Characterization and sources of extractable organic matter from sediment cores of an urban lake (Tasik Perdana), Kuala Lumpur,Malaysia

The extractable organic matter of sediment samples from six sampling sites in Lake Perdana, Kuala Lumpur, was analyzed to characterize the source inputs. The analysis of aliphatic homologous series indicated that terrestrial higher plant waxes can be assigned as the major sources of the identified aliphatic components in the lake sediments. The presence of an unresolved complex mixture of branched and cyclic compounds and a series of hopanes ranging from C₂₇ to C₃₅ reflected the contamination by petroleum residues from urban vehicular emissions brought in by runoff and fallout. The steroids present included stenols and stanols and showed an input of organic matter from higher plants. The detected pentacyclic triterpenoids comprised oleanane, ursane, lupane and friedelane skeletons including unsaturated oxygenated, mono-, di- and triaromatic counterparts. They are recognized as biomarkers for angiosperms. The presence of des-A-triterpenoids and their aromatized derivatives as the major diagenetic products of triterpenoids reflected the degradation of natural organic matter in the sediments occurring under mainly anoxic conditions. In addition, the presence of tetrahymanol and ββ-bishomohopan-32-ol indicated a minor algal/plankton and bacterial input to the sediments.     

Bitumen from Coalport tar tunnel

The Coalport (Shropshire, U.K.) Tar Tunnel bitumen has been known since 1787 and the first geochemical data are reported here. The bitumen was analyzed for molecular markers useful for correlational studies. Gas chromatographic analysis of aliphatic and aromatic hydrocarbons failed to detect any specific major components normally used for genetic correlational and maturational studies. A search for minor and trace components by gas chromatographic-mass fragmentographic analysis showed the presence of triterpenoid hydrocarbons primarily of the 17α (H)-hopane series (C₂₇ to C₃₅, ex. C₂₈) and a C₂₆ to C₃₁ series of ring A/B demethylated hopanes. Two homologous sterane series (C₂₇ to C₂₉) of the 5α, 14β, 17β (H)-sterane and 13β, 17α (H)-diasterane type were also detected. Pophyrins of the DPEP and etio series (C₂₇ to C₄₁, DPEP/etio > 1) were also found. Characterization of their alkyl substitution pattern demonstrated C₁, C₂ and C₃ substituents on the pyrole moieties of the parent petroporphyrins.The molecular markers detected in this bitumen indicate its biogenic origin and show evidence of diagenetic and geothermal maturation processes. The overall geochemical characteristics of the Coalport Tar Tunnel bitumen suggest that it corresponds to a well matured crude oil, which was heavily altered by in-reservoir biodegradation or close to surface exposure.     

Central Mediterranean tephrochronology between 313 and 366 ka: New insights from the Fucino palaeolake sediment succession

Thirty-two tephra layers were identified in the time-interval 313–366 ka (Marine Isotope Stages 9–10) of the Quaternary lacustrine succession of the Fucino Basin, central Italy. Twenty-seven of these tephra layers yielded suitable geochemical material to explore their volcanic origins. Investigations also included the acquisition of geochemical data of some relevant, chronologically compatible proximal units from Italian volcanoes. The record contains tephra from some well-known eruptions and eruptive sequences of Roman and Roccamonfina volcanoes, such as the Magliano Romano Plinian Fall, the Orvieto–Bagnoregio Ignimbrite, the Lower White Trachytic Tuff and the Brown Leucitic Tuff. In addition, the record documents eruptions currently undescribed in proximal (i.e. near-vent) sections, suggesting a more complex history of the major eruptions of the Colli Albani, Sabatini, Vulsini and Roccamonfina volcanoes between 313 and 366 ka. Six of the investigated tephra layers were directly dated by single-crystal-fusion ⁴⁰Ar/³⁹Ar dating, providing the basis for a Bayesian age–depth model and a reassessment of the chronologies for both already known and dated eruptive units and for so far undated eruptions. The results provide a significant contribution for improving knowledge on the peri-Tyrrhenian explosive activity as well as for extending the Mediterranean tephrostratigraphical framework, which was previously based on limited proximal and distal archives for that time interval.     

