Paleoclimatic implications of glacial and postglacial refugia for Pinus pumila in western Beringia

Palynological results from Julietta Lake currently provide the most direct evidence to support the existence of a glacial refugium for Pinus pumila in mountains of southwestern Beringia. Both percentages and accumulation rates indicate the evergreen shrub survived until at least ∼ 19,000 ¹⁴C yr BP in the Upper Kolyma region. Percentage data suggest numbers dwindled into the late glaciation, whereas pollen accumulation rates point towards a more rapid demise shortly after ∼ 19,000 ¹⁴C yr BP. Pinus pumila did not re-establish in any great numbers until ∼ 8100 ¹⁴C yr BP, despite the local presence ∼ 9800 ¹⁴C yr BP of Larixdahurica, which shares similar summer temperature requirements. The postglacial thermal maximum (in Beringia ∼ 11,000-9000 ¹⁴C yr BP) provided Pinus pumila shrubs with equally harsh albeit different conditions for survival than those present during the LGM. Regional records indicate that in this time of maximum warmth Pinus pumila likely sheltered in a second, lower-elevation refugium. Paleoclimatic models and modern ecology suggest that shifts in the nature of seasonal transitions and not only seasonal extremes have played important roles in the history of Pinus pumila over the last ∼ 21,000 ¹⁴C yr BP.     

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.     

Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C₁–C₄, CO₂]). Molecular ratios of LMWHC (C₁/[C₂ + C₃] > 1000) and stable isotopic compositions of methane (δ¹³C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C₁/C₂₊ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C₁–C₄, CO₂]) relative to the other gas types and the virtual lack of ¹⁴C–CH₄ indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C₁–C₄, CO₂)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of ¹⁴C–CH₄ (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.     

Geochemical processes controlling arsenic mobility in groundwater: A case study of arsenic mobilization and natural attenuation

The behavior of As in the subsurface environment was examined along a transect of groundwater monitoring wells at a Superfund site, where enhanced reductive dechlorination (ERD) is being used for the remediation of groundwater contaminated with chlorinated solvents. The transect was installed parallel to the groundwater flow direction through the treatment area. The ERD technology involves the injection of organic C (OC) to stimulate in situ microbial dechlorination processes. A secondary effect of the ERD treatment at this site, however, is the mobilization of As, as well as Fe and Mn. The concentrations of these elements are low in groundwater collected upgradient of the ERD treatment area, indicating that, in the absence of the injected OC, the As that occurs naturally in the sediment is relatively immobile. Batch experiments conducted using sediments from the site inoculated with an Fe(III)- and As(V)-reducing bacterium and amended with lactate resulted in mobilization of As, Fe and Mn, suggesting that As mobilization in the field is due to microbial processes.     

Simultaneous quantification of dissolved organic carbon fractions and copper complexation using solid-phase extraction

Trace metal cycling in natural waters is highly influenced by the amount and type of dissolved organic C (DOC). Although determining individual species of DOC is unrealistic, there has been success in classifying DOC by determining operationally defined fractions. However, current fractionation schemes do not allow for the simultaneous quantification of associated trace metals. Using operational classifications, a scheme was developed to fractionate DOC based on a set of seven solid-phase extraction (SPE) cartridges. The cartridges isolated fractions based on a range of specific mechanisms thought to be responsible for DOC aggregation in solution, as well as molecular weight. The method was evaluated to determine if it can identify differences in DOC characteristics, including differences in Cu–DOC complexation. Results are that: (1) cartridge blanks were low for both DOC and Cu, (2) differences are observed in the distribution of DOC amongst the fractions from various sources that are consistent with what is known about the DOC materials and the mechanisms operative for each cartridge, (3) when present as a free cation, Cu was not retained by non-cationic cartridges allowing the method to be used to assess Cu binding, (4) the capability of the method to provide quantitative assessment of Cu–DOC complexation was demonstrated for a variety of DOC standards, (5) Cu was found to preferentially bind with high molecular weight fractions of DOC, and (6) estimated partitioning coefficients and conditional binding constants for Cu were similar to those reported elsewhere. The method developed describes DOC characteristics based on specific bonding mechanisms (hydrogen, donor–acceptor, London dispersion, and ionic bonding) while simultaneously quantifying Cu–DOC complexation. The method provides researchers a means of describing not only the extent of DOC complexation but also how that complex will be behave in natural waters.     

