Biomarker distributions as indicators for the depositional environment of lacustrine sediments in the Valjevo-Mionica basin (Serbia)

In this study, the molecular composition and biomarker distribution of lacustrine sediments from Val-1 drillhole in the central zone of the western part of the Valjevo-Mionica basin were investigated at depth interval of 0–400 m. Former investigations have shown that the core material can be separated into six depth intervals based on bulk geochemical, mineralogical and sedimentological characteristics. Concerning the quality of organic matter, presence of specific minerals, and high salinity and anoxicity, or alkalinity, three zones are of highest interest, defined at depth intervals of 15–75 m (A), 75–200 m (B) and 360–400 m (F). The first aim of the study was to identify which biomarkers characterize these specific intervals. The second aim, addressing the transitions zones of these intervals, was to extend the changes in the characteristics of the organic substance, to reflect the changes of conditions in the depositional environment as well as to define biomarker parameters which are the most sensitive sedimentological indicators.The sediments from the hypersaline anoxic and alkaline environment show high contribution of algal precursor biomass, what is in accordance with the good quality of organic substances in the sediments from these zones. High squalane content and low content of regular isoprenoid C₂₅ are typical for hypersaline anoxic environment, whereas sediments from alkaline environment have high regular isoprenoid C₂₅ content.Transition to specific sedimentation zones is characterized by change in total organic matter content, and of both free and pyrolysis-derived, and change in hydrogen index value. In the biomarker distributions, more significant changes were detected in distributions of n-alkanes and isoprenoids, compared to polycyclic alkanes. The most intensive changes in alkane distribution are reflected in changes in n-C₁₇ content compared to n-C₂₇, and phytane compared to n-C₁₈. In addition, significant sensitivity was seen in ratios between squalane and n-alkane C₂₆ (hypersaline depositional environment), or isoprenoid C₂₅ and n-alkane C₂₂ for high alkalinity environment.This study showed that Sq/n-C₂₆ ratio can be used to assess the quality of organic substance in immature lacustrine sediments.     

New results on palaeoenvironmental conditions in equatorial Africa derived from alluvial sediments of Cameroonian rivers

The ReSaKo project undertook extended fieldwork across southern Cameroon to explore the palaeoenvironmental information recorded in the alluvial sediments of equatorial African rivers. 160 hand-corings reaching maximum depths of 550 cm were carried out on alluvial ridges and floodplains of major Cameroonian fluvial systems. These multilayered, sandy to clayey alluvia contain sedimentary form-units and palaeosurfaces, which provide excellent additional proxy data archives for the reconstruction of palaeoenvironmental conditions in western equatorial Africa. Coring transects and sedimentary profiles document grain-size shifts and distinguishable sedimentary units in the stratigraphic record, which evidence (fluvial-)morphological adjustments of the fluvial systems in response to external forcing and (river-) intrinsic variability. 76 ¹⁴C-(AMS)-dated samples from organic sediment and macro-rests (fossil organic remains like wood, leafs, etc.) embedded in these sedimentary units indicate Late Pleistocene to recent ages (uncalibrated ¹⁴C-ages: 48–0.2 ka BP). The tentative interpretation of the alluvial record yields excellent additional information on the complex feedbacks between climate, ocean, fluvial as well as ecological systems and human activity in a little-studied region with high sensitive tropical ecosystems. δ¹³C-values (?35.5 to ?18.0‰) of the dated samples indicate the persistence of C₃-dominated gallery forests across the rivers (‘fluvial rain forest refuges’) despite several climatic fluctuations (aridifications, e.g. Last Glacial Maximum around 20 ka BP, Younger Dryas 13–11 ka BP). This research complements earlier results from additional terrestrial and marine proxy data archives on the Late Quaternary history of monsoonal western equatorial Africa.     