Mobility and potential bioavailability of traffic-derived trace metals in a ‘wet–dry’ tropical region,Northern Australia

The aqueous mobility and potential bioavailability of metals and metalloids in road runoff in a ‘wet–dry’ tropical location were assessed by analysing metal and metalloid concentrations in particulate, total dissolved and labile dissolved phases in runoff waters. Road-derived Al, Cu, Pb, Sb and Zn concentrations were substantially elevated in runoff when compared to receiving creek waters. Median dissolved concentrations in road runoff exceeded those in creek waters by up to an order of magnitude. Leaching experiments of road sediments confirmed that several metals and metalloids were released in high concentrations from road sediments. Labile Zn and Cu concentrations measured by diffusion gradients in thin films (DGT) showed that almost all dissolved Zn and up to half of dissolved Cu in runoff waters and in road sediment leachate were potentially bioavailable. Comparisons of dissolved metal concentrations in receiving waters affected by road runoff with ecosystem guideline levels, indicated a risk of reaching toxic levels of Cu and Zn in the receiving waters in the absence of adequate treatment or dilution. Low dilution rates of road runoff are likely to occur during late ‘dry’ season/early ‘wet’ season storms which have the potential to produce high metal concentrations derived from long periods of accumulation of road sediment at a time when creek flow rates are at their annual minimum.     

Temperature dependence of the OH-stretching frequencies in topaz-OH

Hydrogen bonding in topaz-OH, Al₂SiO₄(OH)₂, was investigated by IR spectroscopic analysis of the temperature dependence of the OH-stretching frequencies. Low-temperature spectra ranging from −196 to −160°C prove the existence of four non-equivalent H-positions in the crystal structure from the occurrence of four different OH-bands. With increasing temperature, these bands merge first, above −160°C, into two OH-bands and then above 400°C into one asymmetric broad band. Shifting of the OH-bands is caused by thermally induced hydrogen order–disorder. Low temperature fixes the protons in their positions; increasing temperature induces proton movement and allows switching between the different positions. Autocorrelation analysis of the IR spectra reveals two phase transitions, one at about −155°C from P1 to Pbn2 ₁ characterized as static–dynamic change and the second at about 380°C from Pbn2 ₁ to Pbnm caused by disordering of the protons. The increasing symmetry with temperature is due to advanced proton movement and dynamical averages over the proton distribution densities.     

Mollusc and brachiopod skeletal hard parts: Intricate archives of their marine environment

