Aragonite dissolution on the Bermuda pedestal: Its depth and geochemical significance

The depth distribution of pteropod and planktonic foram tests, and fine-grained (<62 μm) aragonite, high-Mg calcite (12 mode mol.% MgCO₃), and low-Mg calcite has been determined for surface sediments of an area of the eastern slope of the Bermuda pedestal. Over the range 1800–3000 m, fine-grained aragonite and fine-grained high-Mg calcite gradually disappear relative to fine-grained low-Mg calcite, and pteropods gradually disappear relative to planktonic forams. This is interpreted as preferential dissolution of aragonite (and high-Mg calcite) relative to low-Mg calcite over this depth range. Coarse aragonitic debris derived from shallow-water organisms living on the Bermuda platform does not show consistent disappearance over the same depth zone. Chemical analyses of bottom water samples taken at the same time as some of the sediment samples indicate that the degree of saturation with respect to aragonite Ω_A over the zone of aragonite disappearance ranges from 0.55 to 0.85; i.e. major dissolution occurs only at Ω_A values distinctly less than one. These results lend credence to the hypothesis that CaCO₃ dissolution in the oceans, both as aragonite and as calcite, takes place mainly as a response to complex chemical kinetic phenomena and not as a result of the simple attainment of undersaturation (thermodynamic hypothesis) or the resuspension of bottom sediment (hydrodynamic hypothesis).     

Evolution of the late Pleistocene Mojanda–Fuya Fuya volcanic complex (Ecuador), by progressive adakitic involvement in mantle magma sources

The Mojanda–Fuya Fuya Volcanic Complex consists of two nearby volcanoes, Mojanda and Fuya Fuya. The older one, Mojanda volcano (0.6 to 0.2 Ma), was first constructed by andesites and high-silica andesites forming a large stratovolcano (Lower Mojanda). This edifice was capped by a basaltic andesite and andesitic cone (Upper Mojanda), which collapsed later to form a 3-km-wide summit caldera, after large phreatomagmatic eruptions. The Lower Fuya Fuya edifice was constructed by the extrusion of viscous Si-rich andesitic lavas and dacitic domes, and the emission of a thick sequence of pyroclastic-flow and fallout deposits which include two voluminous rhyolitic layers. An intermediate construction phase at Fuya Fuya is represented by a mainly effusive cone, andesitic in composition (San Bartolo edifice), the construction of which was interrupted by a major sector collapse in the Late Pleistocene. Finally, a complex of thick siliceous lavas and domes was emplaced within the avalanche amphitheatre, forming the Upper Fuya Fuya volcanic centre. This paper shows that the general evolution from an effusive to an explosive eruptive style is related to a progressive adakitic contribution to the magma source. Although all the rocks of the complex are included in the medium-K field of continental arcs, the Fuya Fuya suite (61–75 wt.% SiO₂) shows depletion in Y and HREE and high Sr/Y and La/Yb values, compared to the less silicic Mojanda suite (55–66.5 wt.% SiO₂). The Mojanda calc-alkaline suite was generated by partial melting of an adakite-metasomatised mantle source that left a residue with 2% garnet, followed by fractional crystallization of dominant plagioclase + pyroxene + olivine at shallow, intra-crustal depths. For Fuya Fuya, geochemical and mineralogical data suggest either (1) partial melting of a similar metasomatised mantle with more garnet in the residue (4%), followed by fractional crystallization involving plagioclase, amphibole and pyroxene, or (2) mixing of mafic mantle-derived magma from the Mojanda suite and slab melts, followed by the same fractional crystallization process.     

