Geogenic sources and sinks of trace metals in the Larsemann Hills, East Antarctica: Natural processes and human impact

To evaluate the extent of human impact on a pristine Antarctic environment, natural baseline levels of trace metals have been established in the basement rocks of the Larsemann Hills, East Antarctica. From a mineralogical and geochemical point of view the Larsemann Hills basement is relatively homogeneous, and contains high levels of Pb, Th and U. These may become soluble during the relatively mild Antarctic summer and be transported to lake waters by surface and subsurface melt water. Melt waters may also be locally enriched in V, Cr, Co, Ni, Zn and Sri derived from weathering of metabasite pods. With a few notable exceptions, the trace metal concentrations measured in the Larsemann Hills lake waters can be entirely accounted for by natural processes such as sea spray and surface melt water input. Thus, the amount of trace metals released by weathering of basement lithologies and dispersed into the Larsemann Hills environment, and presumably in similar Antarctic environments, is, in general, not negligible, and may locally be substantial. The Larsemann Hills sediments are coarse-grained and contain minute amounts of clay-size particles, although human activities have contributed to the generation of fine-grained material at the most impacted sites. Irrespective of their origin, these small amounts of fine-grained clastic sediments have a relatively small surface area and charge, and are not as effective metal sinks as the abundant, thick cyanobacterial algal mats that cover the lake floors. Thus, the concentration of trace metals in the Larsemann Hills lake waters is regulated by biological activity and thawing-freezing cycles, rather than by the type and amount of clastic sediment supply. (c) 2005 Elsevier Ltd. All rights reserved.

Geochemical changes recorded in Lynch's Crater, Northeastern Australia, over the past 50 ka

There are many geochemical reconstructions of environmental change in the mid and high latitudes but relatively few in the tropical latitudes, despite their considerable potential for reconstructing environmental processes that cannot be identified using more traditional proxies. Here we present one reconstruction of environmental change for the tropics. This reconstruction covers the past 50 ka using a suite of geochemical data from the high-resolution sequence of Lynch's Crater in northeast Queensland, Australia, a region highly sensitive to El Nino-Southern Oscillation (ENSO) activity. The 23 major oxides and trace elements measured Could be summarised by extracting three axes using principal components analysis (accounting for 72% of the variability). The data indicate that the greatest variability in the geochemical data accounted for erosional activity within the catchment that was associated with past changes in the frequency of ENSO activity (though this was less sensitive during wetter periods, probably as a result of buffering by high vegetation cover). The remaining variability was largely explained by elements that form complexes with organic compounds (e.g., humic acids) and those that are important nutrients for specific vegetation types (and therefore a measure of vegetation distribution). For more detailed reconstructions, further work is required to disentangle the complex controls of clements within sedimentary sequences. (c) 2005 Elsevier B.V. All rights reserved.

