Ab initio quantum-mechanical modeling of pyrophyllite [Al2Si4O10(OH)2] and talc [Mg3Si4O10(OH)2] surfaces

Bulk and slab geometry optimizations and calculations of the electrostatic potential at the surface of both pyrophyllite [Al₂Si₄O₁₀(OH)₂] and talc [Mg₃Si₄O₁₀(OH)₂] were performed at Hartree–Fock and DFT level. In both pyrophyllite and talc cases, a modest (001) surface relaxation was observed, and the surface preserves the structural features of the crystal: in the case of pyrophyllite the tetrahedral and octahedral sheets are strongly distorted with respect to the ideal hexagonal symmetry (and basal oxygen are located at different heights along the direction normal to the basal plane), whereas the structure of talc deviates slightly from the ideal hexagonal symmetry (almost co-planar basal oxygen). The calculated distortions are fully consistent with those experimentally observed. Although the potentials at the surface of pyrophyllite and talc are of the same order of magnitude, large topological differences were observed, which could possibly be ascribed to the differences between the surface structures of the two minerals. Negative values of the potential are located above the basal oxygen and at the center of the tetrahedral ring; above silicon the potential is always positive. The value of the potential minimum above the center of the tetrahedral ring of pyrophyllite is ?0.05 V (at 2 Å from the surface), whereas in the case of talc the minimum is ?0.01 V, at 2.7 Å. In the case of pyrophyllite the minimum of potential above the higher basal oxygen is located at 1.1 Å and it has a value of ?1.25 V, whereas above the lower oxygen the value of the potential at the minimum is ?0.2 V, at 1.25 Å; the talc exhibits a minimum of ?0.75 V at 1.2 Å, above the basal oxygen.     

The role of Al in the formation of secondary Ni precipitates on pyrophyllite,gibbsite, talc,and amorphous silica: a DRS study

Formation of secondary Ni precipitates is an important mechanism of Ni retention in neutral and alkaline clay/water systems. However, the structure and composition of these secondary phases, and their stability is still disputable. Using existing structure refinement data and new ab-initio FEFF 7 calculations we show that Ni-edge X-ray absorption fine structure spectroscopy alone may not be able to unequivocally discriminate four possible candidate compounds: α-Ni(OH)₂, the isostructural but Al-substituted layered double hydroxide (Ni-Al LDH), and 1:1 and 2:1 Ni-containing phyllosilicates. Hence, we investigated the potential of diffuse reflectance spectroscopy (DRS) in determining in situ the Ni phase forming in the presence of four sorbents, pyrophyllite, talc, gibbsite, and amorphous silica. The ³A_2g → ³T_1g(F) band (ν2) of octahedrally coordinated Ni²⁺ could be reliably extracted from the reflectance spectra of wet pastes. In the presence of the Al-free talc and amorphous silica, the ν2 band was at ≈14,900 cm⁻¹, but shifted to 15,300 cm⁻¹ in the presence of Al-containing pyrophyllite and gibbsite. This shift suggests that Al is dissolved from the sorbent and substitutes for Ni in brucite-like hydroxide layers of the newly forming precipitate phase, causing a decrease of the Ni-O distances and, in turn, an increase of the crystal-field splitting energy. Comparison with Ni model compounds showed that the band at 14,900 cm⁻¹ is a unique fingerprint of α-Ni(OH)₂, and the band at 15,300 cm⁻¹ of Ni-Al LDH. Although the complete transformation of α-Ni(OH)₂ into a Ni phyllosilicate causes a significant contraction of the Ni hydroxide sheet as indicated by band positions intermediate to those of α-Ni(OH)₂ and Ni-Al LDH, incipient states of silication do not influence Ni-O distances and cannot be detected by DRS. The first evidence for the formation of a precipitate was obtained after 5 min (pyrophyllite), 7 hr (talc), 24 hr (gibbsite), and 3 days (amorphous silica). For both pyrophyllite and talc, where sufficiently long time series were available, the ν2 energy slightly increased as long as the Ni uptake from solution continued (3 days for pyrophyllite, 30 days for talc). This may be explained by a relative decrease of relaxed surface sites due to the growth of crystallites. Our study shows that the formation of both α-Ni(OH)₂ and Ni-Al LDH may effectively decrease aqueous Ni concentrations in soils and sediments. However, Ni-Al LDH seems to be thermodynamically favored when Al is available.     

