Short chain ladderanes: Oxic biodegradation products of anammox lipids

Anammox, the microbial anaerobic oxidation of ammonium by nitrite to produce dinitrogen gas, has been recognized as a key process in both the marine and freshwater nitrogen cycles, and found to be a major sink for fixed inorganic nitrogen in the oceans. Ladderane lipids are unique anammox bacterial membrane lipids that have been used as biomarkers for anammox bacteria in recent and past environmental settings. However, the fate of ladderane lipids during diagenesis is as of yet unknown. In this study, we performed oxic degradation experiments (at 20-100 °C) with anammox bacterial biomass to simulate early diagenetic processes occurring in the water column and at the sediment-water interface. Abundances of C₁₈ and C₂₀ ladderane lipids decreased with increasing temperatures, testifying to their labile nature. The most abundant products formed were ladderane lipids with a shorter alkyl side chain (C₁₄ and C₁₆ ladderane fatty acids), which was unambiguously established using two-dimensional NMR techniques on an isolated C₁₄-[3]-ladderane fatty acid. The most pronounced production of these short-chain lipids was at 40 °C, suggesting that degradation of ladderane lipids was microbially mediated, likely through a β-oxidation pathway. An HPLC-MS/MS method was developed for the detection of these ladderane alteration products in environmental samples and positively tested on various sediments. This showed that the ladderanes formed during degradation experiments also naturally occur in the marine environment. Thus, short-chain ladderane lipids may complement the original longer-chain ladderane lipids as suitable biomarkers for the detection of anammox processes in past depositional environments.     

Comparison of ladderane phospholipid and core lipids as indicators for anaerobic ammonium oxidation (anammox) in marine sediments

We investigated anaerobic ammonium oxidation (anammox) in continental shelf and slope sediments of the Irish and Celtic Seas by using anammox specific ladderane biomarker lipids. We used the presence of an intact ladderane phospholipid as a direct indicator for living anammox bacteria, and compared it with the abundance of ladderane core lipids derived from both living and dead bacterial biomass. All investigated sediments contained ladderane core lipids as well as the intact ladderane phospholipid, in agreement with ¹⁵N-labeling experiments, which revealed anammox activity at all sites. Ladderane core lipid and intact ladderane phospholipid concentrations were significantly correlated (R² = 0.957 and 0.464, respectively) with anammox activity over the transect of the continental shelf and slope sediments. In the Irish Sea (50-100 m water depth) highest abundances of the intact ladderane phospholipid were found in the upper 2 cm of the sediment, indicating a zone of active anammox. A sharp decline further down-core suggested a strong decrease in anammox biomass and rapid degradation of the intact lipids. In comparison, ladderane core lipids were 1-2 orders of magnitude higher in concentration than the intact ladderane phospholipid and accumulated as dead cell remnants with depth. In the slope sediments of the Celtic Sea both ladderane core lipids and the intact ladderane phospholipid were found in sediments at water depths ranging from 500 to 2000 m. Here, anammox seemed to be active at greater depths of the sediment (>2 cm). Mean abundances of both intact and core ladderane lipids in whole sediment cores increased downslope, indicating an increasing importance of anammox in deeper slope sediments.     

Generation of unusual branched long chain alkanes from hydrous pyrolysis of anammox bacterial biomass

Anammox, the microbial anaerobic oxidation of NH₄⁺ by NO₂⁻ to produce N₂, is recognised as a key process in the marine, freshwater and soil N cycles, and has been found to be a major sink for fixed inorganic N in the ocean. Ladderane lipids are unique anammox bacterial membrane lipids used as biomarkers for such bacteria in recent and past environmental settings. However, their fate during diagenesis and early catagenesis is not well constrained. In this study, hydrous pyrolysis experiments were performed on anammox bacterial biomass and the generated aliphatic hydrocarbons, present in oil generated at 220–365 °C, were analysed. A unique class of hydrocarbons was detected, and a representative component was isolated and rigorously identified using 2D nuclear magnetic resonance (NMR) spectroscopy. It consisted of C₂₄ to C₃₁ branched long chain alkanes with two internal ethyl and/or propyl substituents. The alkanes were generated above 260 °C, with maximum generation at 320 and 335 °C. Their stable carbon isotopic values were depleted in ¹³C, similar to carbon isotope values of the original anammox lipids, indicating that they were thermal products generated from lipids of anammox bacterial biomass. A range of sediments from different geological periods where anammox may have been an important process was screened for the presence of these compounds as possible catagenetic products. They were not detected, either because the concentration was too low, or the sediments screened were too immature for them to have been generated, or because the artificially produced products of anammox lipids may not reflect the natural diagenetic and catagenetic products of ladderane lipids.     

