Trace elements in New Zealand ferromanganese nodules: implications for deep sea environments

<p>Ferromanganese nodules are authigenic marine sediments that form over millions of years from the precipitation of Fe oxyhydroxides and Mn oxides from seawater (hydrogenetic-type growth) and sediment pore-water (diagenetic-type growth). Fe-Mn (oxyhydr)oxides grow in layers about nuclei, effectively scavenging minor metals such as Ni, Cu and Co from the waters they grow in. The uptake of different elements into the ferromanganese nodules reflects their environment and mechanism of growth, and these deposits are of interest both as a potential source of metals of economic interest, and as records of changing ocean conditions. This study investigates the composition of 77 ferromanganese nodules from the seafloor around New Zealand. Samples analysed come from locations several thousand kilometres apart under the same water mass (Lower Circumpolar Deep Water – LCDW), but with varying depth, current velocity, and sediment type. The outermost 1 mm rim of each nodule, representing near-modern growth, was sampled to compare with modern environmental parameters including substrate sediment composition and chemical and physical oceanography. Major, minor, and trace element analysis of nodule rims were undertaken, and the authigenic and detrital components examined via leaching experiments to evaluate their relative influence on growth mechanisms. Overall, New Zealand ferromanganese nodules are hydrogenetic in origin. However, there are systematic variations in composition that reflect variable diagenetic influence. Hydrogenetic endmember compositions are defined by samples from two localities in the Southern Ocean that have no evidence for diagenetic influence. Diagenetic influence on nodule composition is exemplified by samples from the two locations in the Tasman Sea, but also include nodules from the Campbell nodule field. Nodules from the Campbell nodule field come from two transects perpendicular to the Campbell Plateau, and the Deep Western Boundary Current (DWBC). Both sediment composition and nodule rim chemistry vary systematically across both transects. Areas closest to the slope have sediment profiles indicating high energy, erosive environments, continental-sourced sand components, and are dominated by nodules with hydrogenetic chemical characteristics similar to those of the Southern Ocean. Further from the slope, the sediment profiles indicate silt dominated sediments of a more oceanic crustal provenance, lower energy environment, and increased influence of oxic diagenetic processes on the major, minor and trace element profiles of the nodules. No hydrothermal contribution was identified in the chemistry of any of the nodules analysed. The physical and chemical properties of the sediment, along with current velocities, were found to be the key influences in diagenetic enrichment in the nodules. The influence of seawater chemistry was difficult to determine due to the lack of direct analyses in the area. Ferromanganese nodule chemistry is a function of the nodule environment, including water body, sediment composition and depth. The authigenic components of nodules can therefore be used to investigate the deep-sea environment. The redox conditions of sediments and the productivity of the overlying water will affect the trace metal constituents of the pore-waters of a sediment (Kuhn et al., 2017). Sediments with a larger fraction of labile organic matter may result in trace element enrichment of the pore-water. Sediments below the CCD will be higher in trace elements than sediments below the CCD (U1413, U1406B, U1402, U1398, U1398, and U1378) due to carbonate matter acting as a dilutant that can limit the supply of trace elements mobilised in the pore-water during diagenesis (Glasby, 2006). Terrigenous clasts such as quartz (Chester, 1990), will also reduce trace element enrichment in the pore-water due to their low reactivity, e.g. for the sediment U1406B, which has a high lithic component (Table 3.2). Sediments with a higher biogenic silica component (such as U1373, U1374, and U1378) (Table 3.2, Table 3.4) are predicted to produce nodules with higher trace element contents (ISA, 2010). In contrast to both the CCZ and Indian Ocean nodules, the Campbell nodule field samples formed above the CCD, and hence in sediments that include a significant carbonate component. This minimises the trace element pore-water enrichment and can account for the lower Cu+Ni+Co contents observed in the Campbell nodule field nodules compared with those that formed below the CCD (CCZ and Indian Ocean).</p>

Trace elements in New Zealand ferromanganese nodules: implications for deep sea environments

