Pervasive autocorrelation of the chemical index of alteration in sedimentary profiles and its palaeoenvironmental implications

The chemical index of alteration has been used widely for reconstruction of the palaeoclimate. However, the mechanisms and environmental factors controlling the chemical index of alteration of sediments are not yet fully understood. In this study, autocorrelations of the chemical index of alteration in nine sedimentary profiles, from both the land and the sea, spanning different geological times, are discussed. The sediments of these profiles have different origins (dust, fluvial or ocean sediments) and are from various climate situations and sedimentary environments. Autocorrelations of chemical index of alteration series are ubiquitously evident in all profiles. It is suggested here that autocorrelations may be caused by post-depositional changes such as persistent weathering and diagenesis. As a result, the chemical index of alteration may not reflect climatic conditions during the time of sediment deposition. This study strongly recommends the confirmation of the reliability and veracity of the chemical index of alteration before it is adopted to evaluate the weathering degree of parent rocks and to reconstruct the past climate. Significant autocorrelations in loess profiles were specifically observed, suggesting that the existing understanding of loess deposition in terms of climate conditions requires re-examination, and that previous reconstructions of rapid climate changes (for example, in centennial-millennial scales) should be treated with caution.

Evolution and variability of the East Asian summer monsoon during the Pliocene: Evidence from clay mineral records of the South China Sea

The Late Pliocene is thought to be characterized by the simultaneous intensification of both the East Asian winter monsoon (EAWM) and East Asian summer monsoon (EASM). However, the evolution of the EASM during the Pliocene remains still controversial and only little is known about the dynamics of the EASM during the Pliocene on orbital time scales. Here we use clay mineral assemblages in sediments from Ocean Drilling Program (ODP) Site 1143 in the southern South China Sea (SCS) to obtain proxy records of past changes in the EASM climate during the Pliocene. Provenance analysis suggests that illite, chlorite and kaolinite originated mainly from the Mekong River drainage area. Smectite was derived mainly from the Indonesian islands. The kaolinite/illite ratio and the chemical index of alteration (CIA) of siliciclastic sediments allowed us to reconstruct the history of chemical weathering and physical erosion of the Mekong River drainage area and thus, the evolution of,the EASM during the Pliocene. Our clay minerals proxy data suggests a stronger EASM during the Early Pliocene than during the Late Pliocene. We propose that the long-term evolution of the EASM has been driven by global cooling rather than the uplift of the Tibetan Plateau. Spectral analysis of kaolinite/ illite ratio displays a set of strong periodicities at 100 ka, 30 ka, 28 ka, 25 ka, and 22 ka. with no clear obliquityrelated signal. Our study suggests that the Pliocene EASM intensity on orbital time scales is not only controlled by the Northern Hemisphere summer insolation, but also strongly influenced by equatorial Pacific ENSO-like ocean atmosphere dynamics. (C) 2010 Elsevier B.V. All rights reserved.

Records of the East Asian winter monsoon from the mud area on the inner shelf of the East China Sea since the mid-Holocene

AMS(14)C dating and analysis of grain size, major elements and clay minerals were applied to Core MZ01 from the mud area on the inner shelf of the East China Sea. Based on the environmentally sensitive grain size, clay mineral and major element assemblages, the history of the East Asia winter monsoon since the mid-Holocene could be reconstructed. These three proxies, mean grain size (>9.71 mu m), chemical index of alteration (CIA) and ratio of smectite to kaolinite in particular, show similar fluctuation patterns. Furthermore, 10 extreme values corresponding to the contemporary cooling events could be recognized since the mid-Holocene; these extreme values are likely to have been caused by the strengthening of the East Asia winter monsoon. The cooling events correlated well with the results of the delta O-18 curves of the Dunde ice core and GISP2, which therefore revealed a regional response to global climate change. Four stages of the East Asia winter monsoon were identified, i.e. 8300-6300 a BP, strong and unstable; 6300-3800 a BP, strong but stable; 3800-1400 a BP, weak and unstable; after 1400 a BP, weak but stable.

