Sulfide Oxidation across Diffuse Flow Zones of Hydrothermal Vents

The sulfide (H₂S/HS^?) that is emitted from hydrothermal vents begins to oxidize abiotically with oxygen upon contact with ambient bottom water, but the reaction kinetics are slow. Here, using in situ voltammetry, we report detection of the intermediate sulfur oxidation products polysulfides [ $ {\text{S}}_{\text{x}}^{2 - } $ ] and thiosulfate [ $ {\text{S}}_{ 2} {\text{O}}_{ 3}^{ 2- } $ ], along with contextual data on sulfide, oxygen, and temperature. At Lau Basin in 2006, thiosulfate was identified in less than one percent of approximately 10,500 scans and no polysulfides were detected. Only five percent of 11,000 voltammetric scans taken at four vent sites at Lau Basin in May 2009 show either thiosulfate or polysulfides. These in situ data indicate that abiotic sulfide oxidation does not readily occur as H₂S contacts oxic bottom waters. Calculated abiotic potential sulfide oxidation rates are <10^?3 ??M/min and are consistent with slow oxidation and the observed lack of sulfur oxidation intermediates. It is known that the thermodynamics for the first electron transfer step for sulfide and oxygen during sulfide oxidation in these systems are unfavorable, and that the kinetics for two electron transfers are not rapid. Here, we suggest that different metal catalyzed and/or biotic reaction pathways can readily produce sulfur oxidation intermediates. Via shipboard high-pressure incubation experiments, we show that snails with chemosynthetic endosymbionts do release polysulfides and may be responsible for our field observations of polysulfides.     

Excess air during aquifer storage and recovery in an arid basin (Las Vegas Valley, USA)

The Las Vegas Valley Water District in Nevada, USA, has operated an artificial recharge (AR) program since 1989. In summer 2001, observations of gas exsolving from tap water prompted a study that revealed total dissolved gas (TDG) pressures approaching 2?atm with a gas composition that it is predominantly air. Measurements of TDG pressure at well heads and in the distribution system indicated two potential mechanisms for elevated TDG pressures: (1) air entrainment during AR operations, and (2) temperature changes between the winter recharge season and the summer withdrawal season. Air entrainment during pumping was investigated by intentionally allowing the forebay (upstream reservoir) of a large pumping station to drawdown to the point of vortex formation. This resulted in up to a 0.7?atm increase in TDG pressure. In general, the solubility of gases in water decreases as the temperature increases. In the Las Vegas Valley, water that acquired a modest amount of dissolved gas during winter artificial recharge operations experienced an increase in dissolved gas pressure (0.04?atm/°C) as the water warmed in the subsurface. A combination of air entrainment during AR operations and its amplification by temperature increase after recharge can account for most of the observed amounts of excess gas at this site.     

Multidegrees‐of‐freedom effective force testing: a feasibility study and robust stability assessment

This paper presents a feasibility study of multidegrees‐of‐freedom effective force testing (MDOF‐EFT). The study is intended to facilitate the development of a force feedback controller and investigation of performance as well as robustness of MDOF‐EFT. First, the dynamics of MDOF‐EFT systems are analytically investigated. Analytical transfer functions of the control plant, the valve‐to‐force relations, showed that the plant is dynamically coupled and the natural frequencies of test structures are the transmission zeros of the plant. Using a set of model parameters from a previous study, a case study that includes controller design, numerical simulations and robust stability assessment is performed. A decoupling loop shaping (DLS) controller consisting of a pseudo inverse of the plant and second‐order loop shaping controllers is adopted as the force feedback controller. It is shown that the DLS controller provides a stable control system while successfully decoupling the control loops and compensating the control‐structure interaction. Numerical simulations demonstrate that the DLS controller enables tracking of static and dynamic forces for multiple actuators. Robust stability of MDOF‐EFT with the DLS controller is assessed using Monte Carlo simulation. The stochastic simulation results show that the DLS controller is stable and robust, providing sufficient stability margins for uncertain models with maximum 50% errors in the estimated system parameters. This paper demonstrates that MDOF‐EFT is feasible with the DLS controller and can be implemented in experimental laboratories. Copyright © 2013 John Wiley & Sons, Ltd.     

Acheulean artifact accumulation and early hominin land use,Garden Route Casino Road,Pinnacle Point,South Africa

An Early Stone Age Acheulean lithic assemblage collected along a 1.5‐km transect at the Garden Route Casino near Pinnacle Point, Mossel Bay, South Africa, was examined in order to assess the relative degree to which assemblage variability is impacted by post‐occupational processes and/or terrain. It was found that post‐occupational variables do vary across the study area, and they affect the positions of artifacts to different degrees. Terrain structure was determined to have minimal effect on artifact movement. Three analysis sections were identified as having artifacts that were likely close to their original positions and compositions. Future interpretations of differential land use can now be tempered with considerations of the post‐occupational processes that formed the recovered assemblage. © 2009 Wiley Periodicals, Inc.     

