High-pressure Raman spectroscopic study of Fo90 hydrous wadsleyite

Raman spectra of monoclinic Fo₉₀ hydrous wadsleyite with 2.4 wt% H₂O have been measured in a diamond-anvil cell with helium as a pressure-transmitting medium to 58.4 GPa at room temperature. The most intense, characteristic wadsleyite modes, the Si–O–Si symmetric stretch at 721 cm⁻¹ and the symmetric stretch of the SiO₃ unit at 918 cm⁻¹, shift continuously to 58.4 GPa showing no evidence of a first order change in the crystal structure despite compression well beyond the stability field of wadsleyite in terms of pressure. The pressure dependence of these two modes is nearly identical for Fo₉₀ hydrous and Fo₁₀₀ anhydrous wadsleyite. A striking feature in the high-pressure Raman spectra of Fo₉₀ hydrous wadsleyite is the appearance of new Raman modes above 9 GPa in the mid-frequency range (300–650 cm⁻¹ at 1-bar and shifted to 500–850 cm⁻¹ at 58.4 GPa) accompanied by a significant growth in their intensities under further compression. In the OH stretching frequency range Fo₉₀ hydrous wadsleyite exhibits a larger number of modes than the Mg end-member phase. The higher number of modes may be due to either additional protonation sites or simply that we observe a different subset of all possible OH modes for each sample. The high-pressure behaviour of the OH stretching modes of Fo₉₀ and Fo₁₀₀ hydrous wadsleyite is consistent: OH stretching modes with frequencies <3,530 cm⁻¹ decrease with increasing pressure whereas the higher-frequency OH modes show a close to constant pressure dependence to at least 13.2 GPa. The approximately constant pressure dependence of the OH modes above 3,530 cm⁻¹ is consistent with protons being located at the O1···O edges around M3.     

Carbon dynamics of paper,engineered wood products and bamboo in landfills: evidence from reactor studies

Background

There has been growing interest in the development of waste-specific decay factors for estimation of greenhouse gas emissions from landfills in national greenhouse gas inventories. Although engineered wood products (EWPs) and paper represent a substantial component of the solid waste stream, there is limited information available on their carbon dynamics in landfills. The objective of this study was to determine the extent of carbon loss for EWPs and paper products commonly used in Australia. Experiments were conducted under laboratory conditions designed to simulate optimal anaerobic biodegradation in a landfill.

Results

Methane generation rates over incubations of 307–677 days ranged from zero for medium-density fibreboard (MDF) to 326 mL CH₄ g^?1 for copy paper. Carbon losses for particleboard and MDF ranged from 0.7 to 1.6%, consistent with previous estimates. Carbon loss for the exterior wall panel product (2.8%) was consistent with the expected value for blackbutt, the main wood type used in its manufacture. Carbon loss for bamboo (11.4%) was significantly higher than for EWPs. Carbon losses for the three types of copy paper tested ranged from 72.4 to 82.5%, and were significantly higher than for cardboard (27.3–43.8%). Cardboard that had been buried in landfill for 20 years had a carbon loss of 27.3%—indicating that environmental conditions in the landfill did not support complete decomposition of the available carbon. Thus carbon losses for paper products as measured in bioreactors clearly overestimate those in actual landfills. Carbon losses, as estimated by gas generation, were on average lower than those derived by mass balance. The low carbon loss for particleboard and MDF is consistent with carbon loss for Australian wood types described in previous studies. A factor for carbon loss for combined EWPs and wood in landfills in Australia of 1.3% and for paper of 48% is proposed.

Conclusions

The new suggested combined decay factor for wood and EWPs represents a significant reduction from the current factor used in the Australian greenhouse gas inventory; whereas the suggested decay factor for paper is similar to the current decay factor. Our results improve current understanding of the carbon dynamics of harvested wood products, and allow more refined estimates of methane emissions from landfills.