Whole-rock geochemistry and Sr-Nd isotopic composition of the pre-rift sequence of the Camamu Basin, northeastern Brazil

Whole-rock geochemistry, combined with Sr-Nd isotopic composition of pelitic sedimentary rocks, have been considered to be useful parameters to estimate not only their provenance but also to make inferences about their depositional environment as well as the weathering processes they have been through. The basal sedimentary units of the basins of the northeastern Brazilian continental margin, particularly those of the pre-rift sequence, have been subject of interest of studies based on chemical and isotopic data, since they lack fossil content to establish their age and, therefore, stratigraphic correlations are difficult. The major and trace element contents as well as Sr-Nd isotopic compositions of whole-rock shale samples from five outcrops attributed to the pre-rift supersequence of the Camamu Basin were analyzed with the purpose of characterizing and obtaining further information that would allow a better correlation between the sites studied. The geochemical data suggest that the rocks exposed in the studied outcrops are part of the same sedimentary unit and that they might be correlated to the Capianga Member of the Alianca Formation of the Reconcavo Basin, exposed to the north of the Camamu Basin. The chemical index of alteration (CIA) suggests conditions associated with a humid tropical/subtropical climate at the time of deposition. Nd isotopic compositions indicate provenance from the Paleoproterozoic rocks of the Sao Francisco craton. The results presented here, therefore, show that the combined use of chemical and isotopic analyses may be of great interest to characterize and correlate lithologically homogeneous clastic sedimentary sequences. (C) 2012 Elsevier Ltd. All rights reserved.

A 350 ka record of climate change from Lake El'gygytgyn, Far East Russian Arctic: refining the pattern of climate modes by means of cluster analysis

Abstract. Rock magnetic, biochemical and inorganic records of the sediment cores PG1351 and Lz1024 from Lake El’gygytgyn, Chukotka peninsula, Far East Russian Arctic, were subject to a hierarchical agglomerative cluster analysis in order to refine and extend the pattern of climate modes as defined by Melles et al. (2007). Cluster analysis of the data obtained from both cores yielded similar results, differentiating clearly between the four climate modes warm, peak warm, cold and dry, and cold and moist. In addition, two transitional phases were identified, representing the early stages of a cold phase and slightly colder conditions during a warm phase. The statistical approach can thus be used to resolve gradual changes in the sedimentary units as an indicator of available oxygen in the hypolimnion in greater detail. Based upon cluster analyses on core Lz1024, the published succession of climate modes in core PG1351, covering the last 250 ka, was modified and extended back to 350 ka. Comparison to the marine oxygen isotope (�18O) stack LR04 (Lisiecki and Raymo, 2005) and the summer insolation at 67.5� N, with the extended Lake El’gygytgyn parameter records of magnetic susceptibility (�LF), total organic carbon content (TOC) and the chemical index of alteration (CIA; Minyuk et al., 2007), revealed that all stages back to marine isotope stage (MIS) 10 and most of the substages are clearly reflected in the pattern derived from the cluster analysis.

Age tie points and geochemistry of sediment cores from the Antarctic continental margin

