Bacterial iron oxide reduction in a terrigenous sediment-impacted tropical shallow marine carbonate system, north Jamaica

Discovery Bay, a carbonate-dominated embayment in north Jamaica, has been subject to inputs for 40 years of iron-rich bauxite sediment associated with the local mining and transport of processed bauxite. As such, this site is an ideal natural laboratory to study the records and impacts of iron oxide inputs upon geochemical, diagenetic, and microbial processes in tropical carbonate sediments.Total Fe contents in sites in the bay not receiving bauxite inputs are negligible and porewater Ca²⁺, SO₄²⁻ and Cl⁻ indicate that bacterial sulphate reduction is an important process. In contrast, surface sediments receiving bauxite inputs contain significant total Fe, from 44 μmol/g in shallow (5 m water depth) sites to 110 μmol/g in deeper (20 m water depth) sites. Up-core increases in total Fe record increased temporal inputs into the bay. Within these Fe-rich sediments porewater data shows the presence of Fe^II released by bacterial Fe^III reduction. There is no direct evidence for significant bacterial sulphate reduction in these sediments. Iron oxides within all bauxite-impacted sediments display a high potential reducibility, from 40% to 80% of the total Fe present as dithionite-extractable Fe^III. Experimental analysis of the potential susceptibility to, and rates of, bacterial Fe^III reduction, utilising Discovery Bay sediment and Shewanella putrefaciens CN32 (a known Fe^III-reducer) has confirmed the high bacterial reducibility of iron oxides within the sediment. Up to 75% of initial dithionite-extractable Fe^III in the sediments was reduced over 15 days.The presence of iron oxides within the Discovery Bay shallow marine carbonate systems has markedly altered the chemical diagenetic processes taking place, with a shift from apparent dominance of bacterial sulphate reduction at non-impacted (Fe-poor) sites, to highly significant bacterial Fe^III reduction in Fe-rich bauxite-impacted sediments. Given the perceived global increases in terrigenoclastic sediment inputs into tropical carbonate systems as a result of land-use and climate changes, coupled with the documented role that iron oxide reduction plays in nutrient and contaminant cycling in sediment systems, more research into the perturbation of early diagenesis by iron oxide inputs is required.     

Importance of CDOM Distribution and Photoreactivity in a Shallow Texas Estuary

This study examined freshwater discharge of dissolved organic matter (DOM) to the shallow Lavaca–Matagorda (LM) Bay estuarine system along the central Texas coast and investigated whether chromophoric DOM (CDOM) photochemical reactions have the potential to stimulate microbial activity within LM estuarine waters. Dissolved organic carbon (DOC) concentrations ranged from 3 to 10 mg C l⁻¹ and CDOM levels (reported as a ₃₀₅) ranged from 8 to 77 m⁻¹ during April and July, 2007, when the LM system was experiencing very high freshwater inputs. DOC and CDOM levels were well-correlated with salinities > 3, but exhibited considerable variability at salinities < 3. CDOM photobleaching rates (i.e., decrease in a ₃₀₅ resulting from exposure to solar radiation) for estuarine samples ranged from 0.014 to 0.021 h⁻¹, corresponding to photobleaching half-lives of 33–50 h. Our data indicate when Matagorda Bay waters photobleach; dissolved organic carbon utilization is enhanced perhaps due to enhanced microbial respiration of biologically labile photoproducts (BLPs). Net ecosystem metabolism calculations indicate that most of the LM system was net heterotrophic during our study. We estimate that BLP formation could support up to 20% of the daily microbial respiratory C demand in LM surface waters and combined with direct photochemical oxygen consumption could have an important influence on O₂ cycles in the LM system.     

