The glauconite–Fe‐illite–Fe‐smectite problem: a critical review

Iron silicate minerals are a significant component of sedimentary systems but their modes of formation remain controversial. Our analysis of published data identifies end‐member compositions and mixtures and allows us to recognize controls of formation of different mineral species. The compositional fields of glaucony, Fe‐illite, Fe–Al smectites are determined in the M⁺/4Si vs. Fe/Sum of octahedral cations (M⁺ = interlayer charge). Solid solutions could exist between these phases. The Fe–Al and Fe‐rich clay minerals form two distinct solid solutions. The earliest phases to be formed are Fe–Al smectites or berthierine depending on the sedimentation rate. Reductive microsystems appear in the vicinity of organic debris in unconsolidated sediments. The Fe is incorporated first in pyrite and then in silicates after oxidation. Potassium ions diffuse from the sea‐water–sediment interface. If not interrupted, the diffusion process is active until reaction completion is reached, i.e. formation of Fe‐illite or glauconite or a mineral assemblage (berthierine–nontronite) according to the available Al ion amounts in the microsystem. Mixed‐layer minerals are formed when the diffusion process is interrupted because of sedimentation, compaction or cementation. Despite the common belief of their value as palaeoenvironment indicators, these minerals can form in a variety of environments and over a period of millions of years during sediment burial.     

Distribution of Fe and Mg between coexisting garnet and hornblende in synthetic and natural systems: an empirical calibration of the garnet–hornblende Fe–Mg geothermometer

Multiple regression analysis of a compilation of the Fe²⁺–Mg distribution between garnet and hornblende from experimental runs on basaltic to intermediate compositions (n=22) and coexisting garnet–clinopyroxene–hornblende from natural (intermediate to basaltic) rocks (n=43) has been performed to define ln K_{D(Fe²⁺/Mg)}^Grt–Hbl as a function of temperature and garnet composition. The regression of data covering a large span in pressure (5–16 kbar), temperature (515–1025°C) and composition yields the ln K_{D(Fe²⁺/Mg)}^Grt–Hbl–P–T compositional relationship (r²=0.93):

where

Application of this expression to natural garnet–hornblende pairs in intermediate to basaltic and semipelitic rock types from various settings gives temperatures that are consistent with other methods.     

Experimental calibration of sapphirine–spinel Fe–Mg exchange thermometer: Implication for constraints on P–T condition of Howard Hills, Napier Complex, East Antarctica

The Fe²⁺–Mg distribution coefficients between sapphirine and spinel:

were experimentally determined at pressures of 9–13 kbar and temperatures of 950–1150 °C using a natural ultrahigh-temperature (UHT) granulite with paragenesis of these minerals from the Napier Complex in East Antarctica [X_Mg = Mg / (Fe + Mg); X_Fe = Fe / (Fe + Mg)]. A new sapphirine–spinel geothermometer has been obtained as:

We applied the exchange thermometer to UHT or high-grade metamorphic rocks that were reported from various complexes in the world. If the K_D values of 2.63–4.34 obtained from low-Cr mineral pairs such as X_Cr^Spr < 0.016 and X_Cr^Spl < 0.047 were substituted into the equation, their temperature conditions would be estimated as 806–1050 °C at 11 kbar. The X_Cr means Cr / (Al + Cr(+ Fe³⁺)). These temperatures are reasonable retrograde or near peak metamorphic condition.     

Nontronite synthesis at low temperatures

The low-temperature synthesis of clay minerals is possible through the aging of freshly prepared hydroxide—silica precipitates. The rapid synthesis of nontronite is only possible at surface temperatures under reducing conditions. Under oxidizing conditions, pure Fe(III)- or pure Al-smectite minerals could not be synthesized at low temperatures. It is only from Fe(II)-containing solutions that nontronite and lembergite, the di-[Fe(III)] and tri-[Fe(II)] octahedral three-layer silicates, are built up in several days at low temperatures. The presence of Fe(II) enables an octahedral layer of the brucite—gibbsite type to be formed. These are necessary for the bidimensional orientation of SiO₄ tetrahedrons, leading to clay-mineral formation. The Fe²⁺ and/or Mg²⁺ ions are necessary for the formation of the Al³⁺- and Fe³⁺-containing three-layer silicate minerals.Under reducing diagenetic conditions, the Fe contents in recent sediments are sufficient to build up Al-rich three-layer minerals under both fresh-water and salt-water conditions.     