     

Transgressions of the man on the moon: climate change,Indigenous expertise,and the posthumanist ethics of place and space

Indigenous peoples have been enrolled in climate change research for decades, participating in data-gathering, as writing collaborators, and serving as the symbolic “canary in the coal mine” for public outreach and policy-making. They have indeed experienced some of the most rapid environmental changes, but rather than emphasize their vulnerabilities, we argue their expertise is narrowly understood in formulating knowledge; the research on climate change has a limited understanding of what it might mean to be inter- or trans-disciplinary because research is formulated exclusively through the assumptions of Enlightenment thought, without sufficiently engaging non-Western subjectivities. Qualitative social sciences and “Indigenous methodologies” can be used to better achieve trans-disciplinarity; in this article we re-tell a story told by Native elders from tribes across Alaska about the “man on the moon.” While literally referring to the US moon landing, elders invoke this story when addressing climate change: it teaches the ethics of the human-nature relationship, developed from a “more-than-human” (or “posthuman”) philosophy. Our data comes from participant-observation and oral history; we draw upon poststructuralist theory, and frame our analysis through the literatures of critical geography, science studies, and American Indian studies. To ensure that Indigenous peoples are not used as props in Western policy agendas, researchers must engage with non-Enlightenment intellectual traditions. More than being a source of data or a symbol of humanity’s ruin, Indigenous wisdom can productively inform sustainable policy agendas to adapt to climate change. What can be learned, for example, is a more-than-human ethics of place and space.     

A fuzzy simulation–optimization approach for optimal estimation of groundwater availability under decision maker uncertainty

As groundwater is a slowly replenishing resource that can be depleted relatively easily, there is a growing interest in actively managing aquifer resources. Participatory, multi-stakeholder driven approaches are increasingly being adopted to plan groundwater use such that the resource is available for present as well as future needs. The state of Texas requires neighboring GCDs (local regulatory bodies) within a groundwater management area (GMA) to engage in joint planning activities and define desired future conditions (DFCs) for the aquifers they regulate. The DFCs are then used to estimate modeled available groundwater which defines how much water is available within an aquifer in a given region. The groundwater joint planning process was modeled using a combined simulation–optimization modeling scheme in this study. The response surface methodology was used to establish regional-scale aquifer stress-response relationships. In addition to average county-wide drawdown, other aquifer responses including stream-aquifer exchanges, coastal-aquifer exchanges and GMA-wide drawdown were considered to define the DFCs. A constrained linear regression was used in conjunction with a regional groundwater flow model to obtain the necessary response functions which formed the basis for a crisp optimization model whose objective was maximizing groundwater production while ensuring that the prescribed DFCs are not violated (constraints). This model was transformed into a fuzzy linear programming model to account for the fact that groundwater planners find it difficult to specify DFCs with a high degree of precision. Using linear membership functions, the decision makers’ preferences were captured using two values––a minimum preferred cut-off and the maximum allowable value for the metric. For estimating groundwater availability, the fuzzy optimization model reconciles production and maximizes the goal and the constraints representing the DFCs. The developed framework was illustrated by applying it to joint planning in Groundwater Management Area 15 in South Texas. The optimization models were highly sensitive to acceptable average drawdowns, while the coastal-aquifer interactions had secondary impacts. The fuzzy optimization model yielded lower estimates of groundwater availability in comparison to the crisp optimization scheme. The fuzzy optimization model is therefore consistent with the precautionary principle and recommended for use in the early stages of groundwater planning where incomplete understanding of the aquifer dynamics precludes specification of precise limits for the DFCs.     

A multi-media planning model for assessing co-located energy and desalination plants

The co-location of desalination plants with existing or proposed power plants can bring forth economic and ecological advantages in terms of reducing the costs of water intake and reducing fish impingement. However, fossil fuel-based power plants are a source of ozone precursors and the added strain of power needed for the energy intensive desalination process increases these pollutants into the atmosphere. Furthermore, withdrawal from brackish water sources puts a stress on slowly replenishing aquifers. Additionally, the resulting concentrate is highly saline and disposal into ecologically sensitive bays and estuaries may be problematic. Balancing these limitations with the need for freshwater is of great importance for sustainability of water scarce arid and semi-arid regions and also requires a holistic multimedia impact evaluation. Therefore, an integrated system of systems approach is adopted in this study and a decision support system that integrates the flow of water, concentrate and resulting pollutants through two engineered (power plant and desalination plant) as well as three natural systems (coastal bay, aquifer and the atmosphere) is developed to study the co-location of a power plant and a desalination plant near the City of Corpus Christi in South Texas. The objective of the model is to minimize the amount of groundwater extraction and minimize the amount of water extracted from the bay to emphasize water and ecosystem conservation, respectively. These objectives, in turn, are subject to various other constraints including (1) conservation of mass; (2) air quality regulations; (3) salinity regulation policies; (4) groundwater management constraints; (5) water demand requirements; and (6) energy demand constraints. The results indicate that when conservation of the aquifer is weighted more, less water is pulled from the aquifer until later time periods. The salinity of the bay increases and creates a need for a greater amount of power necessary to process the saline water which, in turn, enhances the atmospheric loading of ozone precursors. Therefore, the conservation of groundwater scenario is limited by the air quality standards. Alternatively, when the goal is to conserve the ecological integrity of the bay while meeting freshwater demands, the model is bound by the prescribed drawdown constraint that limits the amount of water that can be extracted from the aquifer. The results from the study indicate that blending saline bay water with brackish groundwater and using cleaner burning fossil fuels that have limited air quality impacts will enhance the performance of the co-located power and desalination operations. The results of the study highlight the need for an integrated multimedia evaluation in assessing the feasibility of desalination in areas with marginal air quality.     

