The postglacial history of three Picea species in New England, USA

Given the difficulty of separating the three Picea species—P. glauca, P. mariana, and P. rubens (white, black, and red spruce)—in the pollen record, little is known about their unique histories in eastern North America following deglaciation. Here we report the first use of a classification tree analysis (CART) to distinguish pollen grains of these species. It was successfully applied to fossil pollen from eight sites in Maine and one in Massachusetts. We focused on the late glacial/early Holocene (14,000 to 8000 cal yr B.P.) and the late Holocene (1400 cal yr B.P. to present)—the two key periods since deglaciation when Picea has been abundant in the region. The result shows a shift from a Picea forest of P. glauca and P. mariana in the late glacial to a forest of P. rubens and P. mariana in the late Holocene. The small number of P. rubens grains identified from the late glacial/early Holocene samples (<5%) suggests that that species was either absent or rare at most of the sites. The occurrence and distribution of the three species do not reveal any geographic or temporal trend during late glacial time, but the data suggest that they were distributed in local patches on the landscape. The results of this study indicate that the recent population expansion of Picea (1000 to 500 cal yr B.P.) was likely the first time since deglaciation that P. rubens was abundant in the region.     

Postglacial vegetation history of Mitkof Island, Alexander Archipelago, southeastern Alaska

An AMS radiocarbon-dated pollen record from a peat deposit on Mitkof Island, southeastern Alaska provides a vegetation history spanning ∼12,900 cal yr BP to the present. Late Wisconsin glaciers covered the entire island; deglaciation occurred > 15,400 cal yr BP. The earliest known vegetation to develop on the island (∼12,900 cal yr BP) was pine woodland (Pinus contorta) with alder (Alnus), sedges (Cyperaceae) and ferns (Polypodiaceae type). By ∼12,240 cal yr BP, Sitka spruce (Picea sitchensis) began to colonize the island while pine woodland declined. By ∼11,200 cal yr BP, mountain hemlock (Tsuga mertensiana) began to spread across the island. Sitka spruce-mountain hemlock forests dominated the lowland landscapes of the island until ∼10,180 cal yr BP, when western hemlock (Tsuga heterophylla) began to colonize, and soon became the dominant tree species. Rising percentages of pine, sedge, and sphagnum after ∼7100 cal yr BP may reflect an expansion of peat bog habitats as regional climate began to shift to cooler, wetter conditions. A decline in alders at that time suggests that coastal forests had spread into the island's uplands, replacing large areas of alder thickets. Cedars (Chamaecyparis nootkatensis, Thuja plicata) appeared on Mitkof Island during the late Holocene.     

The Role of One- and Two-Electron Transfer Reactions in Forming Thermodynamically Unstable Intermediates as Barriers in Multi-Electron Redox Reactions

In the aquatic geochemical literature, a redox half-reaction is normally written for a multi-electron process (n > 2); e.g., sulfide oxidation to sulfate. When coupling two multi-electron half-reactions, thermodynamic calculations indicate possible reactivity, and the coupled half-reactions are considered favorable even when there is a known barrier to reactivity. Thermodynamic calculations should be done for one or two-electron transfer steps and then compared with known reactivity to determine the rate controlling step in a reaction pathway. Here, thermodynamic calculations are presented for selected reactions for compounds of C, O, N, S, Fe, Mn and Cu. Calculations predict reactivity barriers and agree with one previous analysis showing the first step in reducing O₂ to O₂ ^? with Fe²⁺ and Mn²⁺ is rate limiting. Similar problems occur for the first electron transfer step in these metals reducing NO₃ ^?, but if reactive oxygen species form or if two-electron transfer steps with O atom transfer occur, reactivity becomes favorable. H₂S and NH₄ ⁺ oxidation in a one-electron transfer step by O₂ is also not favorable unless activation of oxygen can occur. H₂S oxidation by Cu²⁺, Fe(III) and Mn(III, IV) phases in two-electron transfer steps is favorable but not in one-electron steps indicating that (nano)particles with bands of orbitals are needed to accept two electrons from H₂S. NH₄ ⁺ oxidation by Fe(III) and Mn(III, IV) phases is generally not favorable for both one- and two-electron transfer steps, but their reaction with hydroxylamine and hydrazine to form N₂O and N₂, respectively, is favorable. The anammox reaction using hydroxylamine via nitrite reduction is the most favorable for NH₄ ⁺ oxidation. Other chemical processes including photosynthesis and chemosynthesis are considered for these element–element transformations.     