Sandstone diagenesis in the Pattani Basin (Gulf of Thailand): history of water-rock interaction and comparison with the Gulf of Mexico

In the Pattani Basin, a failed-rift basin, extensive water-rock interaction has occurred between subquartzose alluvial sandstones of Miocene age and their pore fluids. Diagenetic rates and pathways have been strongly influenced by high geothermal gradients, high CO₂ fugacities, and low pore water salinities. Depositional pore water was fresh to brackish, depending on the depositional environment of the sediments. Chloride concentrations in modern formation water are believed primarily to reflect the proportions of river and sea water in the depositional environment. However, the concentration of other important solutes and the isotopic composition of the formation waters can not be explained by roportional mixing of these two end-member waters. Dissolution of detrital plagioclase (An = 3) and K- feldspar are reactions of major significance that are reflected chemically in the Na/Cl and K/Cl ratios of the formation water. Despite the high temperature of the sandstones (120–200°C), diagenetic albite does not occur. Geochemical calculations indicate the formation water is undersaturated with respect to both orthoclase and albite. This style of feldspar diagenesis differs significantly from that of sandstones of similar composition in other basins, and has probably influenced other aspects of silicate diagenesis.Important authigenic minerals are: 1. locally abundant calcite cement (δ¹³C= −12.8, δ¹⁸O= −17.3 PDB), an early diagenetic phase that formed at about 60°C; 2. pore-filling kaolinite (δ¹⁸O= 9.9, δD= −83.5SMOW) that was closely associated with feldspar dissolution and formed over a range of temperatures; and 3. fibrous pore-lining and pore-bridging illite (δ¹⁸O = 9.8, δD = − 86.7 SMOW, the last significant cement, formed at temperatures of 120 to 150°C. Potassium/argon dates on illite indicate that sandstone diagenesis took place during a period of rapid sedimentation in the first two-thirds of the burial history.Comparison of Pattani Basin diagenesis with diagenesis of sandstones of similar age in other sedimentary basins demonstrates that chemical diagenesis, relative to mechanical compaction, has been especially rapid in the Pattani Basin. This reflects the effect of high temperatures on reaction rates. The net effect is a high average rate of porosity loss with burial (11% km).     

Simulating coseismic deformation of quartz in the middle crust and fabric evolution during postseismic stress relaxation — An experimental study

Non-steady state deformation and annealing experiments on vein quartz are designed to simulate earthquake-driven episodic deformation in the middle crust. Three types of experiments were carried out using a modified Griggs-type solid medium deformation apparatus. All three start with high stress deformation at a temperature of 400 °C and a constant strain rate of 10^− 4 s^− 1 (type A), some are followed by annealing in the stability field of α-quartz for 14–15 h at zero nominal differential stress and temperatures of 800–1000 °C (type A + B), or by annealing for 15 h at 900 °C and at a residual stress (type A + C).The quartz samples reveal a very high strength > 2 GPa at a few percent of permanent strain. The microstructures after short-term high stress deformation (type A) record localized brittle and plastic deformation. Statisc annealing (type A + B) results in recrystallisation restricted to the highly damaged zones. The new grains aligned in strings and without crystallographic preferred orientation, indicate nucleation and growth. Annealing at non-hydrostatic conditions (type A + C) results in shear zones that also develop from deformation bands or cracks that formed during the preceding high stress deformation. In this case, however, the recrystallised zone is several grain diameters wide, the grains are elongate, and a marked crystallographic preferred orientation indicates flow by dislocation creep with dynamic recrystallisation. Quartz microstructures identical to those produced in type A + B experiments are observed in cores recovered from Long Valley Exploratory Well in the Quaternary Long Valley Caldera, California, with considerable seismic activity.The experiments demonstrate the behaviour of quartz at coseismic loading (type A) and subsequent static annealing (type A + B) or creep at decaying stress (type A + C) in the middle crust. The experimentally produced microfabrics allow to identify similar processes and conditions in exhumed rocks.     

