Metal sources of the Navan carbonate-hosted base metal deposit, Ireland: Nd and Sr isotope evidence for deep hydrothermal convection

Nd and Sr isotope analyses are presented for gangue mineral samples from the giant carbonate-hosted Navan Zn–Pb deposit, Ireland, and for rocks from which Navan metals may have been derived. Analysis of gangue minerals spanning the Navan paragenetic sequence reveals systematic evolution in the composition of the mineralising fluid. Early fluid represented by replacive dolomite exhibits the lowest initial ⁸⁷Sr/⁸⁶Sr ratio (0.7083–0.7086), closest to that of the host limestone and to Lower Carboniferous seawater, and the highest ¹⁴³Nd/¹⁴⁴Nd ratio (0.51161–0.51176). Later generations of dolomite, barite and calcite, which encompass sulphide precipitation, have higher initial ⁸⁷Sr/⁸⁶Sr ratios (maximum 0.7105) and lower initial ¹⁴³Nd/¹⁴⁴Nd ratios (minimum 0.51157). All samples have initial Nd isotope ratios that are too low to have been acquired only from the host limestone. Drill core samples of presumed Ordovician volcanic and sedimentary rocks from beneath the Navan orebody have ¹⁴³Nd/¹⁴⁴Nd and ⁸⁷Sr/⁸⁶Sr ratios at the time of mineralisation of 0.51184–0.51217 and 0.7086–0.7138, respectively. The data are interpreted to indicate mixing of sulphide-rich, limestone-buffered brine, with a metal-bearing hydrothermal fluid, which had passed through sub-Carboniferous rocks, consistent with published fluid inclusion and S isotope data. The ¹⁴³Nd/¹⁴⁴Nd ratio of this basement-derived fluid is too low to have been imparted by flow through the Devonian Old Red Sandstone, as required in models of regional fluid flow in response to Hercynian uplift. Irrespective of whether such regional fluid flow occurred, the hydrothermal Nd must have been derived from sub-Devonian rocks. These conclusions broadly support the hydrothermal convection cell model in which brines, ultimately of surface origin, penetrated to a depth of several kilometres, leaching metals from the rocks through which they passed. The data also support increasing depth of penetration of convection cells with time. Metals were subsequently precipitated in carbonate rocks at sites of mixing with cooler, sulphide-rich fluids. However, comparison of the Navan hydrothermal gangue Nd–Sr isotope data with data from Lower Palaeozoic rocks strongly suggests that the latter cannot alone account for the “basement” signature. As the Navan deposit lies immediately north of the Iapetus Suture, this suggests that the Laurentian margin includes Precambrian basement.     

The First Appearance of Cattle in Denmark Occurred 6000 Years Ago: An Effect of Cultural or Climate and Environmental Changes

Stable carbon and nitrogen isotope ratios from bones of contemporaneous Late Atlantic aurochs and early cattle in eastern Denmark are significantly different and provide information on the origin and feeding strategies of the earliest domestic cattle. The data show that the early cattle were feeding on grass right from the beginning 4000 cal. yr BC. In contrast, the youngest aurochs population primarily browsed and grazed from the dense forest floor resulting in rather negative δ¹³C values measured on bone collagen. The oldest aurochs have similar isotope values to the earlier cattle, whereas the youngest aurochs have similar values to Late Atlantic red deer from the same locality. As eastern Denmark was largely covered by forest, speculations on the origin of the grazing areas are many. The grass may have grown in openings in the forest, at the forest fringe, or more likely on the newly reclaimed coastal land areas exposed by the decreasing rate of eustatic sea‐level rise contemporaneously with isostatic uplift, during the Littorina transgressions. The stable isotope values do not indicate that leaf foddering of the early cattle was of importance.     

