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.     

Multiple-source localization using GPS technology and receivedarrival time structure analysis in an air-deployed system

An efficient and robust method has been developed to locate multiple impulsive sources in an ocean environment. Global position system (GPS) receivers were installed on sonobuoys to obtain their locations within a few meters of accuracy. A sonobuoy field was deployed in a ring-type pattern. Charges were then set off at arbitrary locations within the ring, High-resolution plots were used to obtain direct path and/or first bottom bounce arrivals on each buoy. A model grid of arrival times was constructed, corresponding to the dimensions of the buoy field. A ray model previously developed here at the Applied Research Laboratories at the University of Texas at Austin (ARL:UT) was used to obtain model travel times. The minimum value of the least-square-type error between the real arrival times and the modeled travel times resulted in an unambiguous location of the source, within the limits of the grid spacing chosen. This value was calculated by picking one receiver as the reference and then summing the timing errors of the remaining receivers relative to the reference. Successive iterations with finer grid spacings result in source localization within the accuracy of the buoy locations. The localization routine was extended by allowing permutations of the pulse arrivals on each buoy to account for multiple sources closely separated in time and/or space. An automated correlation technique is presented as an alternative to the leading edge-detection method used here for obtaining relative arrival times. Two proof-of-concept experiments were performed and some results of data obtained at Lake Travis and the Gulf of Mexico are presented     

Kinetic studies of lead(II) uptake by the seagrass Zostera muelleri in water by radiotracing,atomic absorption spectrometry and electrochemical techniques

Evidence was found that uptake of lead from seawater in both model and natural systems by the leaves of the seagrass Zostera muelleri does occur for live, dead and scraped leaves at all the lead concentrations tested. Positive uptake of lead was measured using the three analytical techniques of radio-tracer, differential pulse anodic stripping voltammetry and atomic absorption spectrometry; similar uptake profiles were obtained for each technique. Profiles always showed an initial rapid uptake phase followed by a gradual transition to a plateau phase at which an approximate equilibrium between lead attached to seagrass and free ionic lead in seawater was reached. The presence of active lead uptake processes was indicated in experiments which attempted to remove lead from leaves by a chelating agent.     

Stable carbon-isotopic compositions of lipids isolated from the ammonia-oxidizing chemoautotroph Nitrosomonas europaea

For the ammonia-oxidizing bacterium Nitrosomonas europaea, grown autotrophically using semicontinuous culturing, average biomass was depleted in ¹³C relative to CO₂ dissolved in the medium by ca. 20‰ and the total-lipid extract was depleted in ¹³C relative to biomass by 3.7‰. The n-alkyl lipids (weighted average of fatty acids) and isoprenoid lipids (weighted average of hopanoids) were both depleted in ¹³C relative to biomass by about 9‰. The large depletion in the isoprenoid lipids seems to indicate that isotopic fractionations associated with the biosynthesis of methylerythritol phosphate (MEP) affected at least two carbon positions in each isoprene unit. Among the fatty acids, trans-9-hexadecenoic acid was most depleted (13.0‰ relative to biomass), followed by cis-9- hexadecenoic acid (9.6‰) and hexadecanoic acid (6.9‰). Isotopic relationships between the three acids suggest that significant isotope effects were associated with the desaturation and cis to trans isomerization of fatty acids. Given these observations, hopanoids produced by ammonia-oxidizing bacteria growing in natural waters are likely to be depleted in ¹³C by 26–30‰ relative to dissolved CO₂. Since CO₂ at aquatic oxyclines is often depleted in ¹³C, the range of δ values expected for hopanoids is ca. −34‰ to −55‰. The δ values of geohopanoids observed in numerous studies and attributed to unspecified chemoautotrophs fall within this range.     

Oxidation of pyrite during extraction of carbonate associated sulfate

The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ³⁴S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ³⁴S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ³⁴S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ³⁴S_pyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe³⁺ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H₂O, not O₂. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.     

Recycling in the Puerto Rican mantle wedge, Greater Antilles Island Arc

Abstract The initial volcanic phase of Cretaceous island arc strata in central Puerto Rico, at the eastern end of the extinct Greater Antilles Arc, comprises a 6‐km thick pile of lava and volcanic breccia (Río Majada Group). Preserved within the sequence is a conspicuous shift in absolute abundances of the more incompatible elements, including Th, Nb, and the light rare earth elements (LREE: La, Ce, Pr and Nd). The compositional shift is marked by a decrease in La/Sm from averages of 2.11 in the lowest third of the pile (Formation A) to 1.48 at the top (Formation C), and by a distinctive flattening of LREE segments of chondrite‐normalized REE patterns. i⁸⁷Sr/⁸⁶Sr and ?_Nd average about 0.7035 and 8.2, respectively, in early Formation A basalts. These ranges normally overlap samples from later Formations B and C. Isotope compositions of the latter group are more variable, however, and several samples are considerably more radiogenic than Formation A basalts, such that i⁸⁷Sr/⁸⁶Sr averages almost 0.7042 while ?_Nd‐values decrease to 7.5 in Formation B and C basalts. Theoretical models of non‐modal melting processes in both amphibole peridotite and spinel lherzolite sources provide insight into the origin of depleted Th, Nb, and LREE abundances in Puerto Rican basalts. Low Nb concentrations less than normal mid‐oceanic ridge basalts in Formation A basalts indicate the wedge was slightly depleted by low‐volume decompression fusion due to induced convection in the back‐arc region prior to entry of the source into the arc melting zone. However, depleted patterns in Formation C basalts cannot be generated by relatively greater degrees of decompression fusion in the back‐arc, because addition of the La‐enriched slab‐derived component to more depleted source material invariably produces elevated rather than decreased La/Sm. Refluxing of Formation A harzburgitic residua is similarly precluded. In contrast, the observed patterns are readily reproduced by multistage melting models involving hybridized sources containing normal Formation A lherzolite source material blended with recycled, unrefluxed harzburgite residua. Successful models require hybrid sources containing large volumes of recycled harzburgite (up to 50%) during generation of Formation C basalts. Slightly elevated radiometric Sr and Nd isotopes in a few flows from Formation C are attributed to partial refluxing of the hybrid sources within the wedge.     