Petroleum Hydrocarbon Bioventing Kinetics Determined in Soil Core, Microcosm, and Tubing Cluster Studies

Aerobic biodegradation of vapor-phase petroleum hydrocarbons was evaluated in an intact soil core from the site of an aviation gasoline release. An unsaturated zone soil core was subjected to a flow of nitrogen gas, oxygen, water vapor, and vapor-phase hydrocarbons in a configuration analogous to a biofilter or an in situ bioventing or sparging situation. The vertical profiles of vapor-phase hydrocarbon concentration in the soil core were determined by gas chromatography of vapor samples. Biodegradation reduced low influent hydrocarbon concentrations by 45 to 92 percent over a 0.6-m interval of an intact soil core. The estimated total hydrocarbon concentration was reduced by 75 percent from 26 to 7 parts per million. Steady-state concentrations were input to a simple analytical model balancing advection and first-order biodegradation of hydrocarbons. First-order rate constants for the major hydrocarbon compounds were used to calibrate the model to the concentration profiles. Rate constants for the seven individual hydrocarbon compounds varied by a factor of 4. Compounds with lower molecular weights, fewer methyl groups, and no quaternary carbons tended to have higher rate constants. The first-order rate constants were consistent with kinetic parameters determined from both microcosm and tubing cluster studies at the field site.     

Evaluating legacy contaminants and emerging chemicals in marine environments using adverse outcome pathways and biological effects-directed analysis

Natural and synthetic chemicals are essential to our daily lives, food supplies, health care, industries and safe sanitation. At the same time protecting marine ecosystems and seafood resources from the adverse effects of chemical contaminants remains an important issue. Since the 1970s, monitoring of persistent, bioaccumulative and toxic (PBT) chemicals using analytical chemistry has provided important spatial and temporal trend data in three important contexts; relating to human health protection from seafood contamination, addressing threats to marine top predators and finally providing essential evidence to better protect the biodiversity of commercial and non-commercial marine species. A number of regional conventions have led to controls on certain PBT chemicals over several years (termed ‘legacy contaminants’; e.g. cadmium, lindane, polycyclic aromatic hydrocarbons [PAHs] and polychlorinated biphenyls [PCBs]). Analytical chemistry plays a key role in evaluating to what extent such regulatory steps have been effective in leading to reduced emissions of these legacy contaminants into marine environments. In parallel, the application of biomarkers (e.g. DNA adducts, CYP1A-EROD, vitellogenin) and bioassays integrated with analytical chemistry has strengthened the evidence base to support an ecosystem approach to manage marine pollution problems. In recent years, however, the increased sensitivity of analytical chemistry, toxicity alerts and wider environmental awareness has led to a focus on emerging chemical contaminants (defined as chemicals that have been detected in the environment, but which are currently not included in regulatory monitoring programmes and whose fate and biological impacts are poorly understood). It is also known that natural chemicals (e.g. algal biotoxins) may also pose a threat to marine species and seafood quality. Hence complex mixtures of legacy contaminants, emerging chemicals and natural biotoxins in marine ecosystems represent important scientific, economic and health challenges. In order to meet these challenges and pursue cost-effective scientific approaches that can provide evidence necessary to support policy needs (e.g. the European Marine Strategy Framework Directive), it is widely recognised that there is a need to (i) provide marine exposure assessments for priority contaminants using a range of validated models, passive samplers and biomarkers; (ii) integrate chemical monitoring data with biological effects data across spatial and temporal scales (including quality controls); and (iii) strengthen the evidence base to understand the relationship between exposure to complex chemical mixtures, biological and ecological impacts through integrated approaches and molecular data (e.g. genomics, proteomics and metabolomics). Additionally, we support the widely held view that (iv) that rather than increasing the analytical chemistry monitoring of large number of emerging contaminants, it will be important to target analytical chemistry towards key groups of chemicals of concern using effects-directed analysis. It is also important to evaluate to what extent existing biomarkers and bioassays can address various classes of emerging chemicals using the adverse outcome pathway (AOP) approach now being developed by the Organization for Economic Cooperation and Development (OECD) with respect to human toxicology and ecotoxicology.     