Preliminary evidence for human fecal contamination in corals of the Florida Keys,USA

Corals and reef environments are under increased stress from anthropogenic activities, particularly those in the vicinity of heavily populated areas such as the Florida Keys. The potential adverse impacts of wastewater can affect both the environment and human health; however, because of the high decay rate of bacterial indicators in coral reef waters it has been difficult to document the presence of microbial contaminants and to assign risks in these environments. Here we show initial evidence that microorganisms associated with human feces are concentrated along the surface of coral heads relative to the overlying water column in the Florida Keys. Bacterial indicators (fecal coliform bacteria, enterococci or Clostridium perfringens) were detected in 66.7% of the coral surface microlayer (CSM) samples at levels between five and 1000 CFU/100 ml, but were found infrequently and at low numbers in the overlying water column ( < or = 2.5 CFU/100 ml). Similarly, enterovirus nucleic acid sequences, an indicator of human-specific waste, were detected in 93.3% of the CSM samples and only once in the water column by cell culture. Results show that coral mucus may accumulate enteric microorganisms in reef environments, and may indicate a risk to public and environmental health despite low indicator levels in the surrounding water.     

Multi‐year water balance assessment of a newly constructed wetland,Fort McMurray,Alberta

Oil sands mining in Alberta transforms the boreal landscape of forests and wetlands into open pits, tailings ponds and overburden piles. Whereas reclamation efforts have primarily focused on upland forests, rebuilding wetland systems has recently become a motivation for research. Wetland creation and sustainability in this region is complicated by the sub‐humid climate and salinity of underlying mining material. In 2012, Syncrude Canada Ltd. completed the construction of the Sandhill Fen Watershed (SFW), a 52‐ha upland‐wetland system to evaluate wetland reclamation strategies on soft tailings. SFW includes an active pumping system, upland hummocks, a fen wetland and underdrains. To evaluate the influence of management practices on the hydrology of the system, this study reports the water balance from January 2013 to December 2014, the first 2 years after commissioning. A semi‐distributed approach was taken to examine the fluxes and stores of water in uplands and lowlands. Natural and artificial inputs and outputs were measured using a series of precipitation gauges and pumps, and evapotranspiration was quantified using three eddy covariance towers. A series of near surface wells recorded water table position. Both 2013 and 2014 were normal rainfall years, with 2013 having more and 2014 less snow than normal. In 2013, inflow/outflow from pumping was the predominant hydrological fluxes, resulting in considerable variability in water table position and storage changes throughout the summer. In 2014, the artificial addition of water was negligible, yet the water table remained near the surface in lowland locations, suggesting that wetland conditions could be maintained under current conditions. Evapotranspiration rates between uplands and lowlands were similar between years and sites, ranging from 2.2 ± 1.8 to 2.5 ± 1.2 mm/day and were largely controlled by climate. These rates were less than nearby older upland systems, suggesting that water balance partitioning will change as vegetation develops. Comparison between years and with natural systems provides insight on how management practices influence hydrologic dynamics and the overall water balance of the SFW. Copyright © 2016 John Wiley & Sons, Ltd.     

Tectonic core of a sedimentary drift: a potential ridge propagation feature beneath the Blake Outer Ridge

The Blake Outer Ridge is a 480–kilometer long linear sedimentary drift ridge striking perpendicular to the North American coastline. By modeling free-air gravity anomalies we tested for the presence of a crustal feature that may control the location and orientation of the Blake Outer Ridge. Most of our crustal density models that match observed gravity anomalies require an increase in oceanic crustal thickness of 1–3 km on the southwest side of the Blake Outer Ridge relative to the northeast side. Most of these models also require 1–4 km of crustal thinning in zone 20–30 km southwest of the crest of the Blake Outer Ridge. Although these features are consistent with the structure of oceanic fracture zones, the Blake Outer Ridge is not parallel to adjacent known fracture zones. Magnetic anomalies suggest that the ocean crust beneath this feature formed during a period of mid-ocean ridge reorganization, and that the Blake Outer Ridge may be built upon the bathymetric expression of an oblique extensional feature associated with ridge propagation. It is likely that the orientation of this trough acted as a catalyst for sediment deposition with the start of the Western Boundary Undercurrent in the mid-Oligocene.     

