Metal binding to dissolved organic matter and adsorption to ferrihydrite in shallow peat groundwaters: Application to diamond exploration in the James Bay Lowlands,Canada

The speciation and solubility of kimberlite pathfinder metals (Ni, Nd, Ba and K) in shallow peat groundwaters is investigated over the Yankee, Zulu and Golf kimberlites in the Attawapiskat region, James Bay Lowlands, Canada. The purpose of this study is to examine the relationship between dissolved organic matter (DOM) complexation with kimberlite pathfinder metals and determine the spatial distribution of those metals in shallow peat groundwaters along sampling transects over subcropping kimberlites. Nickel, Nd, Ba and K complexation with DOM and the adsorption of these metals onto ferrihydrite were calculated using Visual MINTEQ 3.0 and the NICA-Donnan database. Calculations predict almost 100% of soluble Nd, Ni and Ba form complexes with DOM at sampling sites with little to no contribution from upwelling groundwater (i.e., dissolved organic C (DOC) concentrations = 40–132 mg/L, pH = 3.9–5.5, and log ionic strength ??3). In only the most ombrotrophic peat groundwater conditions does a majority fraction of K bind to DOM. By contrast, under conditions with large contributions from upwelling groundwaters (i.e., DOC concentrations ?40 mg/L, pH = 5.5–6.5, and log ionic strength = ?3 to ?2), as little as 10% of Nd and Ni, and 0% K and Ba are predicted to complex with DOM. The modeling calculations suggest the dominant control on metal–DOM complexation, particularly with respect to Ni and Nd, is competitive effects for DOM binding sites due to elevated ionic strength where there is evidence of strong groundwater upwelling. Visual MINTEQ modeling of metal adsorption on ferrihydrite surfaces predicts that under strong upwelling conditions, Ni and Nd are scavenged from solution due to increased ferrihydrite precipitation and decreased fractions of metals complexed with DOM. Analytical geochemical data are consistent with model predictions of metal adsorption on ferrihydrite. Total dissolved Ni and Nd concentrations at sites of strong upwelling are up to five times lower than waters with little to no upwelling and log ferrihydrite saturation indices (logSI_ferr) indicate precipitation (values up to 5) at sites of strong groundwater upwelling. Where the majority of Ni and Nd complex with DOM and ferrihydrite is highly under saturated (logSI_ferr = ?18 to ?5), the concentrations of total Ni and Nd are elevated compared to other sites along sampling transects. Metal complexation with DOM effectively inhibits metal scavenging from solution via adsorption and/or from forming secondary mineral precipitates. Also, because alkaline earth metals do not compete strongly with Ni and Nd for adsorption sites on ferrihydrite surfaces, but do compete strongly for insoluble organic sites, Ni and Nd are more likely to adsorb onto ferrihydrite.     

Centennial scale benthic foraminiferal record of late Holocene oceanographic variability in Disko Bugt,West Greenland

A new centennial scale benthic foraminiferal record of late Holocene climate variability and oceanographic changes off West Greenland (Disko Bugt) highlights substantial subsurface water mass changes (e.g. temperature and salinity) of the West Greenland Current (WGC) over the past 3.6 ka BP. Benthic foraminifera reveal a long-term late Holocene cooling trend, which may be attributed to increased advection of cold, low-salinity water masses derived from the East Greenland Current (EGC). Cooling becomes most pronounced from c. 1.7 ka BP onwards. At this point the calcareous Atlantic benthic foraminiferal fauna decrease significantly and is replaced by an agglutinated Arctic fauna. Superimposed on this cooling trend, centennial scale variability in the WGC reveals a marked cold phase at c. 2.5 ka BP, which may correspond to the 2.7 ka BP cooling-event recorded in marine and terrestrial archives elsewhere in the North Atlantic region. A warm phase recognized at c. 1.8 ka BP is likely to correspond to the ‘Roman Warm Period’ and represents the warmest bottom water conditions. During the time period of the ‘Medieval Climate Anomaly’ we observe only a slight warming of the WGC. A progressively more dominant cold water contribution from the EGC on the WGC is documented by the prominent rise in abundance of agglutinated Arctic water species from 0.9 ka BP onwards. This cooling event culminates at c. 0.3 ka BP and represents the coldest episode of the ‘Little Ice Age’.Gradually increased influence of cold, low-salinity water masses derived from the EGC may be linked to enhanced advection of Polar and Arctic water by the EGC. These changes are possibly associated with a reported shift in the large-scale North Atlantic Oscillation atmospheric circulation pattern towards a more frequent negative North Atlantic Oscillation mode during the late Holocene.     

