Arsenic mobility in the ambient sulfidic environment: Sorption of arsenic(V) and arsenic(III) onto disordered mackinawite

Arsenate, As(V), sorption onto synthetic iron(II) monosulfide, disordered mackinawite (FeS), is fast. As(V) sorption decreases above the point of zero surface charge of FeS and follows the pH-dependent concentration of positively charged surface species. No redox reaction is observed between the As(V) ions and the mineral surface over the time span of the experiments. This observation shows that As(V) dominantly forms an outer-sphere complex at the surface of mackinawite. Arsenite, As(III), sorption is not strongly pH-dependent and can be expressed by a Freundlich isotherm. Sorption is fast, although slower than that of As(V). As(III) also forms an outer-sphere complex at the surface of mackinawite. In agreement with previous spectroscopic studies, complexation at low As(V) and As(III) concentration occurs preferentially at the mono-coordinated sulfide edge sites. The K_d (L g⁻¹) values obtained from linear fits to the isotherm data are ∼9 for As(V) and ∼2 for As(III). Stronger sorption of As(V) than As(III), and thus a higher As(III) mobility, may be reflected in natural anoxic sulfidic waters when disordered mackinawite controls arsenic mobility.     

Plio-Pleistocene mammals from Mille-Logya,Ethiopia, and the post-Hadar faunal change

We describe the non-primate mammalian fauna from the late Pliocene to earliest Pleistocene deposits of Mille-Logya in the Lower Awash Valley, Ethiopia, dated to c. 2.9–2.4 Ma, and divided into three successive units: Gafura, Seraitu, and Uraitele. We identify 41 mammalian taxa (including rodents), the most diverse group being the Bovidae, with 17 taxa. While the Gafura assemblage still resembles those from the earlier Hadar Formation, the younger Seraitu assemblage documents a major turnover. While there is little change in the species present across this interval, the relative abundances of various taxa change dramatically, with suids being largely replaced by open-country bovids (Alcelaphini and Antilopini). We interpret this faunal change as reflective of an environmental shift, contemporaneous with the replacement of Australopithecus afarensis by Homo in the area.     

Lake District hillslopes

The Lake District is a region of great scenic beauty in north‐west England that has inspired artists and poets alike, and which comes high on the list of classic geological localities in Great Britain in terms of both bedrock and geomorphological features. With its inspiring views, the Lake District is often portrayed as the product of repeated glaciation, mainly because of the clarity of the erosional and depositional features that can be seen there. But since the last glaciers disappeared other processes have been modifying the landscape, processes that have superimposed their own signatures on to the glacial features. Hillslopes in particular have undergone significant changes, as a result of slope failures in both bedrock and superficial sediments. Although these landforms are not unknown, they have not received the same level of investigation as the glacial features, resulting in a limited appreciation of their spatial distribution and significance in reshaping the landscape. This article outlines the characteristics and origins of some slope failure types, and demonstrates that there is still much to learn about the Lake District landscape.     

Chemical and textural equilibration of garnet during amphibolite facies metamorphism: The influence of coupled dissolution–reprecipitation

Metamorphic equilibration requires chemical communication between minerals and may be inhibited through sluggish volume diffusion and or slow rates of dissolution in a fluid phase. Relatively slow diffusion and the perceived robust nature of chemical growth zoning may preclude garnet porphyroblasts from readily participating in low‐temperature amphibolite facies metamorphic reactions. Garnet is widely assumed to be a reactant in staurolite‐isograd reactions, and the evidence for this has been assessed in the Late Proterozoic Dalradian pelitic schists of the Scottish Highlands. The 3D imaging of garnet porphyroblasts in staurolite‐bearing schists reveals a good crystal shape and little evidence of marginal dissolution; however, there is also lack of evidence for the involvement of either chlorite or chloritoid in the reaction. Staurolite forms directly adjacent to the garnet, and its nucleation is strongly associated with deformation of the muscovite‐rich fabrics around the porphyroblasts. “Cloudy” fluid inclusion‐rich garnet forms in both marginal and internal parts of the garnet porphyroblast and is linked both to the production of staurolite and to the introduction of abundant quartz inclusions within the garnet. Such cloudy garnet typically has a Mg‐rich, Mn‐poor composition and is interpreted to have formed during a coupled dissolution–reprecipitation process, triggered by a local influx of fluid. All garnet in the muscovite‐bearing schists present in this area is potentially reactive, irrespective of the garnet composition, but very few of the schists contain staurolite. The staurolite‐producing reaction appears to be substantially overstepped during the relatively high‐pressure Barrovian regional metamorphism reflecting the limited permeability of the schists in peak metamorphic conditions. Fluid influx and hence reaction progress appear to be strongly controlled by subtle differences in deformation history. The remaining garnet fails to achieve chemical equilibrium during the reaction creating distinctive patchy compositional zoning. Such zoning in metamorphic garnet created during coupled dissolution–reprecipitation reactions may be difficult to recognize in higher grade pelites due to subsequent diffusive re‐equilibration. Fundamental assumptions about metamorphic processes are questioned by the lack of chemical equilibrium during this reaction and the restricted permeability of the regional metamorphic pelitic schists. In addition, the partial loss of prograde chemical and textural information from the garnet porphyroblasts cautions against their routine use as a reliable monitor of metamorphic history. However, the partial re‐equilibration of the porphyroblasts during coupled dissolution–reprecipitation opens possibilities of mapping reaction progress in garnet as a means of assessing fluid access during peak metamorphic conditions.     

