed of primary, low-surface area minerals (olivine, pyroxene, feldspar) with small amounts of attached OM and lignin phenols but a large contribution of microbial-derived carbohydrates. As high-surface area, poorly crystalline (PC) minerals increase in abundance during the second weathering stage (20-400 kyr), the content of mineral-associated OM increased sharply, up to 290 mg C/g MOA, with lignin phenols being favored over carbohydrates in the association with minerals. In the third and final weathering stage (1400-4100 kyr), metastable PC phases transformed into well crystalline secondary Fe and Al (hydr)oxides and kaolin minerals that were associated with less OM overall, and depleted in both lignin and carbohydrate as a fraction of total OM. XPS, the N₂ pore volume data and OM-mineral volumetric ratios suggest that, in contrast to the endmember sites where OM accumulated at the surfaces of larger mineral grains, topsoil MOAs of the 20-400-kyr sites are composed of a homogeneous admixture of small-sized PC minerals and OM, which originated from both adsorption and precipitation processes. The chemical composition of OM in surface-horizon MOAs, however, was largely controlled by the uniform source vegetation irrespective of the substrate age whereas in subsoil horizons, aromatic and carboxylic C correlated positively with oxalate-extractable Al and Si and CuCl₂-extractable Al concentrations representing PC aluminosilicates and Al-organic complexes (r² > 0.85). Additionally, XPS depth profiles suggest a zonal structure of sorbed OM with aromatic carbons being enriched in the proximity of mineral surfaces and amide carbons (peptides/proteins) being located in outer regions of MOAs. Albeit the mineralogical and compositional changes of OM, the rigidity of mineral-associated OM as analyzed by DSC changed little over time. A significantly reduced side chain mobility of sorbed OM was, however, observed in subsoil MOAs, which likely arose from stronger mineral-organic bindings. In conclusion, our study shows that the properties of soil MOAs change substantially over time with different mineral assemblages favoring the association of different types of OM, which is further accentuated by a vertical gradient of OM composition on mineral surfaces. Factors supporting the stabilization of sorbed OM were (i) the surface area and reactivity of minerals (primary or secondary crystalline minerals versus PC secondary minerals), (ii) the association of OM with micropores of PC minerals (via ‘sterically’ enhanced adsorption), (iii) the effective embedding of OM in ‘well mixed’ arrays with PC minerals and monomeric/polymeric metal species, (iv) the inherent stability of acidic aromatic OM components, and (iv) an impaired segmental mobility of sorbed OM, which might increase its stability against desorption and microbial utilization.     

Nitrogen and noble gases in a glass sample from the LEW88516 shergottite

Abstract— A glass separate from the LEW88516 shergottite was analyzed by step-wise combustion for N and noble gases to determine whether it contained trapped gas similar in composition to the martian atmosphere-like component previously observed in lithology C of EETA79001. Excesses of ⁴⁰Ar and ¹²⁹Xe were in fact observed in this glass, although the amounts of these excesses are ≤20% of those seen in the latter meteorite, and are comparable to the amounts seen in whole-rock analyses of LEW88516. The isotopic composition of N in LEW88516 does not show an enrichment in ¹⁵N commensurate with the amount of isotopically-heavy N expected from the noble gases excesses. One must posit some extreme assumptions about the nature of the N components present in LEW88516 in order to allow the presence of the trapped nitrogen component. Alternatively, the N has somehow been decoupled from the noble gases, and was either never present or has been lost.     