Interannual and long-term variation in the nearshore fish community of the mesohaline Hudson River estuary

The detection of long-term shifts in species composition and spatial structuring of aquatic communities may be obscured by high levels of interannual variation. Estuarine fish communities are likely to exhibit high levels of variation owing to the influence of riverine forcing and the importance of anadromous and transient species, whose abundances may not be locally controlled. We describe patterns of interannual variation and long-term shifts in the nearshore fish community of the mesohaline Hudson River estuary based on 21 yr of beach seine sampling conducted annually between late August and mid November. Of the 60 species encountered, the most abundant were Atlantic silversides (Menidia menidia), striped bass (Morone saxatilis), white perch (Morone americana), American shad (Alosa sapidissima), and blueback herring (Alosa aestivalis). Relationships between annual community composition and seasonal flow and temperature regimes were examined with canonical correspondence analysis. Annual variation was most closely correlated with river flows in the 3-mo period preceding fish sampling, indicating a persistent effect of environmental conditions on community structure. Despite significant interannual variation in composition, longer-term trends in community structure were observed. These included declines in catch rates of freshwater and estuarine species and a dramatic increase in the catch of Atlantic silversides, an annual marine species. Associated with these changes were declines in community diversity and increased compositional variation. These results indicate that analyses of temporal changes in community structure need to account for the multiple time scales under which forcing factors and community composition vary.     

Precise/ Small Sample Size Determinations of Lithium Isotopic Compositions of Geological Reference Materials and Modern Seawater by MC-ICP-MS

The Li isotope ratios of four international rock reference materials, USGS BHVO-2, GSJ JB-2, JG-2, JA-1 and modern seawater (Mediterranean, Pacific and North Atlantic) were determined using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). These reference materials of natural samples were chosen to span a considerable range in Li isotope ratios and cover several different matrices in order to provide a useful benchmark for future studies. Our new analytical technique achieves significantly higher precision and reproducibility (< ± O.3%o 2s) than previous methods, with the additional advantage of requiring very low sample masses of ca . 2 ng of Li.     

Petrology of Al- and Cr-rich ophiolitic chromitites from the Muğla,SW Turkey: implications from composition of chromite,solid inclusions of platinum-group mineral,silicate, and base-metal mineral,and Os-isotope geochemistry

Ultramafic rocks around the city of Muğla in SW Turkey are represented by mantle peridotites depleted to various degrees, ranging from cpx-rich harzburgites to depleted harzburgite and dunite. Cpx-rich harzburgites are thought to be the residua left after extraction of MORB-type basalt, from which high-Al chromitite [49.2 < Cr# = 100 × Cr/(Cr + Al) < 53.5] crystallised with a higher proportion of ¹⁸⁷Os/¹⁸⁸Os (average of 0.1361). However, depleted harzburgites are assumed to be the residua left after extraction of hydrous boninitic melt produced by second stage partial melting of already depleted mantle due to a subducting slab, from which high-Cr chromitites (64.2 < Cr# < 85.9) with lower and heterogeneous ¹⁸⁷Os/¹⁸⁸Os ratio (average of 0.1324) were crystallised as a result of melt–rock interaction in a supra-subduction environment. Dunites around the chromite deposits are considered to be the product of melt–peridotite interaction. Most of the chromitites contain high-Cr chromite and display enrichment in IPGE (Os, Ir, Ru) over PPGE (Rh, Pt, Pd), with PGE concentrations between 61 and 1,305 ppb. Consistently, laurite-erlichmanite series minerals with various Os concentrations are found to be the most abundant PGM inclusions in chromite. Os–Ir–Ru alloy, irarsite, and kashinite, as well as Pt–Fe alloy and Pt-oxide, which are not common in ophiolitic chromitites, were also detected as magmatic PGM inclusions. Pentlandite, millerite, and, rarely heazlewoodite form the magmatic inclusions of base-metal sulphide. The presence of olivine and clinopyroxene, as well as hydrous silicate inclusions such as amphibole and phlogopite, in high-Cr chromitite supports the idea that high-Cr chromitites were formed in a supra-subduction environment.     

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.