Determination of Precise and Accurate 51V/50V Isotope Ratios by Multi‐Collector ICP‐MS,Part 2: Isotopic Composition of Six Reference Materials plus the Allende Chondrite and Verification Tests

We present the first measurements of vanadium (V) stable isotopes for six reference materials – USGS PCC‐1, BHVO‐2, BCR‐2, BIR‐1a, GSP‐2 and AGV‐2 – plus the widely available carbonaceous chondrite Allende. We present standard addition and matrix spiking tests to assess the robustness and reproducibility of our data. Standard addition utilised an enriched ⁵⁰V solution designated VISSOX (Vanadium Isotope Standard Solution OXford). We further assessed the veracity of the method by spiking collected sample matrices with the same amount of a V standard solution, whose isotopic composition was defined as 0‰. Standard addition and matrix spiking tests recorded no appreciable artificial isotope fractionation. We estimate that the best currently attainable long‐term reproducibility of stable ⁵¹V/⁵⁰V isotope measurements in complex matrices is 0.15‰, which is in the same order as the reproducibility achievable with standard solutions. Finally, a large range of ～ 1.2‰ in stable V isotopic composition was documented, with ～ 0.5‰ of that variation in high temperature igneous materials alone. The range and resolving power of V stable isotopes, with respect to igneous material, compared favourably with the magnitude of fractionation reported for other non‐traditional stable isotope systems, which bodes well for the utility of this new system.     

The SOLAS air-sea gas exchange experiment (SAGE) 2004

The SOLAS air-sea gas exchange experiment (SAGE) was a multiple-objective study investigating gas-transfer processes and the influence of iron fertilisation on biologically driven gas exchange in high-nitrate low-silicic acid low-chlorophyll (HNLSiLC) Sub-Antarctic waters characteristic of the expansive subpolar zone of the southern oceans. This paper provides a general introduction and summary of the main experimental findings. The release site was selected from a pre-voyage desktop study of environmental parameters to be in the south-west Bounty Trough (46.5°S 172.5°E) to the south-east of New Zealand and the experiment was conducted between mid-March and mid-April 2004. In common with other mesoscale iron addition experiments (FeAX’s), SAGE was designed as a Lagrangian study, quantifying key biological and physical drivers influencing the air-sea gas exchange processes of CO₂, DMS and other biogenic gases associated with an iron-induced phytoplankton bloom. A dual tracer SF₆/³He release enabled quantification of both the lateral evolution of a labelled volume (patch) of ocean and the air-sea tracer exchange at tenths of kilometer scale, in conjunction with the iron fertilisation. Estimates from the dual-tracer experiment found a quadratic dependency of the gas exchange coefficient on windspeed that is widely applicable and describe air-sea gas exchange in strong wind regimes. Within the patch, local and micrometeorological gas exchange process studies (100 m scale) and physical variables such as near-surface turbulence, temperature microstructure at the interface, wave properties and windspeed were quantified to further assist the development of gas exchange models for high-wind environments.There was a significant increase in the photosynthetic competence (F_v/F_m) of resident phytoplankton within the first day following iron addition, but in contrast to other FeAX’s, rates of net primary production and column-integrated chlorophyll a concentrations had only doubled relative to the unfertilised surrounding waters by the end of the experiment. After 15 days and four iron additions totalling 1.1 ton Fe²⁺, this was a very modest response compared to other mesoscale iron enrichment experiments. An investigation of the factors limiting bloom development considered co-limitation by light and other nutrients, the phytoplankton seed-stock and grazing regulation. Whilst incident light levels and the initial Si:N ratio were the lowest recorded in all FeAXs to date, there was only a small seed-stock of diatoms (less than 1% of biomass) and the main response to iron addition was by the picophytoplankton. A high rate of dilution of the fertilised patch relative to phytoplankton growth rate, the greater than expected depth of the surface mixed layer and microzooplankton grazing were all considered as factors that prevented significant biomass accumulation. In line with the limited response, the enhanced biological draw-down of pCO₂ was small and masked by a general increase in pCO₂ due to mixing with higher pCO₂ waters. The DMS precursor DMSP was kept in check through grazing activity and in contrast to most FeAX’s dissolved dimethylsulfide (DMS) concentration declined through the experiment. SAGE is an important low-end member in the range of responses to iron addition in FeAX’s. In the context of iron fertilisation as a geoengineering tool for atmospheric CO₂ removal, SAGE has clearly demonstrated that a significant proportion of the low iron ocean may not produce a phytoplankton bloom in response to iron addition.     

