Low temperature volatile production at the Lost City Hydrothermal Field, evidence from a hydrogen stable isotope geothermometer

Although commonly utilized in continental geothermal work, the water-hydrogen and methane-hydrogen isotope geothermometers have been neglected in hydrothermal studies. Here we report δD-CH₄ and δD-H₂ values from high-temperature, black smoker-type hydrothermal vents and low-temperature carbonate-hosted samples from the recently discovered Lost City Hydrothermal Field. Methane deuterium content is uniform across the dataset at − 120 ± 12‰. Hydrogen δD values vary from − 420‰ to − 330‰ at high-temperature vents to − 700‰ to − 600‰ at Lost City. The application of several geothermometer equations to a suite of hydrothermal vent volatile samples reveals that predicted temperatures are similar to measured vent temperatures at high-temperature vents, and 20-60 °C higher than those measured at the Lost City vents. We conclude that the overestimation of temperature at Lost City reflects 1) that methane and hydrogen are produced by serpentinization at > 110 °C, and 2) that isotopic equilibrium at temperatures < 70 °C is mediated by microbial sulfate reduction. The successful application of hydrogen isotope geothermometers to low-temperature Lost City hydrothermal samples encourages its employment with low-temperature diffuse hydrothermal fluids.     

Part II. Evaluation of Ar-Ar quartz ages: Implications for fluid inclusion retentivity and determination of initial Ar/Ar values in Proterozoic samples

The argon isotope systematics of vein-quartz samples with two different K-reservoirs have been evaluated in detail. Potassium is hosted by ultra-high-salinity fluid inclusions in quartz samples from the Eloise and Osborne iron-oxide-copper-gold (IOCG) deposits of the Mt Isa Inlier, Australia. In contrast, K is hosted by accidentally trapped mica within lower-salinity fluid inclusions of a sample selected from the Railway Fault, 13 km south of the Mt Isa copper mine, Australia. Imprecise apparent ages have been obtained for all of the samples studied and conclusively demonstrate that quartz fluid inclusions are retentive to Ar and have not leaked over billions of years. IOCG samples that host K in fluid inclusions only, have K/Cl values of <1 and the ages obtained represent the maximum ages for mineralization. In contrast, the Railway Fault samples that include accidentally trapped mica have K/Cl values of ?1. Excess ⁴⁰Ar_E plus Cl hosted by fluid inclusions, and radiogenic ⁴⁰Ar_R plus K, are strongly correlated in these samples and define a plane in 3D ⁴⁰Ar-³⁶Ar-K-Cl space. In this case, the plane yields an ‘excess ⁴⁰Ar_E’ corrected age of ∼1030 Ma that is 100’s of Ma younger than nearby Cu-mineralization at Mt Isa. The age is interpreted to reflect ⁴⁰Ar-loss from the accidentally trapped mica into the surrounding fluid inclusions, and is not related to the samples’ age of formation. The initial ⁴⁰Ar/³⁶Ar value of fluid inclusions is widely used to provide information on fluid origin. For the IOCG samples that host K in fluid inclusions only, the initial ⁴⁰Ar/³⁶Ar values are close to the measured values at every temperature of stepped heating experiments. For samples that include accidentally trapped mica, the correction for post-entrapment radiogenic ⁴⁰Ar_R production is significant. Furthermore, because ³⁹Ar_K present in accidentally trapped mica crystals is released at different temperatures to radiogenic ⁴⁰Ar_R lost to the surrounding fluid inclusions, intra-sample ⁴⁰Ar/³⁶Ar variation cannot be reliably documented. The results demonstrate that noble gas analysis is readily applicable to Proterozoic, or older, samples but that if K-mineral impurities are present within quartz the abundance of K must be determined before calculation of mean ⁴⁰Ar/³⁶Ar values that are representative of the samples’ initial composition.     