Formation of the mid-fifteenth century Kuwae caldera (Vanuatu) by an initial hydroclastic and subsequent ignimbritic eruption

In the mid-fifteenth century, one of the largest eruptions of the last 10 000 years occurred in the Central New Hebrides arc, forming the Kuwae caldera (12x6 km). This eruption followed a late maar phase in the pre-caldera edifice, responsible for a series of alternating hydromagmatic deposits and airfall lapilli layers. Tuffs related to caldera formation ( 120 m of deposits on a composite section from the caldera wall) were emitted during two main ignimbritic phases associated with two additional hydromagmatic episodes. The lower hydromagmatic tuffs from the precaldera maar phase are mainly basaltic andesite in composition, but clasts show compositions ranging from 48 to 60% SiO₂. The unwelded and welded ashflow deposits from the ignimbritic phases and the associated intermediate and upper hydromagmatic deposits also show a wide compositional range (60–73% SiO₂), but are dominantly dacitic. This broad compositional range is thought to be due to crystal fractionation. The striking evolution from one eruptive style (hydromagmatic) to the other (magmatic with emission of a large volume of ignimbrites) which occurred either over the tuff series as a whole, or at the beginning of each ignimbritic phase, is the most impressive characteristic of the caldera-forming event. This strongly suggests triggering of the main eruptive phases by magma-water interaction. A three-step model of caldera formation is presented: (1) moderate hydromagmatic (sequences HD 1–4) and magmatic (fallout deposits) activity from a central vent, probably over a period of months or years, affected an area slightly wider than the present caldera. At the end of this stage, intense seismic activity and extrusion of differentiated magma outside the caldera area occurred; (2) unhomogenized dacite was released during a hydromagmatic episode (HD 5). This was immediately followed by two major pyroclastic flows (PFD 1 and 2). The vents spread and intense magma-water interaction at the beginning of this stage decreased rapidly as magma discharge increased. Subsequent collapse of the caldera probably commenced in the southeastern sector of the caldera; (3) dacitic welded tuffs were emplaced during a second main phase (WFD 1–5). At the beginning of this phase, magma-water interaction continued, producing typical hydromagmatic deposits (HD 6). Caldera collapse extended to the northern part of the caldera. Previous C¹⁴ dates and records of explosive volcanism in ice from the south Pole show that the climactic phase of this event occurred in 1452 A.D.     

The role of hydrothermal fluids in sedimentation in saline alkaline lakes: Evidence from Nasikie Engida,Kenya Rift Valley

Saline alkaline lakes that precipitate sodium carbonate evaporites are most common in volcanic terrains in semi‐arid environments. Processes that lead to trona precipitation are poorly understood compared to those in sulphate‐dominated and chloride‐dominated lake brines. Nasikie Engida (Little Magadi) in the southern Kenya Rift shows the initial stages of soda evaporite formation. This small shallow (<2 m deep; 7 km long) lake is recharged by alkaline hot springs and seasonal runoff but unlike neighbouring Lake Magadi is perennial. This study aims to understand modern sedimentary and geochemical processes in Nasikie Engida and to assess the importance of geothermal fluids in evaporite formation. Perennial hot‐spring inflow waters along the northern shoreline evaporate and become saturated with respect to nahcolite and trona, which precipitate in the southern part of the lake, up to 6 km from the hot springs. Nahcolite (NaHCO₃) forms bladed crystals that nucleate on the lake floor. Trona (Na₂CO₃·NaHCO₃·2H₂O) precipitates from more concentrated brines as rafts and as bottom‐nucleated shrubs of acicular crystals that coalesce laterally to form bedded trona. Many processes modify the fluid composition as it evolves. Silica is removed as gels and by early diagenetic reactions and diatoms. Sulphate is depleted by bacterial reduction. Potassium and chloride, of moderate concentration, remain conservative in the brine. Clastic sedimentation is relatively minor because of the predominant hydrothermal inflow. Nahcolite precipitates when and where pCO₂ is high, notably near sublacustrine spring discharge. Results from Nasikie Engida show that hot spring discharge has maintained the lake for at least 2 kyr, and that the evaporite formation is strongly influenced by local discharge of carbon dioxide. Brine evolution and evaporite deposition at Nasikie Engida help to explain conditions under which ancient sodium carbonate evaporites formed, including those in other East African rift basins, the Eocene Green River Formation (western USA), and elsewhere.     