The spectra of hard radiation from radio pulsars

The kinetic equation for the distribution function of relativistic electrons is solved taking into account quasi-linear interactions with waves and radiative processes. Mean values of the pitch angles ψ are calculated. If the particles of the primary beam with Lorentz factors γ_b～10⁶ are resonant, then the condition γ_bψ_b?1 is satisfied, the particle distribution is described by the function f _‖(γ) ∝ γ^?4, and the synchrotron radiation spectrum is characterized by the spectral index α=3/2. On the other hand, if a cyclotron resonance is associated with particles of the high-energy tail of the secondary plasma (γ_t～10⁵), then γ_tψ_t?1, and the distribution function has two parts—f _‖(γ) ∝ γ and f _‖(γ) ∝ γ^?2—which correspond to the spectral indices α₁=+1 and α₂=?0.5. This behavior is similar to that observed for the pulsar B0656+14. The predicted frequency of the maximum ν_m=7.5×10¹⁶ Hz coincides with the peak frequency for this pulsar. The model estimate for the total synchrotron luminosity of a typical radio pulsar with hard radiation L _s =3×10³³ erg/s is in agreement with observed values.     

Belowground productivity of roots and rhizomes in a giant cordgrass marsh

Belowground production of roots and rhizomes in the top 20 cm of soil was 2.2 kg m^?2 yr^?1 based on a maximum minus minimum estimation procedure in a giant cordgrass (Spartina cynosuroides (L.) Roth) marsh in Mississippi. Approximately 1.9 kg m^?2 (86%) of this production occurred in late spring-summer and 0.3 kg m^?2 in late fall. This estimate ignores any production below 20 cm depth and is thus an underestimate. Production values increased to 4.0 kg m^?2 yr^?1 using Smalley’s technique and accounting for decomposition. Aboveground tissues (leaves and stems) were depleted in nitrogen in July which corresponded to peaks in both above- and belowground biomass. The low root/shoot ratio (2.6) on this marsh does not suggest that growth is nutrient limited. Indeed, total productivity (above- and belowground) for this marsh was high (between 4.4 and 6.2 kg m^?2 yr^?1).     

The accuracy of standard enthalpies and entropies for phases of petrological interest derived from density-functional calculations

The internal energies and entropies of 21 well-known minerals were calculated using the density functional theory (DFT), viz. kyanite, sillimanite, andalusite, albite, microcline, forsterite, fayalite, diopside, jadeite, hedenbergite, pyrope, grossular, talc, pyrophyllite, phlogopite, annite, muscovite, brucite, portlandite, tremolite, and CaTiO₃–perovskite. These thermodynamic quantities were then transformed into standard enthalpies of formation from the elements and standard entropies enabling a direct comparison with tabulated values. The deviations from reference enthalpy and entropy values are in the order of several kJ/mol and several J/mol/K, respectively, from which the former is more relevant. In the case of phase transitions, the DFT-computed thermodynamic data of involved phases turned out to be accurate and using them in phase diagram calculations yields reasonable results. This is shown for the Al₂SiO₅ polymorphs. The DFT-based phase boundaries are comparable to those derived from internally consistent thermodynamic data sets. They even suggest an improvement, because they agree with petrological observations concerning the coexistence of kyanite?+?quartz?+?corundum in high-grade metamorphic rocks, which are not reproduced correctly using internally consistent data sets. The DFT-derived thermodynamic data are also accurate enough for computing the P–T positions of reactions that are characterized by relatively large reaction enthalpies (>?100 kJ/mol), i.e., dehydration reactions. For reactions with small reaction enthalpies (a few kJ/mol), the DFT errors are too large. They, however, are still far better than enthalpy and entropy values obtained from estimation methods.     