Identification of arid phases during the last 50 cal. ka BP from the Fuentillejo maar‐lacustrine record (Campo de Calatrava Volcanic Field,Spain)

Geochemical (element analysis, molecular analysis of organic compounds), physical, palynological, mineralogical and sedimentary facies analysis were performed to characterise the sedimentary record in Fuentillejo maar‐lake in the Central Spanish Volcanic Field of Campo de Calatrava, in order to reconstruct the palaeoenvironmental and palaeoclimatic processes which controlled vegetation patterns and deposition of different sedimentary facies. The upper 20 m of core FUENT‐1 show variations in clastic input, water chemistry, vegetation and organic fraction sources in the lake throughout the Late Pleistocene and Holocene. The temporal framework provided by ¹⁴C accelerator mass spectrometry dating allows assigning the sequence to the last 50 cal. ka BP. Arid phases identified in the FUENT‐1 sequence are correlated to Heinrich events (HE) and to stadials of the Dansgaard/Oeschger (D/O) cycles. Siliciclastic facies with high magnetic susceptibility values, high Juniperus pollen content, a low Paq index (aquatic macrophysics proxy index), a decrease in the relative percentage of the n‐C₂₇ and an increase in the n‐C₃₁ alkanes are indicative of arid and colder climatic events related to HE 2, HE 1 and the Younger Dryas (YD). Similar short cold and arid phases during the Holocene were identified at 9.2–8.6, 7.5–7 and 5.5–5 cal. ka BP. In dolomite–mud facies, the pollen data show an increase in the herbs component, mainly – Chenopodiaceae, Artemisia and Ephedra – steppe taxa; a low Paq index, a decrease in the relative percentage of the n‐C₂₇ alkane and an increase in the n‐C₃₁ alkane are also observed. This facies was probably the result of lower lake levels and more saline–alkaline conditions, which can be interpreted as linked to arid–warm periods. These warm and arid phases were more frequent during Marine Isotope Stage (MIS) 3 and the interstadials of MIS 2. HE 4, HE 2, HE 1 and the YD in core FUENT‐1 were immediately followed by increases of warm steppe pollen assemblages that document rapid warming similar to the D/O cycles but do not imply increasing humidity in the area. Fuentillejo hydrology is controlled by changes in the atmospheric and oceanic systems that operated on the North Atlantic region at millennial scale during the last 50 cal. ka BP. Copyright © 2009 John Wiley & Sons, Ltd.     

Characterization of organic matter and depositional environment of Tertiary mudstones from the Sylhet Basin,Bangladesh

The Sylhet Basin of Bangladesh is a sub-basin of the Bengal Basin. It contains a very thick (up to 22 km) Tertiary stratigraphic succession consisting mainly of sandstones and mudstones. The Sylhet succession is divided into the Jaintia (Paleocene–late Eocene), Barail (late Eocene–early Miocene), Surma (middle–late Miocene), Tipam (late Miocene–Pliocene) and Dupitila Groups (Pliocene–Pleistocene), in ascending order. The origin of the organic matter (OM) and paleoenvironment of deposition have been evaluated on the basis of C, N, S elemental analysis, Rock-Eval pyrolysis and gas chromatography–mass spectrometry (GC–MS) analysis of 60 mudstone samples collected from drill core and surface outcrops. Total organic carbon (TOC) content ranges from 0.11% to 1.56%. Sulfur content is low in most samples. TOC content in the Sylhet succession varies systematically with sedimentation rate, with low TOC caused by clastic dilution produced by high sedimentation rates arising from rapid uplift and erosion of the Himalaya.The OM in the succession is characterized by systematic variations in pristane/phytane (Pr/Ph), oleanane/C₃₀ hopane, n-C₂₉/n-C₁₉ alkane, Tm/Ts [17α(H)-22,29,30-trisnorhopane/18α(H)-22,29,30-trisnorhopane] and sterane C₂₉/(C₂₇ + C₂₈ + C₂₉) ratios during the middle Eocene to Pleistocene. Based on biomarker proxies, the depositional environment of the Sylhet succession can be divided into three phases. In the first (middle Eocene to early Miocene), deposition occurred completely in seawater-dominated oxic conditions, with abundant input of terrestrial higher plants, including angiosperms. The second phase (middle to late Miocene) consisted of mainly freshwater anoxic conditions along with a small seawater influence according to eustasic sea level change, with diluted OM derived from phytoplankton and a lesser influence from terrestrial higher plants. Oxygen-poor freshwater conditions prevailed in the third phase (post-late Miocene). Planktonic OM was relatively abundant in this stage, while a high angiosperm influx prevailed at times. T_max values of ca. 450 °C, vitrinite reflectance (R_o) of ca. 0.66% and methylphenanthrene index (MPI 3) of ca. 1 indicate the OM to be mature. The lower part (middle Eocene to early Miocene) of the succession with moderate TOC content and predominantly terrestrial OM could have generated some condensates and oils in and around the study area.     