Matrix Corrections and Error Analysis in High‐Precision SIMS 18O/16O Measurements of Ca–Mg–Fe Garnet

We report technical and data treatment methods for making accurate, high‐precision measurements of ¹⁸O/¹⁶O in Ca–Mg–Fe garnet utilising the Cameca IMS 1280 multi‐collector ion microprobe. Matrix effects were similar to those shown by previous work, whereby Ca abundance is correlated with instrumental mass fractionation (IMF). After correction for this effect, there appeared to be no significant secondary effect associated with Mg/Fe²⁺ for routine operational conditions. In contrast, investigation of the IMF associated with Mn‐ or Cr‐rich garnet showed that these substitutions are significant and require a more complex calibration scheme. The Ca‐related calibration applied to low‐Cr, low‐Mn garnet was reproducible across different sample mounts and under a range of instrument settings and therefore should be applicable to similar instruments of this type. The repeatability of the measurements was often better than ± 0.2‰ (2s), a precision that is similar to the repeatability of bulk techniques. At this precision, the uncertainties due to spot‐to‐spot repeatability were at the same magnitude as those associated with matrix corrections (± 0.1–0.3‰) and the uncertainties in reference materials (± 0.1–0.2‰). Therefore, it is necessary to accurately estimate and propagate uncertainties associated with these parameters – in some cases, uncertainties in reference materials or matrix corrections dominate the uncertainty budget.     

Spectroscopic investigation on the chemical forms of Cu during the synthesis of zeolite X at low temperature

The direct synthesis of zeolites in polluted soils has proved to be a promising process for the stabilization of metals inside these minerals. Nevertheless, more detailed information about this process is still needed in order to better foresee the fate of metals in treated soils. In this work, zeolite X has been synthesized under alkaline conditions in an aqueous solution containing 2500 mg kg⁻¹ of Cu, starting from Na silicate and Al hydroxide at 60 °C. Aluminium, Si and Cu concentrations in the aqueous phase, during zeolite synthesis, were measured over a period of 160 h. The solid products have been characterized over time by XRD, SEM-EDX, ESR, FT-IR, and synchrotron radiation X-ray microbeam absorption near edge structure (μ-XANES) and extended X-ray absorption fine structure (μ-EXAFS) spectroscopy. It appears that the marked reduction of Cu concentration in solution is not only due to a simple precipitation effect, but also to processes connected with the formation of zeolite X which could entrap, inside its porous structure, nano- or micro-occlusions of precipitated Cu hydroxides and/or oxides. In addition, EXAFS observations strengthen the hypothesis of the presence of different Cu phases even at a short-range molecular level and suggest that some of these occlusions could be even bound to the zeolite framework. The results suggest that zeolite formation could be used to reduce the availability of metals in polluted soils.     

How well known are the thermodynamics of Fe–Mg–Ca garnet? Evidence from experimentally determined exchange equilibria

ABSTRACT Many thermodynamic calculations relating to metamorphic rocks hinge on the thermodynamic parameters of garnet. Though some models are widely used, it is not clear whether their underlying premise is correct: that a single set of equations can be written for the activities of the end-members of garnet covering the whole compositional range. A voluminous body of data can be used to constrain the thermodynamics of garnet, namely Fe–Mg exchange experimental data involving garnet and another mineral, particularly clinopyroxene, orthopyroxene and olivine. However, examination of these data reveals inconsistencies, apparently stemming from differences between the thermodynamics of low-Ca and high-Ca garnets, with a boundary of about X^g_Ca= 0.15. In the two regions, for the high P–T of the experimental data, the thermodynamics follow the regular model, with values for the interaction parameters in the low Ca region of about w^g_FeMg= 50R and w_aFe–w^g_MgCa=– 1300R, in which R is the gas constant, and in the high Ca region of about w^g_FeMg= 1100R and w^g_CaFe–w^g_MgCa=– 2200R. Using the subregular, rather than the regular, model does not remove the discrepancy. The cause of the discrepancy needs to be identified if reliable calculations on rocks are to be made.     

