Chemical alteration of tephra in the depositional environment: theoretical stability modelling

The study of the chemical stability of vitreous material in aqueous media is well‐established. There has to date been little consideration of the implications of variations in the chemical durability of tephra in Quaternary tephrochronology. Chemical alteration can take the form of cationic leaching from the matrix, or complete destruction of the silica network, either of which could constrain the ability to chemically identify distal tephra. Here we apply established models of vitreous durability to the published chemical analyses of a large number of Icelandic tephras in order to predict their relative durabilities under equivalent conditions. This suggests that some important tephras have relatively poor chemical stability, and that rhyolitic tephras are, in general, more stable than basaltic. We conclude that tephras should be expected to show predictable differential chemical stability in the post‐depositional environment. Copyright © 2003 John Wiley & Sons, Ltd.     

A high resolution,multiproxy Late‐glacial record of climate change and intrasystem responses in northwest England

A lacustrine carbonate sequence from Hawes Water, Lancashire, UK, has been studied using stable isotopic, lithological, pollen and mineral magnetic analysis. The data reveal four abrupt climatic oscillations in the Late‐glacial Interstadial leading up to the onset of the Loch Lomond Stadial. The data also point to climatic warming relatively early within the stadial, ca. 12 500 GRIP yr, prior to the onset of the Holocene. The oxygen isotope record is taken as a signature of climate forcing against which the response of the lake‐system can be monitored. By adopting this approach it is revealed that the response of the biological system to the rapid climatic oscillations is non‐linear and primarily a function of the antecedent conditions. A significant end‐Devensian isotopic excursion (A) is matched by only minor changes in the cold‐adapted floras and faunas. During the warmer interstadial, the response of the biological ecosystem (events B–D) is clearly influenced by thresholds: major changes in the catchment vegetation associated with relatively minor oscillations in the isotopic signature. The stratigraphical patterns reveal significant lag effects between the onset of climate deterioration and resulting changes in vegetation. Copyright © 2002 John Wiley & Sons, Ltd.     

40Ar/39Ar and oxygen isotope studies of polymetamorphism from Tinos Island, Cycladic blueschist belt, Greece

Abstract Petrological, oxygen isotope and ⁴⁰Ar/³⁹Ar studies were used to constrain the Tertiary metamorphic evolution of the lower tectonic unit of the Cyclades on Tinos. Polyphase high-pressure metamorphism reached pressures in excess of 15 kbar, based on measurements of the Si content in potassic white mica. Temperatures of 450–500° C at the thermal peak of high-pressure metamorphism were estimated from critical metamorphic assemblages, the validity of which is confirmed by a quartz–magnetite oxygen isotope temperature of 470° C. Some ⁴⁰Ar/³⁹Ar spectra of white mica give plateau ages of 44–40 Ma that are considered to represent dynamic recrystallization under peak or slightly post-peak high-pressure metamorphic conditions. Early stages in the prograde high-pressure evolution may be documented by older apparent ages in the high-temperature steps of some spectra. Eclogite to epidote blueschist facies mineralogies were partially or totally replaced by retrograde greenschist facies assemblages during exhumation. Oxygen isotope thermometry of four quartz–magnetite pairs from greenschist samples gives temperatures of 440–470° C which cannot be distinguished from those deduced for the high-pressure event. The exhumation and overprint is documented by decreasing ages of 32–28 Ma in some greenschists and late-stage blueschist rocks, and ages of 30–20 Ma in the lower temperature steps of the Ar release patterns of blueschist micas. Almost flat parts of Ar–Ar release spectra of some greenschist micas gave ages of 23–21 Ma which are assumed to represent incomplete resetting caused by a renewed prograde phase of greenschist metamorphism. Oxygen isotope compositions of blueschist and greenschist facies minerals show no evidence for the infiltration of a δ¹⁸O-enriched fluid. Rather, the compositions indicate that fluid to rock ratios were very low, the isotopic compositions being primarily controlled by those of the protolith rocks. We assume that the fundamental control catalysing the transformation of blueschists into greenschists and the associated resetting of their isotopic systems was the selective infiltration of metamorphic fluid. A quartz–magnetite sample from a contact metamorphic skarn, taken near the Miocene monzogranite of Tinos, gave an oxygen isotope temperature of 555° C and calculated water composition of 9.1%. The value of δ¹⁸O obtained from this water is consistent with a primary magmatic fluid, but is lower than that of fluids associated with the greenschist overprint, which indicates that the latter event cannot be directly related to the monozogranite intrusion.     