n-Alkane evidence for the onset of wetter conditions in the Sierra Nevada,California (USA) at the mid-late Holocene transition, ~ 3.0 ka

n-Alkane biomarker distributions in sediments from Swamp Lake (SL), in the central Sierra Nevada of California (USA), provide evidence for an increase in mean lake level ~ 3000 yr ago, in conjunction with widespread climatic change inferred from marine and continental records in the eastern North Pacific region. Length distributions of n-alkane chains in modern plants growing at SL were determined and compared to sedimentary distributions in a core spanning the last 13 ka. As a group, submerged and floating aquatic plants contained high proportions of short chain lengths (< nC₂₅) compared to emergent, riparian and upland terrestrial species, for which chain lengths > nC₂₇ were dominant. Changes in the sedimentary n-alkane distribution over time were driven by variable inputs from plant sources in response to changing lake level, sedimentation and plant community composition. A shift toward shorter chain lengths (nC_21, nC₂₃) occurred between 3.1 and 2.9 ka and is best explained by an increase in the abundance of aquatic plants and the availability of shallow-water habitat in response to rising lake level. The late Holocene expansion of SL following a dry mid-Holocene is consistent with previous evidence for increased effective moisture and the onset of wetter conditions in the Sierra Nevada between 4.0 and 3.0 ka.     

Hydrocarbon generation from coal,extracted coal and bitumen rich coal in confined pyrolysis experiments

Three sets of pyrolysis experiments were performed on extracted coal (R_o% 0.39), coal (initial bitumen 13.5 mg/g coal) and bitumen enriched coal (total bitumen 80.9 mg/g coal) at two heating rates of 2 °C/h and 20 °C/h in confined systems (gold capsules). For all three experiments, the yields of bitumen, Σn-C₈₊, aromatic components and ΣC_2–5 at first increase and then decrease with increasing EASY%R_o and reach the highest values within the EASY%R_o ranges of 0.67–1.08, 1.07–1.19, 1.46–1.79 and 1.46–1.68, respectively. In contrast, C₁/ΣC_1–5 ratio at first decreases and then increases with EASY%R_o and reaches a minimum value in EASY%R_o range of 0.86–1.08, closely corresponding to the maximum values of the yields of bitumen and Σn-C₈₊. Methane yields increase consistently with EASY%R_o. Nearly half of the maximum yield of methane from kerogen was generated at EASY%R_o > 2.2. The differences in methane yields among the three experiments at the same thermal stress are relatively minor at EASY%R_o < 2.2, but are greater with thermal stress at EASY%R_o > 2.2. This demonstrates that the kerogen always retained relatively more hydrogen and hydrocarbon generative potential at the postmature stage of bitumen rich coal than the extracted coal or coal.The maximum yield of ethane is 20–25% higher in the bitumen rich coal experiment than the extracted coal or coal, while the maximum yields of C₃, C₄ and C₅ in the former are double to triple those in the latter. This result demonstrates that the added bitumen in bitumen rich coal substantially increased the generation of these wet gases. However, the averaged values of activation energies (with the same frequency factors) for both the generation and cracking of individual wet gases are similar and do not show consistent trends among the three experiments. For all three experiments, activation energies for the generation and cracking of wet gases are significantly lower than those in previously published oil pyrolysis experiments with same frequency factors (Pan et al., 2012; Organic Geochemistry 45, 29–47). Methane δ¹³C values at the maximum temperature or EASY%R_o are close to those of initial wet gases, especially C₃, implying that the major part of methane shared a common initial precursor with wet gases, i.e., free and bound liquid alkanes.     