Oil-generation kinetics for organic facies with Type-II and -IIS kerogen in the Menilite Shales of the Polish Carpathians

The Menilite Shales (Oligocene) of the Polish Carpathians are the source of low-sulfur oils in the thrust belt and some high-sulfur oils in the Carpathian Foredeep. These oil occurrences indicate that the high-sulfur oils in the Foredeep were generated and expelled before major thrusting and the low-sulfur oils in the thrust belt were generated and expelled during or after major thrusting. Two distinct organic facies have been observed in the Menilite Shales. One organic facies has a high clastic sediment input and contains Type-II kerogen. The other organic facies has a lower clastic sediment input and contains Type-IIS kerogen. Representative samples of both organic facies were used to determine kinetic parameters for immiscible oil generation by isothermal hydrous pyrolysis and S₂ generation by non-isothermal open-system pyrolysis. The derived kinetic parameters showed that timing of S₂ generation was not as different between the Type-IIS and -II kerogen based on open-system pyrolysis as compared with immiscible oil generation based on hydrous pyrolysis. Applying these kinetic parameters to a burial history in the Skole unit showed that some expelled oil would have been generated from the organic facies with Type-IIS kerogen before major thrusting with the hydrous-pyrolysis kinetic parameters but not with the open-system pyrolysis kinetic parameters. The inability of open-system pyrolysis to determine earlier petroleum generation from Type-IIS kerogen is attributed to the large polar-rich bitumen component in S₂ generation, rapid loss of sulfur free-radical initiators in the open system, and diminished radical selectivity and rate constant differences at higher temperatures. Hydrous-pyrolysis kinetic parameters are determined in the presence of water at lower temperatures in a closed system, which allows differentiation of bitumen and oil generation, interaction of free-radical initiators, greater radical selectivity, and more distinguishable rate constants as would occur during natural maturation. Kinetic parameters derived from hydrous pyrolysis show good correlations with one another (compensation effect) and kerogen organic-sulfur contents. These correlations allow for indirect determination of hydrous-pyrolysis kinetic parameters on the basis of the organic-sulfur mole fraction of an immature Type-II or -IIS kerogen.     

The impact of vegetation on REE fractionation in stream waters of a small forested catchment (the Strengbach case)

Previous studies on waters of a streamlet in the Vosges Mountains (Eastern France) have shown that strontium and rare earth elements (REE) mainly originate from preferential dissolution of apatite during weathering. However, stream water REE patterns normalized to apatite are still depleted in the light REE (LREE, La-Sm) pointing to the presence of an additional LREE depleting process. Vegetation samples are strongly enriched in LREE compared to stream water and their Sr and Nd isotopic compositions are comparable with those of apatite and stream water. Thus, the preferential LREE uptake by vegetation might lead to an additional LREE depletion of surface runoff in the forested catchment. Mass balance calculations indicate, that the yearly LREE uptake by vegetation is comparable with the LREE export by the streamlet and, therefore, might be an important factor controlling LREE depletion in river water. This is underlined by the observation that rivers from arctic and boreal regions with sparse vegetation appear to be less depleted in LREE than rivers from tropical environments or boreal environments with a dense vegetation cover.     

Models of oxic respiration, denitrification and sulfate reduction in zones of coastal upwelling

Coastal upwelling zones support some of the highest rates of primary production in the oceans. The settling and subsequent decomposition of this organic matter promotes oxygen depletion. In the Eastern tropical North and South Pacific and the Arabian Sea, large tracts of anoxic water develop, where intensive N₂ production through denitrification and anammox accounts for about 1/3 of the total loss of fixed nitrogen in the marine realm. It is curious that despite extensive denitrification in these waters, complete nitrate removal and the onset of sulfate reduction is extremely rare. A simple box model is constructed here to reproduce the dynamics of carbon, oxygen and nutrient cycling in coastal upwelling zones. The model is constructed with five boxes, where water is exchanged between the boxes by vertical and horizontal mixing and advection. These primary physical drivers control the dynamics of the system. The model demonstrates that in the absence of nitrogen fixation, the anoxic waters in a coastal upwelling system will not become nitrate free. This is because nitrate is the limiting nutrient controlling primary production, and if nitrate concentration becomes too low, primary production rate drops and this reduces rates of nitrate removal through N₂ production. With nitrogen fixation, however, complete nitrate depletion can occur and sulfate reduction will ensue. This situation is extremely rare in coastal upwelling zones, probably because nitrogen-fixing bacteria do not prosper in the high nutrient, turbid waters as typically in these areas. Finally, it is predicted here that the chemistry of the upwelling system will develop in a similar matter regardless whether N₂ production is dominated by anaerobic ammonium oxidation (anammox) or canonical heterotrophic denitrification.     

