Lead, zinc, and antimony contamination of the Rio Chilco-Rio Tupiza drainage system, Southern Bolivia

An intense, but localized rainfall event in February 2003, led to the severe erosion and failure of a tailings disposal impoundment at the Abarόa Antimony Mine in southern Bolivia. The failure released approximately 5,500 m³ of contaminated tailings into the Rio Chilco-Rio Tupiza drainage system. The impacts of the event on sediment quality are examined and compared to contamination resulting from historic mining operations in the headwaters of the basin. Of primary concern are contaminated floodplain soils located along downstream reaches of the Rio Tupiza which were found to contain lead (Pb), zinc (Zn), and antimony (Sb) concentrations that locally exceed Canadian, German, and Dutch guidelines for agricultural use. Spatial patterns in sediment-borne trace metal concentrations, combined with Pb isotopic data, indicate that Pb, Zn, and Sb are derived from three tributary basins draining the Abarόa, Chilcobija, and Tatasi-Portugalete mining districts. Downstream of each tributary, geographical patterns in trace metal concentrations reflect local geomorphic changes throughout the drainage system. Trace metal concentrations within the Rio Chilco decrease rapidly downstream as a result of dilution by uncontaminated sediments and storage of metal enriched particles (e.g., sulfide minerals) in the channel bed as a result of ongoing aggradation. Storage in the floodplains is limited. These processes significantly reduced the dispersal and, thus, the relative environmental affects of tailings eroded from the Abarόa Mine during the 2003 flood. In contrast, storage of Pb, Zn, and Sb in floodplains along the Rio Tupiza is significant, the majority of which is derived from historic mining operations, particularly mining within the Tatasi-Portugalete district.     

3D numerical modelling of fluid flow in the Val-d’Or orogenic gold district: major crustal shear zones drain fluids from overpressured vein fields

Fluid flow patterns have been determined using oxygen isotope isopleths in the Val-d’Or orogenic gold district. 3D numerical modelling of fluid flow and oxygen isotope exchange in the vein field shows that the fluid flow patterns can be reproduced if the lower boundary of the model is permeable, which represents middle or lower crustal rocks that are infiltrated by a metamorphic fluid generated at deeper levels. This boundary condition implies that the major crustal faults so conspicuous in vein fields do not act as the only major channel for upward fluid flow. The upper model boundary is impermeable except along the trace of major crustal faults where fluids are allowed to drain out of the vein field. This upper impermeable boundary condition represents a low-permeability layer in the crust that separates the overpressured fluid from the overlying hydrostatic fluid pressure regime. We propose that the role of major crustal faults in overpressured vein fields, independent of tectonic setting, is to drain hydrothermal fluids out of the vein field along a breach across an impermeable layer higher in the crust and above the vein field. This breach is crucial to allow flow out of the vein field and accumulation of metals in the fractures, and this breach has major implications for exploration for mineral resources. We propose that tectonic events that cause episodic metamorphic dehydration create a short-lived pulse of metamorphic fluid to rise along zones of transient permeability. This results in a fluid wave that propagates upward carrying metals to the mineralized area. Earthquakes along crustal shear zones cause dilation near jogs that draw fluids and deposit metals in an interconnected network of subsidiary shear zones. Fluid flow is arrested by an impermeable barrier separating the hydrostatic and lithostatic fluid pressure regimes. Fluids flow through the evolving and interconnected network of shear zones and by advection through the rock matrix. Episodic breaches in the impermeable barrier along the crustal shear zones allow fluid flow out of the vein field.     

Quantification of karst aquifer discharge components during storm events through end-member mixing analysis using natural chemistry and stable isotopes as tracers

Karst aquifer components that contribute to the discharge of a water supply well in the Classical Karst (Kras) region (Italy/Slovenia) were quantitatively estimated during storm events. Results show that water released from storage within the epikarst may comprise as much as two-thirds of conduit flow in a karst aquifer following rainfall. Principal components analysis (PCA) and end-member mixing analysis (EMMA) were performed using major ion chemistry and the stable isotopes of water (δ¹⁸O, δ²H) and of dissolved inorganic carbon (δ¹³C_DIC) to estimate mixing proportions among three sources: (1) allogenic river recharge, (2) autogenic recharge, and (3) an anthropogenic component stored within the epikarst. The sinking river most influences the chemical composition of the water-supply well under low-flow conditions; however, this proportion changes rapidly during recharge events. Autogenic recharge water, released from shallow storage in the epikarst, displaces the river water and is observed at the well within hours after the onset of precipitation. The autogenic recharge end member is the second largest component of the well chemistry, and its contribution increases with higher flow. An anthropogenic component derived from epikarstic storage also impacts the well under conditions of elevated hydraulic head, accounting for the majority of the chemical response at the well during the wettest conditions.     

