Results of n-alkane biomarker analyses and paleoclimate reconstruction

The current study presents quantitative reconstructions of tree cover, annual precipitation and mean July temperature derived from the pollen record from Lake Billyakh (65°17'N, 126°47'E, 340 m above sea level) spanning the last ca. 50 kyr. The reconstruction of tree cover suggests presence of woody plants through the entire analyzed time interval, although trees played only a minor role in the vegetation around Lake Billyakh prior to 14 kyr BP (<5%). This result corroborates low percentages of tree pollen and low scores of the cold deciduous forest biome in the PG1755 record from Lake Billyakh. The reconstructed values of the mean temperature of the warmest month ~8-10 °C do not support larch forest or woodland around Lake Billyakh during the coldest phase of the last glacial between ~32 and ~15 kyr BP. However, modern cases from northern Siberia, ca. 750 km north of Lake Billyakh, demonstrate that individual larch plants can grow within shrub and grass tundra landscape in very low mean July temperatures of about 8 °C. This makes plausible our hypothesis that the western and southern foreland of the Verkhoyansk Mountains could provide enough moist and warm microhabitats and allow individual larch specimens to survive climatic extremes of the last glacial. Reconstructed mean values of precipitation are about 270 mm/yr during the last glacial interval. This value is almost 100 mm higher than modern averages reported for the extreme-continental north-eastern Siberia east of Lake Billyakh, where larch-dominated cold deciduous forest grows at present. This suggests that last glacial environments around Lake Billyakh were never too dry for larch to grow and that the summer warmth was the main factor, which limited tree growth during the last glacial interval. The n-alkane analysis of the Siberian plants presented in this study demonstrates rather complex alkane distribution patterns, which challenge the interpretation of the fossil records. In particular, extremely low n-alkane concentrations in the leaves of local coniferous trees and shrubs suggest that their contribution to the litter and therefore to the fossil lake sediments might be not high enough for tracing the Quaternary history of the needleleaved taxa using the n-alkane biomarker method.

n-Alkan-2-ones in peat-forming plants from the Roñanzas ombrotrophic bog (Asturias, northern Spain)

We determined the distribution of lipids (n-alkanes and n-alkan-2-ones) in present-day peat-formingplants in the RoñanzasBog in northernSpain. Consistent with the observation of others, most Sphagnum (moss) species alkanes maximized at C23, whereas the other plants maximized at higher molecular weight (C27 to C31). We show for the first time that plants other than seagrass and Sphagnum moss contain n-alkan-2-ones. Almost all the species analysed showed an n-alkan-2-one distribution between C21 and C31 with an odd/even predominance, maximizing at C27 or C29, except ferns, which maximized at lower molecular weight (C21–C23). We also observed that microbial degradation can be a major contributor to the n-alkan-2-one distribution in sediments as opposed to a direct input of ketones from plants

Discovery of ferromanganese hydrocarbon-related nodules associated with the Meknes mud volcano (Western Moroccan margin)

A suite of ferromanganese nodules were sampled during the MVSEIS-2008 cruise aboard of the R/V Hespérides in the flanks of Meknes mud volcano (Moroccan margin, NE Central Atlantic). The nodules were collected at water depths between 750-850 m within a seabed area characterized by high acoustic backscatter values. Debris of cold water corals and hydrocarbon-derived authigenic carbonate crusts were sampled at same time. The nodules show tabular morphology, up to 20 cm in maximum diameter and 2 kg of weight, brown-reddish external color and they are internally composed by a concentric to complex arrangement of laminae. The results of X-ray diffraction analysis show that these ferromanganese nodules are essentially composed of goethite and lepidocrocite, being Mn-oxides, silicates (quartz and clay minerals) and carbonates (calcite, dolomite and siderite) accessory to occasional minerals. All the samples display micritic to micro-sparitic mosaic under the petrographic microscope which forms massive, laminated or dendritic-mottled textures. The nodules show a high abundance of Fe, minor Mn and low contents of trace metals and REEs. Mature hydrocarbons, as n-alkanes derived from marine bacterial activity, and phenanthrene have been detected in all the ferromanganese nodules analyzed. These nodules display analogous characteristics (textural, mineralogical and geochemical) to the nodules studied by González et al (2009) in the carbonate mud-mounds in the Gulf of Cadiz, offshore Iberian margin. In this way, the same preliminary genetic model proposed for these nodules might be applicable to those find in the Meknes mud volcano. Therefore, the anaerobic oxidation of hydrocarbon-rich fluids within the mud-breccia sediments in the flanks of Meknes mud volcano would induce the formation of early diagenetic Fe-(Mn) carbonate nodules. Thus, the nodules were later exhumed by the erosive action of sea bottom currents generating the replacement of ferromanganese carbonates by Fe-Mn oxy-hydroxides. Thus, the hydrocarbon-rich fluid venting from deep seated reservoirs and erosive action of bottom currents must have been essential actors, as mineralization controls, for ferromanganese nodules generation and evolution. These findings imply that this type of nodules must be considered as new product as derived from the anaerobic/aerobic oxidation of hydrocarbons in areas of active seepages.