Multi-angle backscatter classification and sub-bottom profiling for improved seafloor characterization

This study applies three classification methods exploiting the angular dependence of acoustic seafloor backscatter along with high resolution sub-bottom profiling for seafloor sediment characterization in the Eckernförde Bay, Baltic Sea Germany. This area is well suited for acoustic backscatter studies due to its shallowness, its smooth bathymetry and the presence of a wide range of sediment types. Backscatter data were acquired using a Seabeam1180 (180 kHz) multibeam echosounder and sub-bottom profiler data were recorded using a SES-2000 parametric sonar transmitting 6 and 12 kHz. The high density of seafloor soundings allowed extracting backscatter layers for five beam angles over a large part of the surveyed area. A Bayesian probability method was employed for sediment classification based on the backscatter variability at a single incidence angle, whereas Maximum Likelihood Classification (MLC) and Principal Components Analysis (PCA) were applied to the multi-angle layers. The Bayesian approach was used for identifying the optimum number of acoustic classes because cluster validation is carried out prior to class assignment and class outputs are ordinal categorical values. The method is based on the principle that backscatter values from a single incidence angle express a normal distribution for a particular sediment type. The resulting Bayesian classes were well correlated to median grain sizes and the percentage of coarse material. The MLC method uses angular response information from five layers of training areas extracted from the Bayesian classification map. The subsequent PCA analysis is based on the transformation of these five layers into two principal components that comprise most of the data variability. These principal components were clustered in five classes after running an external cluster validation test. In general both methods MLC and PCA, separated the various sediment types effectively, showing good agreement (kappa >0.7) with the Bayesian approach which also correlates well with ground truth data (r²?>?0.7). In addition, sub-bottom data were used in conjunction with the Bayesian classification results to characterize acoustic classes with respect to their geological and stratigraphic interpretation. The joined interpretation of seafloor and sub-seafloor data sets proved to be an efficient approach for a better understanding of seafloor backscatter patchiness and to discriminate acoustically similar classes in different geological/bathymetric settings.     

Impact of climate and CO2 on a millennium-long tree-ring carbon isotope record

We present one millennium-long (1171-year), and three 100 year long annually resolved δ¹³C tree-ring chronologies from ecologically varying Juniperus stands in the Karakorum Mountains (northern Pakistan), and evaluate their response to climatic and atmospheric CO₂ changes. All δ¹³C records show a gradual decrease since the beginning of the 19th century, which is commonly associated with a depletion of atmospheric δ¹³C due to fossil fuel burning. Climate calibration of high-frequency δ¹³C variations indicates a pronounced summer temperature signal for all sites. The low-frequency component of the same records, however, deviates from long-term temperature trends, even after correction for changes in anthropogenic CO₂. We hypothesize that these high-elevation trees show a response to both climate and elevated atmospheric CO₂ concentration and the latter might explain the offset with target temperature data. We applied several corrections to tree-ring δ¹³C records, considering a range of potential CO₂ discrimination changes over the past 150 years and calculated the goodness of fit with the target via calibration/verification tests (R², residual trend, and Durbin-Watson statistics). These tests revealed that at our sites, carbon isotope fixation on longer timescales is affected by increasing atmospheric CO₂ concentrations at a discrimination rate of about 0.012‰/ppmv. Although this statistically derived value may be site related, our findings have implications for the interpretation of any long-term trends in climate reconstructions using tree-ring δ¹³C, as we demonstrate with our millennium-long δ¹³C Karakorum record. While we find indications for warmth during the Medieval Warm Period (higher than today’s mean summer temperature), we also show that the low-frequency temperature pattern critically depends on the correction applied. Patterns of long-term climate variation, including the Medieval Warm Period, the Little Ice Age, and 20th century warmth are most similar to existing evidence when a strong influence of increased atmospheric CO₂ on plant physiology is assumed.     

Chemical and structural relations of epitaxial xenotime and zircon substratum in sedimentary and hydrothermal environments: a TEM study

