Climatic and environmental controls on speleothem oxygen-isotope values

Variations in speleothem oxygen-isotope values (δ¹⁸O) result from a complicated interplay of environmental controls and processes in the ocean, atmosphere, soil zone, epikarst, and cave system. As such, the controls on speleothem δ¹⁸O values are extremely complex. An understanding of the processes that control equilibrium and kinetic fractionation of oxygen isotopes in water and carbonate species is essential for the proper interpretation of speleothem δ¹⁸O as paleoclimate and paleoenvironmental proxies, and is best complemented by study of site-specific cave processes such as infiltration, flow routing, drip seasonality and saturation state, and cave microclimate, among others. This review is a process-based summary of the multiple controls on δ¹⁸O in the atmosphere, soil, epikarst, and speleothem calcite, illustrated with case studies. Primary controls of δ¹⁸O in the atmosphere include temperature and relative humidity through their role in the multiple isotope “effects”. Variability and modifications of water δ¹⁸O values in the soil and epikarst zones are dominated by evaporation, mixing, and infiltration of source waters. The isotopically effective recharge into a cave system consists of those waters that participate in precipitation of CaCO₃, resulting in calcite deposition rates which may be biased to time periods with optimal dripwater saturation state. Recent modeling, experimental, and observational data yield insight into the significance of kinetic fractionation between dissolved carbonate phases and solid CaCO₃, and have implications for the ‘Hendy’ test. To assist interpretation of speleothem δ¹⁸O time series, quantitative and semi-quantitative δ¹⁸O-climate calibrations are discussed with an emphasis on some of the difficulties inherent in using modern spatial and temporal isotope gradients to interpret speleothems as paleoclimate proxy records. Finally, several case studies of globally significant speleothem paleoclimate records are discussed that show the utility of δ¹⁸O to reconstruct past climate changes in regions that have been typically poorly represented in paleoclimate records, such as tropical and subtropical terrestrial locations. The new approach to speleothem paleoclimatology emphasizes climate teleconnections between regions and attribution of forcing mechanisms. Such investigations allow paleoclimatologists to infer regional to global-scale climate dynamics.     

The impact of scour processes on a smothered reef system in the Irish Sea

The Irish Sea, like many marine areas, is threatened by anthropogenic activities. In particular the Pisces Reef system, a series of smothered rocky reefs are subject to fishing pressures as a result of their position within a Nephrops norvegicus fishery. In an area of sediment deposition and retention the reefs modify the environment by increasing the energy of near-bottom currents which results in localised scouring. This is the first study to attempt to characterise and investigate the ecological functioning of the Pisces Reef system. A multidisciplinary approach was essential for accurate investigation of the area. To facilitate more effective management of the benthic habitats of the Reef system, this study integrates acoustic, seismic, grab sampling and video ground-truthing methods for benthic habitat discrimination. Orientation of the scour hollows also suggest that seabed features could be used to infer dominant flow regimes such as the Irish Sea Gyre. The data revealed significant geology–benthos relationships. A unique biotope was described for the reef habitat and it was demonstrated that scouring may influence community composition through disturbance mechanisms. This study provides preliminary information required for management of a unique habitat within a uniform region.     

Late Quaternary moisture export across Central America and to Greenland: evidence for tropical rainfall variability from Costa Rican stalagmites

We present a high-resolution terrestrial archive of Central American rainfall over the period 100–24 and 8.1–6.5 ka, based on δ¹⁸O time series from U-series dated stalagmites collected from a cave on the Pacific Coast of Costa Rica. Our results indicate substantial δ¹⁸O variability on millennial to orbital time scales that is interpreted to reflect rainfall variations over the cave site. Correlations with other paleoclimate proxy records suggest that the rainfall variations are forced by sea surface temperatures (SST) in the Atlantic and Pacific Oceans in a fashion analogous to the modern climate cycle. Higher rainfall is associated with periods of a warm tropical North Atlantic Ocean and large SST gradients between the Atlantic and Pacific Oceans. Rainfall variability is likely linked to the intensity and/or latitudinal position of the intertropical convergence zone (ITCZ). Periods of higher rainfall in Costa Rica are also associated with an enhanced sea surface salinity gradient on either side of the isthmus, suggesting greater freshwater export from the Atlantic Basin when the ITCZ is stronger and/or in a more northerly position. Further, wet periods in Central America coincide with high deuterium excess values in Greenland ice, suggesting a direct link between low latitude SSTs, tropical rainfall, and moisture delivery to Greenland. Our results indicate that a stronger tropical hydrological cycle during warm periods and large inter-ocean SST gradients enhanced the delivery of low latitude moisture to Greenland.     