Influence of landscape position and vegetation on long-term weathering rates at the Hubbard Brook Experimental Forest, New Hampshire, USA

The spatial variability of long-term chemical weathering in a small watershed was examined to determine the effect of landscape position and vegetation. We sampled soils from forty-five soil pits within an 11.8-hectare watershed at the Hubbard Brook Experimental Forest, New Hampshire. The soil parent material is a relatively homogeneous glacial till deposited ∼14,000 years ago and is derived predominantly from granodiorite and pelitic schist. Conifers are abundant in the upper third of the watershed while the remaining portion is dominated by hardwoods. The average long-term chemical weathering rate in the watershed, calculated by the loss of base cations integrated over the soil profile, is 35 meq m⁻² yr⁻¹—similar to rates in other ∼10 to 15 ka old soils developed on granitic till in temperate climates. The present-day loss of base cations from the watershed, calculated by watershed mass balance, exceeds the long-term weathering rate, suggesting that the pool of exchangeable base cations in the soil is being diminished. Despite the homogeneity of the soil parent material in the watershed, long-term weathering rates decrease by a factor of two over a 260 m decrease in elevation. Estimated weathering rates of plagioclase, potassium feldspar and apatite are greater in the upper part of the watershed where conifers are abundant and glacial till is thin. The intra-watershed variability across this small area demonstrates the need for extensive sampling to obtain accurate watershed-wide estimates of long-term weathering rates.     

Torngat ultramafic lamprophyres and their relation to the North Atlantic Alkaline Province

Geological mapping and diamond exploration in northern Quebec and Labrador has revealed an undeformed ultramafic dyke swarm in the northern Torngat Mountains. The dyke rocks are dominated by an olivine-phlogopite mineralogy and contain varying amounts of primary carbonate. Their mineralogy, mineral compositional trends and the presence of typomorphic minerals (e.g. kimzeyitic garnet), indicate that these dykes comprise an ultramafic lamprophyre suite grading into carbonatite. Recognized rock varieties are aillikite, mela-aillikite and subordinate carbonatite. Carbonatite and aillikite have in common high carbonate content and a lack of clinopyroxene. In contrast, mela-aillikites are richer in mafic silicate minerals, in particular clinopyroxene and amphibole, and contain only small amounts of primary carbonate. The modal mineralogy and textures of the dyke varieties are gradational, indicating that they represent end-members in a compositional continuum.

The Torngat ultramafic lamprophyres are characterized by high but variable MgO (10–25 wt.%), CaO (5–20 wt.%), TiO₂ (3–10 wt.%) and K₂O (1–4 wt.%), but low SiO₂ (22–37 wt.%) and Al₂O₃ (2–6 wt.%). Higher SiO₂, Al₂O₃, Na₂O and lower CO₂ content distinguish the mela-aillikites from the aillikites. Whereas the bulk rock major and trace element concentrations of the aillikites and mela-aillikites overlap, there is no fractional crystallization relation between them. The major and trace element characteristics imply related parental magmas, with minor olivine and Cr-spinel fractionation accounting for intra-group variation.

The Torngat ultramafic lamprophyres have a Neoproterozoic age and are spatially and compositionally closely related with the Neoproterozoic ultramafic lamprophyres from central West Greenland. Ultramafic potassic-to-carbonatitic magmatism occurred in both eastern Laurentia and western Baltica during the Late Neoproterozoic. It can be inferred from the emplacement ages of the alkaline complexes and timing of Late Proterozoic processes in the North Atlantic region that this volatile-rich, deep-seated igneous activity was a distal effect of the breakup of Rodinia. This occurred during and/or after the rift-to-drift transition that led to the opening of the Iapetus Ocean.     