Application of Distributed Temperature Sensing for coupled mapping of sedimentation processes and spatio‐temporal variability of groundwater discharge in soft‐bedded streams

The delineation of groundwater discharge areas based on Distributed Temperature Sensing (DTS) data of the streambed can be difficult in soft‐bedded streams where sedimentation and scouring processes constantly change the position of the fibre optic cable relative to the streambed. Deposition‐induced temperature anomalies resemble the signal of groundwater discharge while scouring will cause the cable to float in the water column and measure stream water temperatures. DTS applied in a looped layout with nine fibre optic cable rows in a 70 × 5 m section of a soft‐bedded stream made it possible to detect variability in streambed temperatures between October 2011 and January 2012. Detailed monthly streambed elevation surveys were carried out to monitor the position of the fibre optic cable relative to the streambed and to quantify the effect of sedimentation processes on streambed temperatures. Based on the simultaneous interpretation of streambed temperature and elevation data, a method is proposed to delineate potential high‐groundwater discharge areas and identify deposition‐induced temperature anomalies in soft‐bedded streams. Potential high‐discharge sites were detected using as metrics the daily minimum, maximum and mean streambed temperatures as well as the daily amplitude and standard deviation of temperatures. The identified potential high‐discharge areas were mostly located near the channel banks, also showing temporal variability because of the scouring and redistribution of streambed sediments, leading to the relocation of pool‐riffle sequences. This study also shows that sediment deposits of 0.1 m thickness already resulted in an increase in daily minimum streambed temperatures and decrease in daily amplitude and standard deviation. Scouring sites showed lower daily minimum streambed temperatures and higher daily amplitude and standard deviation compared with areas without sedimentation and scouring. As a limitation of the approach, groundwater discharge occurring at depositional and scouring areas cannot be identified by the metrics applied. Copyright © 2015 John Wiley & Sons, Ltd.     

Intergranular diffusion rates from the analysis of garnet surfaces: Implications for metamorphic equilibration

Novel approaches to garnet analysis have been used to assess rates of intergranular diffusion between different matrix phases and garnet porphyroblasts in a regionally metamorphosed staurolite‐mica‐schist from the Barrovian‐type area in Scotland. X‐ray maps and chemical traverses of planar porphyroblast surfaces reveal chemical heterogeneity of the garnet grain boundary linked to the nature of the adjacent matrix phase. The garnet preserves evidence of low temperature retrograde exchange with matrix minerals and diffusion profiles documenting cation movement along the garnet boundaries. Garnet–quartz and garnet–plagioclase boundaries preserve evidence of sluggish Mg, Mn and Fe diffusion at comparable rates to volume diffusion in garnet, whereas diffusion along garnet–biotite interfaces is much more effective. Evidence of particularly slow Al transport, probably coupled to Fe³⁺ exchange, is locally preserved on garnet surfaces adjacent to Fe‐oxide phases. The Ca distribution on the garnet surface shows the most complex behaviour, with long‐wavelength heterogeneities apparently unrelated to the matrix grain boundaries. This implies that the Ca content of garnet is controlled by local availability and is thought likely to reflect disequilibrium established during garnet growth. Geochemical anomalies on the garnet surfaces are also linked to the location of triple junctions between the porphyroblasts and the matrix phases, and imply enhanced transport along these channels. The slow rates of intergranular diffusion and the characteristics of different boundary types may explain many features associated with the prograde growth of garnet porphyroblasts. Thus, minerals such as quartz, Fe‐oxides and plagioclase whose boundaries with garnet are characterized by slow intergranular diffusion rates appear to be preferentially trapped as inclusions within porphyroblasts. As such grain boundary diffusion rates may be a significant kinetic impediment to metamorphic equilibrium and garnet may struggle to maintain chemical and textural equilibrium during growth in pelites.     