Origin of the Nchanga copper–cobalt deposits of the Zambian Copperbelt

The Zambian Copperbelt forms the southeastern part of the 900-km-long Neoproterozoic Lufilian Arc and contains one of the world’s largest accumulations of sediment-hosted stratiform copper mineralization. The Nchanga deposit is one of the most significant ore systems in the Zambian Copperbelt and contains two major economic concentrations of copper and cobalt, hosted within the Lower Roan Group of the Katangan Supergroup. A Lower Orebody (copper only) and Upper Orebody (copper and cobalt) occur towards the top of arkosic units and within the base of overlying shales. The sulfide mineralogy includes pyrite, bornite, chalcopyrite, and chalcocite, although in the Lower Orebody, sulfide phases are partially or completely replaced by malachite and copper oxides. Carrollite is the major cobalt-bearing phase and is restricted to fault-propagation fold zones within a feldspathic arenite. Hydrothermal alteration minerals include dolomite, phlogophite, sericite, rutile, quartz, tourmaline, and chlorite. Quartz veins from the mine sequence show halite-saturated fluid inclusions, ranging from ~31 to 38 wt% equivalent NaCl, with homogenisation temperatures (Th_TOT) ranging between 140 and 180°C. Diagenetic pyrites in the lower orebody show distinct, relatively low δ ³⁴S, ranging from −1 to −17‰ whereas arenite- and shale-hosted copper and cobalt sulfides reveal distinctly different δ ³⁴S from −1 to +12‰ for the Lower Orebody and +5 to +18‰ for the Upper Orebody. There is also a clear distinction between the δ ³⁴S mean of +12.1±3.3‰ (n=65) for the Upper Orebody compared with +5.2±3.6‰ (n=23) for the Lower Orebody. The δ ¹³C of dolomites from units above the Upper Orebody give δ ¹³C values of +1.4 to +2.5‰ consistent with marine carbon. However, dolomite from the shear-zones and the alteration assemblages within the Upper Orebody show more negative δ ¹³C values: −2.9 to −4.0‰ and −5.6 to −8.3‰, respectively. Similarly, shear zone and Upper Orebody dolomites give a δ ¹⁸O of +11.7 to +16.9‰ compared to Lower Roan Dolomites, which show δ ¹⁸O of +22.4 to +23.0‰_. Two distinct structural regimes are recognized in the Nchanga area: a weakly deformed zone consisting of basement and overlying footwall siliciclastics, and a moderate to tightly folded zone of meta-sediments of the Katangan succession. The fold geometry of the Lower Roan package is controlled by internal thrust fault-propagation folds, which detach at the top of the lowermost arkose or within the base of the overlying stratigraphy and show vergence towards the NE. Faulting and folding are considered to be synchronous, as folding predominantly occurred at the tips of propagating thrust faults, with local thrust breakthrough. The data from Nchanga suggests a strong link between ore formation and the development of structures during basin inversion as part of the Lufilian Orogeny. Sulfides tend to be concentrated within arenites or coarser-grained layers within shale units, suggesting that host-rock porosity and possibly permeability played a role in ore formation. However, sulfides are also commonly orientated along, but not deformed by, a tectonic fabric or hosted within small fractures that suggest a significant role for deformation in the development of the mineralization. The ore mineralogy, hydrothermal alteration, and stable isotope data lend support to models consistent with the thermochemical reduction of a sulfate- (and metal) enriched hydrothermal fluid, at the site of mineralization. There is no evidence at Nchanga for a contribution of bacteriogenic sulfide, produced during sedimentation or early diagenesis, to the ores.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.Editorial handling: H. Frimmel     

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     

青藏高原东缘缅萨洼金矿成矿流体地质地球化学特征

缅萨洼金矿位于中国中轴构造带的中南段,青藏高原的东缘,赋存于金河-箐河断裂带次级断裂羊坪子韧性剪切带中本文根据对该矿床硫化物流体包裹体的氦氩同位素、硫化物的硫同位素以及与硫化物共生的石英的流体包裹体特征、成分以及氢氧同位素组成的测定,讨论了缅萨洼金矿的成矿流体来源及其矿床成因。结果显示,该矿床硫化物流体包裹体中的3He/4He变化较小,为0.69-0.82,显示了地幔流体参与成矿作用的可能性。而4He的含量变化范围较大,一般在2.19-10.62×10-6cm3STP/g(方铅矿除外)与3He/4He相比,40Ar/36Ar的比值则变化较小,一般为251-509。而硫化物的δ34S同位素变化范围在-1.8-2.2‰,平均值为0.5‰,说明硫的地幔来源。与硫化物共生的石英的流体包裹体的类型主要有富液相的盐水溶液包裹体、富气相的盐水溶液包裹体、三相CO2包裹体、纯液相CO2包裹体以及有机流体包裹体。成矿流体的氢氧同位素则显示成矿流体来源于岩浆水(或地幔流体)与大气降水的混合流体,本文认为,缅萨洼金矿的成矿流体为地幔流体与大气降水的混合流体,是渐新世印度大陆与亚洲大陆碰撞之后,该地区大规模走滑与剪切作用过程中,局部伸展作用的产物。     

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。