Variability of Indian monsoonal rainfall over the past 100 ka and its implication for C3–C4 vegetational change

Oxygen and carbon isotope ratios of soil carbonate and carbon isotope ratios of soil organic matter (SOM) separated from three cores, Kalpi, IITK and Firozpur, of the Ganga Plain, India are used to reconstruct past rainfall variations and their effect on ambient vegetation. The δ¹⁸O values of soil carbonate (δ¹⁸O_SC) analyzed from the cores range from ? 8.2 to ? 4.1‰. Using these variations in δ¹⁸O_SC values we are able, for the first time, to show periodic change in rainfall amount between 100 and 18 ka with three peaks of higher monsoon at about 100, 40 and 25 ka. The estimation of rainfall variations using δ¹⁸O value of rainwater-amount effect suggests maximum decrease in rainfall intensity (~ 20%) during the last glacial maximum. The δ¹³C values of soil carbonate (δ¹³C_SC) and SOM (δ¹³C_SOM) range from ? 6.3 to + 1.6‰ and ? 28.9 to ? 19.4‰, respectively, implying varying proportions of C₃ and C₄ vegetations over the Ganga Plain during the last 100 ka. The comparison between monsoonal rainfall and atmospheric CO₂ with vegetation for the time period 84 to 18 ka indicate that relative abundances of C₃ and C₄ vegetations were mainly driven by variations in monsoonal rainfall.     

Precise indices based on n-alkane distribution for quantifying sources of sedimentary organic matter in coastal systems

Precise indices based on n-alkane signatures were developed in order to determine the sources and composition of sedimentary organic matter (SOM) in coastal systems. The Arcachon Bay (France), a well-studied temperate lagoon, was used as an example of a complex coastal system sheltering a wide diversity of OM sources. Three main groups of sources were well discriminated from their n-alkane signatures: seagrass (Zostera sp.) produced mainly n-C₁₇, n-C₁₉, n-C₂₁, n-C₂₃ and n-C₂₅ alkanes, algae (Rhodophyta, Chlorophyta) produced n-C₁₅ and n-C₁₇ and the terrigenous input [Quercus sp., Spartina sp. and river suspended particulate OM (SPOM)] was characterized by n-C₂₅, n-C₂₇, n-C₂₉, n-C₃₁ and n-C₃₃. From the above and literature n-alkane fingerprints, we developed a set of indices (n-alkane ratios) to quantify the contribution of these three major sources of the SOM. At the Arcachon Bay scale, they indicated that SOM was composed mainly of seagrass (ca. 53 ± 19%) and terrestrial (ca. 41 ± 17%) material, followed by algae (ca. 6 ± 9%). Moreover, the new n-alkane indices exhibited more relevant spatial patterns than classical ones – the TAR (C₂₇ + C₂₉ + C₃₁/C₁₅ + C₁₇ + C₁₉; terrestrial to aquatic ratio) and the P_aq (C₂₃ + C₂₅/C₂₃ + C₂₅ + C₂₉ + C₃₁; aquatic plant %) – with a greater contribution from marine sources in the central part of the lagoon where a high density of Zostera seagrass was observed. Therefore, the development of precise indices adapted to the local diversity of OM sources is needed when using n-alkanes for quantifying the source composition of SOM in complex coastal systems.     

Cosmogenic 3He age estimates of Plio-Pleistocene alluvial-fan surfaces in the Lower Colorado River Corridor,Arizona, USA

Plio-Pleistocene deposits of the Lower Colorado River (LCR) and tributary alluvial fans emanating from the Black Mountains near Golden Shores, Arizona record six cycles of Late Cenozoic aggradation and incision of the LCR and its adjacent alluvial fans. Cosmogenic ³He (³He_c) ages of basalt boulders on fan terraces yield age ranges of: 3.3–2.2 Ma, 2.2–1.1 Ma, 1.1 Ma to 110 ka, < 350 ka, < 150 ka, and < 63 ka. T1 and Q1 fans are especially significant, because they overlie Bullhead Alluvium, i.e. the first alluvial deposit of the LCR since its inception ca. 4.2 Ma. ³He_c data suggest that the LCR began downcutting into the Bullhead Alluvium as early as 3.3 Ma and as late as 2.2 Ma. Younger Q2a to Q4 fans very broadly correlate in number and age with alluvial terraces elsewhere in the southwestern USA. Large uncertainties in ³He_c ages preclude a temporal link between the genesis of the Black Mountain fans and specific climate transitions. Fan-terrace morphology and the absence of significant Plio-Quaternary faulting in the area, however, indicate regional, episodic increases in sediment supply, and that climate change has possibly played a role in Late Cenozoic piedmont and valley-floor aggradation in the LCR valley.     

