Geothermometry, ore geochemistry and fluid flow in the Esperanza Vein, Huachocolpa District (Huancavelica, Peru)

The Esperanza Zn-Pb-Ag vein, owned by Compañía de Minas Buenaventura S.A.A., lies over 4000 to 4650 masl in the Western Cordillera of the Peruvian Central Andes. The Esperanza low sulphidation epithermal vein trends ~E-W along 1500 m; it dips to the South and can be followed to 350 m depth. As other veins of the district, like Teresita and Bienaventurada, it is hosted by intermediate to felsic volcanics (andesitic to dacitic compositions) of the Huachocolpa Group (Middle Miocene to Upper Pliocene). The mineralisation occurs mostly as open space filling related to fracture development during the Quechua III deformational event. Main ore minerals are sphalerite, galena, tetrahedrite, pyrite, chalcopyrite and Ag and Pb sulfosalts; quartz, barite and calcite are the main gangue minerals. Current production grades are ~5% Zn, ~8Oz/t Ag, ~3% Pb; usually very low Cu (mean ~0.04%).

The relationship between soil geochemistry and the bioaccessibility of trace elements in playground soil

A total of 32 samples of surficial soil were collected from 16 playground areas in Madrid (Spain), in order to investigate the importance of the geochemistry of the soil on subsequent bioaccessibility of trace elements. The in vitro bioaccessibility of As, Co, Cr, Cu, Ni, Pb and Zn was evaluated by means of two extraction processes that simulate the gastric environment and one that reproduces a gastric + intestinal digestion sequence. The results of the in vitro bioaccessibility were compared against aqua regia extractions (“total” concentration), and it was found that total concentrations of As, Cu, Pb and Zn were double those of bioaccessible values, whilst that of Cr was ten times higher. Whereas the results of the gastric + intestinal extraction were affected by a high uncertainty, both gastric methods offered very similar and consistent results, with bioaccessibilities following the order: As = Cu = Pb = Zn > Co > Ni > Cr, and ranging from 63 to 7 %. Selected soil properties including pH, organic matter, Fe and CaCO3 content were determined to assess their influence on trace element bioaccessibility, and it was found that Cu, Pb and Zn were predominantly bound to organic matter and, to a lesser extent, Fe oxides. The former fraction was readily accessible in the gastric solution, whereas Fe oxides seemed to recapture negatively charged chloride complexes of these elements in the gastric solution, lowering their bioaccessibility. The homogeneous pH of the playground soils included in the study does not influence trace element bioaccessibility to any significant extent except for Cr, where the very low gastric accessibility seems to be related to the strongly pH-dependent formation of complexes with organic matter. The results for As, which have been previously described and discussed in detail in Mingot et al. (Chemosphere 84: 1386–1391, 2011), indicate a high gastric bioaccessibility for this element as a consequence of its strong association with calcium carbonate and the ease with which these bonds are broken in the gastric solution. The calculation of risk assessments are therefore dependant on the methodology used and the specific environment they address. This has impacts on management strategies formulated to ensure that the most vulnerable of society, children, can live and play without adverse consequences to their health.

Geochemistry and risk assessment of street dust in Luanda, Angola, a tropical urban environment

A total of 92 samples of street dust were collected in Luanda, Angola, were sieved below 100 μm, and analysed by ICP-MS for 35 elements after an aqua-regia digestion. The concentration and spatial heterogeneity of trace elements in the street dust of Luanda are generally lower than in most industrialized cities in the Northern hemisphere. These observations reveal a predominantly “natural” origin for the street dust in Luanda, which is also manifested in that some geochemical processes that occur in natural soils are preserved in street dust: the separation of uranium from thorium, and the retention of the former by carbonate materials, or the high correlation between arsenic and vanadium due to their common mode of adsorption on solid particles in the form of oxyanions. The only distinct anthropogenic fingerprint in the composition of Luanda's street dust is the association Pb–Cd–Sb–Cu (and to a lesser extent, Ba–Cr–Zn). The use of risk assessment strategies has proved helpful in identifying the routes of exposure to street dust and the trace elements therein of most concern in terms of potential adverse health effects. In Luanda the highest levels of risk seem to be associated (a) with the presence of As and Pb in the street dust and (b) with the route of ingestion of dust particles, for all the elements included in the study except Hg, for which inhalation of vapours presents a slightly higher risk than ingestion. However, given the large uncertainties associated with the estimates of toxicity values and exposure factors, and the absence of site-specific biometric factors, these results should be regarded as preliminary and further research should be undertaken before any definite conclusions regarding potential health effects are drawn.