XPS spectra of uranyl minerals and synthetic uranyl compounds. I: The U 4f spectrum

The occurrence and binding energies of the U⁶⁺, U⁵⁺ and U⁴⁺ bands in the U 4f_7/2 peak of 19 uranyl minerals of different composition and structure were measured by XPS. The results suggest that these minerals can be divided into the following four groups: (1) Uranyl-hydroxy-hydrate compounds with no or monovalent interstitial cations; (2) Uranyl-hydroxy-hydrate minerals with divalent interstitial cations; (3) Uranyl-oxysalt minerals with (TO_n) groups (T = Si, P, and C) in which all equatorial O-atoms of the uranyl-polyhedra are shared with (TO_n) groups; (4) Uranyl-oxysalt minerals with (TO_n) groups (T = S and Se), in which some equatorial O-atoms are shared only between uranyl polyhedra. The average binding energies of the U⁶⁺and U⁴⁺ bands shift to lower values with (1) incorporation of divalent cations and (2) increase in the Lewis basicity of the anion group bonded to U. The first observation is a consequence of an increase in the bond-valence transfer from the interstitial species (cations, H₂O) groups to the O-atoms of the uranyl-groups, which results in an electron transfer from O to U⁶⁺. The second trend correlates with an increase in the covalency of the UO bonds with increase in Lewis basicity of the anion group, which results in a shift of the electron density from O to U. The presence of U⁴⁺ on the surface of uranyl minerals can be detected by the shape of the U 4f_7/2 peak, and the occurrence of the U 5f peak and satellite peaks belonging to the U 4f_5/2 peak. The presence of U⁴⁺ in some of the uranyl minerals and synthetics examined may be related to the conditions during their formation. A charge-balance mechanism is proposed for the incorporation of lower-valence U in the structure of uranyl minerals. Exposure of a Na-substituted metaschoepite crystal in air and to Ultra-High Vacuum results in dehydration of its surface structure associated with a shift of the U⁶⁺ bands to higher binding energies. The latter observation indicates a shift in electron density from U to O, which must be related to structural changes inside the upper surface layers of Na-substituted metaschoepite.     

Intermediate sulfidation epithermal gold-base metal deposits in Tertiary subaerial volcanic rocks,Sahinli/Tespih Dere (Lapseki/Western Turkey)

Gold in the Sahinli and Tespih Dere intermediate sulfidation gold-base metal deposits in Western Turkey occurs in relatively deep epithermal quartz veins along with base metal minerals which have epithermal textures, including plumose quartz, vug infills, comb and cockade textures and matrix-supported milled breccias. The total sulfide content of the veins in the area is variable ranging from < 1% to 60% and is dominated by pyrite, galena, sphalerite and chalcopyrite. Sphalerite is Fe-poor (0.6 to 1.4 mol% FeS). Minor amounts of Ag-rich tetrahedrite are present. Primary hydrothermal alteration minerals include illite/muscovite, mixed-layer illite/smectite (11.6 Å) and clinochlore towards the east and, alunite, dickite/nacrite and pyrophyllite towards the west at Sahinli; major illite/muscovite and dickite occur at Tespih Dere and Sarioluk, respectively.Fluid inclusions in main-stage quartz at Sahinli are only liquid-rich, with homogenization temperatures ranging from 220 to 322 °C and the majority of T_h values between 250 and 300 °C. Salinity ranges from 4.3 to 6.9 wt.% NaCl equiv. First ice-melting temperatures (T_mf) between ?24.5 and ?19.0 °C indicate that the fluids were dominated by NaCl – H₂O during mineralization. The relatively higher average T_h at the Tespih Dere deposit (295 °C) is attributed to a relatively deeper level of exposure.Calculated δ¹⁸O values indicate that ore-forming hydrothermal fluids in the study area had δ¹⁸O_H2O ranging from + 1.1 to + 9.7‰ (average = 3.8‰), strongly ¹⁸O-enriched compared with present-day hydrothermal meteoric water in the area (δ¹⁸O = ?8.5‰). δD values of fluid inclusions in quartz range from ?58 to ?93‰ and δD values of clay minerals and alunite from ?40 to ?119‰. δD values from intermediate argillic alteration (average = ?68‰) in the study area are very similar to δD values of the present-day local geothermal system (average δD = ?54‰) whereas δD values from advanced-argillic alteration (average δD = ?33‰) are very different from the present-day local geothermal system.The δ³⁴S values in samples from the Sahinli and Tespih Dere deposits average ?2.9‰ for pyrite; ?3.3‰ for chalcopyrite; ?5.4‰ for sphalerite and ?7.6‰ for galena. These data are consistent with derivation of the sulfur from either igneous rocks or possibly from local wallrock.     