Mantle‐derived and crustal melts dichotomy in northern Greece: spatiotemporal and geodynamic implications

Two distinct groups of subduction‐related (orogenic) granitoid rocks, one Jurassic and the other Tertiary, occur in the area between the Vardar (Axios) Zone and the Rhodope Massif in northern Greece. The two groups of granitoids differ in many respects. The first group shows evolved geochemical characters, it is not associated with mafic facies, and evidence of magmatic interaction between mantle‐ and crustal‐derived melts is lacking. The second group has less evolved geochemical characters, it is associated with larger amount of mafic facies, and magmatic interaction processes between mantle‐derived and crustal melts are ubiquitous as evidenced by mafic microgranular enclaves and synplutonic dykes showing different enrichment in K₂O, Ti, and incompatible elements. This kind of magmatism can be attributed to the complex geodynamic evolution of the area. In particular, we suggest that two successive subduction events related to the closure of the Vardar and the Pindos oceans, respectively, occurred in the investigated area from Late Jurassic to Tertiary. We relate the genesis of Jurassic granitoids to the first subduction event, whereas Tertiary granitoids are associated with the second subduction. Fluids released by the two subducted slabs induced metasomatic processes generating a ‘leopard skin’ mantle wedge able to produce mafic melts ranging from typical calc‐alkaline to ultra‐potassic. Such melts interacted in various amounts with crustal calc‐alkaline anatectic melts to generate the wide spectrum of Tertiary granitoids occurring in the study area. Copyright © 2004 John Wiley & Sons, Ltd.     

Lower and Middle Ordovician conodonts of Laurentian affinity from blocks of limestone in the Rosroe Formation,South Mayo Trough,western Ireland and their palaeogeographic implication

The Middle Ordovician Rosroe Formation consists of some 1350 m of coarse, mainly siliciclastic to volcaniclastic sedimentary rocks, deposited in a submarine fan environment, and is restricted to the southern limb of the South Mayo Trough, western Ireland. Discrete allochthonous blocks, reaching 5 m in size, are present in the formation at several localities. Conodonts recovered from these blocks, collected from two separate locations, are of late Early and mid Mid Ordovician age. The conodonts have high conodont‐alteration indices (CAI 5) indicative of temperatures as high as 300^o to max. 480 °C; some found in the Lough Nafooey area have abnormally high indices (CAI 6), which correspond to temperatures of about 360^o to max. 550 °C. The oldest fauna is dominated by Periodon aff. aculeatus and characterized by Oepikodus evae typical of the Oepikodus evae Zone (Floian Stage; Stage Slices Fl2–3, Lower Ordovician). The younger conodont assemblage, characterized by Periodon macrodentatus associated with Oistodella pulchra, is referred to the P. macrodentatus conodont Biozone (lower Darriwilian; Stage Slices Dw1–2). The Rosroe conodont assemblages are of Laurentian affinity; comparable faunas are well known from several locations along the east to south‐eastern platform margin of Laurentia and the Notre Dame subzone of central Newfoundland, Canada. The faunal composition from the limestone blocks suggests a shelf edge to slope (or fringing carbonate) setting. The faunal assemblages are coeval with, respectively, the Tourmakeady Formation (Floian–Dapingian) and Srah Formation (Darriwilian) in the Tourmakeady Volcanic Group in the eastern part of the South Mayo Trough and probably are derived from the same or similar laterally equivalent short‐lived carbonate successions that accumulated at offshore ‘peri‐Laurentian’ islands, close to and along the Laurentian margin. During collapse of the carbonate system in the late Mid Ordovician, the blocks were transported down a steep slope and into deep‐water by debris flows, mixing with other rock types now found in the coarse polymict clastics of the Rosroe Formation. The faunas fill the stratigraphical ‘gap’ between the Lower Ordovician Lough Nafooey Volcanic Group and the upper Middle Ordovician Rosroe Formation in the South Mayo Trough and represent a brief interval conducive to carbonate accumulation in an otherwise siliciclastic‐ and volcaniclastic‐dominated sedimentary environment. Copyright © 2015 John Wiley & Sons, Ltd.     