Hydrochemistry and isotope geochemistry as tools for groundwater hydrodynamic investigation in multilayer aquifers: a case study from Lomellina, Po plain, South-Western Lombardy, Italy

A multicriteria approach in studying hydrodynamics of a multilayer aquifer system has been used in the Lomellina region (Northern Italy). It involves the reconstruction of the hydrogeological framework coupled to the definition of the hydrochemical and isotopic features of the aquifers. A shallow phreatic aquifer, reaching depths of about 60–80 m from the surface, and deeper aquifers containing confined groundwater, were distinguished. Groundwater generally shows mineralisation decreasing with depth; dissolved ions depict calcium-bicarbonate hydrochemical facies and stable isotopes define the recharge mechanisms, the origin of groundwater, and the hydraulic confinement of deep aquifers. The phreatic aquifer is fed by local infiltration and by streams and irrigation channels. Tritium and Carbon-14 groundwater dating indicate long residence times (on the order of thousands of years) for confined aquifers. The confined aquifers show essentially passive hydrodynamic conditions and maintain a higher piezometric level than the phreatic aquifer. This inhibits the possibility of recent water penetrating far below the surface. The hydrogeological setting of the Lomellina region displays features which are common to other sectors of the Po plain. As a consequence, the results of this study, although conducted on a restricted area, are highly illustrative of groundwater hydrodynamics in large sedimentary aquifers.     

Cyclicity in the Main and Upper Zones of the Bushveld Complex, South Africa: Crystallization from a Zoned Magma Sheet

The major element composition of plagioclase, pyroxene, olivine,and magnetite, and whole-rock ⁸⁷Sr/⁸⁶Sr data are presented forthe uppermost 2·1 km of the layered mafic rocks (upperMain Zone and Upper Zone) at Bierkraal in the western BushveldComplex. Initial ⁸⁷Sr/⁸⁶Sr ratios are near-constant (0·7073± 0·0001) for 24 samples and imply crystallizationfrom a homogeneous magma sheet without major magma rechargeor assimilation. The 2125 m thick section investigated in drillcore comprises 26 magnetitite and six nelsonite (magnetite–ilmenite–apatite)layers and changes up-section from gabbronorite (An₇₂ plagioclase;Mg# 74 clinopyroxene) to magnetite–ilmenite–apatite–fayaliteferrodiorite (An₄₃; Mg# 5 clinopyroxene; Fo₁ olivine). The overallfractionation trend is, however, interrupted by reversals characterizedby higher An% of plagioclase, higher Mg# of pyroxene and olivine,and higher V₂O₅ of magnetite. In the upper half of the successionthere is also the intermittent presence of cumulus olivine andapatite. These reversals in normal fractionation trends definethe bases of at least nine major cycles. We have calculateda plausible composition for the magma from which this entiresuccession formed. Forward fractional crystallization modelingof this composition predicts an initial increase in total iron,near-constant SiO₂ and an increasing density of the residualmagma before magnetite crystallizes. After magnetite beginsto crystallize the residual magma shows a near-constant totaliron, an increase in SiO₂ and decrease in density. We explainthe observed cyclicity by bottom crystallization. Initiallymagma stratification developed during crystallization of thebasal gabbronorites. Once magnetite began to crystallize, periodicdensity inversion led to mixing with the overlying magma layer,producing mineralogical breaks between fractionation cycles.The magnetitite and nelsonite layers mainly occur within fractionationcycles, not at their bases. In at least two cases, crystallizationof thick magnetitite layers may have lowered the density ofthe basal layer of melt dramatically, and triggered the proposeddensity inversion, resulting in close, but not perfect, coincidenceof mineralogical breaks and packages of magnetitite layers. KEY WORDS: layered intrusion; mineral chemistry; isotopes; magma; convection; differentiation     