Diel dissolved oxygen dynamics and eutrophication in a shallow,well-mixed tropical lagoon (Cancun,Mexico)

Bojorquez Lagoon (BL), located on the Mexican Caribbean, has received sewage and dredging impacts as a result of tourism development. The lagoon supports a high diversity of primary producers compared to sheltered adjacent lagoons dominated byThalassia testudinum communities. The Diurnal Curve Method (Odum and Hoskin 1958) was used to measure community metabolism and assess eutrophication in BL by comparing it to the nonimpacted lagoons and to other systems studied with this method. Dissolved oxygen community input to the water column in BL ranged between 8.3 g O₂ m^?2 d^?1 and 41.5 g O₂ m^?2 d^?1 during 1985 and 1986, and averaged 17.1, whereas dissolved oxygen community consumption ranged from 6.4 g O₂ m^?2 d^?1 during 1985 and 1986, and averaged 17.1, whereas dissolved oxygen community consumption ranged from 6.4 g O₂ m^?2 d^?1 to 37.6 g O₂ m^?2 d^?1 and averaged 15.2. These values are higher than those found for the adjacent lagoons and similar coastal lagoons, and are similar to results from other lagoons with sewage or seafood waste discharge. Net flux of oxygen from the community to the water column averaged 1.9 g O₂ m^?2 d^?1 and ranged from ?9.8 g O₂ m^?2 d^?1 to 8.1 g O₂ m^?2 d^?1. These values are low compared to the adjacent lagoons, and close to zero, as in dystrophic environments. Primary productivity, as estimated by oxygen input, increased in BL during the period of study, indicating that eutrophication is proceeding, but the lagoon has not reached yet a level of “critical eutrophication” as defined by Mee (1988).     

Optical and radiative properties of aerosols over Abu Dhabi in the United Arab Emirates

The present study is on the aerosol optical and radiative properties in the short-wave radiation and its climate implications at the arid city of Abu Dhabi (24.42 ^°N, 54.61 ^°E, 4.5 m MSL), in the United Arab Emirates. The direct aerosol radiative forcings (ARF) in the short-wave region at the top (TOA) and bottom of the atmosphere (BOA) are estimated using a hybrid approach, making use of discrete ordinate radiative transfer method in conjunction with the short-wave flux and spectral aerosol optical depth (AOD) measurements, over a period of 3 years (June 2012–July 2015), at Abu Dhabi located at the south-west coast of the Arabian Gulf. The inferred microphysical properties of aerosols at the measurement site indicate strong seasonal variations from the dominance of coarse mode mineral dust aerosols during spring (March–May) and summer (June–September), to the abundance of fine/accumulation mode aerosols mainly from combustion of fossil-fuel and bio-fuel during autumn (October–November) and winter (December–February) seasons. The monthly mean diurnally averaged ARF at the BOA (TOA) varies from ?13.2 Wm^?2 (～?0.96 Wm^?2) in November to ?39.4 Wm^?2 (?11.4 Wm^?2) in August with higher magnitudes of the forcing values during spring/summer seasons and lower values during autumn/winter seasons. The atmospheric aerosol forcing varies from + 12.2 Wm^?2 (November) to 28.2 Wm^?2 (June) with higher values throughout the spring and summer seasons, suggesting the importance of mineral dust aerosols towards the solar dimming. Seasonally, highest values of the forcing efficiency at the surface are observed in spring (?85.0 ± 4.1 W m^?2 τ ^?1) followed closely by winter (?79.2 ± 7.1 W m^?2 τ ^?1) and the lowest values during autumn season (?54 ± 4.3 W m^?2 τ ^?1). The study concludes with the variations of the atmospheric heating rates induced by the forcing. Highest heating rate is observed in June (0.39 K day ^?1) and the lowest in November (0.17 K day ^?1) and the temporal variability of this parameter is linearly associated with the aerosol absorption index.     