A modelling framework for evaluation of the hydrological impacts of nature‐based approaches to flood risk management,with application to in‐channel interventions across a 29‐km2 scale catchment in the United Kingdom

Nature‐based approaches to flood risk management are increasing in popularity. Evidence for the effectiveness at the catchment scale of such spatially distributed upstream measures is inconclusive. However, it also remains an open question whether, under certain conditions, the individual impacts of a collection of flood mitigation interventions could combine to produce a detrimental effect on runoff response. A modelling framework is presented for evaluation of the impacts of hillslope and in‐channel natural flood management interventions. It couples an existing semidistributed hydrological model with a new, spatially explicit, hydraulic channel network routing model. The model is applied to assess a potential flood mitigation scheme in an agricultural catchment in North Yorkshire, United Kingdom, comprising various configurations of a single variety of in‐channel feature. The hydrological model is used to generate subsurface and surface fluxes for a flood event in 2012. The network routing model is then applied to evaluate the response to the addition of up to 59 features. Additional channel and floodplain storage of approximately 70,000 m³ is seen with a reduction of around 11% in peak discharge. Although this might be sufficient to reduce flooding in moderate events, it is inadequate to prevent flooding in the double‐peaked storm of the magnitude that caused damage within the catchment in 2012. Some strategies using features specific to this catchment are suggested in order to improve the attenuation that could be achieved by applying a nature‐based approach.     

A 2000‐year lipid biomarker record preserved in a stalagmite from north‐west Scotland

Previous studies on lipid biomarkers preserved in Chinese stalagmites have indicated that ratios of low‐molecular‐weight (LMW) to high‐molecular‐weight (HMW) n‐alkanes, n‐alkan‐2‐ones, n‐alkanols and n‐alkanoic acids can be used as an index of vegetation versus microbial organic matter input to the system and, by extension, a marker of climatic changes, with increases in the proportion of LMW compounds coinciding with colder periods. Here we test whether this hypothesis is equally applicable to a different geographical region (north‐west Scotland), by examining a stalagmite record of the past 200 years, and a wider range of lipid markers. We also test the applicability of other lipid proxies in this context, including the use of n‐alkane ratios, to interpret vegetation changes, and unsaturated alkanoic acid ratios as climatic indicators. The results show that lipid proxies preserved in stalagmites, and especially those related to vegetation, are potentially extremely useful in palaeoenvironmental research. Of particular value is the use of C₂₇/C₃₁ n‐alkane ratios as a proxy for vegetation change, clearly indicating variations between herbaceous and arboreal cover. This proxy has now been successfully applied to samples from diverse environments, and can be considered sufficiently robust to be of use in analysing future stalagmite records. It will be of particular value in areas where reliable pollen records are not available, as is often the case with deeper cave deposits. However, the division between LMW and HMW aliphatic compounds is not a clear‐cut case of microbial versus plant activity, with the changes in LMW compounds relating more closely to those in their HMW analogues than in specific bacterial biomarkers. The use of unsaturated alkanoic acid ratios here gives conflicting results, with the observed variation through time depending on the isomer measured. The discrepancies between the findings of this study and previous work are likely to be due to the varying controls on the lipids (original organic matter input, and compound degradation), which in turn will be affected by whether the main climatic limiting factor on the soil is temperature or precipitation. This suggests that lipid proxies preserved in stalagmites must be interpreted with care, particularly in the case of bacterial compounds which may be derived from within the cave or from the soil. However, many of these issues can be resolved by the use of multi‐proxy studies. Copyright © 2011 John Wiley & Sons, Ltd.     

Water level observations from unmanned aerial vehicles for improving estimates of surface water–groundwater interaction

Integrated hydrological models are usually calibrated against observations of river discharge and piezometric head in groundwater aquifers. Calibration of such models against spatially distributed observations of river water level can potentially improve their reliability and predictive skill. However, traditional river gauging stations are normally spaced too far apart to capture spatial patterns in the water surface, whereas spaceborne observations have limited spatial and temporal resolution. Unmanned aerial vehicles can retrieve river water level measurements, providing (a) high spatial resolution; (b) spatially continuous profiles along or across the water body, and (c) flexible timing of sampling. A semisynthetic study was conducted to analyse the value of the new unmanned aerial vehicle‐borne datatype for improving hydrological models, in particular estimates of groundwater–surface water (GW–SW) interaction. Mølleåen River (Denmark) and its catchment were simulated using an integrated hydrological model (MIKE 11–MIKE SHE). Calibration against distributed surface water levels using the Differential Evolution Adaptive Metropolis algorithm demonstrated a significant improvement in estimating spatial patterns and time series of GW–SW interaction. After water level calibration, the sharpness of the estimates of GW–SW time series improves by ~50% and root mean square error decreases by ~75% compared with those of a model calibrated against discharge only.