<p>Ferromanganese nodules are authigenic marine sediments that form over millions of years from the precipitation of Fe oxyhydroxides and Mn oxides from seawater (hydrogenetic-type growth) and sediment pore-water (diagenetic-type growth). Fe-Mn (oxyhydr)oxides grow in layers about nuclei, effectively scavenging minor metals such as Ni, Cu and Co from the waters they grow in. The uptake of different elements into the ferromanganese nodules reflects their environment and mechanism of growth, and these deposits are of interest both as a potential source of metals of economic interest, and as records of changing ocean conditions. This study investigates the composition of 77 ferromanganese nodules from the seafloor around New Zealand. Samples analysed come from locations several thousand kilometres apart under the same water mass (Lower Circumpolar Deep Water – LCDW), but with varying depth, current velocity, and sediment type. The outermost 1 mm rim of each nodule, representing near-modern growth, was sampled to compare with modern environmental parameters including substrate sediment composition and chemical and physical oceanography. Major, minor, and trace element analysis of nodule rims were undertaken, and the authigenic and detrital components examined via leaching experiments to evaluate their relative influence on growth mechanisms. Overall, New Zealand ferromanganese nodules are hydrogenetic in origin. However, there are systematic variations in composition that reflect variable diagenetic influence. Hydrogenetic endmember compositions are defined by samples from two localities in the Southern Ocean that have no evidence for diagenetic influence. Diagenetic influence on nodule composition is exemplified by samples from the two locations in the Tasman Sea, but also include nodules from the Campbell nodule field. Nodules from the Campbell nodule field come from two transects perpendicular to the Campbell Plateau, and the Deep Western Boundary Current (DWBC). Both sediment composition and nodule rim chemistry vary systematically across both transects. Areas closest to the slope have sediment profiles indicating high energy, erosive environments, continental-sourced sand components, and are dominated by nodules with hydrogenetic chemical characteristics similar to those of the Southern Ocean. Further from the slope, the sediment profiles indicate silt dominated sediments of a more oceanic crustal provenance, lower energy environment, and increased influence of oxic diagenetic processes on the major, minor and trace element profiles of the nodules. No hydrothermal contribution was identified in the chemistry of any of the nodules analysed. The physical and chemical properties of the sediment, along with current velocities, were found to be the key influences in diagenetic enrichment in the nodules. The influence of seawater chemistry was difficult to determine due to the lack of direct analyses in the area. Ferromanganese nodule chemistry is a function of the nodule environment, including water body, sediment composition and depth. The authigenic components of nodules can therefore be used to investigate the deep-sea environment. The redox conditions of sediments and the productivity of the overlying water will affect the trace metal constituents of the pore-waters of a sediment (Kuhn et al., 2017). Sediments with a larger fraction of labile organic matter may result in trace element enrichment of the pore-water. Sediments below the CCD will be higher in trace elements than sediments below the CCD (U1413, U1406B, U1402, U1398, U1398, and U1378) due to carbonate matter acting as a dilutant that can limit the supply of trace elements mobilised in the pore-water during diagenesis (Glasby, 2006). Terrigenous clasts such as quartz (Chester, 1990), will also reduce trace element enrichment in the pore-water due to their low reactivity, e.g. for the sediment U1406B, which has a high lithic component (Table 3.2). Sediments with a higher biogenic silica component (such as U1373, U1374, and U1378) (Table 3.2, Table 3.4) are predicted to produce nodules with higher trace element contents (ISA, 2010). In contrast to both the CCZ and Indian Ocean nodules, the Campbell nodule field samples formed above the CCD, and hence in sediments that include a significant carbonate component. This minimises the trace element pore-water enrichment and can account for the lower Cu+Ni+Co contents observed in the Campbell nodule field nodules compared with those that formed below the CCD (CCZ and Indian Ocean).</p>

A new kind of invisible gold in pyrite hosted in deformation-related dislocations

Mining of “invisible gold” associated with sulfides in gold ores represents a significant proportion of gold production worldwide. Gold hosted in sulfide minerals has been proposed to be structurally bound in the crystal lattice as a sulfide-gold alloy and/or to occur as discrete metallic nanoparticles. Using a combination of microstructural quantification and nanoscale geochemical analyses on a pyrite crystal from an orogenic gold deposit, we show that dislocations hosted in a deformation low-angle boundary can be enriched in Ni, Cu, As, Pb, Sb, Bi, and Au. The cumulative trace-element enrichment in the dislocations is 3.2 at% higher compared to the bulk crystal. We propose that trace elements were segregated during the migration of the dislocation following the dislocation-impurity pair model. The gold hosted in nanoscale dislocations represents a new style of invisible gold.

The composition of subduction zone fluids and the origin of the trace element enrichment in arc magmas

