Diatoms and ostracods as mid-Holocene palaeoenvironmental indicators,North Stromatolite Lake,Coorong National Park,South Australia ∗

The Holocene carbonate sequence of perennial North Stromatolite Lake, located adjacent to the Coorong Lagoon near Salt Creek, South Australia, includes a prominent sapropelic unit (7 – 12% total organic carbon), in places more than 2 m thick, that was sampled for the purpose of radiocarbon dating and documenting its diatom and ostracod biostratigraphy. The recovered ostracods were also subjected to carbon and oxygen isotopic analysis. The bulk organic matter at the base of the sapropel yielded an uncalibrated ¹⁴C age of 6080 ± 60 y BP. Diatoms, where preserved, are almost exclusively benthic. Stratigraphic variation of the proportions of key indicator species in diatom assemblages records a marked oscillation between oligosaline and eusaline conditions in the hypolimnion during deposition of the sapropel. Ostracod carbon isotope data indicate that the lake at this time was eutrophic, thereby enriching the dissolved inorganic carbon of the hypolimnion in ¹³C. However, the observed secular variation in δ¹³C implies a mid-sapropel drop in productivity, caused by a freshening of the lake. Ostracod δ¹⁸O values display an overall increase through the sapropel consistent with the rising salinity of the hypolimnion. The existence of a flourishing benthic ostracod community, together with the valve ornamentation of Osticythere baragwanathi, indicates that the bottom waters were well oxygenated. Thus, anoxia was not a prerequisite for sapropel accumulation. The biostratigraphy and chemostratigraphy of the sapropel concur in suggesting a lack of climatic uniformity during its deposition, a period of ～1200 years. This study therefore highlights the potential of diatoms and ostracods in shallow perennial alkaline lakes along the Coorong coastal plain as proxies for short-term (10² – 10³ years) Holocene palaeoenvironmental change in southeastern Australia.     

Constraining flow paths of saline groundwater at basin margins using hydrochemistry and environmental isotopes: Lake Cooper,Murray Basin,Australia

Solutes in saline groundwater (total dissolved solids up to 37 000 mg/L) in the Lake Cooper region in the southern margin of the Riverine Province of the Murray Basin are derived by evapotranspiration of rainfall with minor silicate, carbonate and halite dissolution. The distribution of hydraulic heads, salinity, percentage modern carbon (pmc) contents, and Cl/Br ratios imply that the groundwater system is complex with vertical flow superimposed on lateral flow away from the basin margins. Similarities in major ion composition, stable (O, H, and C) isotope, and ⁸⁷Sr/⁸⁶Sr ratios between groundwater from the shallower Shepparton Formation and the deeper Calivil – Renmark aquifer also imply that these aquifers are hydraulically interconnected. Groundwater in the deeper Calivil – Renmark aquifer in the Lake Cooper region has residence times of up to 25 000 years, implying that pre-land-clearing recharge rates were <1 mm/y. As in other regions of the Murray Basin, the low recharge rates account for the occurrence of high-salinity groundwater. Shallow (<20 m) groundwater yields exclusively modern ¹⁴C ages and shows a greater influence of evaporation over transpiration. Both these observations reflect the rise of the regional water-table following land clearing over the last 200 years and a subsequent increase in recharge to 10 – 20 mm/y. The rise of the regional water-table also has increased vertical and horizontal hydraulic gradients that may ultimately lead to the export of salt from the Lake Cooper embayment into the adjacent fresher groundwater resources.     

Oxygen and carbon isotope composition of Gordon Group carbonates (Ordovician), Florentine Valley,Tasmania, Australia

The Gordon Group carbonates consist of biota of the Chlorozoan assemblage, diverse non‐skeletal grains and abundant micrite and dolomite, similar to those of modern warm water carbonates. Cathodoluminescence studies indicate marine, meteoric and some burial cements. Dolomites replacing burrows, mudcracks and micrite formed during early diagenesis.

δ¹⁸O values (‐5 to ‐7%ō PDB) of the non‐luminescent fauna and marine cement are lighter than those of modern counterparts but are similar to those existing within low latitudes during the Ordovician because of the light δ¹⁸O values of Ordovician seawater (‐3 to ‐5%o SMOW). The δ¹⁸O difference (2%o) between marine and meteoric calcite indicates that Ordovician meteoric water was similar to that in modern subtropics. Values of δ¹³C relative to δ¹⁸O indicate that during the Early Ordovician there were higher atmospheric CO₂ levels than at present but during the Middle and Late Ordovician they became comparable with the present because of a change from ‘Greenhouse’ to glacial conditions. δ¹⁸O values of Late Ordovician seawater were heavier than in the Middle Ordovician mainly because of glaciation.