Porphyry Cu–Au and associated polymetallic Fe–Cu–Au deposits in the Beiya Area, western Yunnan Province, south China

The Alkaline porphyries in the Beiya area are located east of the Jinshajiang suture, as part of a Cenozoic alkali-rich porphyry belt in western Yunnan. The main rock types include quartz-albite porphyry, quartz-K-feldspar porphyry and biotite–K-feldspar porphyry. These porphyries are characterised by high alkalinity [(K₂O + Na₂O)% > 10%], high silica (SiO₂% > 65%), high Sr (> 400 ppm) and ⁸⁷Sr/⁸⁶Sr (> 0.706)] ratio and were intruded at 65.5 Ma, between 25.5 to 32.5 Ma, and about 3.8 Ma, respectively. There are five main types of mineral deposits in the Beiya area: (1) porphyry Cu–Au deposits, (2) magmatic Fe–Au deposits, (3) sedimentary polymetallic deposits, (4) polymetallic skarn deposits, and (5) palaeoplacers associated with karsts. The porphyry Cu–Au and polymetallic skarn deposits are associated with quartz–albite porphyry bodies. The Fe–Au and polymetallic sedimentary deposits are part of an ore-forming system that produced considerable Au in the Beiya area, and are characterised by low concentrations of La, Ti, and Co, and high concentrations of Y, Yb, and Sc.The Cenozoic porphyries in western Yunnan display increased alkalinity away from the Triassic Jinshajiang suture. Distribution of both the porphyries and sedimentary deposits in the Beiya area are interpreted to be related to partial melting in a disjointed region between upper mantle lithosphere of the Yangtze Plate and Gondwana continent, and lie within a shear zone between buried Palaeo-Tethyan oceanic lithosphere and upper mantle lithosphere, caused by the subduction and collision of India and Asia.     

The determination of trace elements in Fe–Mn oxide coatings on pebbles using LA-ICP-MS

Iron–manganese oxide coatings form on a wide range of geologic samples where they have the ability to adsorb elements and potentially act as a mineral exploration/environmental monitoring tool. In this study, Fe–Mn oxide coatings on stream pebbles were collected from streams in four study areas located across the province of Newfoundland and Labrador, Canada. The study locations were in areas of former copper mines (Tilt Cove and Betts Cove), carbonate geology (Robinsons River), and a metropolitan area (Rennies River). Collected pebbles underwent a simple sample preparation procedure and were then analyzed for a wide range of elements by LA-ICP-MS after optimization of the operating conditions. Water samples accompanied the pebbles, and these were analyzed for pH, dissolved oxygen, conductivity, and a large selection of elements by ICP-MS. Multivariate statistics, in the form of Principal Component Factor Analysis (PCFA) was performed on both data sets. Graphs of the factor scores from the PCFA produced groupings of the samples that were related to geologic/environmental inputs. The loading of variables in each factor was related to the adsorption of the element either to the MnO₂ or Fe₂O₃ phase with most elements except Cr and Cu displaying preferential adsorption to MnO₂. Elemental Fe–Mn oxide coating concentrations were a result of the element's affinity (chalcophile, lithophile, or siderophile), pH of the environment, stream water concentration, and amount of each oxide phase present. Even with these complications, LA-ICP-MS analysis of Fe–Mn oxides was able to identify areas of heavy metal pollution and locate geologic inputs.     