The biogenic carbonate hard parts of fossil bivalves, cephalopods and brachiopods are among the most widely exploited marine archives of Phanerozoic environmental and climate dynamics research. The advent of novel analytical tools has led many workers to explore non‐traditional geochemical and petrographic proxies, and work performed in neighbouring disciplines sheds light on the complex biomineralization strategies applied by these organisms. These considerations form a strong motivation to review the potential and problems related to the compilation and interpretation of proxy data from bivalve, cephalopod and brachiopod hard parts from the viewpoint of the sedimentologist and palaeoceanographer. Specific focus is on the complex biomineralization pathways of a given dissolved ion or food particle from its aquatic environment via the digestion and biomineralization apparatus in molluscs and brachiopods and its incorporation into a biomineral. Given that molluscs and brachiopods do not secrete their hard parts from seawater but rather from their mantle and periostracum, this paper evaluates differences and similarities of seawater versus that of body fluids. Cephalopods, bivalves and brachiopods exert a strong biological control on biomineralization that, to some degree, may buffer their shell geochemistry against secular changes in seawater chemistry. Disordered (amorphous) calcium carbonate precursor phases, later transformed to crystalline biominerals, may be significant in carbonate archive research due to expected geochemical offset relative to the direct precipitation of stable phases. A reasonable level of understanding of the related mechanisms is thus crucial for those who use these skeletal hard parts as archives of the palaeo‐environment. The impact of what is commonly referred to as ‘biological factors’ on the geochemistry of mollusc and brachiopod hard parts is explored for conventional isotope systems such as carbon, oxygen, strontium and traditionally used element to calcium ratios. In particular, the often used δ¹³C_carb or the Mg/Ca and Sr/Ca elemental proxies are fraught with problems. An interesting new research field represents the analysis, calibration and application of non‐traditional proxies to mollusc and brachiopod hard parts. Examples include the carbonate clumped isotope (Δ₄₇) approach and the analysis of the isotopes of Ca, Mg, N, Li, S or element to Ca ratios such as Li/Ca or B/Ca and rare earth elements. Based on considerations discussed here, a series of “do's and don'ts” in mollusc and brachiopod archive research are proposed and suggestions for future work are presented. In essence, the suggestions proposed here include experimental work (also field experiments) making use of recent archive organisms or, where possible, a reasonable recent analogue in the case of extinct groups. Moreover, the detailed understanding of the architecture of mollusc and brachiopod hard parts and their ultra‐structures must guide sampling strategies for geochemical analyses. Where feasible, a detailed understanding of the diagenetic pathways and the application of multi‐proxy and multi‐archive approaches should form the foundation of fossil carbonate archive research. The uncritical compilation of large data sets from various carbonate‐shelled organisms collected at different locations is not encouraged.     

Levels and distributions of organic source tracers in air and roadside dust particles of Kuala Lumpur,Malaysia

The concentrations of n-alkanes, unresolved complex mixture (UCM), petroleum molecular markers, other tracers of cooking and burning emissions, and natural background in atmospheric particles and roadside dust particles were measured at eight locations in the city center and the suburbs of Kuala Lumpur, Malaysia. Atmospheric particles were collected using high-volume filtration (PM-10, GFF) over 24 h average periods. Road dusts were swept up, dried and sieved. Both types of samples were extracted with dichloromethane/methanol mixture (3:1 v/v) by ultrasonic agitation. The extracts were then fractionated by column chromatography and the alkanes subjected to gas chromatography–mass spectrometry (GC–MS). Total extracts were also analyzed directly by GC–MS after silylation. The molecular distributions of compounds as well as diagnostic geochemical ratios were determined in order to identify the sources of the organic compounds. Samples collected from a rural area and lubricating oils were also analyzed for comparisons. Anthropogenic and biogenic sources such as vehicular emissions, waxes of higher plants, food cooking operations, and biomass and domestic refuse burning processes contributed to the organic matter content of atmospheric and to lesser extent, roadside dust particles.     

Oligo-Miocene shearing along the Ailao Shan–Red River shear zone: Constraints from structural analysis and zircon U/Pb geochronology of magmatic rocks in the Diancang Shan massif, SE Tibet, China

The left-lateral strike-slip shearing along the Ailao Shan–Red River (ASRR) shear zone in the Southeastern Tibet, China, has been widely advocated to be a result of the Indian–Eurasian plate collision and post-collisional processes. The Diancang Shan (DCS) massif, which occurs at the northwestern extension of the Ailao Shan massif, is a typical high-grade metamorphic complex aligned along the ASRR tectonic belt. Structural and microstructural analysis of the plutonic intrusions in the DCS revealed different types of granitic intrusions spatially confined to the shear zone and temporally related to the left-lateral shearing along the ASRR shear zone in the DCS massif. The combined structural and geochronological results of SHRIMP-II and LA-ICP-MS zircon U/Pb isotopic dating have revealed successive magmatic intrusions and crystallization related to the Oligo-Miocene shearing in the DCS massif. The pre-, early- and syn-kinematic emplacements are linked to regional high-temperature deformation (lower amphibolite facies) at relatively deep crustal levels. The zircon U/Pb geochronological results suggest that the left-lateral ductile shearing along the ASRR shear zone was initiated at ca. 31 Ma, culminated between ca. 27 and 21 Ma resulting in high-temperature metamorphic conditions and slowed down at ca. 20 Ma at relatively low-temperatures.     