Symmetries in geology and geophysics

Symmetries have played an important role in a variety of problems in geology and geophysics. A large fraction of studies in mineralogy are devoted to the symmetry properties of crystals. In this paper, however, the emphasis will be on scale-invariant (fractal) symmetries. The earth’s topography is an example of both statistically self-similar and self-affine fractals. Landforms are also associated with drainage networks, which are statistical fractal trees. A universal feature of drainage networks and other growth networks is side branching. Deterministic space-filling networks with side-branching symmetries are illustrated. It is shown that naturally occurring drainage networks have symmetries similar to diffusion-limited aggregation clusters.

Triassic redbeds in the Malaguide Complex (Betic Cordillera — Spain): petrography, geochemistry and geodynamic implications

Sandstone petrography and mudstone mineralogy and geochemistry of Triassic mudstones and sandstones from continental redbeds of the Malaguide Complex (Betic Cordillera, southern Spain) provide useful information on provenance, palaeoclimate and geodynamics during the early stages of the Pangea break-up, and on their diagenetic evolution. The sandstones are quartzarenites to sub-litharenites, with minor lithic fragments and rare feldspars. The mudstone samples show a PAAS like elemental distribution. The samples likely record recycling processes from their metasedimentary basement rocks that significantly affected the weathering indices, and monitors cumulative effects, including a first cycle of weathering at the source rocks. Sandstone composition and chemical–mineralogical features of mudstones record a provenance derived from continental block and recycled orogen that were weathered under warm and episodically wet climate. Source areas were located towards the east of the present-day Malaguide outcrops, and were formed by fairly silicic rock types, made up mainly of Palaezoic metasedimentary rocks, similar to those of the Paleozoic underlying series, with subordinate contributions from magmatic–metamorphic sources, and a rare supply from mafic metavolcanic rocks. Clay-mineral distribution of mudstones is dominated by illite and illite/smectite mixed-layer that result from differences in provenance, weathering, and burial/temperature history. Illite crystallinity values, illitization of kaolinite, occurrence of typical authigenic minerals and apatite fission-track studies, coupled with a subsidence analysis of the whole Malaguide succession suggest burial depths of at least 4–6 km with temperatures of 140–160 °C, typical of the burial diagenetic stage, and confirm the Middle Miocene exhumation of the Betic Internal Domain tectonic stack topped by the Malaguide Complex.

Geochemistry and age model of sediment core BDP96-1

Within the framework of the Baikal Drilling Project (BDP), a 192 m long sediment core (BDP-96-1) was recovered from the Academician Ridge, a submerged topographic high between the North and Central Basins of Lake Baikal. Sedimentological, clay mineralogical and geochemical investigations were carried out on the core interval between 90 and 124 m depth, corresponding to ca. 2.4-3.4 Ma. The aim was to reconstruct the climatic and tectonic history of the continental region during the intensification of Northern Hemisphere glaciation in Late Pliocene time. A major climate change occurred in the Lake Baikal area at about 2.65 Ma. Enhanced physical weathering in the catchment, mirrored in the illite to smectite ratio, and temporarily reduced bioproduction in the lake, reflected by the diatom abundance, evidence a change towards a colder and more arid climate, probably associated with an intensification of the Siberian High. In addition, the coincident onset of distinct fluctuations in these parameters and in the Zr/Al ratio suggests the beginning of the Late Cenozoic high amplitude climate cycles at about 2.65 Ma. Fluctuations in the Zr/Al ratio are traced back to changes in the aeolian input, with high values in warmer, more humid phases due to a weaker Siberian High. Assuming that the sand content in the sediment reflects tectonic pulses, the Lake Baikal area was tectonically active during the entire investigated period, but in particular around 2.65 Ma. Tectonic movements have likely led to a gradual catchment change since about 3.15 Ma from the western towards the eastern lake surroundings, as indicated in the geochemistry and clay mineralogy of the sediments. The strong coincidence between tectonic and climatic changes in the Baikal area hints at the Himalayan uplift being one of the triggers for the Northern Hemisphere Glaciation.