Geochemistry of Some Marine Fe–Mn Nodules and Crusts with Respect to Pt Contents

Bulk chemical analyses for Pt and Pd in marine Fe–Mn nodules and crusts from different provenances are presented, together with a wide range of elements. Platinum contents vary from 70–328 ppb, whereas Pd contents extend from 0.6–4.7 ppb only. Bromine and Pb show strong positive correlations with Pt. Lead is remarkably enriched in Fe–Mn precipitates over seawater, but Br is a conservative‐type element in seawater and shows no enrichment in Fe–Mn precipitates. Hence, the Pt–Br–Pb element association combines two elements, Br and Pb, of extremely contrasting enrichment factors in Fe–Mn precipitates.     

The Grader layered intrusion (Havre-Saint-Pierre Anorthosite, Quebec) and genesis of nelsonite and other Fe–Ti–P ores

The Grader layered intrusion is part of the Havre-Saint-Pierre anorthosite in the Grenville Province (Quebec, Canada). This intrusion has a basin-like morphology and contains significant resources of Fe–Ti–P in ilmenite and apatite. Outcropping lithologies are massive oxide alternating with anorthosite layers, banded ilmenite–apatite–plagioclase rocks and layered oxide apatite (gabbro-)norites. Drill cores provide evidence for stratigraphic variations of mineral and whole rock compositions controlled by fractional crystallization with the successive appearance of liquidus phases: plagioclase and ilmenite followed by apatite, then orthopyroxene together with magnetite, and finally clinopyroxene. This atypical sequence of crystallization resulted in the formation of plagioclase–ilmenite–apatite cumulates or “nelsonites” in plagioclase-free layers. Fine-grained ferrodiorites that cross-cut the cumulates are shown to be in equilibrium with the noritic rocks. The high TiO₂ and P₂O₅ contents of these assumed liquids explains the early saturation of ilmenite and apatite before Fe–Mg silicates, thus the nelsonites represent cumulates rather than crystallized Fe–Ti–P-rich immiscible melts. The location of the most evolved mineral and whole rock compositions several tens of meters below the top of the intrusion, forming a sandwich horizon, is consistent with crystallization both from the base and top of the intrusion. The concentrations of V and Cr in ilmenite display a single fractionation path for the different cumulus assemblages and define the cotectic proportion of ilmenite to 21 wt.%. This corresponds to bulk cotectic cumulates with ca. 8 wt.% TiO₂, which is significantly lower than what is commonly observed in the explored portion of the Grader intrusion. The proposed mechanism of ilmenite-enrichment is the lateral removal of plagioclase due to its relative buoyancy in the dense ferrodiorite melt. This plagioclase has probably accumulated in other portions of the intrusion or has not been distinguished from the host anorthosite.     

Experimental and natural early diagenetic mobility of Sr and Mg in biogenic carbonates

Ammonium acetate dissolution experiments were performed on shell material of the modern bivalves, Crassostrea virginica (calcite) and Mercenaria mercenaria (aragonite). Their purpose was to determine the order of preferential dissolution of Sr, Mg and Ca; these results subsequently were compared with Sr, Mg and Ca data from other Recent as well as ancient mollusks.Results from these experiments suggest the following relative order of abundance of readily exchangeable Mg and Sr in biogenic carbonates: Mg(arag) > Mg(calc) > Sr(calc) > Sr(arag). It is apparent that incongruent dissolution of minerals with different solubilities cannot entirely explain the observed dissolution patterns for Sr, Mg and Ca in these biogenic carbonates. Secular changes in whole shell Mg and Sr concentrations for Recent and unrecrystallized fossil mollusks suggest an order of “ionic mobility” in diagenesis identical to the order of abundance for readily exchangeable ions found in the NH₄Ac dissolution experiments. It is concluded that this “ionic mobility” is due to a post mortem, early diagenetic (pre-recrystallization) approach to equilibrium with the surrounding chemical environment.     