Estudio de la geoquímica orgánica de la Turbera de Las Conchas (Asturias) aplicado a la reconstrucción paleoambiental

ELos biomarcadores (n-alcanos y ácidos n-alcanoicos) presentes en el registro sedimentario de la turbera de Las Conchas (Llanes, Asturias) han permitido identificar períodos de condiciones ambientales húmedas y secas a lo largo de 8.000 años cal BP que pueden ser extrapolados al resto de Europa. Para ello, se analizaron 78 muestras a lo largo de un sondeo de 3,20 m, empleando un cromatógrafo de gases con detector selectivo de masas. Las variaciones en el contenido de biomarcadores se relacionaron con la predominancia de especies de Sphagnum (típicas de condiciones de mayor humedad) o con especies propias de condiciones más secas, como especies de Ericacea (brezos). Se sugiere que los cambios en la distribución de la vegetación están relacionados con las condiciones paleohidrológicas y paleoambientales y, de esta manera, se distinguen cinco períodos secos alternados con cinco períodos húmedos que no están necesariamente unidos a cambios en la temperatura. ABSTRACT Biomarkers (n-alkanes and n-alkanoic acids) present in the sedimentary record of Las Conchas peat bog (Llanes, Asturias) allowed the identification of 5 dry and humid periods in the last 8,000 years cal BP which can be extrapolated to the rest of Europe. For this purpose, 78 samples were analyzed along a core of 3.2 m deep using a gas chromatograph equipped with a selective mass detector. Variations in the biomarker content are related to the predominance of Sphagnum species (typical of humid conditions) or other species typical of dryer conditions, such as Ericacea (heather). This suggests that changes in the distribution of the vegetation were related to palaeohydrological and palaeoenvironmental conditions and, thus, we may distinguish five dry periods alternating with five humid periods which are not necessarily linked to variations in temperature.

Evolución paleoambiental de la Península Ibérica desde hace 1 Ma a partir de los biomarcadores del registro de la Turbera de Padul (Granada)