Geochemistry and grain-size of sediment core PC29A, Quitralco Fjord, Chilean Patagonia

The climate of Chilean Patagonia is strongly influenced by the southern westerlies, which control the amount and latitudinal distribution of precipitation in the southern Andes. In austral summer, the Southern Westerly Wind Belt (SWWB) is restricted to the high latitudes. It expands northward in winter, which results in a strong precipitation seasonality between 35 and 45°S. Here, we present a new precipitation seasonality proxy record from Quitralco fjord (46°S), where relatively small latitudinal shifts in the SWWB result in large changes in precipitation seasonality. Our 1400 yr record is based on sedimentological and geochemical data obtained on a sediment core collected in front of a small river that drains the Patagonian Andes, which makes this site particularly sensitive to changes in river discharge. Our results show Fe/Al and Ti/Al values that are low between 600 and 1200 CE, increasing at 1200-1500 CE, and high between 1500 and 1950 CE. The increasing Fe/Al and Ti/Al values reflect a decrease in mean sediment grain-size from 30 to 20 µm, which is interpreted as a decrease in seasonal floods resulting from an equatorward shift of the SWWB. Our results suggest that, compared to present-day conditions, the SWWB was located in a more poleward position before 1200 CE. It gradually shifted towards the equator in 1200-1500 CE, where it remained in a sustained position until 1950 CE. The comparison of our record with published regional sea surface temperature (SST) reconstructions for the late Holocene shows that equatorward shifts in the SWWB are systematically coeval with decreasing SSTs and vice versa, which resembles fluctuations over glacial-interglacial timescales. We argue that the synchronicity between SST and SWWB changes during the last 1400 years represents the response of the SWWB to temperature changes in the Southern Hemisphere.

Geochemistry and strontium isotopic composition of interstitial waters of marine carbonates

The concentrations and isotopic compositions of strontium in interstitial waters from several DSDP sites, where sediments consist chiefly of carbonate oozes and chalks, are used as indicators of carbonate diagenesis by reference to a recently-produced curve showing detailed variations in the 87Sr/86Sr ratio of seawater with time. Carbonate sediments of the Walvis Ridge show increases in interstitial Sr[2+] concentrations in the upper carbonate-ooze sections with the highest concentrations near the ooze-chalk boundary where maximum rates of carbonate recrystallization occur. Below this, in situ production of Sr[2+] diminishes and there is a diffusive flux of Sr to an underlying sink, presumably volcanogenic sediments or basalts, leading to Sr isotopic disequilibrium between carbonates and interstitial waters. In some other sites, however, there is no apparent Sr sink at depth and isotopic equilibrium is retained. Overall, diffusive smoothing of profiles exerts an important control on the 87Sr/86Sr ratios, although lower ratios than contemporaneous seawater values in the carbonate oozes often correlate with zones of Mg[2+] loss and reflect a combination of a flux of Sr[2+] from the zone of maximum recrystallization rates together with a contribution from the in situ alteration of volcanic matter.

Sedimentology, organic geochemistry, and stable isotopes of core PS2138-1

We studied variations in terrigenous (TOM) and marine organic matter (MOM) input in a sediment core on the northern Barents Sea margin over the last 30 ka. Using a multiproxy approach, we reconstructed processes controlling organic carbon deposition and investigated their paleoceanographic significance in the North Atlantic-Arctic Gateways. Variations in paleo-surface-water productivity are not documented in amount and composition of organic carbon. The highest level of MOM was deposited during 25-23 ka as a result of scavenging on fine-grained, reworked, and TOM-rich material released by the retreating Svalbard/Barents Sea ice sheet during the late Weichselian. A second peak of MOM is preserved because of sorptive protection by detrital and terrigenous organic matter, higher surface-water productivity due to permanent intrusion of Atlantic water, and high suspension load release by melting sea ice during 15.9-11.2 ka.