Geochemical and Sr, Nd, Pb isotope investigation of the New Caledonia ophiolite

The New Caledonia ophiolite hosts one of the largest obducted mantle section in the world, hence providing a unique insight for the study of upper mantle processes. These mantle rocks belong to an “atypical” ophiolitic sequence, which is dominated by refractory harzburgites but it also includes minor spinel and plagioclase lherzolites. Upper crust is notably absent in the ophiolite, with the exception of some mafic-ultramafic cumulates cropping out in the southern part of the island. Although the New Caledonia ophiolite has been under investigation for decades, its ultra-depleted nature has made its characterization an analytical challenge, so that few trace element data are available, while isotopic data are completely missing. In this thesis a comprehensive geochemical study (major, trace element and Sr-Nd-Pb isotopes) of the peridotites and the associated intrusive mafic rocks from the New Caledonia ophiolite has been carried out. The peridotites are low-strain tectonites showing porphyroclastic textures. Spinel lherzolites are undepleted lithotypes, as attested by the presence of 7-8 vol% of Na2O and Al2O3-rich clinopyroxene (up to 0.5 wt% Na2O; 6.5 wt% Al2O3), Fo content of olivine (88.5-90.0 mol%) and low Cr# of spinel (13-17). Conversely, harzburgites display a refractory nature, proven by the remarkable absence of primary clinopyroxene, very high Fo content in olivine (90.9-92.9 mol%), high Mg# in orthopyroxene (89.8-94.2) and Cr# in spinel (39-71). REE contents show abyssal-type patterns for spinel lherzolites, while harzburgites display U-shaped patterns, typical of fore-arc settings. Spinel lherzolites REE compositions are consistent with relatively low degree (8-9%) of fractional melting of a DMM source, starting in the garnet stability field. Conversely, REE models for harzburgites indicate high melting degrees (20-25%) of a DMM mantle source under spinel faies conditions, consistent with hydrous melting in forearc setting. Plagioclase lherzolites exhibit melt impregnation microtextures, Cr- and TiO2-enriched spinels and REE, Ti, Y, Zr progressive increase with respect to spinel lherzolites. Impregnation models indicate that plagioclase lherzolites may derive from spinel lherzolites by entrapment of highly depleted MORB melts in the shallow oceanic lithosphere. Mafic intrusives are olivine gabbronorites with a very refractory composition, as attested by high Fo content of olivine (87.3-88.9 mol.%), very high Mg# of clinopyroxene (87.7-92.2) and extreme anorthitic content of plagioclase (An = 90-96 mol%). The high Mg#, low TiO2 concentrations in pyroxenes and the anorthitic composition of plagioclase point out an origin from ultra-depleted primitive magmas in a convergent setting. Geochemical trace element models show that the parental melts of gabbronorites are primitive magmas with striking depleted compositions, bearing only in part similarities with the primitive boninitic melts of Bonin Islands. The first Sr, Nd and Pb isotope data obtained for the New Caledonia ophiolite highlight the presence of DM mantle source variably modified by different processes. Nd-Sr-Pb isotopic ratios for the lherzolites (+6.98≤epsilon Ndi≤+10.97) indicate a DM source that suffered low-temperature hydrothermal reactions. Harzburgites are characterized by a wide variation of Sr, Nd and Pb isotopic values, extending from DM-type to EM2 compositions (-0.82≤ epsilon Ndi≤+17.55), suggesting that harzburgite source was strongly affected by subduction-related processes. Conversely, combined trace element and Sr-Nd-Pb isotopic data for gabbronorites indicate a derivation from a source with composition similar to Indian-type mantle, but affected by fluid input in subduction environment. These geochemical features point out an evolution in a pre-Eocenic marginal basin setting, possibly in the proximity of a transform fault, for the lherzolites. Conversely, the harzburgites acquired their main geochemical and isotopic fingerprint in subduction zone setting.

Diagenetic processes in ore formation with special reference to the Zambian copperbelt and permian marl slate.

This thesis is concerned with the role of diagenesis in forming ore deposits. Two sedimentary 'ore-types' have been examined; the Proterozoic copper-cobalt orebodies of the Konkola Basin on the Zambian Copperbelt, and the Permian Marl Slate of North East England. Facies analysis of the Konkola Basin shows the Ore-Shale to have formed in a subtidal to intertidal environment. A sequence of diagenetic events is outlined from which it is concluded that the sulphide ores are an integral part of the diagenetic process. Sulphur isotope data establish that the sulphides formed as a consequence of the bacterial reduction of sulphate, while the isotopic and geochemical composition of carbonates is shown to reflect changes in the compositions of diagenetic pore fluids. Geochemical studies indicate that the copper and cobalt bearing mineralising fluids probably had different sources. Veins which crosscut the orebodies contain hydrocarbon inclusions, and are shown to be of late diagenetic lateral secretion origin. RbiSr dating indicates that the Ore-Shale was subject to metamorphism at 529 A- 20 myrs. The sedimentology and petrology of the Marl Slate are described. Textural and geochemical studies suggest that much of the pyrite (framboidal) in the Marl Slate formed in an anoxic water column, while euhedral pyrite and base metal sulphides formed within the sediment during early diagenesis. Sulphur isotope data confirm that conditions were almost "ideal" for sulphide formation during Marl Slate deposition, the limiting factors in ore formation being the restricted supply of chalcophile elements. Carbon and oxygen isotope data, along with petrographic observations, indicate that much of the calcite and dolomite occurring in the Marl Slate is primary, and probably formed in isotopic equilibrium. A depositional model is proposed which explains all of the data presented and links the lithological variations with fluctuations in the anoxicioxic boundary layer of the water column.