Paragenesis and geochemistry of ore minerals in the epizonal gold deposits of the Yangshan gold belt,West Qinling,China

Six epizonal gold deposits in the 30-km-long Yangshan gold belt, Gansu Province are estimated to contain more than 300 t of gold at an average grade of 4.76 g/t and thus define one of China's largest gold resources. Detailed paragenetic studies have recognized five stages of sulfide mineral precipitation in the deposits of the belt. Syngenetic/diagenetic pyrite (Py₀) has a framboidal or colloform texture and is disseminated in the metasedimentary host rocks. Early hydrothermal pyrite (Py₁) in quartz veins is disseminated in metasedimentary rocks and dikes and also occurs as semi-massive pyrite aggregates or bedding-parallel pyrite bands in phyllite. The main ore stage pyrite (Py₂) commonly overgrows Py₁ and is typically associated with main ore stage arsenopyrite (Apy₂). Late ore stage pyrite (Py₃), arsenopyrite (Apy₃), and stibnite occur in quartz ± calcite veins or are disseminated in country rocks. Post-ore stage pyrite (Py₄) occurs in quartz ± calcite veins that cut all earlier formed mineralization. Electron probe microanalyses and laser ablation-inductively coupled plasma mass spectrometry analyses reveal that different generations of sulfides have characteristic of major and trace element patterns, which can be used as a proxy for the distinct hydrothermal events. Syngenetic/diagenetic pyrite has high concentrations of As, Au, Bi, Co, Cu, Mn, Ni, Pb, Sb, and Zn. The Py₀ also retains a sedimentary Co/Ni ratio, which is distinct from hydrothermal ore-related pyrite. Early hydrothermal Py₁ has high contents of Ag, As, Au, Bi, Cu, Fe, Sb, and V, and it reflects elevated levels of these elements in the earliest mineralizing metamorphic fluids. The main ore stage Py₂ has a very high content of As (median value of 2.96 wt%) and Au (median value of 47.5 ppm) and slightly elevated Cu, but relatively low values for other trace elements. Arsenic in the main ore stage Py₂ occurs in solid solution. Late ore stage Py₃, formed coevally with stibnite, contains relatively high As (median value of 1.44 wt%), Au, Fe, Mn, Mo, Sb, and Zn and low Bi, Co, Ni, and Pb. The main ore stage Apy₂, compared to late ore stage arsenopyrite, is relatively enriched in As, whereas the later Apy₃ has high concentrations of S, Fe, and Sb, which is consistent with element patterns in associated main and late ore stage pyrite generations. Compared with pyrite from other stages, the post-ore stage Py₄ has relatively low concentrations of Fe and S, whereas As remains elevated (2.05～3.20 wt%), which could be interpreted by the substitution of As^? for S in the pyrite structure. These results suggest that syngenetic/diagenetic pyrite is the main metal source for the Yangshan gold deposits where such pyrite was metamorphosed at depth below presently exposed levels. The ore-forming elements were concentrated into the hydrothermal fluids during metamorphic devolatilization, and subsequently, during extensive fluid–rock interaction at shallower levels, these elements were precipitated via widespread sulfidation during the main ore stage.     

Mineralogical and geochemical investigations of silicate-rich mine waste from a kyanite mine in central Virginia: implications for mine waste recycling

A kyanite mine in central Virginia produces a silicate-rich waste stream which accumulates at a rate of 450,000–600,000 tons per year. An estimated 27 million tons of this waste stream has accumulated over the past 60 years. Grain size distribution varies between 1.000 and 0.053 mm, and is commonly bimodal with modes typically being 0.425 and 0.250 mm and uniformity coefficients vary from 2.000 to 2.333. Hydraulic conductivity values vary from 0.017 to 0.047 cm/s. Mineralogy of the waste stream consists of quartz, muscovite, kyanite and hematite. Muscovite grains have distinct chemical compositions with significant Na₂O content (1.12–2.66 wt%), TiO₂ content (0.63–1.68 wt% TiO₂) and Fe content, expressed as Fe₂O₃ (up to 1.37 wt%). Major element compositions of samples were dominated by SiO₂ (87.894–90.997 wt%), Al₂O₃ (6.759–7.741 wt%), Fe₂O₃ (1.136–1.283 wt%), and K₂O (0.369–0.606 wt%) with other components being <1.000 wt%. Elements of environmental concern (V, Cr, Ni, Cu, Zn, As, Ag, Sn, Sb, Ba, Hg, Tl, and Pb) were detected; however, the concentrations of all elements except Ni were below that of the kyanite quartzites in the region from which the waste is derived. Both major and trace element compositions indicate minimal variation in composition. The waste stream has potential for recycling. Muscovite is suitable for recycling as a paint pigment or other industrial applications. Muscovite and hematite are commonly intergrown and are interpreted to be material where much of the elements of environmental concern are concentrated. Reprocessing of the waste stream to separate muscovite from other components may enable the waste stream to be used as constructed wetland media for Virginia and nearby states. Recycling of this mine waste may have a positive impact on the local economy of Buckingham County and aid in mitigation of wetland loss.