A late Quaternary sedimentary record of steryl alkyl ethers from offshore southeastern Australia

Steryl alkyl ethers (SAEs) have been reported from marine sediments ranging from Holocene to Lower Cretaceous and their production has been linked to upwelling of cold, nutrient-rich water. However, the lack of continuous stratigraphic records for them has complicated validation of the precise connection of their production, sedimentary distribution and survival to climatic conditions. Here, we report an SAE record that spans the last ca. 135 ka from a core taken offshore southeastern Australia in the Murray Canyons Group region. The SAEs are composed predominantly of C₂₇–C₃₀ steroid moieties with one or two double bonds, ether-bound to C₁₀–C₁₁ alkyl moieties. Some of the SAEs are identical to those reported in marine sediments, whereas others have not been identified previously. They do not exhibit any systematic change in distribution over the past 110 ka but sediments older than 110 ka possess a different assemblage, with a higher amount of constituents containing a C₁₁ alkyl moiety. The SAE accumulation rate increases rapidly during glacial episodes and for intervals characterized by a sharp decline in sea-surface temperature. The results suggest that SAEs may be related to marine eukaryotes that thrive when there is an influx of cold, deep waters in the Murray Canyons Group region, likely triggered by stronger westerlies over southeastern Australia forcing deeper water to reach the surface during glacials.     

Ethane- and propane-producing potential and molecular characterization of an ethanogenic enrichment in an anoxic estuarine sediment

Ethane and propane are low molecular weight hydrocarbons observed widely at trace levels in cold marine sediments where thermogenic sources are considered insignificant, but their biological sources remain poorly constrained. In this study, several C₂ and C₃ compounds including alkenes, alcohols, thiols and carboxylic acids with a C₂ or C₃ skeleton were tested for their relative alkane-producing potential in an anoxic estuary sediment. Maximum conversion efficiency of substrates to ethane or propane was observed in the sediment supplemented with ethylene (up to 38%), followed by additions with ethanethiol (0.01%) and propanethiol (0.003%). Experiments with sterilized sediment, 2-bromoethanesulfonic acid or NaNO₃ were negative for alkane production, suggesting that methanogens were involved in alkane generation. Detailed investigation on ethanogenesis from ethylene showed that this reaction required H₂ but at reasonably low concentration (< 120 nmol dissolved H₂ l⁻¹ slurry) and caused a slight stable carbon isotope effect (ε_{ethane/ethylene} = −8.6 ± 2.4‰). The high ethane-producing potential, reasonable H₂ requirement and extensive occurrence of ethylene make ethylene reduction a plausible explanation for ethane in cold marine sediment. Phylogenetic analysis was first carried out with an ethane-producing enrichment with ethylene as the substrate and showed a dominance of homoacetogenic bacteria and the methanogenic genus Methanocalculus. Although we cannot rule out the possibility that other methanogens in the gene libraries are responsible for ethanogenesis from ethylene, the dominance of Methanocalculus, with its hydrogenotrophic cultured representatives, is in accord with our biogeochemical observation that H₂ is required for this reaction.     

Geochemical signatures of Late Holocene paleo-hydrological changes from Phulera and Pokharan saline playas near the eastern and western margins of the Thar Desert,India

Stratigraphical, mineralogical, geochemical and optical dating methods were used to reconstruct paleo-hydrological changes in two playas (Phulera, 500 mm/a and Pokharan, 200 mm/a) in near extremum climatic regions of the Thar Desert. Sediment successions in shallow profiles from Phulera and Pokharan contain three and four stratigraphic units, respectively, each with characteristic geochemical properties. These units reflect changes in chemical weathering, detrital input, salinity and provide a measure of the changes in precipitation (i.e. monsoon) through time.Sediments from Pokharan suggest short rainfall events during ca. 6.6–4 ka, relatively stable fresh water (higher and persistent rainfall) regime during 4–2.3 ka, and a hyper saline (low rainfall) condition during 2.3–1.1 ka. Sediments at Phulera, record hyper saline (low rainfall) lacustrine conditions during <2.3 ka to >1.4 ka. Higher abundance of gypsum in Pokharan (2.3–1.1 ka) and proto-dolomite in Phulera (2.3–1.4 ka) are nearly synchronous and reflect enhancement of salinity. Selenite crystals in Pokharan and large desiccation cracks in buried horizons at Phulera reflect desiccation of playas at ca. 2 ka. Both playas progressively became less saline after 1.4 ka. Given the regional nature of this record, these changes are attributed to fluctuation of the monsoon over the Indian sub continent.     