The geodynamic and limnological evolution of Balkan Lake Ohrid,possibly the oldest extant lake in Europe

Studies of the upper 447 m of the DEEP site sediment succession from central Lake Ohrid, Balkan Peninsula, North Macedonia and Albania provided important insights into the regional climate history and evolutionary dynamics since permanent lacustrine conditions established at 1.36 million years ago (Ma). This paper focuses on the entire 584-m-long DEEP sediment succession and a comparison to a 197-m-long sediment succession from the Pestani site ~5 km to the east in the lake, where drilling ended close to the bedrock, to unravel the earliest history of Lake Ohrid and its basin development. ²⁶Al/¹⁰Be dating of clasts from the base of the DEEP sediment succession implies that the sedimentation in the modern basin started at c. 2 Ma. Geophysical, sedimentological and micropalaeontological data allow for chronological information to be transposed from the DEEP to the Pestani succession. Fluvial conditions, slack water conditions, peat formation and/or complete desiccation prevailed at the DEEP and Pestani sites until 1.36 and 1.21 Ma, respectively, before a larger lake extended over both sites. Activation of karst aquifers to the east probably by tectonic activity and a potential existence of neighbouring Lake Prespa supported filling of Lake Ohrid. The lake deepened gradually, with a relatively constant vertical displacement rate of ~0.2 mm a⁻¹ between the central and the eastern lateral basin and with greater water depth presumably during interglacial periods. Although the dynamic environment characterized by local processes and the fragmentary chronology of the basal sediment successions from both sites hamper palaeoclimatic significance prior to the existence of a larger lake, the new data provide an unprecedented and detailed picture of the geodynamic evolution of the basin and lake that is Europe’s presumed oldest extant freshwater lake.     

Experimental reactions between olivine and orthopyroxene with phonolite melt: implications for the origins of hydrous amphibole + phlogopite + diopside bearing metasomatic veins

Amphibole + phlogopite + diopside bearing veins are observed in a large number of upper mantle xenoliths, but the composition of the melt that forms them is poorly constrained. Recent data from the Heldburg Phonolite, Central Germany, has shown that phonolite melt will react with olivine and orthopyroxene xenocrysts to form reaction rims of amphibole + phlogopite + diopside at mid-lower crustal pressures. This is the first example of where a melt has reacted with peridotite to form the mineralogy of the metasomatic veins. It is therefore necessary to explore whether a phonolite melt could be the parent melt that forms amphibole + phlogopite + diopside metasomatic veins. Experimental reactions between single crystals of olivine and orthopyroxene with phonolite melt were conducted at upper mantle conditions of 1.0–1.5 GPa and 900–1,000 °C. Melt water contents were varied from anhydrous to >12 wt. H₂O. Olivine reacts to form phlogopite reaction rims with overgrowths of diopside <1,000 °C or rims of secondary olivine >1,000 °C. Orthopyroxene reacts to form amphibole with epitaxial diopside overgrowths <1,000 °C. No reaction rims form when the bulk melt H₂O is lower than ~3.8 wt%. Pressure has little effect over the small range tested. These experiments reproduce reaction rims on olivine and orthopyroxene observed in the Heldburg Phonolite, Central Germany, and suggest that a relatively narrow range of temperatures and melt water contents is required for rim formation. The compositions of rim amphibole, phlogopite and diopside from the experiments have very similar compositions to those from Heldburg but do not match those from metasomatic veins. Phenocrysts from Heldburg are similar to the metasomatic veins, suggesting that a phonolite could potentially form the veins if vein formation is dominated by crystallization rather than reaction and replacement of wall rock phases.