Calibrating a glaciological model of the Greenland ice sheet from the Last Glacial Maximum to present-day using field observations of relative sea level and ice extent

We constrain a three-dimensional thermomechanical model of Greenland ice sheet (GrIS) evolution from the Last Glacial Maximum (LGM, 21 ka BP) to the present-day using, primarily, observations of relative sea level (RSL) as well as field data on past ice extent. Our new model (Huy2) fits a majority of the observations and is characterised by a number of key features: (i) the ice sheet had an excess volume (relative to present) of 4.1 m ice-equivalent sea level at the LGM, which increased to reach a maximum value of 4.6 m at 16.5 ka BP; (ii) retreat from the continental shelf was not continuous around the entire margin, as there was a Younger Dryas readvance in some areas. The final episode of marine retreat was rapid and relatively late (c. 12 ka BP), leaving the ice sheet land based by 10 ka BP; (iii) in response to the Holocene Thermal Maximum (HTM) the ice margin retreated behind its present-day position by up to 80 km in the southwest, 20 km in the south and 80 km in a small area of the northeast. As a result of this retreat the modelled ice sheet reaches a minimum extent between 5 and 4 ka BP, which corresponds to a deficit volume (relative to present) of 0.17 m ice-equivalent sea level. Our results suggest that remaining discrepancies between the model and the observations are likely associated with non-Greenland ice load, differences between modelled and observed present-day ice elevation around the margin, lateral variations in Earth structure and/or the pattern of ice margin retreat.     

Predicting suitability of cockle Austrovenus stutchburyi restoration sites using hydrodynamic models of larval dispersal

An important aspect of shellfish restoration projects is to evaluate whether potential sites are likely to be recolonised naturally once disturbances are removed and habitats are restored. Similarly, if active translocation or reseeding of juveniles or adults is undertaken, it is important to understand whether these introduced populations will be self‐maintaining in future, and whether any seed they produce are likely to be retained within the restored area. We used a combined hydrodynamic and particle tracking model to predict larval dispersion patterns for the common cockle Austrovenus stutchburyi under different hydrodynamic scenarios for seven release locations in Whangarei Harbour, New Zealand. Our results implied that sites varied substantially in their potential for self‐seeding and for exporting seed to other locations. For sites with more restricted dispersal, the model predicted that most larvae originating at these sites would settle inside the release region (68–94% for passive particle simulations), whereas relatively few larvae originating from the other release sites settled at these sites. In contrast, model larvae released from sites exhibiting high connectivity dispersed to all sub‐regions in the harbour, and export outside of the model region was high. Forthcoming field validation of these model predictions will result in better integration of hydrodynamic connectivity in whole estuary restoration programs.     

Relationships between land use and stream invertebrate community structure in a South Island,New Zealand,coastal stream catchment

Macroinvertebrate community composition was compared across streams draining catchments dominated by either native bush, agricultural or urban land uses within the Water of Leith stream catchment near Dunedin, New Zealand. Land use was associated with differences in taxon richness and faunal composition of communities present in each stream. The mean abundance levels of Ephemeroptera, Plecoptera, and Trichoptera were highest in native bush catchments, and lowest in urban catchments. In contrast, the mean abundance of Oligochaeta exhibited the opposite pattern. Increasing dominance of the urban and agricultural streams by pollution tolerant taxa was reflected in the Macroinvertebrate Community Index and Quantitative Macroinvertebrate Community Index scores.     

Efficacy of a multi-metric fish index as an analysis tool for the transitional fish component of the Water Framework Directive

The WFD has introduced an international commitment to assess the ecological status of transitional waters (TWs), within which fish communities are a key biological monitoring component. The Transitional Fish Classification Index (TFCI) outlined in this paper uses 10 ecological measures to analyse fish populations caught from various ecological niches using a variety of gear types within the Thames estuary. These reach and method-specific communities are then compared to a reference population created from a 'healthy' population from TWs of a similar type. The results indicate a progressive downstream increase the quality of fish communities, consistent with previous work; variation between methods can be accounted for by gear selectivity. Overall, the TFCI is an effective communication tool for converting ecological information into an easily understood format for managers, policy makers and the general public.     