Thermal degradation of rye and maize straw: Lipid pattern changes as a function of temperature

Future climatic conditions may coincide with an increased potential for wildfires in grassland and forest ecosystems, whereby charred biomass would be incorporated into soils. Molecular changes in biomass upon charring have been frequently analysed with a focus on black carbon. Aliphatic and aromatic hydrocarbons, known to be liberated during incomplete combustion of biomass have been preferentially analysed in soot particles, whereas determinations of these compounds in charred biomass residues are scarce. We discuss the influence of increasing charring temperature on the aliphatic and aromatic hydrocarbon composition of crop grass combustion residues. Straw from rye, representing C₃ grasses and maize, representing C₄ grasses, was charred in the presence of limited oxygen at 300, 400 and 500 °C. Typical n-alkane distribution patterns with a strong predominance of long chain odd-numbered n-alkanes maximising at C₃₁ were observed in raw straw. Upon combustion at 300 °C aliphatic hydrocarbons in char were dominated by sterenes, whereas at 400 °C sterenes disappeared and medium chain length n-alkanes, maximising around n-C₂₀, with a balanced odd/even distribution were present. At a charring temperature of 500 °C n-alkane chain length shifted to short chain homologues, maximising at C₁₈ with a pronounced predominance of even homologues. Even numbered, short chain n-alkanes in soils may thus serve as a marker for residues of charred biomass. Aromatic hydrocarbons indicate an onset of aromatization of biomass already at 300 °C, followed by severe aromatization upon incomplete combustion at 400–500 °C. The diagnostic composition of aliphatic and aromatic hydrocarbons from charred biomass affords potential for identifying residues from burned vegetation in recent and fossil soils and sediments.     

Stable carbon isotope geochemistry of adsorbed alkane gases in near-surface soils of the Saurashtra Basin,India

The stable carbon isotopic compositions of light hydrocarbon gases adsorbed in near-surface soil and sediments from the Saurashtra basin were characterized for their origin and maturity. Saurashtra is considered geologically prospective for oil and gas reserves; however, a major part of the basin is covered by the Deccan Traps, hindering the exploration of Mesozoic hydrocarbon targets. Surface geochemical prospecting, based on micro-seepage of hydrocarbons from subsurface accumulations, could be advantageous in such areas. In light of this, 150 soil samples were collected from the northwestern part of Saurashtra, around the Jamnagar area, where a thick sedimentary sequence of about 2–3 km exists under 1–1.5 km of Deccan basalt. The concentration of acid desorbed alkane gases from soil samples was found to vary (in ppb) as: methane (C₁) = 3–518; ethane (C₂) = 0–430; propane (C₃) = 0–331; i-butane (iC₄) = 0–297; n-butane (nC₄) = 2–116; i-pentane (iC₅) = 0–31 and n-pentane (nC₅) = 0–23, respectively.Fifteen samples with high concentrations of alkane gases were measured for their δ¹³C₁; δ¹³C₂ and δ¹³C₃ compositions using gas chromatography–combustion-isotope ratio mass spectrometry (GC–C-IRMS). The values for methane varied from ? 27 to ? 45.4‰, ethane from ? 20.9 to ? 27.6‰, and propane from ? 20.4 to ? 29.1‰ versus the Vienna PeeDee Belemnite (VPDB). The carbon isotope ratio distribution pattern represents isotopic characteristics pertaining to hydrocarbon gases derived from thermogenic sources. Comparisons of carbon isotopic signatures and compositional variations with the standard carbon isotopic models suggest that hydrocarbon gases found in the shallow depths of the study area are not of bacterial origin but are formed thermally from deeply buried organic matter, likely to be mainly a terrestrial source rock with a partial contribution from a marine source. These gases may have migrated to the near-surface environment, where they represent an admixture of thermally generated hydrocarbon gases from mixed sources and maturity. The maturity scale (δ¹³C versus Log Ro %) applied to the surface sediment samples of the Jamnagar area indicated the source material to be capable of generating oil and gas. The detection of thermogenic alkane gases in near-surface sediments offers the possibility of hydrocarbons at depth in Saurashtra.     