Dolomitization took place in marine to mixed‐marine waters while the original calcium carbonate was undergoing marine to meteoric diagenesis.     

The origin of tin deposits in the Mount Wells region,Pine Creek Geosyncline,Northern Territory

Tabular steeply dipping cassiterite‐bearing lodes in the Mount Wells region are hosted by lower greenschist fades metasediment of the Pine Creek Geosyncline within the contact aureole of late orogenic granitoids. The latter are predominantly I‐type, but S‐type phases are developed near the sediment‐granitoid contact.

Quartz, cassiterite, pyrite, arsenopyrite, chalcopyrite and pyrrhotite are the main minerals. Two types of lodes are present: (i) Sn‐quartz lodes containing 5–10 vol% sulphide minerals; and (ii) Sn‐sulphide lodes containing ～ 70 vol% sulphide minerals. At the surface, the former appear as normal quartz veins and the latter as hematite‐quartz breccia resulting from the collapse of original sulphide‐rich lodes as a consequence of volume reduction due to oxidation and leaching.

Two stages of quartz veining are recognized in both types of lodes. Cassiterite is present in stage I while stage II is composed of barren quartz with minor pyrite. Late stage III carbonate veinlets are present in Sn‐sulphide lodes. The lode‐wallrock contact is sharp with weak alteration effects confined to the fringe of the lodes. The alteration minerals include sericite, quartz, tourmaline, chlorite, pyrite and minor K‐feldspar.

Four types of fluid inclusions are present in vein quartz and cassiterite: Type A (CO₂ ± H₂O ± CH₄); Type B (H₂O+～ 20% vapour); Type C (H₂O+ < 15% vapour) and Type D (H₂O+ < 15% vapour + NaCl). Early ‘primary’ inclusions represented by Types A and B are present in stage I only and have a well‐defined temperature mode at ～300°C and a salinity range of 1–20 wt% eq NaCl. Types C and D inclusions are ‘secondary’ in stage I and primary in stage II and have a temperature mode at 120–160°C and salinities from about 1 to more than 26 wt% eq NaCl. Variable H₂O‐CO₂ ratios of Type A inclusions and homogenization in CO₂ or H₂O phase at near identical temperature indicate entrapment at the H₂O‐CO₂ solvus and define a pressure of ～ 100 MPa. The melting sequence of frozen inclusions suggests that the ore fluids were mainly H₂O‐CO₂‐CH₄‐Na‐Ca‐Cl brines. This is also confirmed by Raman Laser Spectrometry.

Oxygen and sulphur isotope data are consistent with a magmatic origin of the ore fluids. The δD values are up to 20%0 higher than those expected for magmatic fluids and probably resulted from interaction of the latter with the carbonaceous strata. This interpretation is supported by δ¹³C data on the fluid inclusion CO₂.

Fluid inclusions, stable isotope and mineralogical data are used to approximate the physico‐chemical parameters of the ore fluids which are as follows: T 300°C, m Cl～2, fO₂ ～ 10^‐35, mSS ～ 0.01, Sn ～ 1 ppm, Cu ～ 1 ppm and pH ～ 5.5.

It is suggested that fluids of granitic parentage interacted with the enclosing sediment and picked up CO₂, CH₄ and possibly Ca. The granitic phases became reduced due to this interaction and developed S‐type characteristics. Tin was probably partitioned into the CH₄‐bearing reduced fluids. At some stage the fluid overpressure exceeded the lithostatic lode enforcing failure of the carapace and the intruded rocks by hydraulic fracturing causing CH₄ and CO₂ loss resulting in the precipitation of the ore minerals.     