Tracing nitrogen in volcanic and geothermal volatiles from the Nicaraguan volcanic front

We report new chemical and isotopic data from 26 volcanic and geothermal gases, vapor condensates, and thermal water samples, collected along the Nicaraguan volcanic front. The samples were analyzed for chemical abundances and stable isotope compositions, with a focus on nitrogen abundances and isotope ratios. These data are used to evaluate samples for volatile contributions from magma, air, air-saturated water, and the crust. Samples devoid of crustal contamination (based upon He isotope composition) but slightly contaminated by air or air-saturated water are corrected using N₂/Ar ratios in order to obtain primary magmatic values, composed of contributions from upper mantle and subducted hemipelagic sediment on the down-going plate. Using a mantle endmember with δ¹⁵N = −5‰ and N₂/He = 100 and a subducted sediment component with δ¹⁵N = +7‰ and N₂/He = 10,500, the average sediment contribution to Nicaraguan volcanic and geothermal gases was determined to be 71%. Most of the gases were dominated by sediment-derived nitrogen, but gas from Volcán Mombacho, the southernmost sampling location, had a mantle signature (46% from subducted sediment, or 54% from the mantle) and an affinity with mantle-dominated gases discharging from Costa Rica localities to the south. High CO₂/N_{2 exc.} ratios (N_{2 exc.} is the N₂ abundance corrected for contributions from air) in the south are similar to those in Costa Rica, and reflect the predominant mantle wedge input, whereas low ratios in the north indicate contribution by altered oceanic crust and/or preferential release of nitrogen over carbon from the subducting slab. Sediment-derived nitrogen fluxes at the Nicaraguan volcanic front, estimated by three methods, are 7.8 × 10⁸ mol N/a from ³He flux, 6.9 × 10⁸ mol/a from SO₂ flux, and 2.1 × 10⁸ and 1.3 × 10⁹ mol/a from CO₂ fluxes calculated from ³He and SO₂, respectively. These flux results are higher than previous estimates for Central America, reflecting the high sediment-derived volatile contribution and the high nitrogen content of geothermal and volcanic gases in Nicaragua. The fluxes are also similar to but higher than estimated hemipelagic nitrogen inputs at the trench, suggesting addition of N from altered oceanic basement is needed to satisfy these flux estimates. The similarity of the calculated input of N via the trench to our calculated outputs suggests that little or none of the subducted nitrogen is being recycled into the deeper mantle, and that it is, instead, returned to the surface via arc volcanism.     

Nature and dynamics of phosphorus-containing components of marine dissolved and particulate organic matter

The molecular sources, dynamics and analytical characterizations of the phosphorus (P) containing components of marine dissolved and particulate organic matter (OM) are reviewed. Using a combination of ¹³C and ³¹P nuclear magnetic resonance spectroscopy on samples collected from a depth profile (20-4000 m) at Station Aloha in the North Pacific subtropical gyre, the biomolecular associations of P functional groups in marine OM are identified. Compositional differences between ultrafiltered dissolved organic matter (UDOM; 1-100 nm size fraction) and ultrafiltered particulate organic matter (UPOM; 0.1-60 μm size fraction) as reflected by NMR and elemental analyses indicate that UDOM does not originate from simple solubilization of UPOM, and the aggregation of UDOM is not the primary source of UPOM. Regression analyses indicated a large fraction of the P in UDOM is associated with carbohydrates and amino acids, but not with lipids. Similar analyses for UPOM indicated that P is associated with carbohydrates, amino acids and lipids. The P functional groups also appear to be balanced in their distribution among molecular classes, because they remain in relatively constant proportion throughout the ocean.     

