Sources and biological fractionation of Silicon isotopes in the Eastern Equatorial Pacific

Silicon isotopes in dissolved silicic acid were measured in the upper four kilometers between 4°N and 3°S latitude at 110°W longitude in the eastern Equatorial Pacific. Silicon isotopes became progressively heavier with silicic acid depletion of surface water as expected from biological fractionation. The value of ε estimated by applying a steady-state isotope fractionation model to data from all stations between 4°N and 3°S was −0.77 ± 0.12‰ (std. err.). When the analysis was restricted to those stations whose temperature and salinity profiles indicated that they were directly influenced by upwelling of the Equatorial Undercurrent (EUC), the resulting value of ε was −1.08 ± 0.27‰ (std. err.) similar to the value established in culture studies (−1.1‰). When the non steady state Rayleigh model was applied to the same restricted data set the resulting value of ε was significantly more positive, −0.61 ± 0.16‰ (std. err.). To the extent that the equatorial system approximates a steady state these results support a value of −1.1‰ for the fractionation factor for isotopes of Si in the sea. Without the assumption of steady state the value of ε can only be constrained to be between −0.6 and −1.1‰. Silicic acid in Equatorial Pacific Deep Water below 2000 m had a near constant δ³⁰Si of +1.32 ± 0.05‰. That value is significantly more positive than obtained for North Pacific Deep Water at similar depths at stations to the northwest of our study area (0.9-1.0‰) and it is slightly less positive than new measures of the δ³⁰Si of silicic acid from the silicic acid plume centered over the Cascadia basin in the Northeast Pacific (Si(OH)₄ > 180  μM, δ³⁰Si = +1.46 ± 0.12‰ (SD, n = 4). We show that the data from the equator and Cascadia basin fit a general trend of increasing δ³⁰Si(OH)₄ with increasing silicic acid concentration in the deep sea, but that the isotope values from the Northeast Pacific are anomalously light. The observed level of variation in the silicon isotope composition of deep waters from this single ocean basin is considerably larger than that predicted by current models based on fractionation during opal formation with no isotope effect during dissolution. Confirmation of such high variability in deep water δ³⁰Si(OH)₄ within individual ocean basins will require reassessment of the mechanisms controlling the distribution of isotopes of silicon in the sea.     

Assessment of the historical trace metal contamination of sediments in the Elizabeth River, Virginia

Two sediment cores (Southern Branch, PC-1, and Western Branch, WB-2) were taken from the highly industrialized Elizabeth River, Virginia. The concentrations of trace metals cadmium, cobalt, chromium, copper, nickel, lead and zinc, major elements iron, manganese and aluminum, organic carbon content and the specific surface area of the sediments were determined in each of the cores. Down-core variations in metals varied significantly in each core with maximum contamination events occurring at different times in different portions of the river. In PC-1, maximum metal concentrations were seen after the appearance of (137)Cs. In contrast, the highest levels in WB-2 occurred well before the appearance of (137)Cs. Although stricter environmental regulations have caused a decrease in metal concentrations since the 1980s, the concentrations in the surface sediments of many trace metals were elevated to levels 2-5 times higher than the levels at the bottom of the cores in both the Southern and Western Branches of the river.     

Diagenetic haematite and sulfate assemblages in Valles Marineris

Previous orbital mapping of crystalline gray haematite, ferric oxides, and sulfates has shown an association of this mineralogy with light-toned, layered deposits on the floor of Valles Marineris, in chaos terrains in the canyon’s outflow channels, and in Meridiani Planum. The exact nature of the relationship between ferric oxides and sulfates within Valles Marineris is uncertain. The Observatoire pour la Mineralogie, l’Eau, les Glaces et l’Activite (OMEGA) spectrometer initially identified sulfate and ferric oxides in the layered deposits of Valles Marineris. The Thermal Emission Spectrometer (TES) has also mapped coarse (gray) haematite in or at the base of these deposits. We use Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) spectra and Context Camera (CTX) and High Resolution Imaging Science Experiment (HiRISE) imagery from the Mars Reconnaissance Orbiter (MRO) to explore the mineralogy and morphology of the large layered deposit in central Capri Chasma, part of the Valles Marineris canyon system that has large, clear exposures of sulfate and haematite. We find kieserite (MgSO₄·H₂O) and ferric oxide (often crystalline red haematite) in the lower bedrock exposures and a polyhydrated sulfate without ferric oxides in the upper bedrock. This stratigraphy is duplicated in many other basinal chasmata, suggesting a common genesis. We propose the haematite and monohydrated sulfate formed by diagenetic alteration of a sulfate-rich sedimentary deposit, where the upper polyhydrated sulfate-rich, haematite-poor layers either were not buried sufficiently to convert to a monohydrated sulfate or were part of a later depositional phase. Based on the similarities between the Valles Marineris assemblages and the sulfate and haematite-rich deposits of Meridiani Planum, we hypothesize a common evaporite and diagenetic formation process for the Meridiani Planum sediments and the sulfate-bearing basinal Interior Layered Deposits.     