Differences in reactivities of sedimentary hopane diastereomers when heated in the presence of clays

Mixtures of hopane diastereomers obtained by fractionation of the organic extract from an immature oil shale have been heated in the presence of clay-containing substrates. In experiments conducted at 250°C with an extracted source rock as the substrate, the relative amounts of 17β(H),21β (H)-hopanes were found to decrease with respect to the moretanes and 17α(H),21β(H)-hopanes in a manner parallelling that observed with increasing maturity in sediments. In this case however, the change was shown to be due to the selective removal of the 17β(H),21β(H)-hopanes, rather than conversion of these compounds into the other diastereomers. In order to assess whether the use of elevated temperatures was enhancing processes other than those which operate in natural systems, a second experiment was conducted in which the sample of immature hopanes was heated at 75°C with the very catalytically active substrate aluminum montmorillonite. In this experiment also, the changes in hopane composition was shown to be due to selective removal of 17β(H),21β(H)-hopanes rather than conversion into the corresponding compounds in the other two series of diastereomers. These results suggest that the observed relative depletion of 17β(H),21β(H)-hopanes in sedimentary rocks of increasing maturity may similarly be due to removal by selective catalytic processes, and not to interconversion processes associated with isomerisation at C-17 and C-21 as had previously been believed.     

Ordovician ferrosilicic magmas: Experimental evidence for ultrahigh temperatures affecting a metagreywacke source

Peculiar magmatic rocks were erupted and emplaced at depth at the margin of the Gondwana supercontinent during the Cambro-Ordovician transition. These rocks are characterized by high contents in silica and iron but they do not have equivalents in the high-silica members of the calc-alkaline series. They have particular geochemical signatures, with Al saturation index, ASI > 1, FeO > 2.5 wt.%, MgO > 0.8 wt.% for very low contents in calcium (CaO < 2.0 wt.%), supporting a derivation from near-total melting (> 80 vol.% melt) of metagreywackes. The results from inverse experiments indicate that the most plausible conditions are within the range 1000 °C (excess water) and 1100–1200 °C (subsaturated and dry) at pressures of 1.5 to 2.0 GPa. A tectonic scenario implying melting of subducted sediments within an ascending mantle-wedge plume is suggested for the generation of primary ferrosilicic melts at the Gondwana continental margin during Upper Cambrian to Lower Ordovician times.     

Ultrahigh-temperature metamorphism in the Achankovil Zone: Implications for the correlation of crustal blocks in southern India

The Achankovil Zone of southern India, a NW–SE trending lineament of 8–10 km in width and > 100 km length, is a kinematically debated crustal feature, considered to mark the boundary between the Madurai Granulite Block in the north and the Trivandrum Granulite Block in the south. Both these crustal blocks show evidence for ultrahigh-temperature metamorphism during the Pan-African orogeny, although the exhumation styles are markedly different. The Achankovil Zone is characterized by discontinuous strands of cordierite-bearing gneiss with an assemblage of cordierite + garnet + quartz + plagioclase + spinel + ilmenite + magnetite ± orthopyroxene ± biotite ± K-feldspar ± sillimanite. The lithology preserves several peak and post-peak metamorphic assemblages including: (1) orthopyroxene + garnet, (2) perthite and/or anti-perthite, (3) cordierite ± orthopyroxene corona around garnet, and (4) cordierite + quartz symplectite after garnet. We estimate the peak metamorphic conditions of these rocks using orthopyroxene-bearing geothermobarometers and feldspar solvus which yield 8.5–9.5 kbar and 940–1040 °C, the highest P–T conditions so far recorded from the Achankovil Zone. The retrograde conditions were obtained from cordierite-bearing geothermobarometers at 3.5–4.5 kbar and 720 ± 60 °C. From orthopyroxene chemistry, we record a multistage exhumation history for these rocks, which is closely comparable with those reported in recent studies from the Madurai Granulite Block, but different from those documented from the Trivandrum Granulite Block. An evaluation of the petrologic and geochronologic data, together with the nature of exhumation paths leads us to propose that the Achankovil Zone is probably the southern flank of the Madurai Granulite Block, and not a unit of the Trivandrum Granulite Block as presently believed. Post-tectonic alkali granites that form an array of “suturing plutons” along the margin of the Madurai Granulite Block and within the Achankovil Zone, but are absent in the Trivandrum Granulite Block, suggest that the boundary between the Madurai Granulite Block and the Trivandrum Granulite Block might lie along the Tenmalai shear zone at the southern extremity of the Achankovil Zone.     