La Turbera de Padul, en la Provincia de Granada, ofrece unas posibilidades de estudio muy atractivas desde el punto de vista de la reconstrucción paleoambiental. Se trata de una fosa tectónica subsidente de naturaleza detrítica, a cuyo techo aparecen alternantes niveles de turba. El sondeo, de 107 metros, se realizó en un punto donde los estratos de turba aparecen a mayor profundidad, lo que permite obtener un registro geoquímico orgánico con mucho detalle con una antigüedad de hasta 1Ma. Se tomaron muestras cada 20 cm para el análisis de biomarcadores. Estos biomarcadores se obtuvieron mediante extracción Soxhlet, posterior separación de fracciones de diferente polaridad mediante Cromatografía en Columna, con Gel de Sílice y Alúmina, y posteriormente el análisis e identificación por Cromatografía de Gases - Espectrometría de masas, con confirmación de los compuestos químicos identificados por comparación con Bibliotecas de Espectros de Masas. La datación del sondeo se realizó utilizando distintos métodos como datación por 14C, U/Th, y datación por racemización de aminoácidos. Los resultados dataron el muro del sondeo con una antigüedad de 1 millón de años. El estudio de los biomarcadores ha permitido identificar episodios con distintas características en un escenario complejo, como es la Turbera de Padul, donde el aporte de agua por fusión nival complica la interpretación paleoambiental, y es la responsable de la existencia de la lámina de agua en la turbera en periodos secos con temperaturas elevadas. Se han identificado series de n-alcanos, de n-metilcetonas y series de nalcanoles, que han permitido identificar la aportación de materia orgánica de distintas fuentes al sedimento y por tanto la interpretación paleoambiental. La identificación de diterpenoides fenólicos (cis-Totatol, trans-Totarol y Ferruginol) han permitido identificar episodios de clima templado y húmedo con proliferación de cupresáceas, y precipitaciones abundantes. Por otro lado, se han identificado triterpenoides como el Friedelan-3-ona (Friedelin) y el A-norfriedel-8en-10-ona, cuya relación como precursor (Friedelin) y producto (A-norfriedel-8en-10-ona) ha permitido identificar episodios con fluctuaciones del espesor de la lámina de agua y aporte de material vegetal. ABSTRACT The Bog of Padul, in the province of Granada, offers very attractive possibilities for the study of paleoenvironmental reconstruction. It is a subsiding graben of detrital nature, whose upper part appear alternating peat levels. The core of 107 meters, obtained from a borehole drilled in a place where the layers of peat appear deeper, allowing to obtain organic geochemist information along the last 1 million years. Every 20 cm samples for biomarkers analysis were taken. These biomarkers were obtained by Soxhlet extraction, subsequent separation of fractions of different polarity by column chromatography with silica gel and alumina, and then analyzed and identified by gas chromatography - mass spectrometry, with confirmation of the chemicals identified by comparison to mass spectral libraries. The dating of the core was conducted using different methods such as 14C dating, U/Th, and amino acid racemization dating. The results dated the base of the core to be 1 million years old. The study has identified biomarkers episodes with different characteristics in a complex scenario, such as the Bog of Padul, where the contribution of snowmelt water complicates the paleoenvironmental interpretation, and is responsible for the existence of a sheet of water in dry periods with high temperatures. There have been identified series of n-alkanes, n-methyl ketones and series of n-alkanols that have shown the contribution of different organic matter sources to the sediment and therefore allowed to paleo interpretation. The identification of phenolic diterpenoids (cis-Totatol, trans-Totarol and Ferruginol) have identified episodes of mild and humid climate with proliferation of Cupressaceae, and abundant rainfall. In addition, triterpenoids have been identified, as the friedelan-3-one (friedelin) and the A-norfriedel-8en-10-one, whose relationship as precursor (friedelin) and product (A-norfriedel-8en-10-one) has identified episodes with fluctuations on the thickness of the sheet of water and supply of plant material debris.

Lipid biomarkers in the Enol Lake (Asturias, Northern Spain): coupled natural and human induced environmental history

The lipid content of three cores from Lake Enol (Picos de Europa National Park, Asturias, Northern Spain) was studied. The n-alkane profiles indicated a major input from terrigenous plants [predominance of high molecular weight (HMW) alkanes] since ca. 1695 AD to the water body, although the uppermost cm revealed a predominance of organic matter (OM) derived from algae, as the most abundant alkane was C17. Three units revealing different environmental conditions were defined. Unit A (ca. 1695–1860 AD) in the lowermost parts of ENO13-10 (< 12 cm) and ENO13-15 (< 28 cm) was identified and was characterized by higher OM input and evidence of minimal degradation (high CPI values, predominance of HMW n-alkanoic acids and good correspondence between the predominant n-alkane and n-alkanoic acid chains). These findings could be linked to the Little Ice Age, when cold and humid conditions may have favored an increase in total organic carbon (TOC) and n-alkane and n-alkanoic acid content (greater terrigenous OM in-wash), and may have also reduced bacterial activity. In Unit B (ca. 1860–1980 AD) the lack of correspondence between the n-alkane and n-alkanoic acid profiles of ENO13-10 (12–4 cm) and ENO13-15 (28–8 cm) suggested a certain preferential microbial synthesis of long chain saturated fatty acids from primary OM and/or bacterial activity, coinciding with a decrease in OM input, which could be linked to the global warming that started in the second half of the 19th century. In ENO13-7 the low OM input (low TOC) was accompanied by some bacterial degradation (predominance ofHMWn-alkanoic acids but with a bimodal distribution) in the lowermost 16–5 cm. Evidence of considerable phytoplankton productivity and microbial activity was especially significant in Unit C (ca. 1980–2013 AD) identified in the uppermost part of all three cores (5 cm in ENO13-7, 4 cm in ENO13-10 and 8 cm in ENO13-15), coinciding with higher concentrations of n-alkanes and n-alkanoic acids, which were considered to be linked to warmer and drier conditions, as well as to greater anthropogenic influence in modern times. Plant sterols, such as b-sitosterol, campesterol and stigmasterol, were significantly present in the cores. In addition, fecal stanols, such as 24-ethylcoprostanol from herbivores, were present, thereby indicating a continuous and significant pollution input derived from these animals since the 17th century, being more important in the last 20 years.

