A densification mechanism to model the mechanical effect of methane hydrates in sandy sediments

Recent pore-scale observations and geomechanical investigations suggest the lack of true cohesion in methane hydrate-bearing sediments (MHBSs) and propose that their mechanical behavior is governed by kinematic constrictions at pore-scale. This paper presents a constitutive model for MHBS, which does not rely on physical bonding between hydrate crystals and sediment grains but on the densification effect that pore invasion with hydrate has on the sediment mechanical properties. The Hydrate-CASM extends the critical state model Clay and Sand Model (CASM) by implementing the subloading surface model and introducing the densification mechanism. The model suggests that the decrease of the sediment available void volume during hydrate formation stiffens its structure and has a similar mechanical effect as the increase of sediment density. In particular, the model attributes stress-strain changes observed in MHBS to the variations in sediment available void volume with hydrate saturation and its consequent effect on isotropic yield stress and swelling line slope. The model performance is examined against published experimental data from drained triaxial tests performed at different confining stress and with distinct hydrate saturation and morphology. Overall, the simulations capture the influence of hydrate saturation in both the magnitude and trend of the stiffness, shear strength, and volumetric response of synthetic MHBS. The results are validated against those obtained from previous mechanical models for MHBS that examine the same experimental data. The Hydrate-CASM performs similarly to previous models, but its formulation only requires one hydrate-related empirical parameter to express changes in the sediment elastic stiffness with hydrate saturation.     

Late Pleistocene–Holocene environmental and climatic history of a freshwater paramo ecosystem in the northern Andes

This study presents the first multi-proxy palaeoenvironmental and palaeoclimatic history for northern South America based on the palaeolimnological reconstruction of a pond located in a dry paramo at 3570 masl. During the Last Glacial Maximum (LGM), the study area was under glacial conditions, then during global events Heinrich Stadial 1 (HS1), Bølling–Allerød (BA), and the Younger Dryas (YD), the pond expanded, accumulation rates and proxies for erosion reached the highest values, indicative of humid conditions, with maxima in humidity during the BA and YD. Dry conditions and pond desiccation occurred in the Greenlandian–Northgrippian and by 6010 cal a bp the area was transformed into the mire of today. Comparisons with records from other sites in South America indicate that changes in humidity are most likely controlled by the Intertropical Convergence Zone, mainly during the glacial and postglacial, and by changes in the Pacific Ocean, more pronounced after the YD.     

Shear-wave polarizations in the Peter the First Range indicating crack-induced anisotropy in a thrust-fault regime

Summary. Three-component seismograms of small local earthquakes recorded in the Peter the First Range of mountains near Garm, Tadzhikistan SSR, display shear-wave splitting similar to that previously observed near the North Anatolian Fault in Turkey. The Peter the First Range is in a region of compressional tectonics, whereas the North Anatolian Fault is a comparatively simple strike-slip fault. Detailed analysis of the Turkish records suggests that the splitting is diagnostic of crack-induced anisotropy caused by vertical microcracks aligned parallel to the direction of maximum compression. Preliminary examination of paper records from Garm shows that most shear waves arriving within the shear-wave window display shear-wave splitting, and that the polarizations of leading shear-waves are consistently aligned in a NE/SW direction. The area is complicated and the tectonics are not well-understood, but the NE/SW direction is approximately perpendicular to the compressional axis in many of the fault-plane mechanisms of the earthquakes. These earthquakes are usually at depths between 5 and 12 km, although there are some deeper events nearby.
Parallel shear-wave polarizations, such as those observed, are expected to indicate the strike of nearly vertical parallel microcracks, which would be aligned parallel to the direction of maximum compression. Thus the shear-wave polarizations in the Peter the First Range indicate that the directions of principal stress are reversed in the rock above the earthquake foci where thrust faulting is taking place.     

High-Frequency Response of the Atmospheric Electric Potential Gradient Under Strong and Dry Boundary-Layer Convection

The spectral response of atmospheric electric potential gradient gives important information about phenomena affecting this gradient at characteristic time scales ranging from years (e.g., solar modulation) to fractions of a second (e.g., turbulence). While long-term time scales have been exhaustively explored, short-term scales have received less attention. At such frequencies, space-charge transport inside the planetary boundary layer becomes a sizeable contribution to the potential gradient variability. For the first time, co-located (Évora, Portugal) measurements of boundary-layer backscatter profiles and the 100-Hz potential gradient are reported. Five campaign days are analyzed, providing evidence for a relation between high-frequency response of the potential gradient and strong dry convection.     