Primary productivity inHalodule wrightii: A comparison of techniques based on daily carbon budgets

Bimonthly variations in shoot density, biomass, and blade productivity were used to estimate diel rates of primary productivity in conjunction with in situ measurements of photosynthesis and irradiance for a monospecific meadow ofHalodule wrightii Ascherson in Laguna Madre, Texas. Four separate techniques for estimating areal primary productivity were compared to estimates of primary production calculated from in situ measurements of photosynthesis and continuous recording of underwater light using the H_sat model. The clip and reharvest method, which is commonly used to measure shoot production, provided estimates ranging from 0.003 mol C m^?2 d^?1 in winter to 0.054 mol C m^?2 d^?1 in summer. In contrast, a method using aboveground biomass values, previously determined turnover rates, and belowground: aboveground biomass ratios provided estimates of primary production ranging from 0.04 mol C m^?2 d^?1 (winter) to 0.49 mol C m^?2 d^?1 (spring), similar to values determined from the H_sat model using in situ measurements of photosynthesis and ambient light regimes. Our results indicate that the clip and reharvest method dramatically underestimates primary productivity forH. wrightii, and that the inclusion of belowground biomass in carbon budget calculations is essential to obtaining realistic estimates of plant productivity. *** DIRECT SUPPORT *** A01BY069 00022     

Spatio-Temporal Patterns of Submerged Macrophytes in Three Hydrologically Altered Mediterranean Coastal Lagoons

Rice cultivation in the Ebro Delta (Catalonia, Spain) has inverted the natural hydrological cycles of coastal lagoons and decreased water salinities for over 150 years. Adjustments in the water management practices—in terms of source and amount of freshwater inputs—have resulted in changes in the diversity, distribution and productivity of submerged angiosperms. Between the 1970s and late 1980s, a massive decline of the aquatic vegetation occurred in the Encanyissada–Clot and Tancada lagoons, but little information on the status is available after the recovery of macrophytes in the 1990s. Here, we evaluate the influence of salinity regimes resulting from current water management practices on the composition, distribution, seasonal abundance and flowering rates of submersed macrophytes, as well as on the occurrence of epiphyte and drift macroalgae blooms in three coastal lagoons. Our results show that Ruppia cirrhosa is the dominant species in the Encanyissada lagoon (185.97?±?29.74 g?DW?m^?2?year^?1; 12–27?‰ salinity) and the only plant species found in the Tancada lagoon (53.26?±?10.94 g?DW?m²?year^?1; 16–28?‰ salinity). Flowering of R. cirrhosa (up to 1,011?±?121 flowers?m^?2) was only observed within the Encanyissada and suggests that mesohaline summer conditions may favor these events. In contrast, low salinities in Clot lagoon (～3–12?‰) favor the development of Potamogeton pectinatus (130.53?±?13.79 g?DW?m²?year^?1) with intersperse R. cirrhosa (8.58?±?1.71 g?DW?m^?2) and mixed stands of P. pectinatus and Najas marina (up to ～57 g?DW?m^?2?year^?1) in some reduced areas. The peak biomasses observed during the study are 88 to 95 % lower than maximum values reported in the literature at similar salinities, and there is also little or no recovery in some areas compared to last reports more than 20 years ago. The main management actions to restore the natural diversity and productivity of submersed angiosperms, such as the recovering of the seagrass Zostera noltii, should be the increase of salinity during the period of rice cultivation, by reducing freshwater inputs and increasing flushing connections with the bays.     

Organic matter fluxes and marsh stability in a rapidly submerging estuarine marsh

We studied organic matter cycling in two Gulf Coast tidal, nonsaline marsh sites where subsidence causes marine intrusion and rapid submergence, which mimics increased sea-level rise. The sites experienced equally rapid submergence but different degrees of marine intrusion. Vegetation was hummocked and much of the marsh lacked rooted vegetation. Aboveground standing crop and production, as measured by sequential harvesting, were low relative to other Gulf CoastSpartina patens marshes. Soil bulk density was lower than reported for healthyS. alterniflora growth but that may be unimportant at the current, moderate sulfate levels. Belowground production, as measured by sequential harvesting, was extremely fast within hummocks, but much of the marsh received little or no belowground inputs. Aboveground production was slower at the more saline site (681 g m^?2 yr^?1) than at the less saline site (1,252 g m^?2 yr^?1). Belowground production over the entire marsh surface averaged 1,401 g m^?2 yr^?1 at the less saline site and 585 g m^?2 yr^?1 at the more saline site. Respiration, as measured by CO₂ emissions in the field and corrected for CH₄ emissions, was slower at the less saline site (956 g m^?2 yr^?1) than at the more saline site (1,438 g m^?2 yr^?1), reflecting greater contributions byS. alterniflora at the more saline site which is known to decompose more rapidly thanS. patens. Burial of organic matter was faster at the less saline site (796 g m^?2 yr^?1) than at the more saline site (434 g m^?2, yr^?1), likely in response to faster production and slower decomposition at the less saline site. Thus vertical accretion was faster at the less saline site (1.3 cm yr^?1) than at the more saline site (0.85 cm yr^?1); slower vertical accretion increased flooding at the more saline site. More organic matter was available for export at the less saline site (1,377 g m^?2 yr^?1) than at the more saline site (98 g m^?2 yr^?1). These data indicated that organic matter production decreased and burial increased in response to greenhouse-like conditions brought on by subsidence. *** DIRECT SUPPORT *** A01BY069 00016     