Few high-latitude terrestrial records document the timing and nature of the Cenozoic "Greenhouse" to "Icehouse" transition. Here we exploit the bulk geochemistry of marine siliciclastic sediments from drill cores on Antarctica's continental margin to extract a unique semiquantitative temperature and precipitation record for Eocene to mid-Miocene (~54-13 Ma). Alkaline elements are strongly enriched in the detrital mineral fraction in fine-grained siliciclastic marine sediments and only occur as trace metals in the biogenic fraction. Hence, terrestrial climofunctions similar to the chemical index of alteration (CIA) can be applied to the alkaline major element geochemistry of marine sediments on continental margins in order to reconstruct changes in precipitation and temperature. We validate this approach by comparison with published paleotemperature and precipitation records derived from fossil wood, leaves, and pollen and find remarkable agreement, despite uncertainties in the calibrations of the different proxies. A long-term cooling on the order of >=8°C is observed between the Early Eocene Climatic Optimum (~54-52 Ma) and the middle Miocene (~15-13 Ma) with the onset of transient cooling episodes in the middle Eocene at ~46-45 Ma. High-latitude stratigraphic records currently exhibit insufficient temporal resolution to reconstruct continental aridity and inferred ice-sheet development during the middle to late Eocene (~45-37 Ma). However, we find an abrupt aridification of East Antarctica near the Eocene-Oligocene transition (~34 Ma), which suggests that ice coverage influenced high-latitude atmospheric circulation patterns through albedo effects from the earliest Oligocene onward.

Sediment and pore water geochemistry of sediment cores, Potter Cove, King George Island

Redox-sensitive trace metals (Mn, Fe, U, Mo, Re), nutrients and terminal metabolic products (NO3-, NH4+, PO43-, total alkalinity) were for the first time investigated in pore waters of Antarctic coastal sediments. The results of this study reveal a high spatial variability in redox conditions in surface sediments from Potter Cove, King George Island, western Antarctic Peninsula. Particularly in the shallower areas of the bay the significant correlation between sulphate depletion and total alkalinity, the inorganic product of terminal metabolism, indicates sulphate reduction to be the major pathway of organic matter mineralisation. In contrast, dissimilatory metal oxide reduction seems to be prevailing in the newly ice-free areas and the deeper troughs, where concentrations of dissolved iron of up to 700 µM were found. We suggest that the increased accumulation of fine-grained material with high amounts of reducible metal oxides in combination with the reduced availability of metabolisable organic matter and enhanced physical and biological disturbance by bottom water currents, ice scouring and burrowing organisms favours metal oxide reduction over sulphate reduction in these areas. Based on modelled iron fluxes we calculate the contribution of the Antarctic shelf to the pool of potentially bioavailable iron (Feb) to be 6.9x10**3 to 790x10**3 t/yr. Consequently, these shelf sediments would provide an Feb flux of 0.35-39.5/mg/m**2/yr (median: 3.8 mg/m**2/yr) to the Southern Ocean. This contribution is in the same order of magnitude as the flux provided by icebergs and significantly higher than the input by aeolian dust. For this reason suboxic shelf sediments form a key source of iron for the high nutrient-low chlorophyll (HNLC) areas of the Southern Ocean. This source may become even more important in the future due to rising temperatures at the WAP accompanied by enhanced glacier retreat and the accumulation of melt water derived iron-rich material on the shelf.

Tie points and goechemical analysis from different Holes of ODP Site 165-1002

The fine-grained sediments of the Cariaco Basin, Venezuela, of the last 130 ky, whose deposition history is well characterized, were analyzed geochemically in order to test the validity of sediment bulk geochemistry as an indicator of detrital provenance. Several binary and ternary diagrams as well as the chemical index of alteration (CIA) were tested for their capacity to discriminate the poorly contrasted detrital sources to the Cariaco Basin, and to describe the temporal evolution of the contributions of these different sources. Most of the diagrams tested did not allow a good discrimination of sources or, when sources were well discriminated, did not allow an interpretation of the temporal variations consistent with the known history. A relatively good discrimination of sources and a consistent interpretation of temporal variations were however obtained using Hf vs. Th and La/Yb vs. Gd/Yb binary diagrams, as well as Ti-Zr-Th, Ti-Zr-La, and Lu-Hf-Th ternary diagrams. Compared to the previous studies of the detrital content of the Cariaco Basin sediments, the geochemical approach permitted the recognition of a sediment contribution eroded from the Unare platform and Gulf of Cariaco during rapid sea level oscillations, and the contribution of Saharan eolian particles during the Younger Dryas-Preboreal and MIS6-5 transition. The choice of plotted elements was determined after considering carrier minerals, so that different elements may be informative in different sedimentary contexts. Overall, mineral sorting during transport appears as a major limit to quantitative estimation of the different contributions. In particular mineral sorting leads to the selective enrichment of elements associated with clays (Al, Rb, Th and LREE) in sediments deposited in the basin. Unless the geochemical effect of mineral sorting can be measured, it appears that quantitative provenance analysis should be performed on fractions of similar grain size instead of bulk sediment.