Growth of bultfonteinite and hydrogarnet in metasomatized basalt xenoliths in the B/K9 kimberlite, Damtshaa, Botswana: insights into hydrothermal metamorphism in kimberlite pipes

Metamorphic assemblages within Karoo basalt xenoliths, found within volcaniclastic kimberlite of the B/K9 pipe, Damtshaa, Botswana, constrain conditions of kimberlite alteration. Bultfonteinite and chlorite partially replace the original augite-plagioclase assemblage, driven by the serpentinisation of the kimberlite creating strong chemical potential gradients for Si and Mg. Hydrogarnet and serpentine replace these earlier metamorphic assemblages as the deposits cool. The bultfonteinite (ideally Ca₂SiO₂[OH,F]₄) and hydrogarnet assemblages require a water-rich fluid containing F⁻, and imply hydrothermal alteration dominated by external fluids rather than autometamorphism from deuteric fluids. Bultfonteinite and hydrogarnet are estimated to form at temperatures of ca. 350–250°C, which are similar to those for serpentinisation. Alteration within the B/K9 kimberlite predominantly occurs between 250 and 400°C. We attribute these conditions to increased efficiency of mass transfer and chemical reactions below the critical point of water and a consequence of volume-increasing serpentinisation and metasomatic reactions that take place over this temperature range. A comparison of the B/K9 kimberlite with kimberlites from Venetia, South Africa suggests that the composition and mineralogy of included xenoliths affects the alteration assemblages within kimberlite deposits.     

Experimental analysis of arsenic precipitation during microbial sulfate and iron reduction in model aquifer sediment reactors

Microbial SO₄²⁻ reduction limits accumulation of aqueous As in reducing aquifers where the sulfide that is produced forms minerals that sequester As. We examined the potential for As partitioning into As- and Fe-sulfide minerals in anaerobic, semi-continuous flow bioreactors inoculated with 0.5% (g mL⁻¹) fine-grained alluvial aquifer sediment. A fluid residence time of three weeks was maintained over a ca. 300-d incubation period by replacing one-third of the aqueous phase volume of the reactors with fresh medium every seven days. The medium had a composition comparable to natural As-contaminated groundwater with slightly basic pH (7.3) and 7.5 μM aqueous As(V) and also contained 0.8 mM acetate to stimulate microbial activity. Medium was delivered to a reactor system with and without 10 mmol L⁻¹ synthetic goethite (α-FeOOH). In both reactors, influent As(V) was almost completely reduced to As(III). Pure As-sulfide minerals did not form in the Fe-limited reactor. Realgar (As₄S₄) and As₂S₃(am) were undersaturated throughout the experiment. Orpiment (As₂S₃) was saturated while sulfide content was low (∼50 to 150 μM), but precipitation was likely limited by slow kinetics. Reaction-path modeling suggests that, even if these minerals had formed, the dissolved As content of the reactor would have remained at hazardous levels. Mackinawite (Fe_1 + xS; x ? 0.07) formed readily in the Fe-bearing reactor and held dissolved sulfide at levels below saturation for orpiment and realgar. The mackinawite sequestered little As (<0.1 wt.%), however, and aqueous As accumulated to levels above the influent concentration as microbial Fe(III) reduction consumed goethite and mobilized adsorbed As. A relatively small amount of pyrite (FeS₂) and greigite (Fe₃S₄) formed in the Fe-bearing reactor when we injected a polysulfide solution (Na₂S₄) to a final concentration of 0.5 mM after 216, 230, 279, and 286 days. The pyrite, and to a lesser extent the greigite, that formed did sequester As from solution, containing 0.84 and 0.23 wt.% As on average, respectively. Our results suggest that As precipitation during Fe-sulfide formation in nature occurs mainly in conjunction with pyrite formation. Our findings imply that the effectiveness of stimulating microbial SO₄²⁻ reduction to remediate As contamination may be limited by the rate and extent of pyrite formation and the solubility of As-sulfides.