Constraining Holocene sea‐surface conditions in the south‐western Black Sea using dinoflagellate cysts

This paper presents two dinoflagellate cyst records from the south‐western shelf of the Black Sea. A new site, MAR05‐13, from the Sakarya shelf is described and placed into context with site MAR02‐45, ～250 km distant on the Thracian shelf. The records provide a centennial resolution of surface water conditions in the Holocene. Analysis of the data suggests that the surface salinity of the south‐western shelf increased in a gradual and progressive manner. In the period ～11 000–9000 cal a BP the assemblages suggest surface‐water salinities between 7–13 psu. The initial arrival of euryhaline species, ～8100 cal a BP, is linked to the reconnection of the Black Sea and Marmara Sea. The suggested surface water changes related to the reconnection took approximately 1000 years. Following this initial change in assemblages, a further increase in the number of euryhaline species is noted between 5000 and 4000 cal a BP. This is linked to the establishment of more saline surface‐water conditions, close to present‐day values. The record for MAR05‐13 highlights the complexity of the changes in cyst assemblages during the mid‐Holocene. Copyright © 2012 John Wiley & Sons, Ltd.     

Examining potential genetic links between Jurassic porphyry Cu–Au ± Mo and epithermal Au ± Ag mineralization in the Toodoggone district of North-Central British Columbia,Canada

The Toodoggone district comprises Upper Triassic to Lower Jurassic Hazelton Group Toodoggone Formation volcanic and sedimentary rocks, which unconformably overlie submarine island-arc volcanic and sedimentary rocks of the Lower Permian Asitka Group and Middle Triassic Takla Group, some of which are intruded by Upper Triassic to Lower Jurassic plutons and dikes of the Black Lake suite. Although plutonism occurred episodically from ca. 218 to 191 Ma, the largest porphyry Cu–Au ± Mo systems formed from ca. 202 to 197 Ma, with minor mineralization occurring from ca. 197 to 194 Ma. Porphyry-style mineralization is hosted by small-volume (<1 km³), single-phase, porphyritic igneous stocks or dikes that have high-K calc-alkaline compositions and are comparable with volcanic-arc granites. The Fin porphyry Cu–Au–Mo deposit is anomalous in that it is 16 m.y. older than any other porphyry Cu–Au ± Mo occurrence in the district and has lower REEs. All porphyry systems are spatially restricted to exposed Asitka and Takla Group basement rocks, and rarely, the lowest member of the Hazelton Group (i.e., the ca. 201 Ma Duncan Member). The basement rocks to intrusions are best exposed in the southern half of the district, where high rates of erosion and uplift have resulted in their preferential exposure. In contrast, low- and high-sulfidation epithermal systems are more numerous in the northern half of the district, where the overlying Hazelton Group rocks dominate exposures. Cogenetic porphyry systems might also exist in the northern areas; however, if they are present, they are likely to be buried deeply beneath Hazelton Group rocks. High-sulfidation epithermal systems formed at ca. 201 to 182 Ma, whereas low-sulfidation systems were active at ca. 192 to 162 Ma. Amongst the studied epithermal systems, the Baker low-sulfidation epithermal deposit displays the strongest demonstrable genetic link with magmatic fluids; fluid inclusion studies demonstrate that its ore fluids were hot (>468°C), saline, and deposited metals at deep crustal depths (>2 km). Sulfur, C, O, and Pb isotope data confirm the involvement of a magmatic fluid, but also suggest that the ore fluid interacted with Asitka and Takla Group country rocks prior to metal deposition. In contrast, in the Shasta, Lawyers, and Griz-Sickle low-sulfidation epithermal systems, there is no clear association with magmatic fluids. Instead, their fluid inclusion data indicate the involvement of low-temperature (175 to 335°C), low-salinity (1 to 11 equiv. wt.% NaCl) fluids that deposited metals at shallow depths (<850 m). Their isotope (i.e., O, H, Pb) data suggest interaction between meteoric and/or metamorphic ore fluids with basement country rocks.     