Retailing local food in the Scottish-English borders: A supply chain perspective

Local food is championed as one alternative response to industrial systems of food production and supply. While advocacy for local food is high, there is a lack of empirical evidence about the actual shape and scale of such food supply chains, especially from a retail perspective. Using supply chain diagrams, this paper presents a summary of ‘new’ agro-food geographies for five different retail types—farm shops, butchers, caterers, specialist shops, supermarkets/department stores—that all source local food from suppliers in the Scottish-English borders. Presented as five separate ‘shopping trips’, the paper examines where, how and why retailers source local food. Results reveal the complex nature of local food systems, especially in terms of intra-sector competitive dynamics (with a notable tension between direct forms of retail and established (independent) retailers), links and overlaps with ‘normal’ food retail systems and elastic notions of the ‘local’. The paper also draws a key distinction between locally produced and locally supplied food products.     

Assessment of the mycoflora of commercial poultry feeds sold in the humid tropical environment of Imo State, Nigeria

This study was carried out to identify the common moulds growing in selected commercial poultry feed sold in Owerri, Imo State, Nigeria. Forty-eight bulk samples derived froml92 bags of feeds were collected from broiler starter (BS), broiler finishers (BF), grower mash (GM) and layer mash (LM) across 4 different brands of ommercial poultry feeds, which included Livestock (LF), Top (TF) Guinea (GF) and Vital (VF) feeds. The feed samples were collected during the rainy season months of June, July and August. The common moulds isolated from these feeds were Aspergillus sp., Peicillium sp.,Mucor sp., Yeast sp., Rhizopus sp., Epicoecum sp., Gymnoaseus sp., Cladosporium sp., Mortierella sp. as well as Bacteria. Generally, more organisms were isolated in June than the other months with Mortierella sp. being the only one not isolated in that month. Vital feed with 8 different isolates had the highest diversity of fungal species while the others had between 4 and 5 species. Prevalence rates across the feed types, generally ranged from 18.76% in layer mash to 30.03% in broiler finisher. The four Aspergillus sp. isolated came from GM and BF. This study highlights the need for constant monitoring of moulds in commercial feedstuff produced in the humid tropical environments such as Imo state, Nigeria. There is also the need to routinely include fungal growth nhibitors in commercial feeds since moulds are capable of reducing the nutritional values of feedstuff as well as elaborating pathogenic toxins.     

Total organic carbon in soils and its relation with manganese concentrations in soils and vegetation close to an abandoned manganese mine

This study aimed at quantifying the total organic carbon (TOC) present in soils within the proximity of the Kgwakgwe Mn oxide ore abandoned mine, Botswana, and establish its relationship with Mn concentrations in soils and vegetation based on multivariate and Geographical Information Systems (GIS) analytical techniques. Four hundred soil samples and 200 vegetation set samples were obtained from a 4 km² area close to the abandoned mine. The TOC in soil samples were determined using a carbon/hydrogen/moisture determinator, and Mn concentrations in soils and vegetation by atomic absorption spectrophotometry. Results were processed using the statistical package for social science (SPSS), GIS, and Remote Sensing (RS) techniques with the Integrated Land and Water Information System (ILWIS), Geosoft Oasis Montaj and ArcGIS software packages. The values for TOC in the soil samples from the study area ranged from 0 wt % to 7.91 wt %, with a mean of 1.90 wt %, and at the control area, from 4.07 wt % to 4.86 wt %. The range of concentrations of Mn in soils was from 36 mg/g to 24908 mg/g and for Mn concentrations in the vegetation samples from 26 mg/g to 3611 mg/g with a mean of 598 mg/g. Results of correlation coefficients depicted very weak negative association except Mn in soils/Mn in leaves which was weak but positive. The statistical data yielded four clusters as follows: cluster one consisted mainly of Mn in leaves, cluster two was constituted of Mn in soils, and cluster four had TOC. Cluster three was dominated by the three parameters but with negative t statistic. The spatial presentation of data presented revealed little or no vegetation in the south eastern area and those close to the mine workings, and some significant vegetation in the north western part of the study area. The low TOC in the soils is associated to low vegetation cover which is considered to have been influenced by the soil clay fraction mineralogy and high concentrations of Mn.