Genesis of copper mineralisation,Myall Creek prospect,South Australia

The Myall Creek copper prospect is in unmetamorphosed carbonaceous dolosiltstone and sandstone at the base of the late Proterozoic (Adelaidean) Tapley Hill Formation. It contains disseminated, fine-grained chalcopyrite, zincian tennanite, bornite, chalcocite, pyrite, sphalerite and galena, and irregular to straight chalcopyrite-rich veinlets. Some ore minerals rim and/or partially replace pyrite or clastic grains. There is no evidence of hydrothermal activity. The ³⁴S_CDT values of pyrite and the other sulfides fall in the wide range –3.6 to +44.2. Dolomite in both mineralised and unmineralised samples has ¹³C_PDB values concentrated around –3, and ¹⁸O_SMOW values around +25. It is concluded that the mineralising fluids were near-neutral brines which leached metals from the basement and early Adelaidean rocks. They entered the Tapley Hill sediments at moderately low temperatures via permeable strata and faults. The metals were precipitated by biogenic H₂S, and also fixed by reaction with iron sulfides and, possibly, organic matter. Continuing ascent of brines into the mineralised strata caused breakdown of detrital feldspars and Fe-Ti oxides, and some solution-remobilisation of early-formed sulfides.     

Fluoride-Selective Electrode as a Tool to Evaluate the Degradation of PFAS in Groundwater: A Bench-Scale Investigation

Fluoride (F⁻) concentration in groundwater can be used as an independent measure of the degradation of per- and polyfluoroalkyl substances (PFAS) at contaminated sites. This study assessed the impact of the groundwater matrix, oxidizing reagents, quenching agent, and sample handling procedures (filtration) on determinations of F⁻. F⁻ was quantified using a fluoride-selective electrode (FSE) using matrix spike recovery (acceptable range 75 to 125%) and electrode slope performance (ideal range −54 to −60 mV). For the unaltered aqueous matrices considered (ultrapure water, ultrapure water with sodium chloride, and simulated groundwater), matrix spike recoveries were greater than 93% and acceptable electrode slopes (−59.5 ± 0.2 mV) were obtained. Matrix spike recoveries and electrode slopes when persulfate or permanganate was added were 87 and 93%, and −58.4 ± 1.3 and −47.3 ± 2.2 mV, respectively. Therefore, quantifying F⁻ in matrices containing permanganate should involve use of either a matrix-matched calibration curve or the method of standard additions due to the low electrode slope. The addition of ascorbic acid as a quenching agent resulted in a decrease in matrix spike recoveries to <74% and suggests alternate quenching procedures should be used if an FSE is employed to measure F⁻. Removal of sediments by filtration prior to the addition of the fluoride spike led to improved matrix spike recoveries (>96%), which were otherwise underestimated using the FSE in the presence of sediments. While the FSE may be a quick and portable tool, its significant limitations need to be fully understood before it can be used to quantify the production of F⁻ resulting from the potential degradation of PFAS at field sites.     

Effect of mid-oceanic ballast water exchange on virus-like particle abundance during two trans-Pacific voyages

Ballast water is a potential source of invasive species, including viruses that target a variety of hosts. We sampled ballast during two trans-Pacific voyages and analyzed the efficacy of mid-oceanic exchange in reducing virus-like particle (VLP) abundance. Exchange did not significantly reduce virus abundance during the first voyage (P = 0.874), whereas it reduced viral abundance 3.9-fold from 1.8 × 10⁷ to 0.47 × 10⁷ VLP mL⁻¹ during the second voyage (P < 0.0001). Despite the impact of exchange during the second voyage, virus abundances were not significantly different between exchanged and unexchanged tanks upon arrival in Canada (P = 0.363) and Canadian port water samples (P = 0.502). Regressions between environmental parameters and VLP abundance uncovered negative correlations between salinity and viral abundance during one, and dissolved oxygen and viral abundance during the second voyage. In summary, ballast tanks are highly variable with respect to total virus abundance, and the efficacy of exchange requires investigation into the dynamics of specific viruses.     