A successive steady-state model for simulating freshwater discharges and saltwater wedge profiles at Baffin Bay,Texas

Submarine groundwater discharges (SGD) are an important source of freshwater to coastal bays and estuaries in arid and semi-arid regions. Understanding groundwater flows to these ecologically sensitive bodies is important for coastal environmental sustainability. A management-oriented mathematical model capable of simulating the flow of groundwater into a coastal bay (i.e., submarine groundwater discharge) is developed here using the principles of quasi-steady-state flow and the existence of a sharp interface between the freshwater and the saltwater portions of the aquifer. The model is applied to the Baffin Bay in South Texas, a hypersaline coastal body with no major river discharges. Two global sensitivity approaches (the one-at-a time design; OAT) and the grid-based Monte Carlo sensitivity index are used to identify critical model inputs. The sensitivity of the model inputs to the Nash–Sutcliffe Efficiency (NSE) criterion is calculated making use of synoptic observed SGD measurements made over a period of one tidal cycle. The results of the study indicate that global sensitivity analysis methods are particularly sensitive to the number of model realizations. The ability of these techniques to screen out insensitive model inputs increased with increasing number of realizations. The variability in the identified inputs was more prominent with the OAT sensitivity methods than Monte Carlo-based techniques. In general, the aquifer properties (hydraulic conductivity and aquifer thickness) as well as fluid properties (seawater and fresh water densities) along with the antecedent SGD was noted to be the most sensitive parameters. This result indicates that the implementation of sharp-front coastal–aquifer models can be improved through better hydrogeologic characterization and measuring temperature and salinity data to improve density estimation. The global sensitivity methods also help identify reasonable values for model inputs which can serve as a starting point for advanced calibrations. The results, however, indicated that the model is likely over-parameterized with different input sets yielding similar NSE estimates. Based on these initial parameter estimates, the model was able to capture the general trend in the observed SGD but could not capture the dynamic associated with high water levels in the bay. Pre-calibration global sensitivity analysis is recommended in similar applications as it not only provides insights into future data collection efforts but can also help assess the likely success of model calibration. However, given the variability among the techniques, it is suggested that multiple global sensitivity methods be utilized.     

Temporal variability of freshwater and pore water recirculation components of submarine groundwater discharges at Baffin Bay,Texas

Submarine groundwater discharges (SGDs) are an important source of freshwater as well as nutrients and other chemicals to bays and estuaries. SGDs are particularly important for coastal bodies in arid and semi-arid regions that are not fed by perennial streams. The Baffin Bay, TX is a shallow coastal water body that is weakly connected to the Gulf of Mexico and has no major rivers or streams draining into it. A year-long submarine groundwater discharge measurement study was carried out at the Loyola Beach of the Baffin Bay during the months of July 2005–June 2006. A total of 23 synoptic SGD sampling events were carried out with most events collecting SGD data continuously over a period of 24 h at a 1-min temporal resolution using an ultrasonic seepage meter. The median SGD was noted to be 3.83 cm/d with an inter-quartile range (IQR) of 11.36 cm/d. Four sampling events had anomalously high SGD values (~27–48 cm/d) which are hypothesized to be due to the geologic heterogeneity of the sea bed and meteorological effects. Eight of the 23 sampling events had a negative average SGD flux indicating landward flow. The short-term diurnal variability of SGD was comparable or sometimes higher than the longer-term and between-events variability. No long-term trend could be inferred. In the short-term, SGD measurements showed considerable persistence and the effective sample size analysis indicated each sampling event (consisting of over 1,000 samples) yielded only a handful of statistically independent measurements of SGD. The measured SGD values exhibited both negative (hydraulically controlled) and positive (wave set-up controlled) correlations with the bay water levels. Marine controls appeared to be the most significant SGD drivers and are in turn controlled by prevailing aeolian forcings. The salinity of the SGDs were estimated from measured sonic velocities and used in conjunction with the end-member mixing models to estimate fresh (meteoric) and re-circulated pore-water fractions. The freshwater fraction of the SGD was estimated to vary between nearly 4 and 89 % with a median value of 9.96 % and an IQR of 7.16 %. Three events were noted to have abnormally high freshwater fractions (~28, 50 and 84 %) which are likely artifacts caused by bay water freshening from rainfall and plausible thermal expansion. The meteoric and pore-water partitioning was sensitive to the assumed end-member concentrations. This study provides preliminary estimates for SGDs along the South Texas coast line and is useful for calibrating groundwater flow models and understanding the relative importance of terrestrial and marine controls on SGD. However, the heterogeneous nature of the sedimentary geology of the Texas Gulf Coast implies the SGD fluxes are likely to exhibit considerable spatial variation that has not been characterized yet. Therefore, the study provides useful insights for such future data collection and monitoring activities. The measured SGD values at Baffin Bay, TX are comparable to those reported at other parts of the Gulf of Mexico.     