Marine and terrigenous lipids in coastal sediments from the Peru upwelling region at 15°S: Sterols and triterpene alcohols

The distributions of free 4-desmethyl sterols in sediments from the Peru coastal zone at 15°S have been determined. Major free sterols in the surface sediments include cholesterol, which is mainly derived from zooplankton, and two C₂₈ sterols: 24-methylcholesta-5,24(28)-dien-3β-ol and 24-methylcholesta-5,22E-dien-3β-ol both of which are derived fro diatoms. Their concentrations decrease by almost an order of magnitude in the top 20 cm of sediment depth, indicating that free sterols are rapidly degraded in this sedimentary environment. Lipids from higher plants were also detected: long chain fatty acids and alcohols and various triterpenoid alcohols, including taraxerol, lupeol and α- and β-amyrin. The concentrations of most terrigenous lipids varied by less than a factor of 3 over the same depth, and these changes were not correlated with changes in the concentrations of total organic carbon. Below 3 cm, lipids from higher plants predominated in the extractable lipid distributions due to the more rapid degradation of marine lipids. We postulate that there are significant marine sources of the higher plant sterols 24-ethylcholesterol, 24-ethylcholesta-5,22E-dien-3β-ol and 24-methylcholesterol in these sediments. A high proportion of many of the terrigenous lipids in these sediments are probably transported into the coastal zone by rivers, rather than from the atmosphere, and then redistributed by bottom currents.     

Episodic fluid migration in the Fennoscandian Shield recorded by stable isotopes, rare earth elements and fluid inclusions in fracture minerals at Forsmark, Sweden

Drilling through the Palaeoproterozoic bedrock at Forsmark, central Sweden, during the site investigation for a potential geological repository of highly radioactive nuclear waste has provided high quality drill-core material from the upper 1 km of the Fennoscandian Shield. Analyses of stable isotopes (δ¹³C, δ¹⁸O, δ³⁴S, ⁸⁷Sr/⁸⁶Sr), rare earth elements and fluid inclusions in fracture filling calcite and pyrite from these drill cores have resulted in the discrimination of several episodes of fracture mineralisations. These events represent migration of fluids during a wide range of conditions, ranging from high-temperature hydrothermal to present-day groundwater circulation. Four major events have been distinguished: 1) Precipitation of epidote, chlorite and quartz under hydrothermal conditions (T > 150–200 °C) during the Proterozoic, sometime between 1.8 and 1.1 Ga. 2) Hydrothermal circulation at temperatures close to 200 °C with precipitation of adularia, albite, prehnite, laumontite, calcite and chlorite. Most of these minerals precipitated during a tectonothermal event between 1.1 and 1.0 Ga, possibly in response to far-field effects of the Sveconorwegian orogeny. 3) Precipitation of mainly quartz, calcite, pyrite and asphaltite occurred during the Palaeozoic, at temperatures between 60 and 190 °C (mainly at < 100 °C). Mixing of a fluid emanating from an organic rich overlying sedimentary cover and a deep basinal fluid from the crystalline bedrock is suggested to have caused this precipitation, possibly as a far-field response to the Caledonian orogeny and/or the development of the Caledonian foreland basin. 4) The youngest generation of fracture minerals is associated with formation of clay minerals and calcite with minor occurrences of pyrite and goethite. These minerals have probably precipitated episodically during a long time period (possibly from the Late Palaeozoic to the present) from various fluids at low temperature conditions (< 50 °C). Few calcites in equilibrium with the present groundwater suggest that the ongoing precipitation of calcite is very limited.     

Saline brines and metallogenesis in a modern sediment-filled rift: the Salton Sea geothermal system, California, U.S.A.