新疆准噶尔地区富硫型与贫硫型浅成低温热液金矿床成矿流体与碳、硫、铅同位素

对新疆准噶尔地区浅成低温热液型金矿床中富硫型的阔尔真阔腊金矿、贫硫型的石英滩金矿进行了流依包裹体的均一温度、爆裂温度、包裹体气液相成分、H、O 同位素、矿体围岩及脉石英包裹体 C 同位素、矿体中黄铁矿等 S、Ph 同位素等系统地进行了研究,综合研究表明,本区该类型金矿成矿流体一般温度低、盐度低,来源主要为循环的大气水、矿石中黄铁矿的 S、Pb 同位素均为深源,暗示金的深部来源:矿体石英包裹体中 CO_2的δ~(13)C 为低于-10‰的有机碳,反映了本区年轻的富含有机质的沉积地层参与了金的成矿。此外,本文首次提出了富硫型阔尔真阔腊金矿床成矿流体中有侵入岩浆热液参与,深部有多金属成矿远景;贫硫型石英滩金矿没有侵入岩浆热液的参与,成矿仅与火山古热液活动有关,其成矿较单一。此外,阔尔真阔腊金矿中低温流体活动较强,金矿化也较强:石英滩金矿低温流体活动相对较弱,金矿化也较弱,也体现了该类型金矿床低温流体活动的越强烈,金矿化越强的规律。     

成矿流体演化与成矿物理化学

成矿流体是富含挥发分 (CO2 、CH4等 )是具有较高含盐度的特殊地质流体。本文讨论了在流体演化过程中挥发分的来源 ,指出主要来自水岩作用、有机质分解及地幔去气和岩浆 ;碱金属及卤素同样具有多来源的性质 ,以海水、含盐系淋滤、建造水为主要来源 ,含盐系重熔可以形成富含碱金属的成矿流体。流体演化过程中氢氧同位素、硫同位素的分馏主要与温度、水岩比值或硫源丰度有关。一个重要的结论是 ,成矿流体的形成主要与地质作用有关 ,而流体来源是次要的。海底热水流体的地球化学特征以高δ3 4 S值、中稀土富集及正铕异常为特征。本文总结了热水流体成矿物理化学条件 ,指出水热流体物相点 :1) 10 80℃ ,7.5× 10 8Pa水溶液与硅酸岩熔浆分熔点 ;2 )水溶液的第二个临界点是气水溶液的超临界点 (374.15℃ ,2 .2 1× 10 7Pa) ;3)水溶液的沸点 (≥ 10 0℃ ,≥ 1× 10 5Pa) ;4)水溶液的冰点 (≤ 0℃ ,1× 10 5Pa) ;5 )H2 O CO2 体系的不混溶温度点 (2 6 6℃ ,2 .15×10 8Pa[1 3 ] 等是重要的成矿相变点。     

Isotopic constraints on growth conditions of multiphase calcite–pyrite–barite concretions in Carboniferous mudstones

Carbonate concretions in the Lower Carboniferous Caton Shale Formation contain diagenetic pyrite, calcite and barite in the concretion matrix or in different generations of septarian fissures. Pyrite was formed by sulphate reduction throughout the sediment before concretionary growth, then continued to form mainly in the concretion centres. The septarian calcites show a continuous isotopic trend from δ¹³C=?28·7‰ PDB and δ¹⁸O=?1·6‰ PDB through to δ¹³C=?6·9‰ PDB and δ¹⁸O=?14·6‰ PDB. This trend arises from (1) a carbonate source initially from sulphate reduction, to which was added increasing contributions of methanogenic carbonate; and (2) burial/temperature effects or the addition of isotopically light oxygen from meteoric water. The concretionary matrix carbonates must have at least partially predated the earliest septarian cements, and thus used the same carbonate sources. Consequently, their isotopic composition (δ¹³C=?12·0 to ?10·1‰ PDB and δ¹⁸O=?5·7 to ?5·6‰ PDB) can only result from mixing a carbonate cement derived from sulphate reduction with cements containing increasing proportions of carbonate from methanogenesis and, directly or indirectly, also from skeletal carbonate. Concretionary growth was therefore pervasive, with cements being added progressively throughout the concretion body during growth. The concretions contain barite in the concretion matrix and in septarian fissures. Barite in the earlier matrix phase has an isotopic composition (δ³⁴S=+24·8‰ CDT and δ¹⁸O=+16·4‰ SMOW), indicating formation from near‐surface, sulphate‐depleted porewaters. Barites in the later septarian phase have unusual isotopic compositions (δ³⁴S=+6 to +11‰ CDT and δ¹⁸O=+8 to +11‰ SMOW), which require the late addition of isotopically light sulphate to the porewaters, either from anoxic sulphide oxidation (using ferric iron) or from sulphate dissolved in meteoric water. Carbon isotope and biomarker data indicate that oil trapped within septarian fissures was derived from the maturation of kerogen in the enclosing sediments.     