First-principles phase diagram calculations for the system NaCl–KCl: The role of excess vibrational entropy

First principles phase diagram calculations were performed for the system NaCl–KCl. Plane-wave pseudopotential calculations of formation energies were used as a basis for fitting cluster expansion Hamiltonians, both with and without an approximation for the excess vibrational entropy (S_VIB). Including S_VIB dramatically improves the agreement between calculated and experimental phase diagrams: experimentally, the consolute point is {X_C = 0.348, T_C = 765 K}_Exp; without S_VIB, it is {X_C = 0.46, T_C ≈ 1630 K}_Calc; with S_VIB, it is {X_C = 0.43, T_C ≈ 930 K}_Calc.     

Late Quaternary highstands at Lake Chilwa,Malawi: Frequency,timing and possible forcing mechanisms in the last 44 ka

The extensive shoreline deposits of Lake Chilwa, southern Malawi, a shallow water body today covering 600 km² of a basin of 7500 km², are investigated for their record of late Quaternary highstands. OSL dating, applied to 36 samples from five sediment cores from the northern and western marginal sand ridges, reveal a highstand record spanning 44 ka. Using two different grouping methods, highstand phases are identified at 43.7–33.3 ka, 26.2–21.0 ka and 17.9–12.0 ka (total error method) or 38.4–35.5 ka, 24.3–22.3 ka, 16.2–15.1 ka and 13.5–12.7 ka (Finite Mixture Model age components) with two further discrete events recorded at 11.01 ± 0.76 ka and 8.52 ± 0.56 ka. Highstands are comparable to the timing of wet phases from other basins in East and southern Africa, demonstrating wet conditions in the region before the LGM, which was dry, and a wet Lateglacial, which commenced earlier in the southern compared to northern hemisphere in East Africa. We find no evidence that wet phases are insolation driven, but analysis of the dataset and GCM modelling experiments suggest that Heinrich events may be associated with enhanced monsoon activity in East Africa in both timing and as a possible causal mechanism.     

Clay mineral variations in Holocene terrestrial sediments from the Indus Basin

We employed X-ray diffraction methods to quantify clay mineral assemblages in the Indus Delta and flood plains since ~ 14 ka, spanning a period of strong climatic change. Assemblages are dominated by smectite and illite, with minor chlorite and kaolinite. Delta sediments integrate clays from across the basin and show increasing smectite input between 13 and 7.5 ka, indicating stronger chemical weathering as the summer monsoon intensified. Changes in clay mineralogy postdate changes in climate by 5–3 ka, reflecting the time needed for new clay minerals to form and be transported to the delta. Samples from the flood plains in Punjab show evidence for increased chemical weathering towards the top of the sections (6–< 4 ka), counter to the trend in the delta, at a time of monsoon weakening. Clay mineral assemblages within sandy flood-plain sediment have higher smectite/(illite + chlorite) values than interbedded mudstones, suggestive of either stronger weathering or more sediment reworking since the Mid Holocene. We show that marine records are not always good proxies for weathering across the entire flood plain. Nonetheless, the delta record likely represents the most reliable record of basin-wide weathering response to climate change.     

Stable isotopes reflect the ecological stability of two high-elevation mammals from the late Quaternary of Colorado

The vertebrate fossil record of Cement Creek Cave, Colorado, spans from > 45,000 yr ago to the present and represents the richest stratified series of high-elevation (> 2900 m) mammal remains known from the late Quaternary of North America. Stable carbon and oxygen isotope analyses of tooth enamel were used to assess potential ecological responses of two species found commonly throughout the cave, Yellow-bellied marmots (Marmota flaviventris) and Bushy-tailed woodrats (Neotoma cinerea), to late Quaternary climate and environmental changes of the Southern Rocky Mountains. Results indicate that despite such perturbations, the dietary ecologies of both species were maintained across this period. Neither taxon shifted to consuming C₄ taxa or different C₃ functional groups; similarly, no significant shifts in surface water use were detected. Variations in enamel δ¹³C were observed, however, that represent the physiological responses of high-elevation plants to changing levels of late Quaternary atmospheric CO₂. While our findings extend both the geographic and elevational record of this plant CO₂ response, they simultaneously highlight the ecological stability of high-elevation M. flaviventris and N. cinerea during climate changes of late Quaternary magnitude.     

