Kinetic analysis of cation exchange in birnessite using time-resolved synchrotron X-ray diffraction

In this study, we applied time-resolved synchrotron X-ray diffraction (TRXRD) to develop kinetic models that test a proposed two-stage reaction pathway for cation exchange in birnessite. These represent the first rate equations calculated for cation exchange in layered manganates. Our previous work has shown that the substitution of K, Cs, and Ba for interlayer Na in synthetic triclinic birnessite induces measurable changes in unit-cell parameters. New kinetic modeling of this crystallographic data supports our previously postulated two-stage reaction pathway for cation exchange, and we can correlate the kinetic steps with changes in crystal structure. In addition, the initial rates of cation exchange, R (ų min⁻¹), were determined from changes in unit-cell volume to follow these rate laws: R = 1.75[]^0.56, R = 41.1[]^1.10, R = 1.15[]^0.50. Thus, the exchange rates for Na in triclinic birnessite decreased in the order: Cs ? K > Ba. These results are likely a function of hydration energy differences of the cations and the preference of the solution phase for the more readily hydrated cation.     

Hypogeal geological survey in the “Grotta del Re Tiberio” natural cave (Apennines, Italy): a valid tool for reconstructing the structural setting

As karst systems are natural windows to the underground, speleology, combined with geological surveys, can be useful tools for helping understand the geological evolution of karst areas. In order to enhance the reconstruction of the structural setting in a gypsum karst area (Vena del Gesso, Romagna Apennines), a detailed analysis has been carried out on hypogeal data. Structural features (faults, fractures, tectonic foliations, bedding) have been mapped in the ”Grotta del Re Tiberio” cave, in the nearby gypsum quarry tunnels and open pit benches. Five fracture systems and six fault systems have been identified. The fault systems have been further analyzed through stereographic projections and geometric-kinematic evaluations in order to reconstruct the relative chronology of these structures. This analysis led to the detection of two deformation phases. The results permitted linking of the hypogeal data with the surface data both at a local and regional scale. At the local scale, fracture data collected in the underground have been compared with previous authors’ surface data coming from the quarry area. The two data sets show a very good correspondence, as every underground fracture system matches with one of the surface fracture system. Moreover, in the cave, a larger number of fractures belonging to each system could be mapped. At the regional scale, the two deformation phases detected can be integrated in the structural setting of the study area, thereby enhancing the tectonic interpretation of the area (e.g., structures belonging to a new deformation phase, not reported before, have been identified underground). The structural detailed hypogeal survey has, thus, provided very useful data, both by integrating the existing information and revealing new data not detected at the surface. In particular, some small structures (e.g., displacement markers and short fractures) are better preserved in the hypogeal environment than on the surface where the outcropping gypsum is more exposed to dissolution and recrystallization. The hypogeal geological survey, therefore, can be considered a powerful tool for integrating the surface and log data in order to enhance the reconstruction of the deformational history and to get a three-dimensional model of the bedrock in karst areas.     

A sediment budget for a grazed semi-arid catchment in the Burdekin basin, Australia

In catchments adjacent to the Great Barrier Reef World Heritage Area in Queensland, Australia, there is a growing concern that sediments and nutrients being exported from the land are having a detrimental effect on coral reef communities. There is a need to determine the processes and rates of erosion from the major land use types, so that management intervention can be initiated to reduce sediment yields where required. This paper presents a sediment budget for Weany Creek, a 13.5 km² grazed semi-arid sub-catchment of the Burdekin River catchment, Australia. A range of field methods was used to measure erosion from hillslopes, gullies and stream banks, as well as identify the amount of sediment being deposited and remobilised on the bed of gullies and the stream network. The data suggests that at least during drought conditions, the primary erosion source in this catchment is gully erosion. However, the largest source of sediment in the budget is actually associated with the remobilisation of in-channel sediment stores. Overall, the sediment budget is comprised of  81% coarse material and 19% fine sediment and an agreement between the fine sediment yield estimated in the sediment budget and the yield measured at the catchment outlet is within 10%. The total sediment yield estimated for this catchment is  4205 t yr^− 1 and is much lower than expected for a catchment of this size. This may reflect the drought conditions during the measurement period; however, there is also the possibility that the primary erosion sources have been exhausted, and the rates of sediment loss may be much lower now than they may have been in the past. Nonetheless, the results show that stored sediment, which may have been deposited in the channel many decades ago, is an important contributor to end of catchment sediment yields and warrants further investigation.     