The annual silica cycle of the North Pacific subtropical gyre

Silica cycling in the upper 175 m of the North Pacific Subtropical Gyre was examined over a two year period (January 2008-December 2009) at the Hawaii Ocean Time-series (HOT) station ALOHA. Silicic acid concentrations in surface waters ranged from 0.6 to 1.6 ??M, exhibiting no clear seasonal trends. Biogenic silica concentrations and silica production rates increased by an order of magnitude each summer following stratification of the upper 50 m reaching values of 157 nmol Si L⁻¹ and 81 nmol Si L⁻¹ d⁻¹, in 2008 and 2009, respectively. Sea surface height anomalies together with analyses of variability in isothermal surfaces at 150-175 m indicated that the summer periods of elevated biogenic silica were associated with anticyclonic mesoscale features during both years. Lithogenic silica concentrations increased in the spring during the known period of maximum atmospheric dust concentrations with maximum values of 36 nmol Si L⁻¹ in the upper 10 m. Dust deposition would enhance levels of dissolved iron in surface waters, but there was no response of diatom biomass or silica production to increases in near-surface ocean lithogenic silica concentrations suggesting iron sufficiency of diatom silica production rates.Low ambient silicic acid concentrations restricted silica production rates to an average of 43% of maximum potential rates. Si sufficiency only occurred during the summer period when diatom biomass was elevated suggesting that bloom diatoms are adapted to exploit low silicic acid concentrations. Annual silica production at HOT is estimated to be 63 mmol Si m⁻² a⁻¹ with summer blooms contributing 29% of the annual total. Diatoms are estimated to account for 3-7% of total phytoplankton primary productivity, but 9-20% of organic carbon export confirming past suggestions that diatoms are relatively minor contributors to primary productivity and autotrophic biomass, but important contributors to new and export production in oligotrophic open-ocean ecosystems.Annual silica production at HOT is nearly 4-fold lower than estimates at the Bermuda Atlantic Time-series Study (BATS) site in the Sargasso Sea from the 1990s, but annual silica export at the base of the euphotic zone is similar between the two gyres indicating very different balances between silica production and its loss in surface waters. On a relative basis, BATS is a more productive system with respect to silica, where biogenic silica is recycled with high efficiency in surface waters; in contrast the NPSG is a lower productivity system with respect to silica, but where lower recycling efficiency leads to a much higher fraction of new silica production. The two gyres show contrasting long-term trends in diatom biomass as biogenic silica concentrations at HOT have been increasing since 1997, but they have been decreasing at BATS suggesting very different forcing of decadal trends in the contribution of diatoms in carbon cycling between these gyres. Combining the data from both gyres indicates that globally subtropical gyres produce 13 Tmol Si a⁻¹, which is only 51% of previous estimates reducing the contribution of subtropical gyres to 5-7% of global annual marine silica production.     

ON NOT EXCLUDING HALF OF THE HUMAN IN HUMAN GEOGRAPHY

Much research in human geography has been, often inadvertently, sexist. We first propose some reasons for this and then review the feminist contributions in other disciplines. The bulk of the paper examines some examples of sexist bias in the content, methods, and purposes of geographic research, suggests the nature of the damage that such bias inflicts on geographic knowledge, and identifies ways in which nonsexist geography might emerge.     

Multiple techniques for mineral identification on Mars:: a study of hydrothermal rocks as potential analogues for astrobiology sites on Mars

Spectroscopic studies of Mars analog materials combining multiple spectral ranges and techniques are necessary in order to obtain ground truth information for interpretation of rocks and soils on Mars. Two hydrothermal rocks from Yellowstone National Park, Wyoming, were characterized here because they contain minerals requiring water for formation and they provide a possible niche for some of the earliest organisms on Earth. If related rocks formed in hydrothermal sites on Mars, identification of these would be important for understanding the geology of the planet and potential habitability for life. XRD, thermal properties, VNIR, mid-IR, and Raman spectroscopy were employed to identify the mineralogy of the samples in this study. The rocks studied here include a travertine from Mammoth Formation that contains primarily calcite with some aragonite and gypsum and a siliceous sinter from Octopus Spring that contains a variety of poorly crystalline to amorphous silicate minerals. Calcite was detected readily in the travertine rock using any one of the techniques studied. The small amount of gypsum was uniquely identified using XRD, VNIR, and mid-IR, while the aragonite was uniquely identified using XRD and Raman. The siliceous sinter sample was more difficult to characterize using each of these techniques and a combination of all techniques was more useful than any single technique. Although XRD is the historical standard for mineral identification, it presents some challenges for remote investigations. Thermal properties are most useful for minerals with discrete thermal transitions. Raman spectroscopy is most effective for detecting polarized species such as CO₃, OH, and CH, and exhibits sharp bands for most highly crystalline minerals when abundant. Mid-IR spectroscopy is most useful in characterizing Si-O (and metal-O) bonds and also has the advantage that remote information about sample texture (e.g., particle size) can be determined. Mid-IR spectroscopy is also sensitive to structural OH, CO₃, and SO₄ bonds when abundant. VNIR spectroscopy is best for characterizing metal excitational bands and water, and is also a good technique for identification of structural OH, CO₃, SO₄, or CH bonds. Combining multiple techniques provides the most comprehensive information about mineralogy because of the different selection rules and particle size sensitivities, in addition to maximum coverage of excitational and vibrational bands at all wavelengths. This study of hydrothermal rocks from Yellowstone provides insights on how to combine information from multiple instruments to identify mineralogy and hence evidence of water on Mars.     

A Review of “Villages,Women and the Success of Dairy Cooperatives in India: Making Place for Rural Development”

Conceptual advances for understanding the organization of family farms have not yet initiated parallel debates about how they might be aligned with the methods used to understand them. Customization of a novel research approach—farm life history—for an investigation of the socioeconomic organization of forty Australian farms responds to this literature gap. Individual farm life histories were initiated using farm tours (truck journeys) in which changes to the composition of land parcels prompted research conversations. The researcher and participants benefited from using motorized transport and traveling while talking, but the benefits were experienced unevenly across research encounters.