Biomarkers and inorganic proxies in the paleoenvironmental reconstruction of mires: The importance of landscape in Las Conchas (Asturias, Northern Spain)

We determined the lipid distributions (n-alkanes, n-alkan-2-ones, n-alkanoic acids), total organic carbon (TOC), total nitrogen (TN), Ca/Mg and ash content in Las Conchas mire, a 3.2 m deep bryophyte-dominated mire in Northern Spain covering 8000 cal yr BP. Bog conditions developed in the bottom 20 cm of the profile, and good preservation of organic matter (OM) was inferred from n-alkanoic acid distribution, with the exception of the uppermost 20 cm (last ca. 200 yr). Microbial synthesis of long chain saturated fatty acids from primary OM likely produced a dominance of short chain n-alkanoic acids with a bimodal distribution, as well as the lack of correspondence between the n-alkane and n-alkanoic acid profiles in the upper 20 cm. This was accompanied by an increase in ash content, a decrease in TOC and variation in n-alkane ratios, thereby suggesting significant changes in the mire, namely drainage and transformation to a meadow, in the last ca. 200 yr. The distribution of n-alkan-2-ones indicated an increase in bacterial source from the bottom of the record to 94 cm, whereas their distribution in the upper part could be attributed mainly to plant input and/or the microbial oxidation of n-alkanes. The different n-alkane proxies showed variations, which we interpreted in terms of changes in vegetation (Sphagnum vs. non-Sphagnum dominated phases) during the last 8000 cal yr BP. C23 was the most abundant homolog throughout most of the record, thereby suggesting dominant humid conditions alternating with short drier phases. However, such humid conditions were not linked to paleoclimatic variation but rather to geomorphological characteristics: Las Conchas mire, at the base of the Cuera Range, receives continuous runoff—even during drier periods—which is not necessarily accompanied by additional mineral input to peat, producing the development of Sphagnum moss typical of waterlogged ecotopes and damp habitats. Thus, although geochemical proxies indicated an ombrotrophic regime in the mire, geomorphological characteristics may make a considerable contribution to environmental conditions.

Palaeoenvironmental reconstruction of Las Conchas Mire (Asturias, N. Spain) from the ketone and fatty acid record= reconstrucción paleoambiental de la Turbera de las Conchas (Asturias, N. España)a partir del registro de cetonas y ácidos grasos

Se han estudiado los biomarcadores, principalmente cetonas y ácidos, preservados en el registro de 3.2 m de la Turbera de Las Conchas. Las cetonas reflejan cierta actividad bacteriana desde 94 cm hasta la base del registro, Los ácidos grasos reflejan una buena preservación de la materia orgánica, salvo en los 20 cm superiores en los que hay indicios de oxidación microbiana de alcanos .The biomarkers, mainly ketones and fally aclds, preserved In 3.2 m deep Las Conchas Mire have been studied, Kelones reflect certain bacterial activity from 94 cm to the bottom of the record. Falty aclds indlcate a good preservation of the organlc matter, wlth the exception of the uppermost 20 cm In whlch mlcroblal oxldation of alkanes are likely to occur

Atmospheric PM and volatile organic compounds released from Mediterranean shrubland wildfires