Generation of reactive oxygen species in different fractions of the coelomocytes of holothurian Eupentacta fraudatrix in response to the thermostable toxin of Yersinia pseudotuberculosis in vitro

Pure fraction (92%–95%) of phagocytes (FP) and a mixture of amoebocytes (62%) and morula cells (38%)-FPMC- of the holothurianEupentacta fraudatrix' (Holothuroidea, Dendrochirota) were obtained by using ficoll-verographine step gradient. Basal production of reactive oxygen species (ROS) in FP quantified by using reduction of nitroblue tetrazolium (NBT) was more than twice that in FPMC. Thermostable toxin ofYersinia pseudotuberculosis (TST) at different concentrations (0.2; 0.5; 2.5 μg/ml, but not 0.1 μg/ml) stimulated NBT reduction in FPMC after 24 h incubation. In FP, TST at concentrations of 0.1 and 0.2 μg/ml inhibited and at concentrations of 0.5 and 2.5 μg/ml stimulated NBT reduction after 24 h incubation. Maximal effect was observed in FP and FPMC at TST concentrations of 0.5 and 0.2 μg/ml, respectively. Addition of catalase (0.7 μg/ml) to the cells treated with TST (2.5 μg/ml) was followed by a decrease in NBT reduction compared to that under toxin treatment alone. TST stimulated superoxide dismutase activity in concentration-dependent manner (maximum at 0.5 μg/ml concentration in FP) after 24 h treatment, and this stimulation was prevented by a commercial catalase. Plant lectin concanavalin A stimulated NBT reduction more than 5-fold in FPMC compared to the control. With addition of TST, lectin stimulated ROS to lesser extent than that with lectin alone. When catalase, TST, and lectin were added into the FPMC simultaneously, ROS increase was similar to that under lectin treatment alone. On the whole, data obtained indicated that ROS generation in holothurian coelomocytes especially occurs in both stimulated and not stimulated phagocytes, and that changes in ROS production by these cells may be one of the mechanisms of antibacterial protection of holothurians. This work was financially supported by the Russian Foundation for Fundamental Research Grant (No. 00-04-48949).     

Palaeotemperature reconstructions of the European permafrost zone during marine oxygen isotope Stage 3 compared with climate model results

A palaeotemperature reconstruction based on periglacial phenomena in Europe north of approximately 51 °N, is compared with high‐resolution regional climate model simulations of the marine oxygen isotope Stage 3 (Stage 3) palaeoclimate. The experiments represent Stage 3 warm (interstadial), Stage 3 cold (stadial) and Last Glacial Maximum climatic conditions. The palaeotemperature reconstruction deviates considerably for the Stage 3 cold climate experiments, with mismatches up to 11 °C for the mean annual air temperature and up to 15 °C for the winter temperature. However, in this reconstruction various factors linking climate and permafrost have not been taken into account. In particular a relatively thin snow cover and high climatic variability of the glacial climate could have influenced temperature limits for ice‐wedge growth. Based on modelling the 0 °C mean annual ground temperature proves to be an appropriate upper temperature limit. Using this limit, mismatches with the Stage 3 cold climate experiments have been reduced but still remain. We therefore assume that the Stage 3 ice wedges were generated during short (decadal time‐scale) intervals of extreme cold climate, below the mean temperatures indicated by the Stage 3 cold climate model simulations. Copyright © 2003 John Wiley & Sons, Ltd.     

Sea‐surface temperature and salinity changes in the northwest Pacific since the Last Glacial Maximum

The oxygen isotope records of both benthic and planktonic Foraminifera in five piston cores, collected from the region between the Oyashio and Kuroshio Currents near Japan, clearly show the marked latitudinal shifts of these two currents during the past 25 kyr. Under the present hydrographic condition, a clear relationship between the sea‐surface temperature (SST) and oxygen isotope differences from benthic to planktonic Foraminifera is observed in this region. Using this relationship, we find decreased SSTs of 12–13°C (maximum 15°C) in the southernmost core site at the Last Glacial Maximum (LGM), indicating the Oyashio Current shifted southward. The SSTs at the southern two core sites abruptly increased more than 10°C at 10–11 ka, suggesting the Kuroshio Current shifted northward over these sites at 10–11 ka. In contrast, the northern two core sites have remained under the influence of the cold Oyashio Current for the past 25 kyr. With the reasonable estimate of bottom‐water temperature decrease of 2.5°C at the LGM, the SSTs estimated by this new method give exactly the same SST values calculated from Mg/Ca ratio of planktonic Foraminifera, allowing palaeosea‐surface salinities to be reconstructed. The result suggests that the ice volume effect was 1.0 ± 0.1‰ at the LGM. Copyright © 2004 John Wiley & Sons, Ltd.     