Control of the phytoplankton response during the SAGE experiment: A synthesis

The SOLAS Air-Sea Gas Exchange (SAGE) experiment was conducted in Sub-Antarctic waters off the east coast of the South Island of New Zealand in the late summer of 2004. This mesoscale iron enrichment experiment was unique in that chlorophyll a (chl a) and primary productivity were only 2× OUT stations values toward the end of the experiment and this enhancement was due to increased activity of non-diatomaceous species. In addition, this enhancement in activity appeared to occur without a significant build up of particulate organic carbon. Picoeukaryotes (<2 ??m) were the only members of the phytoplankton assemblage that showed a statistically significant increase, a doubling in biomass. To better understand the controls of phytoplankton growth and biomass, we present results from a series of on-deck perturbation experiments conducted during SAGE. Results suggest that the pico-dominated phytoplankton assemblage was only weakly inhibited by iron. Diatoms with high growth rates comprised a small (<1%) fraction of the phytoplankton assemblage, were likely iron limited, and potentially further limited by silicic acid and therefore did not significantly contribute to bloom dynamics. On deck experiments and comparison of SAGE with other iron addition experiments suggested that neither light availability nor deep mixed layers limited phytoplankton growth. Although no substantial increase in grazing rate or specific phytoplankton growth rate was detected, microzooplankton biomass doubled over SAGE as a result of an increase in cell size. The importance of microzooplankton grazing was highlighted by the fact that they were capable of consuming 15-49% of the total phytoplankton production per day. Removal was highest on eukaryotic picophytoplankton production with a mean value of 72% (29-143%). Patch dilution played an important role during SAGE; the mean patch net algal growth:dilution rate, 1.13 (0.4-2.2) was the lowest reported for a mesoscale iron enrichment experiment. Phytoplankton biomass, estimated by chlorophyll a, only accumulated when phytoplankton growth exceeded grazing and when net algal growth exceeded dilution rate. The SAGE results highlight the function of the smallest phytoplankton size fraction described by the ecumenical Iron Hypothesis. Thus, adding iron to HNLC-low silicic acid regions during certain times of the year may simply transfer more carbon through the microbial food web. A primary implication of this study is that any iron-mediated gain in fixed carbon with this set of environmental conditions has a high probability of being recycled in surface waters.     

Microbial Diversity of the Hypersaline Sidi Ameur and Himalatt Salt Lakes of the Algerian Sahara

Microbial populations within hypersaline lakes often exhibit high activities of photosynthesis, dissimilatory sulphate reduction and other processes and, thus, can have profound impacts on biogeochemical cycles of carbon, nitrogen, sulphur and other important elements within arid lands. To further understand these types of ecosystems, the physicochemical and biological properties of Sidi Ameur and Himalatt Salt Lakes in the Algerian Sahara were examined and compared. Both lakes were relatively neutral in pH (7.2-7.4) and high in salt, at 12% and 20% (w/v) salinity for Himalatt and Sidi Ameur Lakes, respectively, with dominant ions of sodium and chloride. The community compositions of microbes from all three domains (Bacteria, Archaea and Eukarya) were surveyed through the use of 16S and 18S ribosomal gene amplification and clone library clustering using amplified ribosomal DNA restriction analysis (ARDRA) in conjunction with DNA sequencing and analysis. A high level of microbial diversity, particularly among the bacteria of the Himalatt Salt Lake and archaea of Sidi Ameur Lake, was found within these environments. Representatives from all known halophilic bacterial phyla as well as 6 different genera of halophilic archaea were identified. Moreover, several apparently novel phylotypes among both archaea and bacteria were revealed.     

Hydration of mantle olivine under variable water and oxygen fugacity conditions

The incorporation of H into olivine is influenced by a significant number of thermodynamic variables (pressure, temperature, oxygen fugacity, etc.). Given the strong influence that H has on the solidus temperature and rheological behavior of mantle peridotite, it is necessary to determine its solubility in olivine over the range of conditions found in the upper mantle. This study presents results from hydration experiments carried out to determine the effects of pressure, temperature, and the fugacities of H₂O and O₂ on H solubility in San Carlos olivine at upper mantle conditions. Experiments were carried out at 1–2 GPa and 1,200 °C using a piston-cylinder device. The fugacity of O₂ was controlled at the Fe⁰–FeO, FeO–Fe₃O₄, or Ni⁰–NiO buffer. Variable duration experiments indicate that equilibration is achieved within 6 h. Hydrogen contents of the experimental products were measured by secondary ion mass spectrometry, and relative changes to the point defect populations were investigated using Fourier transform infrared spectroscopy. Results from our experiments demonstrate that H solubility in San Carlos olivine is sensitive to pressure, the activity of SiO₂, and the fugacities of H₂O and O₂. Of these variables, the fugacity of H₂O has the strongest influence. The solubility of H in olivine increases with increasing SiO₂ activity, indicating incorporation into vacancies on octahedral lattice sites. The forsterite content of the olivine has no discernible effect on H solubility between 88.17 and 91.41, and there is no correlation between the concentrations of Ti and H. Further, in all but one of our experimentally hydrated olivines, the concentration of Ti is too low for H to be incorporated dominantly as a Ti-clinohumite-like defect. Our experimentally hydrated olivines are characterized by strong infrared absorption peaks at wavenumbers of 3,330, 3,356, 3,525, and 3,572 cm^?1. The heights of peaks at 3,330 and 3,356 cm^?1 correlate positively with O₂ fugacity, while those at 3,525 and 3,572 cm^?1 correlate with H₂O fugacity.     