土工格栅低温下蠕变特性试验研究

土工格栅蠕变特性是影响土工格栅加筋结构长期工作性能的重要因素。通过室内蠕变试验,对土工格栅的低温蠕变特性进行了试验研究,结果表明,塑料土工格栅在低温下蠕变特性与常温下明显不同,20 ℃常温状态下1 000 h后,当伸长率接近14 %时且60 % Pmax（Pmax为断裂强度）下,变形仍没有稳定迹象,而在同等荷载下-20 ℃低温状态时,仅100余小时,变形就趋于稳定,且伸长率不足2.5 %。结果表明塑料土工格栅蠕变性能受温度影响很大,并且温度越低蠕变值越小。     

外加剂对低温水泥浆性能的影响试验研究

为解决在普通硅酸盐水泥（P.O42.5）或混凝土施工中遭遇低温环境而不能顺利凝固的问题。对普遍使用的硅酸盐水泥进行了基础性能测试试验,使用早强剂与高效减水剂对水泥进行调整性能,寻找出最佳的调整方案,对比调整前后水泥浆及水泥石强度等各项数据。结果表明10%早强剂、2‰JSS高效减水剂的调整方案较好地改善了水泥浆的流动性、凝结时间、水化热放热速率、结石率及水泥石的早期强度等问题。研究成果对低温条件下的混凝土施工有一定的参考价值。     

Comment on the studies of oxygen isotope fractionation between calcium carbonates and water at low temperatures by Zhou and Zheng (2003; 2005)

Experimental and theoretical aspects of oxygen isotope fractionation in the system calcite-water at low temperatures were critically examined. Contrary to the claim made by Zhou and Zheng [Zhou G.-T., and Zheng Y.-F. (2003) An experimental study of oxygen isotope fractionation between inorganically precipitated aragonite and water at low temperatures. Geochim. Cosmochim. Acta67, 387-399], there is excellent agreement between fractionation factors that were experimentally determined by means of slow, inorganic precipitation of calcite from solutions and those obtained largely from theoretical, statistical-mechanical calculations of the reduced partition function ratios. This agreement strongly suggests that calcite was precipitated from a solution very close to isotopic equilibrium. However, recently Zhou and Zheng [Zhou G.-T., and Zheng Y.-F. (2005) Effect of polymorphic transition on oxygen isotope fractionation between aragonite, calcite and water: a low-temperature experimental study. Am. Miner.90, 1121-1130] presented, without any explanation, conclusions on these major aspects that contradict the previous statements of Zhou and Zheng (2003). The apparent discrepancy in calcite-water oxygen isotope fractionation between experimental and theoretical studies discussed by Zhou and Zheng (2003) originates from the “mineral-water interaction” term in the modified increment method, which was developed by one of the authors (Y.-F. Zheng). We call for evidence for the theoretical nature of the modified increment method, which has never been presented in any of Zheng’s papers. Without such evidence, great caution must be exercised in using fractionation factors derived from the modified increment method.     

Emplacement of Semail–Emirates ophiolite at ridge–trench collision

The Oman‐Emirates is the largest and best‐exposed ophiolite; consequently, it has attracted significant interest among scientists, together with serious conflicts. Most geologists regard this ophiolite as having formed in an intra‐oceanic subduction zone before being accreted to the Arabian continent. Here, we propose an alternative scenario, supported by detailed field observations and integrated geophysics. The smaller Emirates part of the ophiolite was forced into a nearby continent, in the pre‐collision stage of Tethyan closure. The contraction led to the exhumation of the mantle floor of segmented basins accreted in a rifted system similar to the present‐day Gulf of California. The implied high temperature–high pressure metamorphism and the range of geochemical signatures were introduced during the process of rifting, whereas the larger Oman ophiolite was emplaced by obduction onto and along the subducting continental shore. This Ridge–Trench–Transform system might call for a new process to obduct over continents in particular Tethyan ophiolites.     

Late Miocene increasing exhumation rates in the eastern part of the Alps – implications from low temperature thermochronology

A new set of apatite fission‐track and apatite (U–Th)/He data reveals a hitherto undated late Miocene exhumation pulse in the eastern part of the Eastern Alps. While distinct parts of the study area, including the Seckauer Tauern, have been at near surface conditions (<100 °C) since the Eocene, the neighbouring Niedere Tauern experienced enhanced cooling and exhumation in the middle Miocene and again at the late Miocene/Pliocene boundary. Middle Miocene exhumation is interpreted as a result of tectonic escape and convergence that operated simultaneously during lateral extrusion of the Eastern Alps. As the higher late Miocene/Pliocene exhumation rates are restricted to a single tectonic block, namely the Niedere Tauern, we infer a tectonic trigger that is probably related to a change in the external stress field that affected the Alps during this time.     