Rutile occurrence and trace element behavior in medium-grade metasedimentary rocks: example from the Erzgebirge, Germany

Metamorphic textures in medium-grade (~500–550°C) metasedimentary rocks from the Erzgebirge give evidence of prograde rutile crystallization from ilmenite. Newly-crystallized grains occur as rutile-rich polycrystalline aggregates that pseudomorph the shape of the ilmenites. In-situ trace element data (EMP and SIMS) show that rutiles from the higher-grade samples record large scatter in Nb content and have Nb/Ti ratios higher than coexisting ilmenite. This behavior can be predicted using prograde rutile crystallization from ilmenite and indicates that rutiles are reequilibrating their chemistry with remaining ilmenites. On the contrary, rutiles from the lowest grade samples (~480°C) have Nb/Ti ratios that are similar to the ones in ilmenite. Hence, rutiles from these samples did not equilibrate their chemistry with remaining ilmenites. Our data suggest that temperature may be one of the main factors determining whether or not the elements are able to diffuse between the phases and, therefore, reequilibrate. Newly-crystallized rutiles yield temperatures (from ~500 to 630°C, Zr-in-rutile thermometry) that are in agreement with the metamorphic conditions previously determined for the studied rocks. In quartzites from the medium-grade domain (~530°C), inherited detrital rutile grains are detected. They are identified by their distinct chemical composition (high Zr and Nb contents) and textures (single grains surrounded by fine grained ilmenites). Preliminary calculation, based on grain size distribution of rutile in medium-grade metapelites and quartzites that occur in the studied area, show that rutiles derived from quartzites can be anticipated to dominate the detrital rutile population, even if quartzites are a minor component of the exposure.     

Characterization of permineralized kerogen from an Eocene fossil fern

The processes of organic maturation that occur during the permineralization of fossils and the detailed chemistry of the resulting products are incompletely understood. Primary among such processes is the geochemical alteration of biological matter to produce kerogen, such as that which comprises the cell walls of the fossils studied here: essentially unmetamorphosed, Eocene plant axes (specimens of the fossil fern Dennstaedtiopsis aerenchymata cellularly permineralized in cherts of the Clarno Formation of Oregon and the Allenby Formation of British Columbia). The composition and molecular structure of the kerogen that comprises the cell walls of such axes were analyzed using ultraviolet Raman spectroscopy (UV–Raman), solid state ¹³C nuclear magnetic resonance spectroscopy (¹³C NMR) and pyrolysis–gas chromatography–mass spectrometry (py–GC–MS).Cellularly well-preserved fern axes from both geologic units exhibit similar overall molecular structure, being composed primarily of networks of aromatic rings and polyene chains that, unlike more mature kerogens, lack large polycyclic aromatic hydrocarbon (PAH) constituents. The cell walls of the Allenby Formation specimens are, however, less altered than those of the Clarno chert, exhibiting more prevalent oxygen-containing and alkyl functional groups and comprising a greater fraction of rock mass.The study represents the first demonstration of the effectiveness (and limitations) of the combined use of UV–Raman, ¹³C NMR and py–GC–MS for the analysis of the kerogenous cell walls of chert-permineralized vascular plants.     

Rapid incorporation of lipids into macromolecules during experimental decay of invertebrates: Initiation of geopolymer formation

Diagenetic alteration is critical for the preservation of fossil cuticles of plant and animal origin and to the formation of kerogen. The process takes place over millions of years, but the stage at which it is initiated is not known. Laboratory decay experiments were carried out on shrimps, scorpions and cockroaches to monitor changes in the chitin–protein of the arthropod cuticle and associated lipids. The cockroach and scorpion exoskeleton remained largely unaltered morphologically, but the shrimp experienced rapid decomposition within a month, which progressed through the 44 week duration of the experiment as revealed using electron microscopy. Mass spectrometry and ¹³C NMR (nuclear magnetic resonance) spectroscopy revealed the association of an n-alkyl component with labile lipids, such as fatty acids with up to 24 carbon atoms, which were incorporated into the decaying macromolecule. The scorpion and cockroach cuticle did not reveal the incorporation of additional lipids, indicating that decay is important in initiating in situ lipid association. This experiment provides evidence that lipids can become associated with carbohydrate and proteinaceous macromolecules during the very early stages of decay, representing the first stage in the transformation process that contributes to the aliphatic rich composition ubiquitous in organic fossils and kerogen.