Uranium speciation and stability after reductive immobilization in aquifer sediments

It has generally been assumed that the bioreduction of hexavalent uranium in groundwater systems will result in the precipitation of immobile uraninite (UO₂). In order to explore the form and stability of uranium immobilized under these conditions, we introduced lactate (15 mM for 3 months) into flow-through columns containing sediments derived from a former uranium-processing site at Old Rifle, CO. This resulted in metal-reducing conditions as evidenced by concurrent uranium uptake and iron release. Despite initial augmentation with Shewanella oneidensis, bacteria belonging to the phylum Firmicutes dominated the biostimulated columns. The immobilization of uranium (∼1 mmol U per kg sediment) enabled analysis by X-ray absorption spectroscopy (XAS). Tetravalent uranium associated with these sediments did not have spectroscopic signatures representative of U-U shells or crystalline UO₂. Analysis by microfocused XAS revealed concentrated micrometer regions of solid U(IV) that had spectroscopic signatures consistent with bulk analyses and a poor proximal correlation (μm scale resolution) between U and Fe. A plausible explanation, supported by biogeochemical conditions and spectral interpretations, is uranium association with phosphoryl moieties found in biomass; hence implicating direct enzymatic uranium reduction. After the immobilization phase, two months of in situ exposure to oxic influent did not result in substantial uranium remobilization. Ex situ flow-through experiments demonstrated more rapid uranium mobilization than observed in column oxidation studies and indicated that sediment-associated U(IV) is more mobile than biogenic UO₂. This work suggests that in situ uranium bioimmobilization studies and subsurface modeling parameters should be expanded to account for non-uraninite U(IV) species associated with biomass.     

The effects of two benthic chamber stirring systems on the diffusive boundary layer,oxygen flux,and passive flow through model macrofauna burrows

Diffusive boundary layers (DBL), sediment oxygen flux, and natural passive flow through model macrofauna burrows were compared in two benthic chambers: one with a conventional rotational stirrer and the other with a two-dimensional flow diffuser system. Oxygen microprobe profiles showed that at similar velocities the mean diffusive boundary layer (DBL) thickness induced by a conventional rotor stirrer (453±118 μm) was not significantly different to that produced by the diffuser system (403±53 μm). The rotor produced twice as much DBL spatial variability (coefficient of variation 27%) as the diffuser (CV 11%). Variability between the rotor system’s DBL transect replicates was also two times greater (average CV of 22%) compared to the diffuser (CV 14%). At equivalent stirring speeds over experimental sediments, mean O₂ consumption rates were also not significantly different between the two systems. The diffuser induced consistently greater (16–37%) passive Bernoullian flow through model macrofauna borrows irrespective of the position of inhalant-exhalent openings. The rotor stimulated anomalous burrow flow regimes over a greater area of the chamber floor (36%) compared to the diffuser (23%). Depending on vent orientation the rotor was shown to reverse (exhalent to inhalant) burrow flow regimes in the central 9% of the chamber floor. This artifact of radial pressure and velocity differentials may have severe implications for tube dwelling infauna that rely on unidirectional flow. The diffuser system more closely mimicked natural two-dimensional water flow over the sediment surface and structures therein and is likely to give more representative results when measuring benthic processes within incubation devices.     