The Salton Sea geothermal system (SSGS) is the site of active hydrothermal metamorphism and metallogenesis in the delta of the Colorado River, which partially fills the Salton Trough rift zone at the head of the Gulf of California. Growth of the delta across the rift has isolated the northern part of the Salton Trough since the Pleistocene, forming the evaporative Salton Sea basin whose sediments host the SSGS. More than 70 commercial geothermal wells, including a 3.2 km deep research borehole drilled as part of the Salton Sea Scientific Drilling Project (SSSDP), are yielding a wealth of new data from this system.Within the SSGS, active greenschist facies metamorphism is occuring at temperatures 365°C at only 2–3 km depth, by reaction of NaCaKFeMnCl brines with the deltaic and lacustrine Pilo-Pleistocene sediments. Two kinds of base metal ore mineralization occur at depth: stratabound diagenetic Fe sulfides, and epigenetic vertical veins containing FeZnCuPb sulfides and Fex oxides. The vein mineralization occurs as two types: an older, reduced carbonate-sulfide assemblage, and a modern, oxidized, silicate-hematite-sulfide assemblage. The earlier assemblage formed at temperatures up to 100°C higher than the ambient temperatures measured in the wells today, implying that cooler, oxidized fluids have displaced hot, reduced fluids.A sharp interface between shallow fluids containing <12 wt % TDS and deep hypersaline brines containing 15–27 wt % TDS exists in the SSGS. The deeper hypersaline brines are rich in base metals (Fe 1500 ppm, Mn 1000 ppm, Zn 500 ppm) whereas the overlying lower-salinity fluids contain less than 100 ppm each of Fe, Mn and Zn. The modern silicate-hematite-sulfide vein assemblage is precipitating where the two fluids appear to be mixing. The two fluid types also have distincty different δ¹⁸O and δD relations. The shallow lower-salinity fluids have only partially-exchanged oxygen with deltaic and lacustrine host rocls. The deep hypersaline brines have exchanged oxygen extensively at 250°C with the deltaic sediments. δD values of the hypersaline brines are typically lighter than either the lower-salinity fluids or the modern evaporating groundwaters occupying the Salton Trough, implying a different source for the original fluids.The high salinities of the geothermal brines are derived from a combination of evaporation of fossil lakewaters, groundwater dissolution of shallow lacustrine evaporites, and subsurface hydrothermal metamorphism of buried lacustrine evaporites. Episodic filling and desiccation of the closed Salton Sea basin has allowed cold saline brines to form and percolate down into the sedimentary section. In some wells anyhydrite meta-evaporites and interbedded solution collapse breccias occur at 1 km depth. The anyhydrite contains fluid inclusions that are saturated in halite at their homogenization temperatures of 300°C, recording the hydrothermal dissolution of bedded salt. Based on Sr and Pb isotopic data and whole-rock chemical data, the source of the metals in the hypersaline brines is from leaching of the host sediments. However, the origin of reduced S for ore mineralization remains an enigma. δ³⁴S values for vein sulfides cluster uniformly around zero per mil, implying that an isotopically-homogeneous source of reduced sulfide exists in the brines. It is possible that the vein sulfides receive a constribution from a magmatic S source.Movement and mixing of brines of different chemistry and oxidation states play a major role in ore genesis. Our model envisages an early stage in which a deep brine pool accumulated at depth in the sedimentary section by partial section by partial evaporation of basin and dissolution of bedded salts. Intrusion of rift-related basaltic magma into the base of the sedimentary caused heatingand fracturing of the sediments, resulting in precipitation of the carbonate-sulfide veins during pore fluid expulsion. Heating also caused a diapir of the hypersaline brine to rise and displace colder, less saline, shallower pore fluids. This brine intrusion was accompanied by pervasive and extensive mineralization. As this diapir cooled it began to move downward, drawing in shallow, more oxidized fluids and causing the formation of the modern silicate-hematite-sulfide vein ore zone.     

Fluid inclusion and stable isotope study of the Cobre–Babilonia polymetallic epithermal vein system, Taxco district, Guerrero, Mexico

The Cobre–Babilonia vein system formed during a single major hydrothermal stage and is part of the Taxco district in Guerrero, southern Mexico. Homogenization and ice melting temperatures range from 160 to 290 °C and from − 11.6 to − 0.5 °C, respectively. We determined an approximate thermal gradient of 17 to 20 °C per 100 m using fluid inclusions. A thermal peak marked by the 290 °C isotherm is interpreted as a major feeder channel to the veins. The highest content of Zn + Pb in ore coincides with the 220 and 240 °C isotherms. Salinities of mineralizing fluids range from 0.8 to 15.6 wt.% NaCl equiv, and are distributed in two populations that can be related with barren or ore-bearing vein sections, with 0.8 to 6 wt.% NaCl equiv and 7 to 15.6 wt.% NaCl equiv, respectively. δ¹³C and δ¹⁸O water values from calcite from the Cobre–Babilonia vein system and the Esperanza Vieja and Guadalupe mantos range − 5.4‰ to − 10.4‰ and 9.9‰ to 13.4‰, respectively. δ³⁴S values range from 0‰ to 3.2‰ and − 0.7‰ to − 4.3‰ in sphalerite, − 4‰ to 0.9‰ in pyrite, and − 1.4‰ to − 5.5‰ in galena. Both fluid inclusion and stable isotope data are compatible with magmatic and meteoric sources for mineralizing fluids. Also, sulfur isotope compositions suggest both magmatic and sedimentary sources for sulfur.     