Xenotime overgrowths on detrital zircon in siliciclastic sediments have been reported in numerous studies. However, in natural samples, solid solution of zircon and xenotime is limited to near-end-member compositions. In order to characterize the interface region between both minerals and to draw inferences on the growth mechanisms of authigenic xenotime, we studied xenotime overgrowths on detrital zircon grains from two Phanerozoic sandstone samples with contrasting post-depositional histories. In one sample, the small (≤10 μm), pyramidal xenotime overgrowths are of diagenetic origin and grew without major discontinuity on the detrital zircon grain. The second sample shows up to >50-μm-wide, porous and inclusion-rich, hydrothermal xenotime overgrowths on detrital zircon, whereas the transition zone between both minerals is accompanied by large pore volume. Chemical compositions of the xenotime precipitates from the two samples differ particularly in Y, REE, Th and Sc concentrations, whereas high MREE availability in the diagenetic sample and the presence of Sc in the hydrothermal sample, respectively, appear to have promoted xenotime growth. Transmission electron microscopy on electron-transparent foils cut from the interface region shows that both the diagenetic xenotime and the hydrothermal xenotime are crystalline and grew in optical and crystallographic continuity to their detrital zircon substrata. Only a narrow transition zone (≤90 nm—diagenetic sample, 200–300 nm—hydrothermal sample) between zircon and xenotime is in part made up of nanometre-scale crystalline domains that are slightly distorted and may have formed from dissolution–re-precipitation processes at the zircon rim along with precipitation from the respective fluid.     

North Atlantic climate impact on early late‐glacial climate oscillations in the south‐eastern Alps inferred from a multi‐proxy lake sediment record

High‐resolution multi‐proxy analyses of a sediment core section from Lake Jeserzersee (Saissersee) in the piedmont lobe of the Würmian Drau glacier (Carinthia, Austria) reveal pronounced climatic oscillations during the early late glacial (ca. 18.5–16.0k cal a BP). Diatom‐inferred epilimnetic summer water temperatures show a close correspondence with temperature reconstructions from the adjacent Lake Längsee record and, on a hemispheric scale, with fluctuations of ice‐rafted debris in the North Atlantic. This suggests that North Atlantic climate triggered summer climate variability in the Alps during the early late glacial. The expansion of pine (mainly dwarf pine) between ca. 18.5 and 18.1k cal a BP indicates warming during the so‐called ‘Längsee oscillation’. The subsequent stepwise climate deterioration between ca. 18.1 and 17.6k cal a BP culminated in a tripartite cold period between ca. 17.6 and 16.9k cal a BP with diatom‐inferred summer water temperatures 8.5–10 °C below modern values and a shift from wet to dry conditions. This period probably coincides with a major Alpine glacier advance termed the Gschnitz stadial. A warmer interval between ca. 16.9 and 16.4k cal a BP separates this cold phase from a second, shorter and less pronounced cold phase between ca. 16.4 and 16.0k cal a BP, which is thought to correlate with the Clavadel/Senders glacier advance in the Alps. The following temperature increase, coupled with wet (probably snow‐rich) conditions, caused the expansion of birch during the transition period to the late glacial interstadial. Copyright © 2011 John Wiley & Sons, Ltd.     

A comparison between Mgii and Caii spectroheliograms

A detailed photometric comparison between a Mgii K filterheliogram and a nearly simultaneous Caii K spectroheliogram is presented. The comparison shows a close correspondence in both location and intensity of the bright features on the Sun with a correlation coefficient of 0.92 ± 0.02 between the Mgii and the Caii intensities in active regions.A small flare is most likely observed in the Mgii heliogram giving a substantial contribution to the recorded intensity.We also estimate theoretically the heights in the solar atmosphere at which the Mgii K and Caii K lines are formed. Taking into account the general shape of the line profiles and the different passbands used in the recordings we arrive at an average height of formation of 1700–1900 km above the photosphere for these particular heliograms.     

Numerical simulations of granular dynamics II: Particle dynamics in a shaken granular material

Surfaces of planets and small bodies of our Solar System are often covered by a layer of granular material that can range from a fine regolith to a gravel-like structure of varying depths. Therefore, the dynamics of granular materials are involved in many events occurring during planetary and small-body evolution thus contributing to their geological properties.We demonstrate that the new adaptation of the parallel N-body hard-sphere code pkdgrav has the capability to model accurately the key features of the collective motion of bidisperse granular materials in a dense regime as a result of shaking. As a stringent test of the numerical code we investigate the complex collective ordering and motion of granular material by direct comparison with laboratory experiments. We demonstrate that, as experimentally observed, the scale of the collective motion increases with increasing small-particle additive concentration.We then extend our investigations to assess how self-gravity and external gravity affect collective motion. In our reduced-gravity simulations both the gravitational conditions and the frequency of the vibrations roughly match the conditions on asteroids subjected to seismic shaking, though real regolith is likely to be much more heterogeneous and less ordered than in our idealised simulations. We also show that collective motion can occur in a granular material under a wide range of inter-particle gravity conditions and in the absence of an external gravitational field. These investigations demonstrate the great interest of being able to simulate conditions that are to relevant planetary science yet unreachable by Earth-based laboratory experiments.