Pacific Atmospheric Sulfur Experiment (PASE): dynamics and chemistry of the south Pacific tropical trade wind regime

The Pacific Atmospheric Sulfur Experiment (PASE) was a comprehensive airborne study of the chemistry and dynamics of the tropical trade wind regime (TWR) east of the island of Kiritibati (Christmas Island, 157º, 20?? W, 2º 52?? N). Christmas Island is located due south of Hawaii. Geographically it is in the northern hemisphere yet it is 6?C12º south of the intertropical convergence zone (ITCZ) which places it in the southern hemisphere meteorologically. Christmas Island trade winds in August and September are from east south east at 3?C15 ms^?1. Clouds, if present, are fair weather cumulus located in the middle layer of the TWR which is frequently labeled the buffer layer (BuL). PASE provided clear support for the idea that small particles (80 nm) were subsiding into the tropical trade wind regime (TWR) where sulfur chemistry transformed them to larger particles. Sulfur chemistry promoted the growth of some of these particles until they were large enough to activate to cloud drops. This process, promoted by sulfur chemistry, can produce a cooling effect due to the increase in cloud droplet density and changes in cloud droplet size. These increases in particle size observed in PASE promote additional cooling due to direct scattering from the aerosol. These potential impacts on the radiation balance in the TWR are enhanced by the high solar irradiance and ocean albedo of the TWR. Finally because of the large area involved there is a large factional impact on earth??s radiation budget. The TWR region near Christmas Island appears to be similar to the TWR that persists in August and September, from southwest of the Galapagos to at least Christmas Island. Transport in the TWR between the Galapagos and Christmas involves very little precipitation which could have removed the aerosol thus explaining at least in part the high concentrations of CCN (??300 at 0.5% supersaturation) observed in PASE. As expected the chemistry of sulfur in the trade winds was found to be initiated by the emission of DMS into the convective boundary layer (BL, the lowest of three layers). However, the efficiency with which this DMS is converted to SO₂ has been brought into further question by this study. This unusual result has come about as result of our using two totally different approaches for addressing this long standing question. In the first approach, based on accepted kinetic rate constants and detailed steps for the oxidation of DMS reflecting detailed laboratory studies, a DMS to SO₂ conversion efficiency of 60?C73% was determined. This range of values lies well within the uncertainties of previous studies. However, using a completely different approach, involving a budget analysis, a conversion value of 100% was estimated. The latter value, to be consistent with all other sulfur studies, requires the existence of a completely independent sulfur source which would emit into the atmosphere at a source strength approximately half that measured for DMS under tropical Pacific conditions. At this time, however, there is no credible scientific observation that identifies what this source might be. Thus, the current study has opened for future scientific investigation the major question: is there yet another major tropical marine source of sulfur? Of equal importance, then, is the related question, is our global sulfur budget significantly in error due to the existence of an unknown marine source of sulfur? Pivotal to both questions may be gaining greater insight about the intermediate DMS oxidation species, DMSO, for which rather unusual measurements have been reported in previous marine sulfur studies. The 3 pptv bromine deficit observed in PASE must be lost over the lifetime of the aerosol which is a few days. This observation suggests that the primary BrO production rate is very small. However, considering the uncertainties in these observations and the possible importance of secondary production of bromine radicals through aerosol surface reactions, to completely rule out the importance of bromine chemistry under tropical conditions at this time cannot be justified. This point has been brought into focus from prior work that even at levels of 1 pptv, the effect of BrO oxidation on DMS can still be quite significant. Thus, as in the case of DMS conversion to SO₂, future studies will be needed. In the latter case there will need to be a specific focus on halogen chemistry. Such studies clearly must involve specific measurements of radical species such as BrO.     