Biomarker evidence for anammox in the oxygen minimum zone of the Eastern Tropical North Pacific

Anaerobic oxidation of ammonium (anammox) is an important process in the marine N cycle. It has been estimated to contribute up to 50% of N loss from the ocean and is especially prevalent within the oxygen minimum zone (OMZ). We studied the presence and distribution of anammox in the extended OMZ of the Eastern Tropical North Pacific (ETNP) using ladderane fatty acids (FAs), specific biomarkers for anammox bacteria. The validity of ladderane FAs as a proxy for anammox bacteria was demonstrated by their excellent correspondence with anammox 16S rRNA functional gene abundances and their expression and intact polar ladderane lipid concentrations in suspended particulate matter (SPM) from the Arabian Sea. In the ETNP, SPM was collected from various water depths at four stations along a northwest to southeast cruise transect and ladderane FAs were analysed at each station. In all SPM samples where ladderanes were detected, C₁₈ ladderane FAs were on average fivefold more abundant than C₂₀ ladderane FAs. Maximum ladderane FA concentrations (1.1–2.3 ng l⁻¹) were recorded at 400–600 m, often corresponding to the depth of the secondary nitrite maximum. At one of the four stations, a second maximum in concentration was noted at a shallower depth (85 m), coinciding with higher nitrite availability at this depth. This suggests that nitrite, along with oxygen, may be a limiting factor for anammox activity in the ETNP. Anammox lipids were abundant within the OMZ at all stations and concentrations were comparable to those in other OMZs, suggesting that anammox may be responsible for a significant loss of N from the OMZ of the ETNP.     

Fluid geochemistry in the Ivigtut cryolite deposit, South Greenland

The 1.27 Ga old Ivigtut (Ivittuut) intrusion in South Greenland is world-famous for its hydrothermal cryolite deposit [Na₃AlF₆] situated within a strongly metasomatised A-type granite stock. This detailed fluid inclusion study characterises the fluid present during the formation of the cryolite deposit and thermodynamic modelling allows to constrain its formation conditions.Microthermometry revealed three different types of inclusions: (1) pure CO₂, (2) aqueous-carbonic and (3) saline-aqueous inclusions. Melting temperatures range between − 23 and − 15 °C for type 2 and from − 15 to − 10 °C for type 3 inclusions. Most inclusions homogenise between 110 and 150 °C into the liquid.Stable isotope compositions of CO₂ and H₂O were measured from crushed inclusions in quartz, cryolite, fluorite and siderite. The δ¹³C values of about − 5‰ PDB are typical of mantle-derived magmas. The differences between δ¹⁸O of CO₂ (+ 21 to + 42‰ VSMOW) and δ¹⁸O of H₂O (− 1 to − 21.7‰ VSMOW) suggest low-temperature isotope exchange. δD (H₂O) ranges from − 19 to − 144‰ VSMOW. The isotopic composition of inclusion water closely follows the meteoric water line and is comparable to Canadian Shield brines. Ion chromatography revealed the fluid's predominance in Na, Cl and F. Cl/Br ratios range between 56 and 110 and may imply intensive fluid–rock interaction with the host granite.Isochores deduced from microthermometry in conjunction with estimates for the solidification of the Ivigtut granite suggest a formation pressure of approximately 1–1.5 kbar for the fluid inclusions. Formation temperatures of different types of fluid inclusions vary between 100 and 400 °C. Thermodynamic modelling of phase assemblages and the extraordinary high concentration in F (and Na) may indicate that the cryolite body and its associated fluid inclusions could have formed during the continuous transition from a volatile-rich melt to a solute-rich fluid.     

Primary curvature in the Mid-Continent Rift: Paleomagnetism of the Portage Lake Volcanics (northern Michigan, USA)

Rocks of the North American Mid-Continent Rift (MCR) in the Keweenaw Peninsula of northern Michigan display a change in structural trend from east to west, varying in strike from 100° in the east to 35° farther west, before returning to a more east–west trend of 80° near Wisconsin. In general, curvature can be described either as of primary origin, meaning that the arc developed in its present curved state, or as of secondary origin, when the arc formed from an initially straighter geometry. A powerful tool in evaluating the origin and degree of curvature in any deformed belt is paleomagnetism, where coincident change in declination and strike is evidence for secondary curvature. Several paleomagnetic studies have been completed on rift-related sedimentary rocks, as well as lava flows, from the MCR in the Lake Superior region. Paleomagnetic directions for the sedimentary rocks vary much more in declination than in inclination, possibly reflecting a vertical axis rotation. If secondary rotation has affected the sedimentary rocks, then underlying volcanic rocks should also demonstrate a similar rotation.Thirty-one sites were collected from the Portage Lake Volcanics in the most highly curved part of the Keweenaw Peninsula in the Upper Peninsula of Michigan. Sites were chosen to maximize the variation in structural trend. Thermal demagnetization results showed two components in samples from most sites, a lower temperature A component (< 580 °C) as well as a higher temperature B component (> 580 °C). Both components were tested for primary remanence using a conglomerate test. The A component, carried by magnetite, passes the conglomerate test at a 95% confidence level, and is therefore considered a primary remanence. The B component, carried by hematite, fails at the 95% level and is considered a secondary magnetization. Most importantly, declination of the primary (A) magnetization between sites shows no correlation with strike, demonstrating that vertical axis rotations cannot explain the curvature of the Mid-Continent Rift. We conclude that curvature in the Lake Superior Region is a primary feature, likely reflecting a pre-existing zone of weakness that was exploited during rifting.     