Solar wind noble gases and nitrogen in metal from lunar soil 68501

Abstract Noble gases and N were analyzed in handpicked metal separates from lunar soil 68501 by a combination of step-wise combustions and pyrolyses. Helium and Ne were found to be unfractionated with respect to one another when normalized to solar abundances, for both the bulk sample and for all but the highest temperature steps. However, they are depleted relative to Ar, Kr and Xe by at least a factor of 5. The heavier gases exhibit mass-dependent fractionation relative to solar system abundance ratios but appear unfractionated, both in the bulk metal and in early temperature steps, when compared to relative abundances derived from lunar ilmenite 71501 by chemical etching, recently put forward as representing the abundance ratios in solar wind. Estimates of the contribution of solar energetic particles (SEP) to the originally implanted solar gases, derived from a basic interpretation of He and Ne isotopes, yield values of about 10%. Analysis of the Ar isotopes requires a minimum of 20% SEP, and Kr isotopes, using our preferred composition for solar wind Kr, yield a result that overlaps both of these values. It is possible to reconcile the data from these gases if significant loss of solar wind Ar, Kr and presumably Xe has occurred relative to the SEP component, most likely by erosive processes that are mass independent, although mass-dependent losses (Ar > Kr > Xe) cannot be excluded. If such losses did occur, the SEP contribution to the solar implanted gases must have been no more than a few percent. Nitrogen is a mixture of indigenous meteoritic N, whose isotopic composition is inferred to be relatively light, and implanted solar N, which has probably undergone diffusive redistribution and fractionation. If the heavy noble gases have not undergone diffusive loss, then N/Ar in the solar wind can be inferred to be at least several times the accepted solar ratio. The solar wind N appears, even after correction for fractionation effects, to have a minimum δ¹⁵N value ≥+150‰ and a more probable value ≥+200‰.     

Effects of eastern redcedar encroachment on soil hydraulic properties along Oklahoma's grassland‐forest ecotone

In north‐central Oklahoma eastern redcedar (Juniperus virginiana), encroachment into grassland is widespread and is suspected of reducing streamflow, but the effects of this encroachment on soil hydraulic properties are unknown. This knowledge gap creates uncertainty in understanding the hydrologic effects of eastern redcedar encroachment and obstructs fact‐based management of encroached systems. The objective of this study was to quantify the effects of eastern redcedar encroachment into tallgrass prairie on soil hydraulic properties. Leaf litter depth, soil organic matter, soil water repellency, soil water content, sorptivity, and unsaturated hydraulic conductivity were measured near Stillwater, OK, along 12 radial transects from eastern redcedar trunks to the center of the grassy intercanopy space. Eastern redcedar encroachment in the second half of the 20th century caused the accumulation of 3 cm of hydrophobic leaf litter near the trunks of eastern redcedar trees. This leaf litter was associated with increased soil organic matter in the upper 6 cm of soil under eastern redcedar trees (5.96% by mass) relative to the grass‐dominated intercanopy area (3.99% by mass). Water repellency was more prevalent under eastern redcedar than under grass, and sorptivity under eastern redcedar was 0.10 mm s^?1/2, one seventh the sorptivity under adjacent prairie grasses (0.68 mm s^?1/2). Median unsaturated hydraulic conductivity under grass was 2.52 cm h^?1, four times greater than under eastern redcedar canopies (0.57 cm h^?1). Lower sorptivity and unsaturated hydraulic conductivity would tend to decrease infiltration and increase runoff, but other factors such as rainfall interception by the eastern redcedar canopy and litter layer, and preferential flow induced by hydrophobicity must be examined before the effects of encroachment on streamflow can be predicted. Copyright © 2011 John Wiley & Sons, Ltd.     

P–V–T equation of state of Mn3Al2Si3O12 spessartine garnet

The thermoelastic parameters of synthetic Mn₃Al₂Si₃O₁₂ spessartine garnet were examined in situ at high pressure up to 13 GPa and high temperature up to 1,100 K, by synchrotron radiation energy dispersive X-ray diffraction within a DIA-type multi-anvil press apparatus. The analysis of room temperature data yielded K ₀ = 172 ± 4 GPa and K ₀ ^′  = 5.0 ± 0.9 when V _0,300 is fixed to 1,564.96 Å³. Fitting of P–V–T data by means of the high-temperature third-order Birch–Murnaghan EoS gives the thermoelastic parameters: K ₀ = 171 ± 4 GPa, K ₀ ^′  = 5.3 ± 0.8, (?K _0,T /?T) _P  = ?0.049 ± 0.007 GPa K^?1, a ₀ = 1.59 ± 0.33 × 10^?5 K^?1 and b ₀ = 2.91 ± 0.69 × 10^?8 K^?2 (e.g., α _0,300 = 2.46 ± 0.54 × 10^?5 K^?1). Comparison with thermoelastic properties of other garnet end-members indicated that the compression mechanism of spessartine might be the same as almandine and pyrope but differs from that of grossular. On the other hand, at high temperature, spessartine softens substantially faster than pyrope and grossular. Such softening, which is also reported for almandine, emphasize the importance of the cation in the dodecahedral site on the thermoelastic properties of aluminosilicate garnet.     