Wildfires produce a significant release of gases and particles affecting climate and air quality. In the Mediterranean region, shrublands significantly contribute to burned areas and may show specific emission profiles. Our objective was to depict and quantify the primary-derived aerosols and precursors of secondary particulate species released during shrubland experimental fires, in which fire-line intensity values were equivalent to those of moderate shrubland wildfires, by using a number of different methodologies for the characterization of organic and inorganic compounds in both gas-phase and particulate-phase. Emissions of PM mass, particle number concentrations and organic and inorganic PMx components during flaming and smouldering phases were characterized in a field shrubland fire experiment. Our results revealed a clear prevalence of K+ and SO42- as inorganic ions released during the flaming-smouldering processes, accounting for 68 to 80% of the inorganic soluble fraction. During the residual-smouldering phases, in addition to K+ and SO42-, Ca2+ was found in significant amounts probably due the predominance of re-suspension processes (ashes and soil dust) over other emission sources during this stage. Concerning organic markers, the chromatograms were dominated by phenols, n-alkanals and n-alkanones, as well as by alcohol biomarkers in all the PMx fractions investigated. Levoglucosan was the most abundant degradation compound with maximum emission factors between 182 and 261 mg kg-1 in PM2.5 and PM10 respectively. However, levoglucosan was also observed in significant amounts in the gas-phase. The most representative organic volatile constituents in the smoke samples were alcohols, carbonyls, acids, monocyclic and bicyclic arenes, isoprenoids and alkanes compounds. The emission factors obtained in this study may contribute to the validation and improvement of national and international emission inventories of this intricate and diffuse emission source.

Dissolved CO2 and Alkane Gas in Clay Formations

Characterization of dissolved CO2 and alkane gas in clayrocks may help assessing the confinement properties of geological barriers considered as potential host rocks for a deep geological disposal as well as for caprocks of gas storages. A monitoring of alkanes with CO2, combined with carbon isotopes was performed on core samples coming from Underground Research Laboratories (Bure, Mont Terri, Tournemire) and the Schlattingen borehole in France and Switzerland. Composition of hydrocarbon gas and delta C-13 of methane strongly suggest a dominant thermogenic origin of methane which is mixed with a bacterial origin for the Toarcian shales, Pliensbachien and Callovian-Oxfordian clayrocks. Results also evidence the contrasted behavior of CO2, which is controlled by chemical equilibrium between pore water and carbonate mineralogy, compared to the alkanes which are present in the porosity as a stock of dissolved gases which can be depleted during degassing experiments. (C) 2015 The Authors. Published by Elsevier B.V.

Chromatographic fractionation of bitumen from sediments and presence of glycerol ethers in immature sediments (Table 2)

Alkanes having unusual saturated isoprenoidal and methyl-branched structures have been isolated from the bitumen of several sediments. The methanogenic biomarkers 2,6,10,15,19-pentamethyleicosane and squalane were found in sediments which also contained bacteriogenic glycerol ethers. However, in one ether-containing sediment, 2,6,10,13,17,21-hexamethyldocosane was tentatively identified and this compound was found in place of the established alkane biomarkers. Other hydrocarbons found were regular C21 and C23 isoprenoid alkanes, compounds which cannot be derived from phytol; two isoprenoids of the type 3,7,11.-polymethylalkane, previously reported only in petroleums; 8-methylheptadecane, a probable biomarker for cyanobacteria and a number of its homologs and other methyl-branched alkanes. Ubiquitous branched-chain alkylbenzenes and a homology of trimethylalkylbenzenes were also isolated. Most, or all, of the compounds reported here are probably not catagenetic products but may represent direct algal or bacterial bioinputs.

Organic geochemistry of ODP Hole 162-985A sediments

Dark, organic-rich sediments were recovered from the lower Miocene section (~16.6 Ma) in Hole 985A in the Norway Basin during Ocean Drilling Program Leg 162. Organic carbon and total sulfur contents of the dark sediments showed a maximum concentration of 5.6 and 26.1 wt%, respectively. Sulfur enrichment in the sediments indicates that these dark layers were formed under anoxic conditions in bottom water. Four dark and eight greenish gray sediment samples, ranging in age from early Miocene to Pleistocene, were analyzed for lipid-class compounds (aliphatic hydrocarbons, fatty alcohols, and sterols) using gas chromatography (GC) and GC/mass spectrometry to better understand the formation processes of the organic-rich dark layers and to reconstruct the paleoenvironmental changes. The molecular distributions of n-alkanes and fatty alcohols indicate that terrigenous organic matter largely contributed to both types of sediments. Significant amounts of hopanoid hydrocarbons, such as diploptene and hop-17(21)-ene, however, were detected characteristically in the dark sediments, which suggests that prokaryotes such as methane-oxidizing bacteria or cyanobacteria may have significantly contributed to the formation of these organic-rich, dark sediments. These results indicate that the bottom waters of the Norway Basin had been subjected to anoxic conditions during the early Miocene.