Estimating suspended sediment concentrations from turbidity measurements and the calibration problem

In situ turbidity meters are being increasingly used to generate continuous records of suspended sediment concentration in rivers. However, the usefulness of the information obtained depends heavily on the existence of a close relationship between fluctuations in suspended sediment concentration and turbidity and the calibration procedure that relates suspended sediment concentration to the turbidity meter's signal. This study assesses the relationship between suspended sediment concentration and turbidity for a small (1·19 km²) rural catchment in southern Brazil and evaluates two calibration methods by comparing the estimates of suspended sediment concentration obtained from the calibrated turbidity readings with direct measurements obtained using a USDH 48 suspended sediment sampler. With the first calibration method, the calibration relationship is derived by relating the turbidity readings to simultaneous measurements of concentration obtained from suspended sediment samples collected from the vicinity of the turbidity probe during flood events. With the second method, the calibration is based on the readings obtained from the turbidity meter when the probe immersed in samples of known concentration prepared using soils collected from the catchment. Overall, there was a close link between fluctuations in suspended sediment concentration and turbidity in the stream at the outlet of the catchment, and the estimates of sediment concentration obtained using the first calibration method corresponded closely with the conventionally measured sediment concentrations. However, use of the second calibration method introduced appreciable errors. When the estimated sediment concentrations were compared with the measured values, the mean errors were ± 122 mg l^?1 and + 601 mg l^?1 for the first and second calibration procedures respectively. Copyright © 2007 John Wiley & Sons, Ltd.     

Transient climate changes in a perturbed parameter ensemble of emissions-driven earth system model simulations

We describe results from a 57-member ensemble of transient climate change simulations, featuring simultaneous perturbations to 54 parameters in the atmosphere, ocean, sulphur cycle and terrestrial ecosystem components of an earth system model (ESM). These emissions-driven simulations are compared against the CMIP3 multi-model ensemble of physical climate system models, used extensively to inform previous assessments of regional climate change, and also against emissions-driven simulations from ESMs contributed to the CMIP5 archive. Members of our earth system perturbed parameter ensemble (ESPPE) are competitive with CMIP3 and CMIP5 models in their simulations of historical climate. In particular, they perform reasonably well in comparison with HadGEM2-ES, a more sophisticated and expensive earth system model contributed to CMIP5. The ESPPE therefore provides a computationally cost-effective tool to explore interactions between earth system processes. In response to a non-intervention emissions scenario, the ESPPE simulates distributions of future regional temperature change characterised by wide ranges, and warm shifts, compared to those of CMIP3 models. These differences partly reflect the uncertain influence of global carbon cycle feedbacks in the ESPPE. In addition, the regional effects of interactions between different earth system feedbacks, particularly involving physical and ecosystem processes, shift and widen the ESPPE spread in normalised patterns of surface temperature and precipitation change in many regions. Significant differences from CMIP3 also arise from the use of parametric perturbations (rather than a multimodel ensemble) to represent model uncertainties, and this is also the case when ESPPE results are compared against parallel emissions-driven simulations from CMIP5 ESMs. When driven by an aggressive mitigation scenario, the ESPPE and HadGEM2-ES reveal significant but uncertain impacts in limiting temperature increases during the second half of the twenty-first century. Emissions-driven simulations create scope for development of errors in properties that were previously prescribed in coupled ocean–atmosphere models, such as historical CO₂ concentrations and vegetation distributions. In this context, historical intra-ensemble variations in the airborne fraction of CO₂ emissions, and in summer soil moisture in northern hemisphere continental regions, are shown to be potentially useful constraints, subject to uncertainties in the relevant observations. Our results suggest that future climate-related risks can be assessed more comprehensively by updating projection methodologies to support formal combination of emissions-driven perturbed parameter and multi-model earth system model simulations with suitable observational constraints. This would provide scenarios underpinned by a more complete representation of the chain of uncertainties from anthropogenic emissions to future climate outcomes.