Mineralogical and Geochemical Constraints on the Genesis of the Carbonate‐Hosted Jebel Ghozlane Pb–Zn Deposit (Nappe Zone,Northern Tunisia)

The Pb–Zn deposit at Jebel Ghozlane, in the Nappe zone (northern Tunisia), is hosted by Triassic dolostones and Eocene limestones and is located along faults and a thrust‐sheet boundary. The sulfide mineralization of the deposit consists mainly of galena and sphalerite and occurs as vein, stockwork, breccia, dissemination and replacement ores. Three hydrothermal stages are involved in the formation of the ores: stage I is dominated by celestite‐barite, hydrothermal dolomite DII, colloform sphalerite, and galena I; stage II consist of galena II; and stage III contains calcite. Galena in the deposit yielded average ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios of 18.705, 15.667 and 38.734, respectively, suggesting a single upper crustal source reservoir for metals. Trace element data indicate the presence of Zn‐ and As‐free galena and As‐rich galena (with 0.2–0.5% As). Sphalerite contains 0.4% As, 0.7–0.9% Cd and 0.1–1.5% Fe. Microthermometric analysis of fluid inclusions in celestite shows that the deposit formed from fluids composed of heterogeneous mixtures of saline (19.5 ± 1 wt% NaCl eq.) aqueous solutions sourced from basinal brines, and gaseous CO₂‐rich phases bearing low amounts of CH₄, N₂ and/or H₂S, at temperatures of 172 ± 5°C.     

The origin of the Maozu carbonate-hosted Pb–Zn deposit,southwest China: Constrained by C–O–S–Pb isotopic compositions and Sm–Nd isotopic age

The Maozu Pb–Zn deposit, located on the western margin of the Yangtze Block, southwest China, is a typical carbonate-hosted deposit in the Sichuan–Yunnan–Guizhou Pb–Zn metallogenic province with Pb + Zn reserves of about 2.0 million tonnes grading 4.15 wt.% Pb and 7.25 wt.% Zn. Its ore bodies are hosted in Sinian (635–541 Ma) Dengying Formation dolostone and show stratiform, vein and irregular textures. Ores are composed of sphalerite, galena, pyrite, calcite, dolomite, quartz and fluorite with massive, banded, disseminated and veined structures. The C–O–Sm–Nd isotopic compositions of hydrothermal calcites and S–Pb isotopic compositions of sulfides were analyzed to constrain the origin of the Maozu deposit. δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcites range from −3.7‰ to −2.0‰ and +13.8‰ to +17.5‰, respectively, and plot near the marine carbonate rocks field in a plot of δ¹³C_PDB vs. δ¹⁸O_SMOW, with a negative correlation. It suggests that CO₂ in the hydrothermal fluids was mainly originated from marine carbonate rocks, with limited influence from sedimentary organic matter. δ³⁴S_CDT values of sulfides range from +9.9‰ to +19.2‰, similar to that of Cambrian to Triassic seawater sulfate (+15‰ to +35‰) and evaporate (+15‰ to +30‰) in the Cambrian to Triassic sedimentary strata. It suggests that reduced sulfur was derived from evaporate in sedimentary strata by thermo chemical sulfate reduction. Sulfides have low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.129–18.375, ²⁰⁷Pb/²⁰⁴Pb = 15.640–15.686 and ²⁰⁸Pb/²⁰⁴Pb = 38.220–38.577) that plot in the field between upper crust and the orogenic belt evolution curve in the plot of ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb, and similar to that of age corrected Proterozoic basement rocks (Dongchuan and Kunyang Groups). This indicates that ore-forming metals were mainly derived from basement rocks. Hydrothermal calcite yields a Sm–Nd isotopic age of 196 ± 13 Ma, possibly reflecting the timing of Pb–Zn mineralization in the SYG province, younger than the Permian Emeishan mantle plume (∼260 Ma). All data combined suggests that hydrothermal fluids circulated through basement rocks where they picked up metals and migrated to surface, mixed with reduced sulfur-bearing fluids and precipitated metals. Ore genesis of the Maozu deposit is different from known magmatic–hydrothermal, Sedimentary Exhalative or Mississippi Valley-types, which maybe represent a unique ore deposit type, named as the SYG-type.     

Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates,nicotianamine, and phytosiderophore,and new Fe isotopic measurements in higher plants

Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ～3‰ (⁵⁶Fe/⁵⁴Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ～1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate₂ and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ⁵⁶Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.     