Phosphorus biological cycle in the different Suaeda salsa marshes of the Yellow River estuary, China

Much uncertainty exists in the phosphorus (P) cycle in the marshes of the intertidal zone. This study explored the P cycling in the two Suaeda salsa marshes [middle S. salsa marsh (MSM) and low S. salsa marsh (LSM)] of the Yellow River estuary during April 2008 to November 2009. Results showed seasonal fluctuations and vertical distributions of P in different S. salsa marsh soils, and variations in P content in different parts of plants due to water and salinity status. The N/P ratios of the different S. salsa were 9.87 ± 1.23 and 15.73 ± 1.77, respectively, indicating that plant growth in MSM was limited by N, while that in LSM was limited by both N and P. The S. salsa litter in MSM released P to the environment throughout the year, while that in LSM immobilized P from the environment at all times. The P absorption coefficients of S. salsa in MSM and LSM were very low (0.0010 and 0.0001, respectively), while the biological cycle coefficients were high (0.739 and 0.812, respectively). The P turnovers among compartments of MSM and LSM showed that the uptake amounts of roots were 0.4275 and 0.0469 g m^?2 year^?1 and the values of aboveground parts were 1.1702 and 0.1833 g m^?2 year^?1, the re-translocation quantities from aboveground parts to roots were 0.8544 and 0.1452 g m^?2 year^?1, the translocation amounts from roots to soil were 0.0137 and 0.0012 g m^?2 year^?1, the translocation quantities from aboveground living bodies to litter were 0.3157 and 0.0381 g m^?2 year^?1, and the annual return quantities from litter to soil were less than 0.0626 and ?0.0728 g m^?2 year^?1 (minus represented immobilization), respectively. P was an important limiting factor in S. salsa marshes, especially in LSM. S. salsa was seemingly well adapted to the low-nutrient condition and the vulnerable habitat, and the nutrient enrichment due to the import of N and P from the Yellow River estuary would be a potential threat to the S. salsa marshes.     

Numerical simulation of the origin of red sandstone and Cu accumulation in pore solutions

Interaction of igneous rocks with river (rain) water in the systems granite-water, basalt-water, and dunite-water open with respect to carbon dioxide (PCO₂ = 10^?4, 10^?3, and 10^?2 bar) and oxygen (PO₂ from 10^?81 to 10^?1 bar) is numerically simulated at 25 and 50°C and a mass ratio of water and rock R/W ≤ 10. Equilibrium simulations indicate that, first, the differences in the mineralogical composition of the transformation products of the igneous rocks are insignificant, and second, Cu extraction from minerals of the rocks is optimal at Eh from +200 to ?100 mV. Simulations of the systems with regard for the dissolution rates of minerals indicate that the chemical weathering time of the rocks is few hundred thousands years.     

Geotechnical characterisation of stratocone crater wall sequences, White Island Volcano, New Zealand

