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 fusion crust of the Winchcombe meteorite: A preserved record of atmospheric entry processes

Fusion crusts form during the atmospheric entry heating of meteorites and preserve a record of the conditions that occurred during deceleration in the atmosphere. The fusion crust of the Winchcombe meteorite closely resembles that of other stony meteorites, and in particular CM2 chondrites, since it is dominated by olivine phenocrysts set in a glassy mesostasis with magnetite, and is highly vesicular. Dehydration cracks are unusually abundant in Winchcombe. Failure of this weak layer is an additional ablation mechanism to produce large numbers of particles during deceleration, consistent with the observation of pulses of plasma in videos of the Winchcombe fireball. Calving events might provide an observable phenomenon related to meteorites that are particularly susceptible to dehydration. Oscillatory zoning is observed within olivine phenocrysts in the fusion crust, in contrast to other meteorites, perhaps owing to temperature fluctuations resulting from calving events. Magnetite monolayers are found in the crust, and have also not been previously reported, and form discontinuous strata. These features grade into magnetite rims formed on the external surface of the crust and suggest the trapping of surface magnetite by collapse of melt. Magnetite monolayers may be a feature of meteorites that undergo significant degassing. Silicate warts with dendritic textures were observed and are suggested to be droplets ablated from another stone in the shower. They, therefore, represent the first evidence for intershower transfer of ablation materials and are consistent with the other evidence in the Winchcombe meteorite for unusually intense gas loss and ablation, despite its low entry velocity.     

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.     

High‐ to ultrahigh‐temperature metamorphism in the lower crust: An example resulting from Hikurangi Plateau collision and slab rollback in New Zealand

Lower crustal xenoliths erupted from an intraplate diatreme reveal that a portion of the New Zealand Gondwana margin experienced high‐temperature (HT) to ultrahigh‐temperature (UHT) granulite facies metamorphism just after flat slab subduction ceased at c. 110–105 Ma. P–T calculations for garnet–orthopyroxene‐bearing felsic granulite xenoliths indicate equilibration at ~815 to 910°C and 0.7 to 0.8 GPa, with garnet‐bearing mafic granulite xenoliths yielding at least 900°C. Supporting evidence for the attainment of HT and UHT conditions in felsic granulite comes from re‐integration of exsolution in feldspar (~900–950°C at 0.8 GPa), Ti‐in‐zircon thermometry on Y‐depleted overgrowths on detrital zircon grains (932°C ± 24°C at aTiO₂ = 0.8 ± 0.2), and correlation of observed assemblages and mineral compositions with thermodynamic modelling results (≥850°C at 0.7 to 0.8 GPa). The thin zircon overgrowths, which were mainly targeted by drilling through the cores of grains, yield a U–Pb pooled age of 91.7 ± 2.0 Ma. The cause of Late Cretaceous HT‐UHT metamorphism on the Zealandia Gondwana margin is attributed to collision and partial subduction of the buoyant oceanic Hikurangi Plateau in the Early Cretaceous. The halt of subduction caused the fore‐running shallowly dipping slab to rollback towards the trench position and permitted the upper mantle to rapidly increase the geothermal gradient through the base of the extending (former) accretionary prism. This sequence of events provides a mechanism for achieving regional HT–UHT conditions in the lower crust with little or no sign of this event at the surface.     

High-resolution historical records from Pettaquamscutt River basin sediments: 2. Pb isotopes reveal a potential new stratigraphic marker

A high-resolution record of Pb deposition in Rhode Island over the past 250 yr was constructed using a sediment core from the anoxic Pettaquamscutt River basin. The sedimentary Pb concentration record shows the well-described maximum associated with leaded gasoline usage in the United States. Diminished Pb variability during recorded periods of local industrial activity (1735 to 1847) supports the greater importance of regional atmospheric lead transport vs. local inputs. The Pb isotopic composition at this site shows a clear maximum in anthropogenic ²⁰⁶Pb/²⁰⁷Pb in the mid-1800s. Similar peaks have also been observed in sediments from Chesapeake Bay and the Great Lakes, suggesting a common source. Possible causes for this event include mining and smelting of Pb ores in the Upper Mississippi Valley district, which accounted for almost all Pb production in the United States in that period. The timing of this event can provide an important stratigraphic marker for sediments deposited in the past 200 yr in the Northeastern United States. The downcore profile of anthropogenic ²⁰⁶Pb/²⁰⁷Pb provides a classic example of how changes in the mixture of ores for production of tetraethyl lead caused a regional-scale shift in the sedimentary record, and suggests that coal could have played a secondary role in Pb emissions after 1920.     