Continental crust and lithospheric mantle interaction beneath North China: isotopic evidence from granulite xenoliths in Hannuoba, Sino-Korean craton

Mafic granulite and pyroxenite xenoliths from Cenozoic alkaline basalts at Hannuoba, Hebei Province, North China have been selected for a systematic geochemical and Sr–Nd–Pb isotopic study, which provides a unique opportunity to explore nature of the lower crust and the interaction between the continental crust and lithospheric mantle beneath an Archean craton. The major, compatible and incompatible elements and radiogenic isotopes of these xenoliths suggest great chemical heterogeneity of the lower crust beneath the Hannuoba region. Petrological and geochemical evidences indicate a clear cumulate origin, and most likely, they are related to basaltic underplating in different geological episodes. However, the Sr–Nd–Pb isotopic compositions of the xenoliths reveal a profound enriched source signature (EM I) with some influence of EM II, which implies that some portion of pre-existing, old metasomatized subcontinental lithospheric mantle could have played an important role in their genesis. It is suggested that the interaction between continental crust and subcontinental mantle as manifested by basaltic underplating would be closely related to regional tectonic episodes and geodynamic processes in the deep part of subcontinental lithospheric mantle.     

Celestite formation, bacterial sulphate reduction and carbonate cementation of Eocene reefs and basinal sediments (Igualada, NE Spain)

Petrographic and geochemical studies of an Upper Eocene reef and associated basinal sediments from the mixed carbonate–siliciclastic fill of the south‐eastern Pyrenean foreland basin near Igualada (NE Spain) provide new insights into the evolution of subsurface hydrology during the restriction of a marine basin. The reef deposits are located on delta‐lobe sandstones and prodelta marls, which are overlain by hypersaline carbonates and Upper Eocene evaporites. Authigenic celestite (SrSO₄) is an important component in the observed diagenetic sequences. Celestite is a significant palaeohydrological indicator because its low solubility constrains transportation of Sr²⁺ and SO₄^2? in the same diagenetic fluid. Stable isotopic analyses of carbonates in the reef indicate that meteoric recharge was responsible for aragonite stabilization and calcite cementation. Sulphur and oxygen isotope geochemistry of the celestite demonstrates that it formed from residual sulphate after bacterial sulphate reduction, but also requires that there was a prior episode of sulphate recycling. Meteoric water reaching the reef and basinal areas was most probably charged with SO₄^2? from the dissolution of younger Upper Eocene marine evaporites. This sulphate, combined with organic matter present in the sediments, fuelled bacterial sulphate reduction in the meteoric palaeoaquifer. Strontium for celestite precipitation was partly derived in situ from dissolution of aragonite corals in the reef and basinal counterparts. However, ⁸⁷Sr/⁸⁶Sr data also suggest that Sr²⁺ was partly derived from dissolution of overlying evaporites. Mixing of these two fluids promoted celestite formation. The carbonate stable isotopic data suggest that the local meteoric water was enriched in ¹⁸O compared with that responsible for stabilization of other reefs along the basin margin. Furthermore, meteoric recharge at Igualada post‐dated evaporite deposition in the basin, whereas other parts of the same reef complex were stabilized before evaporite formation. This discrepancy resulted from the spatial distribution of continental siliciclastic units that acted as groundwater conduits.