Geotechnical characterisation is undertaken for 3 broad units comprising the bulk of the stratigraphy identified on White Island Volcano, Bay of Plenty, New Zealand, an active island stratovolcano. Field and laboratory measurements were used to describe rock mass characteristics for jointed lava flow units, and ring shear tests were undertaken to derive residual strength parameters for joint infilling materials within the lavas. Rock Mass Rating (RMR) and Geological Strength Index (GSI) values were calculated and converted to Mohr-Coulomb strength parameters using the Hoek-Brown criterion. Backanalysis of known landslide scarps was used to derive strength parameters for brecciated rock masses and hydrothermally altered rock masses. Andesite lava flows have high intact strength (σ_ci = 184 ± 50 MN m^− 2; γ = 24.7 ± 0.3 kN m^− 3) and typically 3 wide, infilled joint sets, one parallel to flow direction and two steeply inclined, with spacings of 0.3-1.7 m. Joints are rough, with estimated friction angles for clean joints of ?_j = 42-47°. Joint infill materials are clayey silts derived from weathering of wall rocks and primary volcanic sources; they have low plastic (54%) and liquid (84%) limits and residual strength values of c_r = 0 kN m^− 2 and ?_r = 23.9 ± 3.1°. RMR values range from 70 to 73, giving calculated strength parameters of c′ = 1161-3391 kN m^− 2 and ?′ = 50.5-62.3°. Backanalysis suggests brecciated rock masses have c′ = 0 kN m^− 2 and ?′ = 35.4°, whereas GSI observations in the field suggest higher cohesion (c′ = 306-719 kN m^− 2) and a range of friction angles bracketing the backanalysed result (?′ = 30.6-41.7°). Hydrothermally altered rock masses have c′ = 369 kN m^− 2 and ?′ = 14.9°, indicating considerable loss of strength, especially frictional resistance, compared with the fresh lava units. Values measured at outcrop scale in this study are in keeping with other published values for similar volcanic edifices; backanalysed data suggest weaker rock mass properties than those determined at outcrop. This is interpreted as a scale issue, whereby rock mass characteristics of a large rock mass (crater wall scale) are weaker than those of small outcrops, due in part to the overestimation of friction angle from measurements on small exposures.     

Burrow distributions and population estimates for the fiddler crabsUca spinicarpa andUca longisignalis in a Gulf of Mexico salt marsh

The distribution of fiddler crab (Uca spinicarpa andU. longisignalis) burrows in coastal marsh habitats is described, and the influence of substratum characteristics on the distributions of each is examined. Burrow densities were higher in vegetated areas than in sparsely vegetated and nonvegetated areas. Elevation and landward distance from shoreline (water's edge) also co-varied with burrow densities along transects. Burrow aperture diameters and burrow numbers m^?2 exhibited seasonal variations for both species ofUca. The depth of burrows increased with increased distance from the water's edge (approximate mean sea level) along transects into the marsh. A significant correlation between burrow aperture diameter and carapace width of the inhabitant enabled subsequent estimates of size and biomass in populations. Mean burrow densities forU. longisignalis ranged from a high of 182 m^?2 in September 1992 to a low of 26 m^?2 in May–June 1992. Mean burrow densities forU. spinicarpa ranged from a high of 46 m^?2 in March April 1993 to a low of 29 m^?2 in May–June 1992. Estimates of mean biomass ranged from 17.6 g AFDW m^?2 to 13.2 g AFDW m^?2 for aU. longisignalis-dominated site and from 6.5 g AFDW m^?2 to 4.9 g AFDW m^?2 for aU. spinicarpa dominated site. Field observations and laboratory soil-choice tests demonstrated that, in mixed populations,U. spinicarpa preferred to burrow in substrates of higher percent clay than didU. longisignalis.     

Concentration of Mn and separation from Fe in sediments—I. Kinetics and stoichiometry of the reaction between birnessite and dissolved Fe(II) at 10°C

Redox reactions between Fe²⁺ in solution and Mn-oxides are proposed as a mechanism for concentration of Mn in sediments both during weathering and diagenesis in marine sediments, e.g. the formation of Mn-nodules.If such a mechanism is to be effective, then reaction rates between Fe²⁺ and Mn-oxides should be fast. The kinetics and stoichiometry of the reaction between dissolved Fe²⁺ and synthetically prepared birnessite (Mn₇O₁₃·5H₂O) were studied experimentally in the pH range 3–6.Results show a stoichiometry which at pH < 4 conforms to a simple reaction between Fe²⁺ and birnessite, releasing Mn²⁺ and Fe³⁺ to the solution. At pH > 4 FeOOH is precipitated and excess Fe²⁺ consumption compared to the theoretical stoichiometry is observed. The excess Fe²⁺ consumption is not due to a formation of a quantitative MnOOH layer but rather to adsorption.Reaction kinetics are very fast at pH < 4 and change at pH 4 to a slower mechanism. At pH > 4 the reaction is fast initially until 17% of the bimessite has dissolved and changes then to a slower stage. The later stage can be described by the equation: $\text{J = km}{}_0\text{(H}{}^{\mathrm{+}}\text{)}{}^{\mathrm{?0.45}}\text{[Fe}{}^{\mathrm{2+}}\text{]}{}^{\mathrm{\gamma }}\text{(}\text{m}\text{m}{}_0\text{)}{}^{\mathrm{\beta }}$ where J is the overall rate of Mn²⁺ release, m₀ and m the mass of birnessite at time t = 0 and t > 0, β = 6.76?0.94 pH and γ has values of 0.76 at pH 5 and 0.39 at pH 6. The rate constant k is 7.2·10^?7 moles s^?1 g^?1 (moles/1)^?0.31 at pH 5 and 9.6·10^?8 moles s^?1 g^?1 (moles/1)^0.06 at pH 6.Diffusion calculations show that the rate is controlled by surface reaction and it is tentatively proposed that the availability of vacancies in octahedral [MnO₆]sheets of the birnessite surface could be rate controlling. It is concluded that reactions between Fe(II) and birnessite, and probably other Mn-oxides, are fast enough to be important in natural environments at the earth surface.     

