Production of a molybdophore during metal-targeted dissolution of silicates by soil bacteria

Although many bioessential metals are scarce in natural water and rock systems, microbial secretion of high-affinity ligands for metal extraction from solid phases has only been documented for Fe. However, we have discovered that Mo is extracted from a silicate by a high-affinity ligand (a possible “molybdophore”) secreted by an N₂-fixing soil bacterium. The putative molybdophore, aminochelin, is secreted as a siderophore under Fe-depleted conditions, but is also secreted under Fe-sufficient, Mo-depleted conditions. Presumably, molybdophore production facilitates uptake of Mo for use in Mo enzymes. In contrast, an Fe-requiring soil bacterium without a special Mo requirement only enhances the release of Fe from the silicate. Fractionation of Mo stable isotopes during uptake to cells may provide a “fingerprint” for the importance of chelating ligands in such systems. Many such metal-specific ligands secreted by prokaryotes for extraction of bioessential metals, their effects on Earth materials, and their possible utility in the recovery of economic metals remain to be discovered.     

6: Classification of VMS deposits: Lessons from the South Uralides

VMS deposits of the South Urals developed within the evolving Urals palaeo-ocean between Silurian and Late Devonian times. Arc-continent collision between Baltica and the Magnitogorsk Zone (arc) in the south-western Urals effectively terminated submarine volcanism in the Magnitogorsk Zone with which the bulk of the VMS deposits are associated. The majority of the Urals VMS deposits formed within volcanic-dominated sequences in deep seawater settings. Preservation of macro and micro vent fauna in the sulphide bodies is both testament to the seafloor setting for much of the sulphides but also the exceptional degree of preservation and lack of metamorphic overprint of the deposits and host rocks. The deposits in the Urals have previously been classified in terms of tectonic setting, host rock associations and metal ratios in line with recent tectono-stratigraphic classifications. In addition to these broad classes, it is clear that in a number of the Urals settings, an evolution of the host volcanic stratigraphy is accompanied by an associated change in the metal ratios of the VMS deposits, a situation previously discussed, for example, in the Noranda district of Canada.Two key structural settings are implicated in the South Urals. The first is seen in a preserved marginal allochthon west of the Main Urals Fault where early arc tholeiites host Cu–Zn mineralization in deposits including Yaman Kasy, which is host to the oldest macro vent fauna assembly known to science. The second tectonic setting for the South Urals VMS is the Magnitogorsk arc where study has highlighted the presence of a preserved early forearc assemblage, arc tholeiite to calc-alkaline sequences and rifted arc bimodal tholeiite sequences. The boninitc rocks of the forearc host Cu–(Zn) and Cu–Co VMS deposits, the latter hosted in fragments within the Main Urals Fault Zone (MUFZ) which marks the line of arc-continent collision in Late Devonian times. The arc tholeiites host Cu–Zn deposits with an evolution to more calc-alkaline felsic volcanic sequences matched with a change to Zn–Pb–Cu polymetallic deposits, often gold-rich. Large rifts in the arc sequence are filled by thick bimodal tholeiite sequences, themselves often showing an evolution to a more calc-alkaline nature. These thick bimodal sequences are host to the largest of the Cu–Zn VMS deposits.The exceptional degree of preservation in the Urals has permitted the identification of early seafloor clastic and hydrolytic modification (here termed halmyrolysis sensu lato) to the sulphide assemblages prior to diagenesis and this results in large-scale modification to the primary VMS body, resulting in distinctive morphological and mineralogical sub-types of sulphide body superimposed upon the tectonic association classification.It is proposed that a better classification of seafloor VMS systems is thus achievable using a three stage classification based on (a) tectonic (hence bulk volcanic chemistry) association, (b) local volcanic chemical evolution within a single edifice and (c) seafloor reworking and halmyrolysis.     

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.     

Experimental determination of REE partition coefficients between zircon,garnet and melt: a key to understanding high‐T crustal processes

The partitioning of rare earth elements (REE) between zircon, garnet and silicate melt was determined using synthetic compositions designed to represent partial melts formed in the lower crust during anatexis. The experiments, performed using internally heated gas pressure vessels at 7 kbar and 900–1000 °C, represent equilibrium partitioning of the middle to heavy REE between zircon and garnet during high‐grade metamorphism in the mid to lower crust. The D_REE (zircon/garnet) values show a clear partitioning signature close to unity from Gd to Lu. Because the light REE have low concentrations in both minerals, values are calculated from strain modelling of the middle to heavy REE experimental data; these results show that zircon is favoured over garnet by up to two orders of magnitude. The resulting general concave‐up shape to the partitioning pattern across the REE reflects the preferential incorporation of middle REE into garnet, with D_Gd (zircon/garnet) ranging from 0.7 to 1.1, D_Ho (zircon/garnet) from 0.4 to 0.7 and D_Lu (zircon/garnet) from 0.6 to 1.3. There is no significant temperature dependence in the zircon–garnet REE partitioning at 7 kbar and 900–1000 °C, suggesting that these values can be applied to the interpretation of zircon–garnet equilibrium and timing relationships in the ultrahigh‐T metamorphism of low‐Ca pelitic and aluminous granulites.     