Occurrence and composition of solid bitumens from the Bulonggoer Devonian paleo-oil reservoir,North Xinjiang,China

The Bulonggoer paleo-oil reservoir (BPR) on the northwest Junggar Basin is the first Devonian paleo-oil reservoir discovered in North Xinjiang, China. Solid bitumens occur within sandstone pores and as veins filling fractures. Samples of both types were analyzed using stable carbon isotope and reflectance measurements, as well as molecular biomarker parameters.The extremely positive δ¹³C values and biomarker indicators of depositional environment/lithology, such as pristane/phytane (Pr/Ph), C₂₉/C₃₀ hopane, diasteranes/regular steranes and dibenzothiophene/phenanthrene ratios, indicate a siliciclastic source for the BPR and their deposition in a highly reducing hypersaline environment. The presence of long chain n-alkanes and abundant tetracyclic diterpanes, C₂₀–C₂₁ tricyclic terpanes and perylene are indicators of higher plant organic matter input. Moreover, the bimodal distribution of C₂₇ > C₂₈ < C₂₉ regular steranes and abundant methyltriaromatic steroids also support a contribution of microalgae as well as higher plants organic matter. The similar molecular composition and thermal maturity parameters indicate that the reservoir and veined solid bitumens were altered from a common paleo-petroleum, which originated from peak oil window matured source rocks.All solid bitumens from the BPR are characterized by relatively low bitumen reflectance values (Rb% < 0.7), suggesting that they were generated from low temperature processes rather than oil thermal cracking. Comparatively, the Rb% values for veined bitumens are higher than reservoir bitumens, indicating that the veined bitumens occurred earlier and experienced higher thermal conditions.     

The evolution of coastal barrier systems: a case study of the Middle-Late Pleistocene Wilderness barriers,South Africa

Barrier systems contain lengthy, but complex, records of long-term environmental fluctuations. The Wilderness embayment, South Africa, contains a system of shore-parallel barriers reaching up to 200 m above modern sea level. This study reports the results of chronological, topographical (both on- and off-shore), sedimentological and micromorphological analyses within the Wilderness embayment. Sixty-one new luminescence ages from sixteen sites in unconsolidated dunes and three separate barriers are presented which, when combined with previously published luminescence ages from the area, provide a high-resolution chronological framework for the emplacement and evolution of the barrier system. The preserved barriers have been constructed within at least the last two glacial–interglacial cycles with notable phases between 241–221 ka, 159–143 ka, 130–120 ka, 92–87 ka and post 6 ka. Multiple phases of barrier construction occurred during sea-level highstands, with sediment deposition on each individual barrier occurring over at least two interglacials. Holocene evolution of the system sheds light on earlier events, with dune preservation occurring only during early regression from the Mid-Holocene highstand. Tectonic stability at Wilderness allowed glacio-eustatically formed shorelines to occupy similar positions on multiple occasions. This, in conjunction with a relatively humid climate and a well-vegetated landscape, enabled deflated sediment from beaches to form dunes which stacked upon each other to form an extensive and complex vertical accretionary sequence. Repeated erosion and recycling of pre-existing barriers as well as barrier construction on what is currently the off-shore platform during still-stands in sea-level regressional cycles, when sea levels dropped below ca ?50 m from the present day, has added to the complexity of the preserved terrestrial barrier record. The Wilderness barrier system contrasts with barriers developed elsewhere in the world where higher rates of crustal uplift have allowed preservation of a more complete and more widely spaced palaeorecord. This research also shows the utility of integrating off-shore topography as revealed by bathymetry, with terrestrial topographic data for the better understanding of the evolution of palaeo-coastlines and the preserved dune record found on present-day coastal plains. Local variation in the topography of the continental shelf at Wilderness has generated spatial and temporal complexity within the sedimentary records of individual barriers as well as having a significant influence on preservation.