Geochemical variation among small eruptive centers in the central SVZ of the Andes: An evaluation of subduction, mantle and crustal influences

Subduction zone magmatism is an important and extensively studied topic in igneous geochemistry. Recent studies focus on from where arc magmas are generated, how subduction components (fluids or melts) are fluxed into the source of the magmas, and whether or how the subduction components affect partial melting processes beneath volcanic arcs at convergent boundaries. ^ At 39.5°S in the Central Southern Volcanic Zone of the Andes, Volcano Villarrica is surrounded by a suite of Small Eruptive Centers (SEC). The SECs are located mostly to the east and northeast of the stratovolcano and aligned along the Liquine-Ofqui Fault Zone, the major fracture system in this area. Former studies observed the geochemical patterns of the SECs differ distinctively from those of V. Villarrica and suggested there may be a relationship between the compositions of the volcanic units and their edifice sizes. This work is a comprehensive geochemical study on the SECs near V. Villarrica, using a variety of geochemical tracers and tools including major, trace and REE elements, Li-Be-B elements, Sr-Nd-Pb isotopes and short-lived isotopes such as U-series and 10Be. In this work, systematic differences between the elemental and isotopic compositions of the SECs and those of V. Villarrica are revealed and more importantly, modeled in terms of magmatic processes occurring at continental arc margins. Detailed modeling calculations in this work reconstruct chemical compositions of the primary magmas, source compositions, compositions and percentages of different subduction endmembers mixed into the source, degrees of partial melting and different time scales of the SECs and V. Villarrica, respectively. Geochemical characteristics and possible origins of the two special SECs—andesitic Llizan, with crustal signatures, and Rucapillan, to the northwest toward the trench, are also discussed in this work. ^

A geochemical study of crustal plutonic rocks from the southern Mariana Trench forearc: Relationship to volcanic rocks erupted during subduction initiation

Two suites of intermediate-felsic plutonic rocks were recovered by dredges RD63 and RD64 (R/V KK81-06-26) from the northern wall of the Mariana trench near Guam, which is located in the southern part of the Izu-Bonin-Mariana (IBM) island arc system. The locations of the dredges are significant as the area contains volcanic rocks (forearc basalts and boninites) that have been pivotal in explaining processes that occur when one lithospheric plate initially begins to subduct beneath another. The plutonic rocks have been classified based on petrologic and geochemical analyses, which provides insight to their origin and evolution in context of the surrounding Mariana trench. Based on whole rock geochemistry, these rocks (SiO2: 49-78 wt%) have island arc trace element signatures (Ba, Sr, Rb enrichment, Nb-Ta negative anomalies, U/Th enrichment), consistent with the adjacent IBM volcanics. Depletion of rare earth elements (REEs) relative to primitive mantle and excess Zr and Hf compared to the middle REEs indicate that the source of the plutonic rocks is similar to boninites and transitional boninites. Early IBM volcanic rocks define isotopic fields (Sr, Pb, Nd and Hf-isotopes) that represent different aspects of the subduction process (e.g., sediment influence, mantle provenance). The southern Mariana plutonic rocks overlap these fields, but show a clear distinction between RD63 and RD64. Modeling of the REEs, Zr and Hf shows that the plutonic suites formed via melting of boninite crust or by crystallization from a boninite-like magma rather than other sources that are found in the IBM system. The data presented support the hypothesis that the plutonic rocks from RD63 and RD64 are products of subduction initiation and are likely pieces of middle crust in the forearc exposed at the surface by faulting and serpentine mudvolcanoes. Their existence shows that intermediate-felsic crust may form very early in the history of an intra-oceanic island arc system. Plutonic rocks with similar formation histories may exist in obducted suprasubduction zone ophiolites and would be evidence that felsic-intermediate forearc plutonics are eventually accreted to the continents.

Development of an enhanced hydro-geochemical model to address mercury-speciation fate and transport in aquatic environments

An awareness of mercury (Hg) contamination in various aquatic environments around the world has increased over the past decade, mostly due to its ability to concentrate in the biota. Because the presence and distribution of Hg in aquatic systems depend on many factors (e.g., pe, pH, salinity, temperature, organic and inorganic ligands, sorbents, etc.), it is crucial to understand its fate and transport in the presence of complexing constituents and natural sorbents, under those different factors. An improved understanding of the subject will support the selection of monitoring, remediation, and restoration technologies. The coupling of equilibrium chemical reactions with transport processes in the model PHREEQC offers an advantage in simulating and predicting the fate and transport of aqueous chemical species of interest. Thus, a great variety of reactive transport problems could be addressed in aquatic systems with boundary conditions of specific interest. Nevertheless, PHREEQC lacks a comprehensive thermodynamic database for Hg. Therefore, in order to use PHREEQC to address the fate and transport of Hg in aquatic environments, it is necessary to expand its thermodynamic database, confirm it and then evaluate it in applications where potential exists for its calibration and continued validation. The objectives of this study were twofold: 1) to develop, expand, and confirm the Hg database of the hydrogeochemical PHREEQC to enhance its capability to simulate the fate of Hg species in the presence of complexing constituents and natural sorbents under different conditions of pH, redox, salinity and temperature; and 2) to apply and evaluate the new database in flow and transport scenarios, at two field test beds: Oak Ridge Reservation, Oak Ridge, TN and Everglades National Park, FL, where Hg is present and is of much concern. Overall, this research enhanced the capability of the PHREEQC model to simulate the coupling of the Hg reactions in transport conditions. It also demonstrated its usefulness when applied to field situations.