Late Quaternary sea‐level change and evolution of Belfast Lough,Northern Ireland: new offshore evidence and implications for sea‐level reconstruction

The interplay of eustatic and isostatic factors causes complex relative sea‐level (RSL) histories, particularly in paraglacial settings. In this context the past record of RSL is important in understanding ice‐sheet history, earth rheology and resulting glacio‐isostatic adjustment. Field data to develop sea‐level reconstructions are often limited to shallow depths and uncertainty exists as to the veracity of modelled sea‐level curves. We use seismic stratigraphy, 39 vibrocores and 26 radiocarbon dates to investigate the deglacial history of Belfast Lough, Northern Ireland, and reconstruct past RSL. A typical sequence of till, glacimarine and Holocene sediments is preserved. Two sea‐level lowstands (both max. ?40 m) are recorded at c. 13.5 and 11.5k cal a bp . Each is followed by a rapid transgression and subsequent periods of RSL stability. The first transgression coincides temporally with a late stage of Meltwater Pulse 1a and the RSL stability occurred between c. 13.0 and c. 12.2k cal a bp (Younger Dryas). The second still/slowstand occurred between c. 10.3 and c. 11.5k cal a bp . Our data provide constraints on the direction and timing of RSL change during deglaciation. Application of the Depth of Closure concept adds an error term to sea‐level reconstructions based on seismic stratigraphic reconstructions.     

Diagnosing snow accumulation errors in a rain‐snow transitional environment with snow board observations

Diagnosing the source of errors in snow models requires intensive observations, a flexible model framework to test competing hypotheses, and a methodology to systematically test the dominant snow processes. We present a novel process‐based approach to diagnose model errors through an example that focuses on snow accumulation processes (precipitation partitioning, new snow density, and snow compaction). Twelve years of meteorological and snow board measurements were used to identify the main source of model error on each snow accumulation day. Results show that modeled values of new snow density were outside observational uncertainties in 52% of days available for evaluation, while precipitation partitioning and compaction were in error 45% and 16% of the time, respectively. Precipitation partitioning errors mattered more for total winter accumulation during the anomalously warm winter of 2014–2015, when a higher fraction of precipitation fell within the temperature range where partition methods had the largest error. These results demonstrate how isolating individual model processes can identify the primary source(s) of model error, which helps prioritize future research.     

Constraints on the timing and conditions of high‐grade metamorphism,charnockite formation and fluid–rock interaction in the Trivandrum Block,southern India

Incipient charnockites have been widely used as evidence for the infiltration of CO₂‐rich fluids driving dehydration of the lower crust. Rocks exposed at Kakkod quarry in the Trivandrum Block of southern India allow for a thorough investigation of the metamorphic evolution by preserving not only orthopyroxene‐bearing charnockite patches in a host garnet–biotite felsic gneiss, but also layers of garnet–sillimanite metapelite gneiss. Thermodynamic phase equilibria modelling of all three bulk compositions indicates consistent peak‐metamorphic conditions of 830–925 °C and 6–9 kbar with retrograde evolution involving suprasolidus decompression at high temperature. These models suggest that orthopyroxene was most likely stabilized close to the metamorphic peak as a result of small compositional heterogeneities in the host garnet–biotite gneiss. There is insufficient evidence to determine whether the heterogeneities were inherited from the protolith or introduced during syn‐metamorphic fluid flow. U–Pb geochronology of monazite and zircon from all three rock types constrains the peak of metamorphism and orthopyroxene growth to have occurred between the onset of high‐grade metamorphism at c. 590 Ma and the onset of melt crystallization at c. 540 Ma. The majority of metamorphic zircon growth occurred during protracted melt crystallization between c. 540 and 510 Ma. Melt crystallization was followed by the influx of aqueous, alkali‐rich fluids likely derived from melts crystallizing at depth. This late fluid flow led to retrogression of orthopyroxene, the observed outcrop pattern and to the textural and isotopic modification of monazite grains at c. 525–490 Ma.