Bank-derived carbonate sediment transport and dissolution in the Hawaiian Archipelago

This investigation used two approaches to examine the flux of bank-derived carbonate particles and determine the potential influence of benthic carbonate particle dissolution on the carbon chemistry of the waters around the Hawaiian Archipelago. First, the particle flux near several representative carbonate banks in the Hawaiian Archipelago was measured and compared with the flux at a distal site (ALOHA) approximately 100 km north of Oahu, Hawaii. The results of four sediment trap deployments on three carbonate banks in the Hawaiian Archipelago demonstrate that the flux of bank-derived carbonate particles are consistently one to two orders of magnitude higher than the fluxes at the distal station. Furthermore, the mineralogy of the carbonate flux near the banks, which includes very soluble bank-derived aragonite and magnesian calcite particles, is distinctly different from that of the distal fluxes. Second, the chemistry of the waters at each bank station along the archipelago was characterized and compared with the chemistry of the distal waters to determine if differences in the particle flux were reflected in the carbon chemistry. Higher alkalinity and carbonate ion concentrations were observed around all of the banks studied. The saturation state of these waters suggests that the dissolution of some magnesian calcite and aragonite phases could explain the higher alkalinity values. Calculations suggest that the dissolution of benthically-derived aragonite and magnesian calcite may be an important component of the North Pacific alkalinity budget and a potential sink for anthropogenic CO₂.     

Determining the uniqueness of best-fit trishear models

We show the application of a simulated annealing algorithm to trishear inverse modeling. The algorithm traverses the parameter space in search for best-fit models without being trapped in local minima, and thus sampling for more possible solutions globally. Simulated annealing is a robust and efficient technique to determine the uniqueness of best-fit trishear models; the spread of possible trishear models that can fit a structure. We first apply the algorithm to a decameter-size, contractional fault-propagation fold in west-central Taiwan, for which there is an exceptional exposure of pre-growth and growth strata. Simulated annealing shows that even for this complete fold dataset with low uncertainties, there is a range of models and fault slip/uplift histories that can fit the data, with the consequent implications for the assessment of seismic hazard. We then apply the algorithm to a kilometer-size, extensional fault-propagation fold, the Hadahid monocline, Gulf of Suez Rift, Egypt. In this monocline there is only surface coverage in the footwall anticline areas and the algorithm was used to delimit the range of possible models that can fit the data and their uncertainties, thus avoiding biases in the interpretation. Simulated annealing suggests that the along-strike structural variability of the monocline can result from along-strike variability in fault slip, fault propagation to fault slip ratio and depth of fault nucleation. Both examples illustrate the benefits of searching for a possible range of models rather than a precise best-fit model when modeling fault-propagation folds. In an attempt to understand which parameters control fault development, and also how the spread of possible solutions varies with fold growth, we apply the algorithm to four sequential stages of a published, analog clay model of an extensional forced fold. The inversions of the natural examples and the analog model suggest that the spread of the possible models is a manifestation of the data uncertainties, the suitability of the trishear model, fold evolution, and rock mechanical properties.     

Tessellations in GIS: Part I—putting it all together

This article attempts to describe the role of tessellated models of space within the discipline of geographic information systems (GIS)—a speciality coming largely out of geography and land surveying, where there was a strong need to represent information about the land’s surface within a computer system rather than on the original paper maps. We look at some of the basic operations in GIS, including dynamic and kinetic applications. We examine issues of topology and data structures and produce a tessellation model that may be widely applied both to traditional “object” and “field” data types. Based on this framework, it can be argued that tessellation models are fundamental to our understanding and processing of geographical space, and provide a coherent framework for understanding the “space” in which we exist. This first article examines static structures, and a subsequent article looks at “change”—what happens when things move.     