Net Primary Productivity of <Emphasis Type="Italic">Spartina densiflora</Emphasis> Brong in an SW Atlantic Coastal Salt Marsh

Coastal marshes are known as organic matter producers. The goal of this work is to study tiller demography, standing biomass, and net aerial primary productivity (NAPP) in a Spartina densiflora coastal wetland, using a method applied to permanent sample plots located at two sites differing in topographic location, a regularly flooded zone [relative low marsh (LM)] and an irregularly flooded one [relative high marsh (HM)]. Measurements were made every 2 months during the 2005–2007 period. The annual NAPP was estimated to be 2,599?±?705 gDW m^?2?year^?1 for the HM and 2,181?±?605 gDW m^?2?year^?1 and 602?±?154 gDW m^?2?year^?1 for the first and second period of the LM populations, respectively, showing a seasonal pattern reaching maximum values in summer. The reduced NAPP values of the LM sites in the second year was associated with an extremely high precipitation period related to the 2007–2008 El Niño event.     

Biodegradation of forest floor organic matter bound to minerals via different binding mechanisms

Mineral-associated organic matter (OM) represents a large reservoir of organic carbon (OC) in natural environments. The factors controlling the extent of the mineral-mediated OC stabilization, however, are poorly understood. The protection of OM against biodegradation upon sorption to mineral phases is assumed to result from the formation of strong bonds that limit desorption. To test this, we studied the biodegradation of OM bound to goethite (α-FeOOH), pyrophyllite, and vermiculite via specific mechanisms as estimated from OC uptake in different background electrolytes and operationally defined as ‘ligand exchange’, ‘Ca²⁺ bridging’, and ‘van der Waals forces’. Organic matter extracted from an Oa forest floor horizon under Norway spruce (Picea abies (L.) Karst) was reacted with minerals at dissolved OC concentrations of ∼5-130 mg/L at pH 4. Goethite retained up to 30.1 mg OC/g predominantly by ‘ligand exchange’; pyrophyllite sorbed maximally 12.5 mg OC/g, largely via ‘van der Waals forces’ and ‘Ca²⁺ bridging’, while sorption of OM to vermiculite was 7.3 mg OC/g, mainly due to the formation of ‘Ca²⁺ bridges’. Aromatic OM components were selectively sorbed by all minerals (goethite ? phyllosilicates). The sorption of OM was strongly hysteretic with the desorption into 0.01 M NaCl being larger for OM held by ‘Ca²⁺ bridges’ and ‘van der Waals forces’ than by ‘ligand exchange’. Incubation experiments under aerobic conditions (initial pH 4; 90 days) revealed that OM mainly bound to minerals by ‘ligand exchange’ was more resistant against mineralization than OM held by non-columbic interactions (‘van der Waals forces’). Calcium bridges enhanced the stability of sorbed OM, especially for vermiculite, but less than the binding via ‘ligand exchange’. Combined evidence suggests that the extent and rate of mineralization of mineral-associated OM are governed by desorption. The intrinsic stability of sorbed OM as related to the presence of resistant, lignin-derived aromatic components appears less decisive for the sorptive stabilization of OM than the involved binding mechanisms. In a given environment, the type of minerals present and the solution chemistry determine the operating binding mechanisms, thereby the extent of OM sorption and desorption, and thus ultimately the bioavailability of mineral-associated OM.