Spatial pattern of localized disturbance along a Southeastern salt marsh tidal creek

Geomorphology may be an important predictor of vegetation pattern in systems where suceptibility to disturbance is unevenly distributed across the landscape. Salt marsh communities exhibit spatial pattern in vegetation at a variety of spatial scales. In coastal Georgia, the low marsh is a virtual monoculture ofSpartina alterniflora interspersed with patches of species that are more typical of the high marsh. These localized disturbances are most likely created by wrack mats, mats of dead vegetation which can compact and smother underlying vegetation creating bare patches for colonization by high marsh species. We investigated the spatial pattern of disturbed patches along a 2 km section of Dean Creek, a tidal creek at the southwestern end of Sapelo Island, Georgia, U.S. We used a discriminant model to explore the relationship between tidal creek morphology (e.g., the presence of drainage channels and creek bends) and the spatial distribution of disturbed patches. The model predicted vegetation pattern along the creek with relatively high accuracy (>70%). Areas where water movement is slowed or multidirectional (e.g., along creek bends and near drainage channels) were most susceptible to disturbance. Our findings suggest an important functional linkage between geomorphology and vegetation pattern in salt marsh communities.     

New Reference Materials and Assessment of Matrix Effects for SIMS Measurements of Oxygen Isotopes in Garnet

Accurate ion microprobe analysis of oxygen isotope ratios in garnet requires appropriate reference materials to correct for instrumental mass fractionation that partly depends on the garnet chemistry (matrix effect). The matrix effect correlated with grossular, spessartine and andradite components was characterised for the Cameca IMS 1280HR at the SwissSIMS laboratory based on sixteen reference garnet samples. The correlations fit a second‐degree polynomial with maximum bias of ca. 4‰, 2‰ and 8‰, respectively. While the grossular composition range 0–25% is adequately covered by available reference materials, there is a paucity of them for intermediate compositions. We characterise three new garnet reference materials GRS2, GRS‐JH2 and CAP02 with a grossular content of 88.3 ± 1.2% (2s), 83.3 ± 0.8% and 32.5 ± 3.0%, respectively. Their micro scale homogeneity in oxygen isotope composition was evaluated by multiple SIMS sessions. The reference δ¹⁸O value was determined by CO₂ laser fluorination (δ¹⁸O_LF). GRS2 has δ¹⁸O_LF = 8.01 ± 0.10‰ (2s) and repeatability within each SIMS session of 0.30–0.60‰ (2s), GRS‐JH2 has δ¹⁸O_LF = 18.70 ± 0.08‰ and repeatability of 0.24–0.42‰ and CAP02 has δ¹⁸O_LF = 4.64 ± 0.16‰ and repeatability of 0.40–0.46‰.     

A review of paired catchment studies for determining changes in water yield resulting from alterations in vegetation

Paired catchment studies have been widely used as a means of determining the magnitude of water yield changes resulting from changes in vegetation. This review focuses on the use of paired catchment studies for determining the changes in water yield at various time scales resulting from permanent changes in vegetation. The review considers long term annual changes, adjustment time scales, the seasonal pattern of flows and changes in both annual and seasonal flow duration curves. The paired catchment studies reported in the literature have been divided into four broad categories: afforestation experiments, deforestation experiments, regrowth experiments and forest conversion experiments. Comparisons between paired catchment results and a mean annual water balance model are presented and show good agreement between the two methodologies. The results highlight the potential underestimation of water yield changes if regrowth experiments are used to predict the likely impact of permanent alterations to a catchment's vegetation. An analysis of annual water yield changes from afforestation, deforestation and regrowth experiments demonstrates that the time taken to reach a new equilibrium under permanent land use change varies considerably. Deforestation experiments reach a new equilibrium more quickly than afforestation experiments. The review of papers reporting seasonal changes in water yield highlights the proportionally larger impact on low flows. Flow duration curve comparison provides a potential means of gaining a greater understanding of the impact of vegetation on the distribution of daily flows.     

Underwater Explosion Treatment of Marine Soft Foundation

The consolidation of soft foundation is a problem that commonly appears in harbor construction engineering on muddy coast. Introduced in this paper is the experimental study on underwater explosion treatment of soft foundation, including the regulations of explosion hollow development and medium movement, the law of similarity of densification and settlement of filled stone mass by shock wave pressure and explosion energy and their construction technologies, etc. A number of projects have been completed by applying this new technique, and the technique itself has been proved practicable.     

Indian summer monsoon during the last two millennia

The monsoon is a large‐scale feature of the tropical atmospheric circulation, affecting people and economies in the world's most densely populated regions. Future trends due to natural variability and human‐induced climate changes are uncertain. Palaeoclimate records can improve our understanding of monsoon dynamics and thereby reduce this uncertainty. Palaeoclimate records have revealed a dramatic decrease in the Asian summer monsoon since the early Holocene maximum 9 ka BP. Here we focus on the last 2 ka, where some records indicate an increasing trend in the summer monsoon. Analysing Globigerina bulloides upwelling records from the Arabian Sea, we find the weakest monsoon occurred 1500 a BP, with an increasing trend towards the present. Copyright © 2010 John Wiley & Sons, Ltd.