Elucidation of different forms of organic carbon in marine sediments from the Atlantic coast of Spain using thermal analysis coupled to isotope ratio and quadrupole mass spectrometry

Analysis of river, estuary and marine sediments from the Atlantic coast of Spain using thermogravimetry–differential scanning calorimetry–quadrupole mass spectrometry–isotope ratio mass spectrometry (TG–DSC–QMS–IRMS) was used to (a) distinguish bulk chemical hosts for C within a sediment and humic acid fraction, (b) track C pools with differing natural C isotope ratios and (c) observe variation with distance from the coast. This is the first application of such a novel method to the characterisation of organic matter from marine sediments and their corresponding humic acid fractions. Using thermal analysis, a labile, a recalcitrant and a refractory carbon pool can be distinguished. Extracted humic fractions are mainly of recalcitrant nature. The proportion of refractory carbon is greatest in marine sediments and humic acid fractions. Quadrupole mass spectrometry confirmed that the greatest proportion of m/z 44 (CO₂) and m/z 18 (H₂O) were detected at temperatures associated with recalcitrant carbon (510–540 °C). Isotope analysis detected progressive enrichment in δ¹³C for the sediment samples with an increase in marine influence. Isotopic heterogeneity in the refractory organic matter in marine sediments could be due to products of anthropogenic origin or natural combustion products. Isotope homogeneity of humic acids confirms the presence of terrigenous C in marine sediments, allowing the terrestrial input to be characterised.     

Dolomitic marbles and associated calc-silicates, Tandilia belt, Argentina: Geothermobarometry, metamorphic evolution, and P–T path

The metamorphic evolution of dolomitic marbles and associated calc-silicate rocks from Punta Tota (NE Tandilia belt, Buenos Aires province, Argentina) has been evaluated through petrographic, geothermobarometric, and fluid inclusion studies. Thin beds of dolomitic marble are intercalated in amphibolites and constitute the upper part of a stratified basement sequence, which starts at the base with garnet migmatites showing a great abundance of pegmatitic segregates, overlain by biotite–garnet gneisses. Peak metamorphic conditions are estimated at 750–800 °C and 5–6 kb, followed by near isobaric cooling to about 500–450 °C and 5.5–6.5 kb. Anhydrous progressive metamorphic assemblages in both marbles (Fo + Cal + Dol + Cpx + Spl) and adjacent calc-silicate rocks (Cpx + An + Cal + Qtz) strongly retrogressed to hydrous minerals (Tr, Tlc, Grs, Czo, Srp) with decreasing temperatures and increasing water activities. The intense rehydration of the rocks relates to the emplacement of volatile-rich pegmatitic bodies (Qtz + Pl + Kfs + Bt + Grt), which also resulted in the crystallization of clinochlore + phlogopite in the marble and biotite + muscovite in the adjacent calc-silicate rocks. Metamorphic reactions based on textural relations and evaluated on a suitable petrogenetic grid, combined with geothermobarometric results and fluid inclusion isochores, indicate a metamorphic evolution along a counterclockwise P–T path. Two probable geotectonic settings for the determined P–T trajectory are proposed: (1) thinning of the crust and overlying supracrustal basin in an ensialic intraplate tectonic setting and (2) development of a marginal back-arc basin, associated with an oceanic–continental convergent plate margin. In both models, the initial extensional regime is followed by a compressional stage, with overthickening of the basement and supracrustal rocks, during the climax of the Transamazonian cycle at approximately 1800 Ma ago. Continuous convergence and blockage of structures produce transition to transcurrent tectonics (transpression) with a consequent moderate uplift.     