MTBE, TBA, and TAME Attenuation in Diverse Hyporheic Zones

Groundwater contamination by fuel-related compounds such as the fuel oxygenates methyl tert -butyl ether (MTBE), tert -butyl alcohol (TBA), and tert -amyl methyl ether (TAME) presents a significant issue to managers and consumers of groundwater and surface water that receives groundwater discharge. Four sites were investigated on Long Island, New York, characterized by groundwater contaminated with gasoline and fuel oxygenates that ultimately discharge to fresh, brackish, or saline surface water. For each site, contaminated groundwater discharge zones were delineated using pore water geochemistry data from 15 feet (4.5 m) beneath the bottom of the surface water body in the hyporheic zone and seepage-meter tests were conducted to measure discharge rates. These data when combined indicate that MTBE, TBA, and TAME concentrations in groundwater discharge in a 5-foot (1.5-m) thick section of the hyporheic zone were attenuated between 34% and 95%, in contrast to immeasurable attenuation in the shallow aquifer during contaminant transport between 0.1 and 1.5 miles (0.1 to 2.4 km). The attenuation observed in the hyporheic zone occurred primarily by physical processes such as mixing of groundwater and surface water. Biodegradation also occurred as confirmed in laboratory microcosms by the mineralization of U- ¹⁴C-MTBE and U-¹⁴C-TBA to ¹⁴CO₂ and the novel biodegradation of U- ¹⁴C-TAME to ¹⁴CO₂ under oxic and anoxic conditions. The implication of fuel oxygenate attenuation observed in diverse hyporheic zones suggests an assessment of the hyporheic zone attenuation potential (HZAP) merits inclusion as part of site assessment strategies associated with monitored or engineered attenuation.     

Northwest Africa 773: lunar mare breccia with a shallow-formed olivine-cumulate component, inferred very-low-Ti (VLT) heritage, and a KREEP connection

Lunar meteorite Northwest Africa 773 (herein referred to as NWA773) is a breccia composed predominantly of mafic volcanic components, including a prominent igneous clast lithology. The clast lithology is an olivine-gabbro cumulate, which, on the basis of mineral and bulk compositions, is a hypabyssal igneous rock related compositionally to volcanic components in the meteorite. The olivine-gabbro lithology exhibits cumulus textures and, in our largest section of it, includes some 48% olivine (Fo₆₄ to Fo₇₀, average Fo₆₇), 27% pigeonite (En₆₀Fs₂₄Wo₁₆ to En₆₇Fs₂₇Wo₆), 11% augite (En₅₀Fs₁₇Wo₃₃ to En₄₇Fs₁₃Wo₄₀), 2% orthopyroxene (En₇₀Fs₂₆Wo₄), 11% plagioclase (An₈₀ to An₉₄), and trace barian K-feldspar, ilmenite, Cr-spinel, RE-merrillite, troilite, and Fe-Ni metal. The Mg/Fe ratios of the mafic silicates indicate equilibration of Fe and Mg; however, the silicates retain compositional variations in minor and trace elements that are consistent with intercumulus crystallization. Accessory mineralogy reflects crystallization of late-stage residual melt. Both lithologies (breccia and olivine cumulate) of the meteorite have very-low-Ti (VLT) major-element compositions, but with an unusual trace-element signature compared to most lunar VLT volcanic compositions, i.e., relative enrichment in light REE and large-ion-lithophile elements, and greater depletion in Eu than almost all other known lunar volcanic rocks. The calculated composition of the melt that was in equilibrium with pyroxene and plagioclase of the cumulate lithology exhibits a KREEP-like REE pattern, but at lower concentrations. Melt of a composition calculated to have been in equilibrium with the cumulate assemblage, plus excess olivine, yields a major-element composition that is similar to known green volcanic glasses. One volcanic glass type from Apollo 14 in particular, green glass B, type 1, has a very low Ti concentration and REE characteristics, including extremely low Eu concentration, that make it a candidate parent melt for the olivine-gabbro cumulate. We infer an origin for the parent melt of NWA773 volcanic components by assimilation of a trace-element-rich partial or residual melt by a magnesian, VLT magma deep in the lunar crust or in the mantle prior to transportation to the near-surface, accumulation of olivine and pyroxene in a shallow chamber, eruption onto a volcanic surface, and incorporation of components into local, predominantly volcanic regolith, prior to impact mixing of the volcanic terrain and related hypabyssal setting, and ejection from the surface of the Moon. Volcanic components such as these probably occur in the Oceanus Procellarum region near the site of origin of the green volcanic glasses found in the Apollo 14 regolith.     