Dependence of microbial magnetite formation on humic substance and ferrihydrite concentrations

Iron mineral (trans)formation during microbial Fe(III) reduction is of environmental relevance as it can influence the fate of pollutants such as toxic metal ions or hydrocarbons. Magnetite is an important biomineralization product of microbial iron reduction and influences soil magnetic properties that are used for paleoclimate reconstruction and were suggested to assist in the localization of organic and inorganic pollutants. However, it is not well understood how different concentrations of Fe(III) minerals and humic substances (HS) affect magnetite formation during microbial Fe(III) reduction. We therefore used wet-chemical extractions, magnetic susceptibility measurements and X-ray diffraction analyses to determine systematically how (i) different initial ferrihydrite (FH) concentrations and (ii) different concentrations of HS (i.e. the presence of either only adsorbed HS or adsorbed and dissolved HS) affect magnetite formation during FH reduction by Shewanella oneidensis MR-1. In our experiments magnetite formation did not occur at FH concentrations lower than 5 mM, even though rapid iron reduction took place. At higher FH concentrations a minimum fraction of Fe(II) of 25-30% of the total iron present was necessary to initiate magnetite formation. The Fe(II) fraction at which magnetite formation started decreased with increasing FH concentration, which might be due to aggregation of the FH particles reducing the FH surface area at higher FH concentrations. HS concentrations of 215-393 mg HS/g FH slowed down (at partial FH surface coverage with sorbed HS) or even completely inhibited (at complete FH surface coverage with sorbed HS) magnetite formation due to blocking of surface sites by adsorbed HS. These results indicate the requirement of Fe(II) adsorption to, and subsequent interaction with, the FH surface for the transformation of FH into magnetite. Additionally, we found that the microbially formed magnetite was further reduced by strain MR-1 leading to the formation of either dissolved Fe(II), i.e. Fe²⁺, in HEPES buffered medium or Fe(II) carbonate (siderite) in bicarbonate buffered medium. Besides the different identity of the Fe(II) compound formed at the end of Fe(III) reduction, there was no difference in the maximum rate and extent of microbial iron reduction and magnetite formation during FH reduction in the two buffer systems used. Our findings indicate that microbial magnetite formation during iron reduction depends on the geochemical conditions and can be of minor importance at low FH concentrations or be inhibited by adsorption of HS to the FH surface. Such scenarios could occur in soils with low iron mineral or high organic matter content.     

Trace element abundances in andesites

Abundance data for Cs, Rb, Tl, Ba, Pb, Sr, the rare earths, Th, U, Zr, Hf, Sn, Nb, Mo, Mn, Cu, Co, Ni, Sc, V, Cr, Ag, Sb and the major elements are reported for two andesites and a dacite from Saipan, nine andesites and a dacite from Bougainville and two andesites from Fiji. The Saipan rocks are low-K varieties and contain notably low abundances of Rb, Ba, Th and U and have rare earth patterns subparallel to chondritic patterns. The Bougainville andesites include low-Si and high-K varieties which have higher concentrations of the large cations. The Fijian samples are close to the average circum-Pacific andesite and have rareearth patterns sub-parallel to those of sedimentary rocks.All the andesites contain characteristically low (< 20 ppm) values for Ni and have Ni/Co ratios < 1, and V/Ni ratios > 10.These data preclude derivation of calc-alkaline rocks by mixing of upper crustal material or by fractional crystallisation from basaltic parents. A two stage model is proposed involving sea-floor spreading and transportation of the oceanic crust down the dipping seismic plane into the mantle where it is remelted to form andesites.