Pb isotope and geochemical record of Arctic sediments

Elemental and Pb isotope measurements were performed on leachates and residues from surface sediments and two <50 cm cores (MC04 and MC16) collected along a NE-SW transect through Fram Strait. Geochemical and isotopic properties of residues from surface sediments define three distinct spatial domains within the Strait: 1) the easternmost edge of the Strait; 2) the eastern part of the Strait off the Svalbard margins; and 3) the western part of the Strait, influenced by supplies from Svalbard, the Nordic seas with possible contributions from northwestern Siberian margins, and sea ice and water outflow from the Arctic, respectively. Core MC16, in the third domain beneath the outflowing Arctic waters, spans the Last Glacial Maximum present interval. Sediments from this core were leached to obtain detrital (residues) and exchangeable (leachates) fractions. Detrital supplies to core MC16 are believed to originate mainly from melting of the overlying sea ice and thus can be used to document changes in Arctic sedimentary sources. Detrital 206Pb/204Pb and 208Pb/206Pb ratios illustrate two mixing trends, Trends A and B, corresponding to the pre- and post-Younger Dryas (YD) intervals, respectively. These trends represent binary mixtures with a common end-member (Canadian margins) and either a Siberian (Trend A) or Greenland (Trend B) margin end-member. The YD is marked by an isotopic excursion toward the Canadian end-member, suggesting a very active Beaufort Gyre possibly triggered by massive drainage of the Laurentide ice sheet. Pb isotope compositions of leachates, thought to represent the signature of the overlying water masses, define a unique linear trend coincident with Trend A. This suggests that water masses acquired their signature through exchange with particulate fluxes along the Canadian and Siberian continental margins.

Magnetic and mineralogical analyses of Ganzi and Luochuan sections

We present a first combined environmental magnetic and geochemical investigation of a loess-paleosol sequence (<55 ka) from the Chuanxi Plateau on the eastern margin of the Tibetan Plateau. Detailed comparison between the Ganzi section and the Luochuan section from the Chinese Loess Plateau (CLP) allows quantification of the effects of provenance and climate on pedogenic magnetic enhancement in Chinese loess. Rare earth element patterns and clay mineral compositions indicate that the Ganzi loess originates from the interior of the Tibetan Plateau. The different Ganzi and CLP loess provenances add complexity to interpretation of magnetic parameters in terms of the concentration and grain size of eolian magnetic minerals. Enhanced paleosol magnetism via pedogenic formation of ferrimagnetic nanoparticles is observed in both sections, but weaker ferrimagnetic contributions, finer superparamagnetic (SP) particles and stronger chemical weathering are found in the Ganzi loess, which indicates the action of multiple pedogenic processes that are dominated by the combined effects of mean annual precipitation (MAP), potential evapotranspiration (PET), organic matter and aluminium content. Under relatively high MAP and low PET conditions, high soil moisture favours transformation of ferrimagnetic minerals to hematite, which results in a relatively higher concentration of hematite but weaker ferrimagnetism of Ganzi loess. Initial growth of superparamagnetic (SP) particles is also documented in the incipient loess at Ganzi, which directly reflects the dynamic formation of nano-sized pedogenic ferrimagnets. A humid pedogenic environment with more organic matter and higher Al content also helps to form finer SP particles. We therefore propose that soil water balance, rather than solely rainfall, dominates the type, concentration and grain size of secondary ferrimagnetic minerals produced by pedogenesis.