Petrology of the 1979 eruption of Soufriere volcano,St. Vincent,Lesser Antilles

Major element, trace element, and Sr isotope data are used to study the temporal variation in the chemistry of the ejecta from the 1979 eruption of Soufriere volcano, St. Vincent, and to compare the compositions of the 1979 and 1971/2 magmas. Both the 1971/2 and 1979 products were basaltic andesites almost identical in petrography. A small temporal variation in chemistry is apparent in the 1979 samples but these cannot be related to the 1971/2 lava by fractional crystallisation of phenocryst phases, and the two eruptions may therefore have sampled different batches of magma. ⁸⁷Sr/⁸⁶Sr ratios of the two magmas were identical within analytical error.Microprobe analyses of phenocryst phases and glasses from the 1979 ejecta are presented. Clinopyroxene phenocryst cores with very high Mg/Fe ratios indicate that the basaltic andesites are products of fractionation of magnesian parents. Such magmas are represented by lavas on St. Vincent similar to the microphyric alkali picrites found to the south in Grenada. A common origin for the basaltic andesites of both islands by fractional crystallisation of picritic magmas is suggested. Dacitic glass is abundant in the groundmass of scoria blocks from the eruption. It does not represent the liquid originally in equilibrium with the phenocryst phases, but rather this liquid modified by quench crystallisation. Published interpretations suggesting that dacitic glass compositions in tephra from eruptions of the Soufriere are evidence of mixed-magma eruptions are therefore rejected.     

Rare earth elements (REE) and yttrium in stream waters, stream sediments, and Fe-Mn oxyhydroxides: Fractionation, speciation, and controls over REE + Y patterns in the surface environment

We have collected ∼500 stream waters and associated bed-load sediments over an ∼400 km² region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into “dissolved” (<0.45 μm), labile (hydroxylamine) and detrital sediment fractions to investigate REE fractionation, and in particular, with respect to the development of Ce and Eu anomalies in oxygenated surface environments. Surface waters are typically LREE depleted ([La/Sm]_NASC ranges from 0.16 to 5.84, average = 0.604, n = 410; where the REE are normalized to the North America Shale Composite), have strongly negative Ce anomalies ([Ce/Ce^∗]_NASC ranges from 0.02 to 1.25, average = 0.277, n = 354), and commonly have positive Eu anomalies ([Eu/Eu^∗]_NASC ranges from 0.295 to 1.77, average = 0.764, n = 84). In contrast, the total sediment have flatter REE + Y patterns relative to NASC ([La/Sm]_NASC ranges from 0.352 to 1.12, average = 0.778, n = 451) and are slightly middle REE enriched ([Gd/Yb]_NASC ranges from 0.55 to 3.75, average = 1.42). Most total sediments have negative Ce and Eu anomalies ([Ce/Ce^∗]_NASC ranges from 0.097 to 2.12, average = 0.799 and [Eu/Eu^∗]_NASC ranges from 0.39 to 1.43, average = 0.802). The partial extraction sediments are commonly less LREE depleted than the total sediments ([La/Sm]_NASC ranges from 0.24 to 3.31, average = 0.901, n = 4537), more MREE enriched ([Gd/Yb]_NASC ranges from 0.765 to 6.28, average = 1.97) and Ce and Eu anomalies (negative and positive) are more pronounced.The partial extraction recovered, on average ∼20% of the Fe in the total sediment, ∼80% of the Mn, and 21-29% of the REEs (Ce = 19% and Y = 32%). Comparison between REEs in water, partial extraction and total sediment analyses indicates that REEs + Y in the stream sediments have two primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO₂/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.