The Balance Between Capturing Phosphorus from Manure and Wastewater and the Demand for Crop Fertilizer in Italy

Phosphorus (P) is an essential nutrient required for plant growth and at the same time a costly pollutant, which can cause eutrophication of water bodies. Modern agriculture relies heavily on mineral fertilisers, which contain phosphorus derived from phosphate rock, because, without regular applications, crop yields would be limited. Since phosphate rock is a non-renewable resource, there are growing concerns regarding future phosphorus scarcity and the sustainability of modern agriculture. For many farmers, animal manure was once a means of maintaining soil fertility, but now it presents a major operational problem. This study evaluated the possibility of recycling phosphorus on a national and regional scale in Italy, using major sources of manure and wastewater. These results were successively compared with an estimate of the agricultural demand for phosphorus. Considering the quantity of phosphorus fertilizer that was applied to the soil–plant system, for the years 2001–2010, the annual phosphorus requirement of Italian crops was about 101,000 t of P. Therefore, the phosphorus source comprising animal manure and civil/industrial waste (117,500 t of P and 40,000 t of P, respectively) could potentially satisfy the average annual agronomic phosphorus demand. Regarding the geographical distribution of phosphorus supply and demand on a regional scale, areas with a large deficit of phosphorus included Calabria, Puglia and Marche. However, when only livestock waste was considered, Sicily, Umbria and Friuli could also be considered to be regions experiencing a phosphorus deficit.

     

Be exposure ages of a rock avalanche and a late glacial moraine in Alta Valtellina, Italian Alps

A rock avalanche deposit was investigated in order to understand the chronological evolution of geological hazards and to evaluate the interaction of the triggering geodynamic processes in the valley Val Viola, Italian Alps. The deposit is situated west of the Alpe Dosdé, in a permafrost area with deep-seated gravitational deformations (DSGD) along a tectonic line. Based on its geomorphologic context, the rock avalanche was first interpreted as a result of slope stress release without exact timing. This hypothesis was tested by measuring the ¹⁰Be exposure date of quartz from one boulder from the rock avalanche. The age of 7430±460 years places the event in the early Holocene. The timing of the last deglaciation was constrained using the inner late glacial moraine of a moraine doublet in the valley Alpe Dosdé situated at an altitude between 2140 and 2120 m a.s.l. west of the rock avalanche. The ¹⁰Be concentrations of quartz yield minimum exposure ages of 11,480±670 and 10,850±820 years. Different proposals for potential triggering factors of the rock avalanche include (a) melting of the local valley glacier and slope stress release in the Val Viola, likely to play a minor role as trigger, because of the time delay between the deglaciation and the rock avalanche event. More likely are (b) enhanced crustal seismicity induced by post-glacial regional isostatic glacial rebound coupled with tectonic stress or/and (c) climate conditions with higher temperatures around 7430±460 years, resulting in an upwards movement of the permafrost limit and destabilization of the rock walls.     

The Intertidal Burrowing Crab <Emphasis Type="Italic">Neohelice</Emphasis> (=<Emphasis Type="Italic">Chasmagnathus</Emphasis>) <Emphasis Type="Italic">granulata</Emphasis> Positively Affects Foraging of Rodents in South Western Atlantic Salt Marshes

The role of positive and indirect interactions is often crucial in communities with intense abiotic stress such as salt marshes. The burrowing crab, Neohelice (=Chasmagnathus) granulata, is the dominant benthic macroinvertebrate of southwest Atlantic marshes (southern Brazil to Northern Argentinean Patagonia), having strong direct and indirect effects on marsh soil and, in consequence, on marsh vegetation and primary consumers. In this work, we investigate if this crab indirectly modifies habitat use by the granivorous rodents, Akodon azarae and Oligoryzomys flavescens, by increasing nutrient availability and thus enhancing seed production by the marsh plant Spartina densiflora. The study was conducted at the Mar Chiquita Coastal Lagoon, Argentina (37°32′ S). Rodent frequencies in S. densiflora were positively correlated with crab densities throughout the low and middle marsh. Additionally, the highest quality of S. densiflora and inflorescence density was recorded at the highest crab densities. Experimental manipulation of crab densities shows that N. granulata indirectly enhances the performance of S. densiflora (e.g., decreased fiber content and C/N ratios) and increases density of seeds. Moreover, N. granulata also facilitates S. densiflora seed availability to rodents by concentrating them in sediment mound at their burrows entrances. Experimental rodent exclusions showed that rodent species used S. densiflora seeds, a variable positively related to crab burrow density. Thus, our results show that N. granulata drives the granivorous rodent distribution and the intensity of seeds–rodent interaction trough facilitative and indirect interactions in marsh community.     