Development of the mixed conifer forest in northern New Mexico and its relationship to Holocene environmental change

Chihuahueños Bog (2925 m) in the Jemez Mountains of northern New Mexico contains one of the few records of late-glacial and postglacial development of the mixed conifer forest in southwestern North America. The Chihuahueños Bog record extends to over 15,000 cal yr BP. An Artemisia steppe, then an open Picea woodland grew around a small pond until ca. 11,700 cal yr BP when Pinus ponderosa became established. C/N ratios, δ¹³C and δ¹⁵N values indicate both terrestrial and aquatic organic matter was incorporated into the sediment. Higher percentages of aquatic algae and elevated C/N ratios indicate higher lake levels at the opening of the Holocene, but a wetland developed subsequently as climate warmed. From ca. 8500 to 6400 cal yr BP the pond desiccated in what must have been the driest period of the Holocene there. C/N ratios declined to their lowest Holocene levels, indicating intense decomposition in the sediment. Wetter conditions returned after 6400 cal yr BP, with conversion of the site to a sedge bog as groundwater levels rose. Higher charcoal influx rates after 6400 cal yr BP probably result from greater biomass production rates. Only minor shifts in the overstory species occurred during the Holocene, suggesting that mixed conifer forest dominated throughout the record.     

Decoupling of stalagmite-derived Asian summer monsoon records from North Atlantic temperature change during marine oxygen isotope stage 5d

The Asian monsoon is an important component of the global climate system. Seasonal variations in wind, rainfall, and temperature associated with the Asian monsoon systems affect a vast expanse of tropical and subtropical Asia. Speleothem-derived summer monsoon variation in East Asia was previously found to be closely associated with millennial-scale change in temperature in the North Atlantic region between 75 and 10 ka. New evidence recovered from East Asia, however, suggests that the teleconnection between summer monsoon in East Asia and temperature change in the North Atlantic region may have significantly reduced during 120 to ~ 110 ka, a period directly after the full last interglaciation and corresponding roughly to marine oxygen isotope stage 5d. This reduction may be due to the low ice volume in the North Hemisphere at that time, which makes the millennial-scale change in temperature in the North Atlantic region less effective in influencing the Asian summer monsoon. This is important for investigating the mechanisms controlling the Asian summer monsoon and the paleoclimatic teleconnection between East Asia and the North Atlantic region, and for predicting monsoon-associated precipitation in East Asia under a global-warming trend.     

Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS

We have developed a technique for the accurate and precise determination of ³⁴S/³²S isotope ratios (δ³⁴S) in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We have examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. Use of high resolution sector-field mass spectrometry removes major isobaric interferences from O₂⁺. Standard-sample bracketing is used to correct for the instrumental mass bias of unknown samples. Background on sulfur masses arising from memory effects and residual oxygen-tailing are typically minor (< 0.2‰, within analytical error), and are mathematically removed by on-peak zero subtraction and by bracketing of samples with standards determined at the same signal intensity (within 20%). Matrix effects are significant (up to 0.7‰) for matrix compositions relevant to many natural sulfur-bearing minerals. For solution analysis, sulfur isotope compositions are best determined using purified (matrix-clean) sulfur standards and sample solutions using the chemical purification protocol we present. For in situ analysis, where the complex matrix cannot be removed prior to analysis, appropriately matrix-matching standards and samples removes matrix artifacts and yields sulfur isotope ratios consistent with conventional techniques using matrix-clean analytes. Our method enables solid samples to be calibrated against aqueous standards; a consideration that is important when certified, isotopically-homogeneous and appropriately matrix-matched solid standards do not exist. Further, bulk and in situ analyses can be performed interchangeably in a single analytical session because the instrumental setup is identical for both. We validated the robustness of our analytical method through multiple isotope analyses of a range of reference materials and have compared these with isotope ratios determined using independent techniques. Long-term reproducibility of S isotope compositions is typically 0.20‰ and 0.45‰ (2σ) for solution and laser analysis, respectively. Our method affords the opportunity to make accurate and relatively precise S isotope measurement for a wide range of sulfur-bearing materials, and is particularly appropriate for geologic samples with complex matrix and for which high-resolution in situ analysis is critical.     

Occurrence and evolution of the Xiaotangshan hot spring in Beijing, China

Thermal groundwater occurs in bedrock aquifers consisting of the dolomite of the Wumishan Group of the Jixianin System and the Cambrian carbonate in the Xiaotangshan geothermal field near the northern margin of the North China Plain, China. The hot water in the geothermal field of basin-type discharges partly in the form of the Xiaotangshan hot spring under natural conditions. The hot water has TDS of less than 600 mg/L and is of Na·Ca-HCO₃ type. The geothermal water receives recharge from precipitation in the mountain area with elevation of about 500 m above sea level to the north of the spring. Thermal groundwater flows slowly south and southeast through a deep circulation with a residence time of 224 years estimated with the Ra–Rn method. The Xiaotangshan hot spring dried up in the middle of the 1980s owing to the increasing withdrawal of the hot water in the geothermal field in the past decades. The water level of the geothermal system still falls continually at an annual average rate of about 2 m, although water temperature changes very little, indicating that the recharge of such a geothermal system of basin-type is limited. Over-exploitation has a dramatic impact on the geothermal system, and reduction in exploitation and reinjection are required for the sustainable usage of the hot water.