Sediment colour reflectance spectroscopy as a proxy for wet/dry cycles at Lake El'gygytgyn,Far East Russia,during Marine Isotope Stages 8 to 12

Marine Isotope Stage 11 has been proposed as an analogue for the present interglacial interval; yet, terrestrial climate records from both this region and time interval are rare. The sediments deposited at Lake El'gygytgyn (67°30′N, 172°5′E) in Far East Russia contain a 3·56 Ma record of climate variability. This study presents a high‐resolution record of sediment colour change from Marine Isotope Stage 8 to 12 (ca 275 to 475 ka) and demonstrates the link between lake catchment processes and climate variability. The hue colour parameter, calculated from data collected via colour reflectance spectroscopy in the visible spectrum (380 to 720 nm), exhibits correspondence with global climate records. Determining the source of sediment colour changes was achieved through detailed mineralogical and sedimentological methods, and linked to colour changes through a series of colour sensitivity tests. Mineralogical data, measured by X‐ray diffraction, reveal fluctuations in concentrations of clay minerals corresponding to colour changes. Further analyses of the clay mineral assemblages show no change in relative clay mineral abundances, yet demonstrate a lake catchment dominated by physical weathering processes. Using measured mineral abundances, reconstructions of sediment colour based on colour reflectance mineral standards link mineral and clay mineral content to overall sediment colour. Colour sensitivity tests demonstrate the ability of iron oxide minerals to stain sediments red. Additionally, colour sensitivity to organic matter content was tested, suggesting that organic content drives variability in the red portion of the spectrum and darkens the overall colour signal. Sediment colour is then ultimately linked to physical weathering of bedrock minerals, with small amounts of chemical weathering producing iron oxides during wet intervals. Fluctuations in the sediment colour reveal a high‐resolution record of wet/dry cycles, and provide new information about wet periods for the Russian Arctic region not yet understood from other lake proxy records.     

Volcanic activity at Tvashtar Catena, Io

Galileo's Solid State Imager (SSI) observed Tvashtar Catena four times between November 1999 and October 2001, providing a unique look at a distinctive high latitude volcanic complex on Io. The first observation (orbit I25, November 1999) resolved, for the first time, an active extraterrestrial fissure eruption; the brightness temperature was at least 1300 K. The second observation (orbit I27, February 2000) showed a large (∼500 km²) region with many, small, hot, regions of active lava. The third observation was taken in conjunction with Cassini imaging in December 2000 and showed a Pele-like, annular plume deposit. The Cassini images revealed an ∼400 km high Pele-type plume above Tvashtar Catena. The final Galileo SSI observation of Tvashtar (orbit I32, October 2001), revealed that obvious (to SSI) activity had ceased, although data from Galileo's Near Infrared Mapping Spectrometer (NIMS) indicated that there was still significant thermal emission from the Tvashtar region. In this paper, we primarily analyze the style of eruption during orbit I27 (February 2000). Comparison with a lava flow cooling model indicates that the behavior of the Tvashtar eruption during I27 does not match that of simple advancing lava flows. Instead, it may be an active lava lake or a complex set of lava flows with episodic, overlapping eruptions. The highest reliable color temperature is ∼1300 K. Although higher temperatures cannot be ruled out, they do not need to be invoked to fit the observed data. The total power output from the active lavas in February 2000 was at least ¹⁰¹¹ W.     

Polymer amide in the Allende and Murchison meteorites

It has been proposed that exothermic gas phase polymerization of amino acids can occur in the conditions of a warm dense molecular cloud to form hydrophobic polymer amide (HPA) (McGeoch and McGeoch 2014). In a search for evidence of this presolar chemistry Allende and Murchison meteorites and a volcano control were diamond burr‐etched and Folch extracted for potential HPA yielding 85 unique peaks in the meteorite samples via matrix‐assisted laser desorption time‐of‐flight mass spectrometry (MALDI TOF/MS). The amino acids after acid hydrolysis in Allende were below the level of detection but many of the Allende peaks via the more sensitive MALDI/TOF analysis could be fitted to a polymer combination of glycine, alanine, and alpha‐hydroxyglycine with high statistical significance. A similar significant fit using these three amino acids could not be applied to the Murchison data indicating more complex polymer chemistry.     