Geochemical data and radiocarbon ages of organic matter fractions and bacteriohopanepolyol data of sediment core GeoB6518-1 from the Congo River basin

The age of organic material discharged by rivers provides information about its sources and carbon cycling processes within watersheds. While elevated ages in fluvially-transported organic matter are usually explained by erosion of soils and sediments, it is commonly assumed that mainly young organic material is discharged from flat tropical watersheds due to their extensive plant cover and high carbon turnover. Here we present compound-specific radiocarbon data of terrigenous organic fractions from a sedimentary archive offshore the Congo River in conjunction with molecular markers for methane-producing land cover reflecting wetland extent in the watershed. We find that the Congo River has been discharging aged organic matter for several thousand years with increasing ages from the mid- to the Late Holocene. This suggests that aged organic matter in modern samples is concealed by radiocarbon from nuclear weapons testing. By comparison to indicators for past rainfall changes we detect a systematic control of organic matter sequestration and release by continental hydrology mediating temporary carbon storage in wetlands. As aridification also leads to exposure and rapid remineralization of large amounts of previously stored labile organic matter we infer that this process may cause a profound direct climate feedback currently underestimated in carbon cycle assessments.

Geochemical analysis of two sediment cores from the southern Mendeleev Ridge

We present results of an inorganic geochemical pore water and sediment study conducted on Quaternary sediments from the western Arctic Ocean. The sediment cores were recovered in 2008 from the southern Mendeleev Ridge during RV Polarstern Expedition ARK-XXIII/3. With respect to sediment sources and depositional processes, peaks in Ca/Al, Mg/Al, Sr/Al and Sr/Mg indicate enhanced input of both ice-rafted (mainly dolomite) and biogenic carbonate during deglacial warming phases. Distinct and repetitive brown layers enriched in Mn (oxyhydr)oxides occur mostly in association with these carbonate-rich intervals. For the first time, we show that the brown layers are also consistently enriched in scavenged trace metals Co, Cu, Mo and Ni. The bioturbation patterns of the brown layers, specifically well-defined brown burrows into the underlying sediments, support formation close to the sediment-water interface. The Mn and trace metal enrichments were probably initiated under warmer climate conditions. Both river runoff and melting sea ice delivered trace metals to the Arctic Ocean, but also enhanced seasonal productivity and organic matter export to the sea floor. As Mn (oxyhydr)oxides and scavenged trace metals were deposited at the sea floor, a co-occurring organic matter "pulse" triggered intense diagenetic Mn cycling at the sediment-water interface. These processes resulted in the formation of Mn and trace metal enrichments, but almost complete organic matter degradation. As warmer conditions ceased, reduced riverine runoff and/or a solid sea ice cover terminated the input of riverine trace metal and fresh organic matter, and greyish-yellowish sediments poor in Mn and trace metals were deposited. Oxygen depletion of Arctic bottom waters as potential cause for the lack of Mn enrichments during glacial intervals is highly improbable. While the original composition and texture of the brown layers resulted from specific climatic conditions (including transient Mn redox cycling at the sediment-water interface), pore water data show that early diagenetic Mn redistribution is still affecting the organic-poor sediments in several meters depth. Given persistent steady state diagenetic conditions, purely authigenic Mn-rich brown layers may form, while others may completely vanish. The degree of diagenetic Mn redistribution largely depends on the depositional environment within the Arctic Ocean, the availability of Mn and organic matter, and seems to be recorded by the Co/Mo ratios of single Mn-rich layers. We conclude that brown Arctic sediment layers are not necessarily synchronous features, and correlating them across different parts of the Arctic Ocean without additional age control is not recommended.

Geochemical parameters of sediments and waters in areas of ocean barrier zones

Geochemical barrier zones play an important role in determining various physical systems and characteristics of oceans, e.g. hydrodynamics, salinity, temperature and light. In the book each of more than 30 barrier zones are illustrated and defined by physical, chemical and biological parameters. Among the topics discussed are processes of inflow, transformation and precipitation of the sedimentary layer of the open oceans and more restricted areas such as the Baltic, Black and Mediterranean Seas.