The spatial and temporal distribution of grain‐size breaks in turbidites

Grain‐size breaks are surfaces where abrupt changes in grain size occur vertically within deposits. Grain‐size breaks are common features in turbidites around the world, including ancient and modern systems. Despite their widespread occurrence, grain‐size breaks have been regarded as exceptional, and not included within idealized models of turbidity current deposition. This study uses ca 100 shallow sediment cores, from the Moroccan Turbidite System, to map out five turbidite beds for distances in excess of 2000 km. The vertical and spatial distributions of grain‐size breaks within these beds are examined. Five different types of grain‐size break are found: Type I – in proximal areas between coarse sand and finer grained structureless sand; Type II – in proximal areas between inversely graded sand overlain by finer sand; Type III – in proximal areas between sand overlain by ripple cross‐laminated finer sand; Type IV – throughout the system between clean sand and mud; and Type V – in distal areas between mud‐rich (debrite) sand and mud. This article interprets Types I and V as being generated by sharp vertical concentration boundaries, controlled by sediment and clay concentrations within the flows, whilst Types II and III are interpreted as products of spatial/temporal fluctuations in flow capacity. Type IV are interpreted as the product of fluid mud layers, which hinder the settling of non‐cohesive grains and bypasses them down slope. Decelerating suspensions with sufficient clay will always form cohesive layers near to bed, promoting the generation of Type IV grain‐size breaks. This may explain why Type IV grain‐size breaks are widespread in all five turbidites examined and are commonplace within turbidite sequences studied elsewhere. Therefore, Type IV grain‐size breaks should be understood as the norm, not the exception, and regarded as a typical feature within turbidite beds.     

Petrogenesis of main group pallasite meteorites based on relationships among texture,mineralogy, and geochemistry

Main group pallasite meteorites are samples of a single early magmatic planetesimal, dominated by metal and olivine but containing accessory chromite, sulfide, phosphide, phosphates, and rare phosphoran olivine. They represent mixtures of core and mantle materials, but the environment of formation is poorly understood, with a quiescent core–mantle boundary, violent core–mantle mixture, or surface mixture all recently suggested. Here, we review main group pallasite data sets and petrologic characteristics, and present new observations on the low‐MnO pallasite Brahin that contains abundant fragmental olivine, but also rounded and angular olivine and potential evidence of sulfide–phosphide liquid immiscibility. A reassessment of the literature shows that low‐MnO and high‐FeO subgroups preferentially host rounded olivine and low‐temperature P₂O₅‐rich phases such as the Mg‐phosphate farringtonite and phosphoran olivine. These phases form after metal and silicate reservoirs back‐react during decreasing temperature after initial separation, resulting in oxidation of phosphorus and chromium. Farringtonite and phosphoran olivine have not been found in the common subgroup PMG, which are mechanical mixtures of olivine, chromite with moderate Al₂O₃ contents, primitive solid metal, and evolved liquid metal. Lower concentrations of Mn in olivine of the low‐MnO PMG subgroup, and high concentrations of Mn in low‐Al₂O₃ chromites, trace the development and escape of sulfide‐rich melt in pallasites and the partially chalcophile behavior for Mn in this environment. Pallasites with rounded olivine indicate that the core–mantle boundary of their planetesimal may not be a simple interface but rather a volume in which interactions between metal, silicate, and other components occur.     

Germanium isotope measurements of high-temperature geothermal fluids using double-spike hydride generation MC-ICP-MS

We present a double-spike isotope dilution MC-ICP-MS technique for the determination of germanium (Ge) isotope fractionation. Using this technique we determined Ge isotope compositions of geothermal spring fluids, a Columbia River Basalt sample, and an in-house diatom standard. Our technique uses a ⁷³Ge/⁷⁰Ge double spike in combination with hydride generation for Ge extraction from the sample matrix. Fractionation is determined on the ⁷⁴Ge/⁷²Ge mass ratio. The double spike allows us to effectively correct analytical isotope fractionation. Our external standard reproducibility is 0.4‰ (2 SD) over the course of several months. The minimum quantity of Ge needed for isotope analysis is approximately 2 ng. Consistent with previous work on geothermal fluids, Ge in the geothermal spring samples presented here is enriched over Si as compared to low temperature weathering signatures. This observation is typically interpreted as Ge exclusion during silicate mineral precipitation (e.g., quartz). Our isotope results indicate that the analyzed high temperature fluids fractionate Ge isotopes with a range in δ⁷⁴Ge between −0.4‰ and −1.4‰ relative to a Columbia River basalt. We cautiously interpret the observed fractionation as preferential removal of heavy Ge isotopes out of solution during cooling of the hydrothermal fluid and subsequent precipitation of quartz.