Effect of basin physical characteristics on solute fluxes in nine alpine/subalpine basins,Colorado, USA

Alpine/subalpine basins may exhibit substantial variability in solute fluxes despite many apparent similarities in basin characteristics. An evaluation of controls on spatial patterns in solute fluxes may allow development of predictive tools for assessing basin sensitivity to outside perturbations such as climate change or deposition of atmospheric pollutants. Relationships between basin physical characteristics, determined from geographical information system (GIS) tools, and solute fluxes and mineral weathering rates were explored for nine alpine/subalpine basins in Rocky Mountain National Park, Colorado, using correlation analyses for 1993 and 1994 data. Stream‐water nitrate fluxes were correlated positively with basin characteristics associated with the talus environment; i.e., the fractional amounts of steep slopes (≥ 30°), unvegetated terrain and young debris (primarily Holocene till) in the basins, and were correlated negatively with fractional amounts of subalpine meadow terrain. Correlations with nitrate indicate the importance of the talus environment in promoting nitrate flux and the mitigating effect of areas with established vegetation, such as subalpine meadows. Total mineral weathering rates for the basins ranged from about 300 to 600 mol ha^?1 year^?1. Oligoclase weathering accounted for 30 to 73% of the total mineral weathering flux, and was positively correlated with the amount of old debris (primarily Pleistocene glacial till) in the basins. Although calcite is found in trace amounts in bedrock, calcite weathering accounted for up to 44% of the total mineral weathering flux. Calcite was strongly correlated with steep slope, unvegetated terrain, and young debris—probably because physical weathering in steep‐gradient areas exposes fresh mineral surfaces that contain calcite for chemical weathering. Oligoclase and calcite weathering are the dominant sources of alkalinity in the basins. However, atmospherically deposited acids consume much of the alkalinity generated by weathering of calcite and other minerals in the talus environment. Published in 2001 by John Wiley & Sons, Ltd.     

Historical changes in sediment and phosphorus loading to the upper Mississippi River: mass-balance reconstructions from the sediments of Lake Pepin

Long-term changes in sediment and phosphorus loading to the upper Mississippi River were quantified from an array of 25 sediment cores from Lake Pepin, a large natural impoundment downstream of the Minneapolis-St Paul metropolitan area. Cores were dated and stratigraphically correlated using ²¹⁰Pb, ¹³⁷Cs, ¹⁴C, magnetic susceptibility, pollen analysis, and loss-on-ignition. All cores show a dramatic increase in sediment accumulation beginning with European settlement in 1830. Accumulation rates are highest and show the greatest post-settlement increases in the upper end of the lake. Present-day sediment-phosphorus concentrations are roughly twice those of pre-settlement times, and the Fe/Al-bound fraction makes up a greater portion of the total. Diatom assemblages record a marked increase in nutrient availability over the last 200 years, changing from clear-water benthic forms and mesotrophic planktonic taxa in pre-settlement times to exclusively planktonic assemblages characteristic of highly eutrophic conditions today. Lake-water total-phosphorus concentrations, estimated by weighted averaging regression and calibration, increased from 50 to 200 μg l⁻¹ during this period. Sediment loading to Lake Pepin from the Mississippi River has increased by an order of magnitude since 1830. Modern fluxes are about 900,000 metric tons annually, and are more than 80% detrital mineral matter. About 17% of the lake’s volume in 1830 has been replaced by sediment, and at current accumulation rates the remainder will be filled in another 340 years. Phosphorus accumulation in Lake Pepin sediments has increased 15-fold since 1830, rising from 60 to 900 metric tons annually. This rise represents a sevenfold increase in phosphorus loading from the Mississippi River coupled with more efficient retention of phosphorus inflows by bottom sediments. More efficient trapping of phosphorus in Lake Pepin over the last century resulted from higher rates of sediment burial. The most dramatic changes in nutrient and sediment inputs to Lake Pepin have occurred since 1940, although gradual increases began shortly following European settlement. Sediment accumulation rates rose sharply between 1940 and 1970 and then leveled off, while phosphorus inflows record their largest increases after 1970. This is one of eight papers dedicated to the “Recent Environmental History of the Upper Mississippi River” published in this special issue of the Journal of Paleolimnology. D. R. Engstrom served as guest editor of the special issue.