Surface mean temperature from the observational stations and multiple reanalyses over the Tibetan Plateau

The Tibetan Plateau (TP), also called the “Third pole”, is sensitive to climate change due to extensive areas at high elevation presently dominated by snow and ice. In this study, observed surface temperature trends at 150 stations over the TP during 1979–2018 are analyzed and compared with surface temperatures from multiple reanalyses (NCEP1, NCEP2, ERA-Interim, MERRA, JRA55). Observed warming at the stations has a mean annual rate of 0.46 °C/decade during 1979–2018. Although all reanalyses underestimate observed temperatures (cold bias), most reproduce much of the inter-decadal variations of surface temperature shown in the observations. Absolute errors of mean surface temperature (reanalysis minus observation) are closely correlated with elevation errors, suggesting that parts of the cold bias can be interpreted by elevation errors of reanalysis. After elevation-temperature correction, about half of the cold bias is typically eliminated, more for both ERA-Interim and JRA55. Compared with the observations, corrected NCEP2 surface temperatures still have larger cold biases, and fail to capture the overall warming over the TP. Since the elevation-temperature correction fails to improve trend magnitudes even when a significant proportion of the bias has been removed, this suggests that a more sophisticated modeling of the lapse rate in each reanalysis is required to realistically model warming trends across complex topography.

     

Seasonal patterns in zooplankton community structure on the Newfoundland and Labrador Shelf

We report on the patterns in zooplankton community structure on the Newfoundland and Labrador Shelf from seasonal collections along oceanographic sections during 2000–2007. We use a combination of constrained and unconstrained multivariate methods to assess latitudinal and cross shelf patterns in community structure. Both physical and biological features of the region are dominated by the cross-shelf gradient in water mass characteristics although there is evidence of a latitudinal gradient that may be a reflection of the influence of freshwater outflow from the Arctic. All analyses reveal a strong and consistent pattern in species composition among water masses that extends across spring, summer and autumn, although there are some variations that occur among seasons that reflect differences in development state of certain taxa. The strong association between community structure and water mass characteristics in the region may be the result of the Newfoundland and Labrador Shelf being at the intersection of several major oceanographic domains, bounded by strong Labrador and Gulf Stream currents, that allows the formation and persistence of well defined zooplankton communities. Our findings have implications for the region’s potential as a monitoring location for long term changes in ocean state.     

P–V–T equation of state of Ca3Al2Si3O12 grossular garnet

The thermoelastic parameters of synthetic Ca₃Al₂Si₃O₁₂ grossular garnet were examined in situ at high-pressure and high-temperature by energy dispersive X-ray diffraction, using a Kawai-type multi-anvil press apparatus coupled with synchrotron radiation. Measurements have been conducted at pressures up to 20 GPa and temperatures up to 1,650 K: this P, T range covered the entire high-P, T stability field of grossular garnet. The analysis of room temperature data yielded V _0,300 = 1,664 ± 2 ?³ and K ₀ = 166 ± 3 GPa for K^￠₀ K^{\prime}_{0} fixed to 4.0. Fitting of our P–V–T data by means of the high-temperature third order Birch–Murnaghan or the Mie–Grüneisen–Debye thermal equations of state, gives the thermoelastic parameters: (∂K _0,T /∂T) _P  = −0.019 ± 0.001 GPa K⁻¹ and α _0,T  = 2.62 ± 0.23 × 10⁻⁵ K⁻¹, or γ ₀ = 1.21 for fixed values q ₀ = 1.0 and θ ₀ = 823 (Isaak et al. Phys Chem Min19:106–120, 1992). From the comparison of fits from two different approaches, we propose to constrain the bulk modulus of grossular garnet and its pressure derivative to K _T0 = 166 GPa and K^￠_T0 K^{\prime}_{T0}  = 4.03–4.35. Present results are compared with previously determined thermoelastic properties of grossular-rich garnets.