Geochemical and biogeochemical parameters of Black Sea waters and suspended matter

The monograph focuses on the analysis of data addressing the problem of H2S contamination and oxic-anoxic interface in the Black Sea. Regularities of the fine structure of vertical distribution of oxygen, hydrogen sulfide, biogenic elements, organic substances, suspended matter, and metals of the iron-manganese group in the area of contact of aerobic and anaerobic waters have been revealed. Also effects of biochemical, physico-chemical and dynamic processes on their vertical distribution have been examined. Sulfate reduction in seawater and bottom sediments has been studied. Quantitative estimates of H2S fluxes at the water - bottom sediment and O2-H2S interfaces have been done. Features of H2S oxidation have been studied, its budget in the Black Sea has been calculated. Multiyear spatial-temporal variability of the oxic-anoxic interface has been investigated.

San Francisco Coastal System grain size and geochemical data for sand provenance study

Over 150 million cubic meter of sand-sized sediment has disappeared from the central region of the San Francisco Bay Coastal System during the last half century. This enormous loss may reflect numerous anthropogenic influences, such as watershed damming, bay-fill development, aggregate mining, and dredging. The reduction in Bay sediment also appears to be linked to a reduction in sediment supply and recent widespread erosion of adjacent beaches, wetlands, and submarine environments. A unique, multi-faceted provenance study was performed to definitively establish the primary sources, sinks, and transport pathways of beach sized-sand in the region, thereby identifying the activities and processes that directly limit supply to the outer coast. This integrative program is based on comprehensive surficial sediment sampling of the San Francisco Bay Coastal System, including the seabed, Bay floor, area beaches, adjacent rock units, and major drainages. Analyses of sample morphometrics and biological composition (e.g., Foraminifera) were then integrated with a suite of tracers including 87Sr/86Sr and 143Nd/144Nd isotopes, rare earth elements, semi-quantitative X-ray diffraction mineralogy, and heavy minerals, and with process-based numerical modeling, in situ current measurements, and bedform asymmetry to robustly determine the provenance of beach-sized sand in the region.

(Table 2) Petrophysical, petrological, and geochemical characteristics of ODP Hole 163-990A sediments

Ocean Drilling Program Hole 990A penetrated 131 m of subaerially emplaced Paleocene flood basalts on the Southeast Greenland margin with a recovery of 74%. Shipboard P-wave velocity (Vp), density, and magnetic susceptibility were measured with 2- to 15-cm intervals on the core. Individual flow units were divided into four zones based on the observed petrophysical characteristics. From the top, these are Zone I (<7 m thick with a Vp of ~2.5 km/s), Zone II (3-5 m thick with a strongly increasing Vp from 2.5 to 5.5 km/s), Zone III (up to 20 m thick with a Vp of ~5.5-6.0 km/s), and Zone IV (<2 m thick with a strongly decreasing Vp from 6.0 to 2.5 km/s). Eighteen samples were selected from three of the fourteen penetrated basalt units for geochemical, petrological, and petrophysical studies focusing on the altered, low-velocity upper lava Zones I and II. Zone I is strongly altered to >50% clay minerals (smectite) and iron hydroxides, and the petrophysical properties are primarily determined by the clay properties. Zone II is intermediately altered with 5%-20% clay minerals, where the petrophysical properties are a function of both the degree of alteration and porosity variations. Shipboard and shore-based measurements of the same samples show that storage permanently lowers the elastic moduli of basalt from Zones I to III. This is related to the presence of even small quantities of swelling clays. The data show that alteration processes are important in determining the overall seismic properties of flood basalt constructions. The degree and depth of alteration is dependent on the primary lava flow emplacement structures and environment. Thus, the interplay of primary emplacement and secondary alteration structures determine the elastic properties of basalt piles. Rock property theories for sand-clay systems are further used to model the physical property variations in these altered crystalline rocks.

(Table T1) Geochemical composition of coastal sediments from the Schleswig-Holstein Wadden Sea, Germany

Approximately quantitative values are presented on the mineral content of the clay and silt fractions of marine sediments from the Wadden Sea. Considering the extent of clay mineral transformation and neoformation in a marine environment, it is believed to be insignificant, because of the sea water and pore solutions of the sediments seem to represent - with the exception of a small Mg-surplus - a kind of equilibrium solution for three- and four-layer minerals, which neither favors a considerable base fixation nor base release. Therefore, illite neoformation during halmyrolysis or early diagenesis seems to be impossible, especially because of unfavourable relations of potassium to all other cations in the sea water. Obviously the neoformation of illite takes place only during later diagenetic stages. The processes of clay mineral neoformation in a marine environment are probably restricted to the formation of amorphous (Mg-)Fe-Si-particles which may be first steps in the formation of chamosites, chlorites or smectites.