The characteristics and source of laminated mud at Lake Barrine, Northeast Australia

In a small (1 km²) crater lake in the Australian upland tropics (17°15′S, 145°38′E, 721 m a.s.l.), laminated mud has accumulated throughout the past 5 ka. It is limited to a central region below 50–67 m of water where it is protected by a monimolimnion. The contents of the laminae (e.g., total lake products, organic detritus, diatoms, pollen grains, vivianite crystals) distinguish two contrasting types, namely detritus-rich and detritus-poor. Judged against radiocarbon dates over long sequences, these couplets are not annual. Gravimetric, mineralogical and chemical observations on the mud, and on suspended organic and inorganic matter caught through several periods, indicate some diagenetic changes across the mud–water interface. Diatom analyses do not assist in relating mud type to source or period of origin. The most likely mechanism of lamination is that continuous deposition of clay, with small and varied detrital accompaniment, is periodically enhanced by greater detrital input. This occurs in some, but not all, periods of winter isothermy when ground temperatures fall to zero and below on several consecutive nights. This leads to the stirring of sediments in water shallower than 50 m and their relocation in the deeper meromictic zone. Fine variations in, e.g., diatom content, partly independent of lamination type, probably contain a wealth of detail about the lake’s environmental history.     

Spectroscopic and Chromatographic studies of organic carbon in Recent marine sediments from the Peruvian Upwelling Zone

Early diagenesis of organic matter in sediments from two sites in the Peruvian Upwelling Zone (12°05′S, 77°39′W; 15°17′S, 75°24′W) has been studied by observing changes in the total organic carbon and lipid and humin fractions with depth. Transformations of the total carbon and humin fraction have been characterized by conventional and time-dependent solid state NMR techniques, while lipid diagenesis was monitored by measuring the concentration of sterols in the same sedimentary horizons. Both the quantity of total sterols and the relative abundances of individual sterols vary with sampling location, suggesting a difference in the input of biomass to the sediments at the two sites. Total sterol concentrations decrease with depth at both sites, but the loss of sterols occurs much more slowly at the more anoxic northern site, where sedimentation rates and organic carbon contents are approximately twice those at the southern site. ¹³C-NMR spectra of the total organic carbon and the humin fraction suggest that humin-like compounds are an original component of the sedimentary biomass, and dipolar-dephased spectra of the humin residue indicate that diagenetic alterations of the humin fraction are occurring even in these very young sediments. Conventional and time-dependent spectroscopic data support the hypothesis that humin formation results from selective preservation of microbially-resistant biopolymers which are an original component of the sedimentary biomass combined with loss of certain labile compounds.     

Eclogite and pyroxenite xenoliths from off-craton kimberlites near the Kaapvaal Craton, South Africa

Mantle xenoliths brought to the surface by kimberlite magmas along the south-western margin of the Kaapvaal craton in South Africa can be subdivided into eclogites sensu stricto, kyanite eclogites and orthopyroxene eclogites, all containing omphacite, and garnet clinopyroxenites and garnet websterites characterised by diopside. Texturally, chemically (major elements) and thermally, we observe an evolution from garnet websterites (T_EG = 742–781 °C) towards garnet clinopyroxenites (T_EG = 715–830 °C) and to eclogites (T_EG = 707–1056 °C, mean value of 913 °C). Pressures calculated for orthopyroxene-bearing samples suggest upper mantle conditions of equilibration (P = 16–33 kb for the garnet websterites, 18 kb for a garnet clinopyroxenite and 23 kb for an opx-bearing eclogite). The overall geochemical similarity between the two groups of xenoliths (omphacite-bearing and diopside-bearing) as well as the similar trace element patterns of clinopyroxenes and garnet suggest a common origin for these rocks. Recently acquired oxygen isotope data on garnet (δ¹⁸O_gnt = 5.25–6.78 ‰ for eclogites, δ¹⁸O_gnt = 5.24–7.03 ‰ for garnet clinopyroxenites) yield values ranging from typical mantle values to other interpreted as resulting from low-temperature alteration or precursors sea-floor basalts and associated rocks. These rocks could then represent former magmatic oceanic rocks that crystallised from a same parental magma as plagioclase free diopside-bearing and plagioclase-bearing crustal rocks. During subduction, these oceanic rock protoliths equilibrated at mantle depth, with the plagioclase-bearing rocks converting to omphacite and garnet-bearing lithologies (eclogites sensu largo), whereas the plagioclase-free diopside-bearing rocks converted to diopside and garnet-bearing lithologies (garnet websterites and garnet clinopyroxenites).