Geochemistry and stable isotope record of the hydtrothermally altered lower sheeted dike complex in ODP Hole 140-504B

Drilling during Legs 137 and 140 of the Ocean Drilling Program deepened Hole 504B, the only hole to penetrate through the volcanic section and into the underlying hydrothermally altered sheeted dike complex, by 438.1 m to a total depth of 2000.4 meters below seafloor. This paper presents the secondary mineralogy, bulk-rock sulfur contents, and stable isotopic (O, S) compositions, plus oxygen isotopic compositions of secondary minerals from the lower sheeted dike complex drilled during Legs 137 and 140. Various evidence indicates higher temperatures of hydrothermal alteration in the lower dikes than in the upper dikes, including: the local presence of secondary clinopyroxene in the lower dikes; secondary anorthite and hornblende in the lower dikes vs. mainly actinolite and albite-oligoclase in the upper dikes; generally increasing Al and Ti contents of amphibole downward in the dike section; and greater 18O depletions of the lower dikes (d18O = 3.6-5.0 per mil) compared with the upper dikes. Early high-temperature alteration stages (T = 350°-500°C) resulted in 18O depletions and losses of metals (Cu, Zn) and sulfur from the rocks. Local incorporation of reduced seawater sulfate led to elevated d34S values of sulfide in the rocks (up to 2.5 per mil). Quartz + epidote formed in crosscutting veins at temperatures of 310°-320°C from more evolved fluids (d18O = 1 per mil). Late-stage lower-temperature (~250°C) reactions producing albite, prehnite, and zeolites in the rocks caused slight 18O enrichments, but these were insufficient to offset the 18O depletions caused by earlier higher-temperature reactions. Addition of anhydrite to the rocks during seawater recharge led to increased S contents of rocks that had previously lost S during axial hydrothermal alteration, and to further increases in d34S values of total S in the rocks (up to 12 per mil). Despite the evidence for seawater recharge to near the base of the sheeted dike complex, the paucity of late zeolites in the lower dikes suggests that late-stage, off-axis circulation was mainly restricted to the volcanics and shallowest dikes, or to localized high-permeability zones (faults) at depth.

Geochemistry and isotopic ratios of basalts from ODP Leg 163 sites

Voluminous, subaerial magmatism resulted in the formation of extensive seaward-dipping reflector sequences (SDRS) along the Paleogene Southeast Greenland rifted margin. Drilling during Leg 163 recovered basalts from the SDRS at 66ºN (Site 988) and 63ºN (Sites 989 and 990). The basalt from Site 988 is light rare-earth-element (REE) enriched (La(n)/Yb(n) = 3.4), with epsilon-Nd(t=60) = 5.3, 87Sr/86Sr = 0.7034, and 206Pb/204Pb = 17.98. It is similar to tholeiites recovered from the Irminger Basin during Leg 49 and to light-REE-enriched tholeiites from Iceland. Drilling at Site 989, the innermost of the sites on the 63ºN transect, was proposed to extend recovery of the earliest part of the SDRS initiated during Leg 152. These basalts are, however, younger than those from Site 917 and are compositionally similar to basalts from the more seaward Sites 990 and 915. Many of the basalts from Sites 989 and 990 show evidence of contamination by continental crust (e.g., epsilon-Nd(t=60) extends down to -3.7, 206Pb/204Pb extends down to 15.1). We suggest that the contaminant is a mixture of Archean granulite and amphibolite and that the most contaminated basalts have assimilated ~5% of crust. Uncontaminated basalts are isotopically similar to basalts from Site 918, on the main body of the SDRS, and are light-REE depleted. Consistent with previous models of the development of this margin, we show that at the time of formation of the basalts from Sites 989 and 990 (1) melting was at relatively shallow levels in a fully-fledged rift zone; (2) fragments of continental crust were present in the lithosphere above the zones of melt generation; and (3) the sublithospheric mantle was dominated by a depleted Icelandic plume component.