The partitioning of major and trace elements between eclogite and aqueous fluids with variable salinity was studied at 700–800 °C and 4–6 GPa in piston cylinder and multi anvil experiments. Fluid compositions were determined using the diamond trap technique combined with laser ablation ICP-MS measurements in the frozen state. In addition to NaCl, SiO2 is the main solute in the fluids. The fluid/eclogite partition coefficients of the large ion lithophile elements (LILE), such as Rb, Cs, Sr, and Ba as well as those of the light rare earths (LREE), of Pb, and of U increase by up to three orders of magnitude with salinity. These elements will therefore be efficiently transported by saline fluids. On the other hand, typical high field strength elements, such as Ti, Nb, and Ta, are not mobilized even at high salinities. Increasing temperature and pressure gradually increases the partitioning into the fluid. In particular, Th is mobilized by silica-rich fluids at 6 GPa already at low salinities. We show that we can fully reproduce the trace element enrichment pattern of primitive arc basalts by adding a few percent of saline fluid (with 5–10 wt% Cl) released from the basaltic slab to the zone of melting in the mantle wedge. Assuming 2 wt% of rutile in the eclogite equilibrated with the saline fluid produces a negative Nb Ta anomaly that is larger than in most primitive arc basalts. Therefore, we conclude that the rutile fraction in the subducted eclogite below most arcs is likely < 1 wt%. In fact, saline fluids would even produce a noticeable negative Nb Ta anomaly without any rutile in the eclogite residue. Metasomatism by sediment melts alone, on the other hand, is unable to produce the enrichment pattern seen in arc basalts. We, therefore, conclude that at least for primitive arc basalts, the release of hydrous fluids from the basaltic part of the subducted slab is the trigger for melting and the main agent of trace element enrichment. The contribution of sediment melts to the petrogenesis of these magmas is likely negligible. In the supplementary material, we provide a “Subduction Calculator” in Excel format, which allows the calculation of the trace element abundance pattern in primitive arc basalts as function of fluid salinity, the amount of fluid released from the basaltic part of the subducted slab, the fluid fraction added to the source, and the degree of melting.

Trace-elemental and petrographic constraints on the severity of hydrographic restriction in the silled Midland Basin during the late Paleozoic ice age

Enrichment of redox-sensitive trace elements in ancient marine shales is conventionally believed to be controlled by marine benthic redox conditions, whereas the influence of hydrographic conditions on trace element enrichment pattern has been rarely considered. Here, we present newly obtained data sets from the Upper Pennsylvanian organic-rich Cline Shale in the Midland Basin, Texas, to illustrate the influence of hydrographic circulation on the trace-element enrichment pattern and the stratigraphic record of mudrocks. Various lithofacies, including siliceous mudrocks, argillaceous mudrocks, skeletal-bearing argillaceous mudrocks, calcareous mudrocks, and wackestone, are identified in the Cline Shale. Significant changes in the trace-element enrichment pattern, mineral composition, texture of framboidal pyrite, and other bulk geochemical parameters in different lithofacies are interpreted to have been caused by high-amplitude and high-frequency glacio-eustatic sea-level oscillations in the silled Midland Basin during the late Paleozoic ice age. Specifically, glacio-eustatic sea-level falls generally resulted in the severe isolation of the Midland Basin from the Panthalassic Ocean, highly restricted hydrographic circulation, long deep-water renewal time, euxinic bottom-water conditions, depleted seawater Mo (molybdenum) in the silled basin, and low sediment Mo/TOC (total organic carbon), coupled with significant extrabasinal detrital quartz input, forming siliceous mudrocks. Enhanced phosphorus cycling and excellent preservation conditions are considered to be responsible for the high TOC observed in siliceous mudrocks. In contrast, glacio-eustatic sea-level rises substantially enhanced water exchange between the basin and the Panthalassic Ocean, created overall suboxic to anoxic bottom-water conditions, resupplied seawater Mo, elevated sediment Mo/TOC, and increased platform carbonate production in the basin, forming calcareous mudrocks and wackestone.

Gradual and selective trace-element enrichment in slab-released fluids at sub-arc depths

The geochemical signature of magmas generated at convergent margins greatly depends on the nature of fluids and melts released during subduction. While major- and trace-elements transport capacity of ultrahigh pressure (UHP) hydrous-silicate melts has been investigated, little is known about solute enrichment and fractionation in UHP (>3.5–4 GPa) solute-rich aqueous fluids released along colder geothermal gradients. Here, we performed in situ LA-ICP-MS trace-element analyses on selected UHP prograde-to-peak fluid inclusions trapped in a kyanite-bearing quartzite from Sulu (China). The alkali-aluminosilicate-rich aqueous fluid released from the meta-sediments by dehydration reactions is enriched in LILE, U, Th, Sr, and REE. Inclusions trapped at increasing temperature (and pressure) preserve a gradual and selective trace-element enrichment resulting from the progressive dissolution of phengite and carbonate and the partial dissolution of allanite/monazite. We show that, at the investigated P-T conditions, aqueous fluids generated by dissolution of volatile-bearing minerals fractionate trace-element distinctly from hydrous-silicate melts, regardless of the source lithology. The orogenic/post-orogenic magmas generated in a mantle enriched by metasomatic processes involving either solute-rich aqueous fluids or hydrous-silicate melts released by the slab at UHP conditions can preserve evidence of the nature of these agents.