TAZ-level variation in work trip mode choice between 1990 and 2000 and the presence of rail transit

Rail transit continues to be a popular alternative for cities as a tool for alleviating automobile congestion and for redeveloping areas into transit and pedestrian-friendly environments. Ideally, rail transit will draw trips away from cars, but the quantitative work that tests this notion has often been either case studies of neighborhoods, in which conclusions are tough to generalize, or citywide comparisons where important spatial variation is lost in aggregation. This study seeks to narrow this gap in the research by using multivariate analysis of covariance to isolate the effect of covariates and cities on changes in work trip mode choice at the traffic analysis zone (TAZ) level for nine cities between 1990 and 2000. The results suggest differences by city in the change at the TAZ level of the proportion of people driving alone and taking transit. Increases in transit usage were associated with cities that built rail transit, while increases in automobile commuting and decreases in transit usage were associated with cities that did not.     

The Contribution of Groundwater Discharge to Nutrient Exports from a Coastal Catchment: Post-Flood Seepage Increases Estuarine N/P Ratios

Four months of daily nutrient and radon (a natural groundwater tracer) observations at the outlet of a heavily drained coastal wetland illustrated how episodic floods and diffuse groundwater seepage influence the biogeochemistry of a sub-tropical estuary (Richmond River, New South Wales, Australia). Our observations downstream of the Tuckean Swamp (an acid sulphate soil floodplain) covered a dry stage, a flood triggered by a 213-mm rain event and a post-flood stage when surface water chemistry was dominated by groundwater discharge. Significant correlations were found between radon and ammonium and N/P ratios and between radon and dissolved organic nitrogen (DON) during the post-flood stage. While the flood lasted for 14?% of the time of the surface water time series, it accounted for 18?% of NH₄, 32?% of NO _x , 66?% of DON, 58?% of PO₄ and 55?% of dissolved organic phosphorus (DOP) catchment exports. Over the 4-month study period, groundwater fluxes of 35.0, 3.6, 36.3, 0.5 and 0.7?mmol?m^?2?day^?1 for NH₄, NO _x , DON, PO₄ and DOP, respectively, were estimated. The groundwater contribution to the total surface water catchment exports was nearly 100?% for ammonium, and <20?% for the other nutrients. Post-flood groundwater seepage shifted the system from a DON to a dissolved inorganic N-dominated system and doubled N/P ratios in surface waters. We hypothesise that the Richmond River Estuary N/P ratios may reflect a widespread trend of tidal rivers and estuaries becoming more groundwater-dominated and phosphorus-limited as coastal wetlands are drained for agriculture, grazing and development.     

15,000-yr pollen record of vegetation change in the high altitude tropical Andes at Laguna Verde Alta, Venezuela

Pollen analysis of sediments from a high-altitude (4215 m), Neotropical (9°N) Andean lake was conducted in order to reconstruct local and regional vegetation dynamics since deglaciation. Although deglaciation commenced 15,500 cal yr B.P., the area around the Laguna Verde Alta (LVA) remained a periglacial desert, practically unvegetated, until about 11,000 cal yr B.P. At this time, a lycopod assemblage bearing no modern analog colonized the superpáramo. Although this community persisted until 6000 cal yr B.P., it began to decline somewhat earlier, in synchrony with cooling following the Holocene thermal maximum of the Northern Hemisphere. At this time, the pioneer assemblage was replaced by a low-diversity superpáramo community that became established 9000 cal yr B.P. This replacement coincides with regional declines in temperature and/or available moisture. Modern, more diverse superpáramo assemblages were not established until 4600 cal yr B.P., and were accompanied by a dramatic decline in Alnus, probably the result of factors associated with climate, humans, or both. Pollen influx from upper Andean forests is remarkably higher than expected during the Late Glacial and early to middle Holocene, especially between 14,000 and 12,600 cal yr B.P., when unparalleled high values are recorded. We propose that intensification of upslope orographic winds transported lower elevation forest pollen to the superpáramo, causing the apparent increase in tree pollen at high altitude. The association between increased forest pollen and summer insolation at this time suggests a causal link; however, further work is needed to clarify this relationship.