Assimilation of carbonate country rock by the parent magma of the Panzhihua Fe-Ti-V deposit（SW China）：Evidence from stable isotopes

The Panzhihua intrusion in southwest China is part of the Emeishan Large Igneous Province and host of a large Fe-Ti-V ore deposit.During emplacement of the main intrusion,multiple generations of mafic dykes invaded carbonate wall rocks,producing a large contact aureole.We measured the oxygen-isotope composition of the intrusions,their constituent minerals,and samples of the country rock.Magnetite and plagioclase from Panzhihua intrusion haveδ¹⁸O values that are consistent with magmatic equilibrium, and formed from magmas withδ¹⁸O values that were 1-2‰higher than expected in a mantle-derived magma.The unmetamorphosed country rock has highδ¹⁸O values,ranging from 13.2‰（sandstone） to 24.6-28.6‰（dolomite）.The skarns and marbles from the aureole have lowerδ¹⁸O andδ¹³C values than their protolith suggesting interaction with fluids that were in exchange equilibrium with the adjacent mafic magmas and especially the numerous mafic dykes that intruded the aureole.This would explain the alteration ofδ¹⁸O of the dykes which have significantly higher values than expected for a mantle-derived magma.Depending on the exactδ¹⁸O values assumed for the magma and contaminant, the amount of assimilation required to produce the elevatedδ¹⁸O value of the Panzhihua intrusion was between 8 and 13.7 wt.%,assuming simple mixing.The exact mechanism of contamination is unclear but may involve a combination of assimilation of bulk country rock,mixing with a melt of the country rock and exchange with CO₂-rich fluid derived from decarbonation of the marls and dolomites.These mechanisms,particularly the latter,were probably involved in the formation of the Fe-Ti-V ores.     

Le magmatisme basique calcoalcalin d'âge dévono-dinantien du nord du Massif Central,témoin d'une marge active hercynienne: arguments géochimiques et isotopiques Sr/Nd

Abstract

Samples of volcanic rocks from the main outcrops of Devono-Dinantian series in northern Massif-Central have been studied for Sr and Nd isotopes and immobile incompatible trace elements. In addition, two intrusive bodies of dioritic composition have been dated at 365 ± 3 Ma (Aydat) and 360 ± 1 Ma (Beaumont-Huriel), using the U/Pb zircon method. Together with geochemical data, these ages show that all the studied rocks belong to the same igneous episode. Based on trace element and radiogenic isotopes (⁸⁷Sr/⁸⁶Sr_i from 0,7041 to 0,7057; εNd_i from +1.5 to +5.0), the Late Devonian and Early Carboniferous igneous rocks bear distinct similarities with magmas produced in modern active margin settings. Combined with independent evidence for the occurrence of Devonian oceanic lithosphere in the northern branch of the Variscides, these geochemical affinities suggest that southward subduction of oceanic crust prevailed during the Late Devonian in northern Massif-Central. As a corollary, it appears that true continent-continent collision did not occur before Early Carboniferous times. © 2002 Éditions scientifiques et médicales Elsevier SAS. All rights reserved.     

广东鹦鹉岭钨多金属矿床中黑云母花岗岩LA-ICP-MS锆石U-Pb定年和Hf同位素特征及其地质意义

钦杭成矿带不仅是扬子与华夏陆块的碰撞拼接带,而且也是华南地区独具特色的铜金和钨锡多金属成矿带。本文以鹦鹉岭钨钼多金属矿床含矿岩体-黑云母花岗岩为研究对象,首次开展了锆石 LA-ICP-MS U-Pb 同位素定年和Hf同位素特征研究。获得其锆石²⁰⁶Pb/²³⁸U同位素加权平均年龄为81.3±0.6Ma,其与已获得的辉钼矿Re-Os等时线年龄83.0±1.7Ma在误差范围内基本一致,表明鹦鹉岭多金属矿床成岩成矿作用同时发生于晚白垩世,即中生代燕山晚期。该岩体的锆石ε_Hf（t）值大多数为负值,少部分大于0,变化于-5.72~1.40,平均值为-2.09,表明其主要成岩物质来自于壳源。ε_Hf（t）-t图解上,ε_Hf（t）均落在球粒陨石演化线之下,呈弱亏损的特征,指示地壳部分熔融的岩浆可能有少量地幔物质的加入。两阶段模式年龄t_DM2=1.06~1.51Ga,指示成岩物质主要来源于中元古代古老地壳岩石的部分熔融。结合已有的地球化学、岩石学和区内高精度成岩成矿年龄资料,表明鹦鹉岭钨多金属矿床形成于华南岩石圈伸展-减薄的环境下。