Organic nitrogen chemistry during low-grade metamorphism

Most of the organic nitrogen (N_org) on Earth is disseminated in crustal sediments and rocks in the form of fossil nitrogen-containing organic matter. The chemical speciation of fossil N_org within the overall molecular structure of organic matter changes with time and heating during burial. Progressive thermal evolution of organic matter involves phases of enhanced elimination of N_org and ultimately produces graphite containing only traces of nitrogen. Long-term chemical and thermal instability makes the chemical speciation of N_org a valuable tracer to constrain the history of sub-surface metamorphism and to shed light on the subsurface biogeochemical nitrogen cycle and its participating organic and inorganic nitrogen pools. This study documents the evolutionary path of N_org speciation, transformation and elimination before and during metamorphism and advocates the use of X-ray photoelectron spectroscopy (XPS) to monitor changes in N_org speciation as a diagnostic tool for organic metamorphism. Our multidisciplinary evidence from XPS, stable isotopes, traditional quantitative coal analyses, and other analytical approaches shows that at the metamorphic onset N_org is dominantly present as pyrrolic and pyridinic nitrogen. The relative abundance of nitrogen substituting for carbon in condensed, partially aromatic systems (where N is covalently bonded to three C atoms) increases exponentially with increasing metamorphic grade, at the expense of pyridinic and pyrrolic nitrogen. At the same time, much N_org is eliminated without significant nitrogen isotope fractionation. The apparent absence of Rayleigh-type nitrogen isotopic fractionation suggests that direct thermal loss of nitrogen from an organic matrix does not serve as a major pathway for N_org elimination. Instead, we propose that hot H, O-containing fluids or some of their components gradually penetrate into the carbonaceous matrix and eliminate N_org along a progressing reaction front, without causing nitrogen isotope fractionation in the residual N_org in the unreacted core of the carbonaceous matrix. Before the reaction front can reach the core, an increasing part of core N_org chemically stabilizes in the form of nitrogen atoms substituting for carbon in condensed, partially aromatic systems forming graphite-like structural domains with delocalized π-electron systems (nitrogen atoms substituting for “graphitic” carbon in natural metamorphic organic matter). Thus, this nitrogen species with a conservative isotopic composition is the dominant form of residual nitrogen at higher metamorphic grade.     

Coal combustion by-product quality at two stoker boilers: Coal source vs. fly ash collection system design

Fly ashes from two stoker boilers burning Pennsylvanian Eastern Kentucky high volatile A bituminous coal blends were examined for their petrology and chemistry. The source coals have similar trace element contents. One of the ash collection systems was retrofitted with a baghouse (fabric filter) system, collecting a finer fly ash at a cooler flue gas temperature than the plant that has not been reconfigured. The baghouse ash has a markedly higher trace element content than the coarser fly ash from the other plant. The enhanced trace element content is most notable in the As concentration, reaching nearly 9000 ppm (ash basis) for one of the collection units. Differences in the ash chemistry are not due to any substantial differences in the coal source, even though the coal sources were from different counties and from different coal beds, but rather to the improved pollution control system in the steam plant with the higher trace element contents.     

Progression in sulfur isotopic compositions from coal to fly ash: Examples from single-source combustion in Indiana

Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur (< 1%) Danville Coal Member of the Dugger Formation and the other is the high-sulfur (> 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in δ³⁴S for sulfur species within and between the low-sulfur and high-sulfur coal. The δ³⁴S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the δ³⁴S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the δ³⁴S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of δ³⁴S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in δ³⁴S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition.The δ³⁴S values for fly ash from the high-sulfur Springfield coal (averaging 9.7‰) are greatly enriched in ³⁴S relative to those in the parent coal (averaging 2.2‰). This indicates a fractionation of sulfur isotopes during high-sulfur coal combustion. By contrast, the δ³⁴S values for fly-ash samples from the low-sulfur Danville coal average 10.2‰, only slightly enriched in ³⁴S relative to those from the parent coal (average 7.5‰). The δ³⁴S values for bulk S determined directly from the fly-ash samples show close correspondence with the δ³⁴S values for SO₄^− 2 leached from the fly ash in the low-sulfur coal, suggesting that the transition from pyrite to sulfate occurred via high-temperature oxidation during coal combustion.