Electronic environments in carrollite, CuCo2S4, determined by soft X-ray photoelectron and absorption spectroscopy

Fracture surfaces of a natural carrollite specimen have been characterised by synchrotron and conventional X-ray photoelectron spectroscopy and near-edge X-ray absorption spectroscopy. For the synchrotron X-ray measurements, the mineral surfaces were prepared under clean ultra high vacuum and were unoxidised. The characterisation was undertaken primarily to establish unequivocally the oxidation state of the Cu in the mineral, but also to obtain information on the electronic environments of the Co and S, and on the surface species. Experimental and simulated Cu L_2,3-edge absorption spectra confirmed an oxidation state of Cu^I, while Co 2p photoelectron and Co L_2,3 absorption spectra were largely consistent with the Co^III established previously by nuclear magnetic resonance spectroscopy. S 2p photoelectron spectra provided no evidence for S to be present in the bulk in more than one state, and were consistent with an oxidation state slightly less negative than S^-II. Therefore it was concluded that carrollite can be best represented by Cu^ICo^III₂(S₄)^-VII. The Cu^I oxidation state is in agreement with that expected for Cu tetrahedrally coordinated by S, but is in disagreement with the Cu^II deduced previously from some magnetic, magnetic resonance and Cu L-edge X-ray absorption spectroscopic measurements. A significant concentration of S species with core electron binding energies both lower and higher than the bulk value were formed at fracture surfaces, and these entities were assigned to monomeric and oligomeric surface S species. The density of Cu d states calculated for carrollite differed from that previously reported but was consistent with the observed Cu L₃ X-ray absorption spectrum. The initial oxidation of carrollite in air under ambient conditions was confirmed to be congruent, unlike the incongruent reaction undergone by a number of non-thiospinel sulfide minerals.     

Regional‐scale sedimentation process models from airborne gamma ray remote sensing and digital elevation data

Airborne gamma ray survey data were used to provide information on potassium, thorium and uranium concentrations in surface soil and rock in arid central Australia. Spatial patterns in these radioelements allow tracing of paths of sediment at catchment scale. Survey elevation data are combined with contour data to produce digital elevation models for terrain analysis, tracing of sediment flow paths and modelling of extreme floods. Gamma ray data show consistent variation with slope, a limited range of drainage areas, and erosion/deposition models derived from the conservation of mass equation. Supply‐limited sediment transport models give a reasonable reproduction of observed radioelement distribution but some elements of the distribution pattern reflect the area inundated by 500–1000 year floods rather than the effects of simple downslope movement. Partial area sediment supply models are derived by downstream accumulation of erosion and deposition rates calculated using the conservation of mass equation with transport laws based on slope alone and stream power. Comparison with observed radioelement patterns suggests that both transport laws apply in different parts of the landscape. Regional‐scale sediment transport models will require a range of models depending on location in the landscape and event frequency. This approach may allow estimation of sediment delivery ratios. Copyright © 2001 John Wiley & Sons, Ltd.     

Keck observations of near-Earth asteroids in the thermal infrared

We present the results of thermal-infrared observations of 20 near-Earth asteroids (NEAs) obtained in the period March 2000-February 2002 with the 10-m Keck-I telescope on Mauna Kea, Hawaii. The measured fluxes have been fitted with thermal-model emission continua to determine sizes and albedos. This work increases the number of NEAs having measured albedos by 35%. The spread of albedos derived is very large (p_v=0.02−0.55); the mean value is 0.25, which is much higher than that of observed main-belt asteroids. In most cases the albedos are in the ranges expected for the spectral types, although some exceptions are evident. Our results are consistent with a trend of increasing albedo with decreasing size for S-type asteroids with diameters below 20 km. A number of objects are found to have unexpectedly low apparent color temperatures, which may reflect unusual thermal properties. However, the results from our limited sample suggest that high thermal-inertia, regolith-free objects may be uncommon, even amongst NEAs with diameters of less than 1 km. We discuss the significance of our results in the light of information on these NEAs taken from the literature and the uncertainties inherent in applying thermal models to near-Earth asteroids.