Fractionation of sulfur isotopes during laboratory synthesis of pyrite at low temperatures

The reaction products and the accompanying sulfur isotope fractionations during the reaction of H₂S with goethite in aqueous media at 22–24°C for periods from 0.5 hr to 65 days were studied. Fine-grained pyrite formed within two days and was isotopically 0.8‰ lighter than the H₂S source. After 65 days reaction time the pyrite had nearly the same isotopic value as the H₂S. Aqueous precipitation of pyrite from H₂S and goethite at room temperature involved three major steps, namely: (1) the rapid oxidation of H₂S and reduction of Fe³⁺ during which elemental S is formed; (2) the formation of acid-volatile sulfides and the disappearance of elemental S; and (3) the formation of pyrite at the expense of acid-volatile sulfides.     

Carbon and oxygen isotopes of Maastrichtian–Danian shallow marine carbonates: Yacoraite Formation, northwestern Argentina

The Maastrichtian–Danian limestones of the Yacoraite Formation (northwestern Argentina) show carbon and oxygen isotopic values consistent with shallow marine conditions. The members of the formation respond to different sedimentary environments and are characterised by distinctive stable isotopes and geochemistry. The basal Amblayo Member is composed of high-energy dolomitic limestones and limestones with positive isotopic values (+2‰ δ¹³C, +2‰ δ¹⁸O). The top of the member reveals an isotopic shift of δ¹³C (−5‰) and δ¹⁸O (−10‰), probably related to a descent in the sea level. The sandy Güemes Member has isotopically negative (−2‰ δ¹³C, −1‰ δ¹⁸O) limestones, principally controlled by water mixing, decreased organic productivity, and compositional changes in the carbonates. The isotopically lighter limestones are calcitic, with a greater terrigenous contribution and different geochemical composition (high Si–Mn–Fe–Na, low Ca–Mg–Sr). These isotopic and lithological changes relate to the Cretaceous–Palaeogene transition. The Alemanía Member, composed of dolomitic limestones and pelites, represents a return to marine conditions and shows a gradual increase in isotopic values, reaching values similar to those of the Amblayo Member. The Juramento Member, composed of stromatolite limestones, shows isotopic variations that can be correlated with the two well-defined, shallowing-upward sequences of the member.     

Pressure–temperature evolution of lawsonite eclogite in Sivrihisar; Tavşanlı Zone–Turkey

The Cretaceous blueschist belt, Tavşanlı Zone, representing the subducted and exhumed northern continental margin of the Anatolide–Tauride platform is exposed in Western Anatolia. The Sivrihisar area east of Tavşanlı is made up of tectonic units consisting of i) metaclastics and conformably overlying massive marbles (coherent blueschist unit), ii) blueschist-eclogite unit, iii) marble–calcschist intercalation and iv) metaperidotite slab. The metaclastics are composed of jadeite–lawsonite–glaucophane and jadeite–glaucophane–chloritoid schists, phengite phyllites, and calcschists with glaucophane–lawsonite metabasite layers. The blueschist-eclogite unit representing strongly sheared, deeply buried and imbricated tectonic slices of accreted uppermost levels of the oceanic crust with minor metamorphosed serpentinite bodies consists of lawsonite-bearing eclogitic metabasites (approximately 90% of the field), lawsonite eclogites, metagabbros, serpentinites, pelagic marbles, omphacite–glaucophane–lawsonite metapelites and metacherts. The mineral assemblage of the lawsonite eclogite (garnet + omphacite > 70%) is omphacite, garnet, lawsonite, glaucophane, phengite and rutile. Lawsonite eclogite lenses are enclosed by garnet–lawsonite blueschist envelopes.Textural evidence from lawsonite eclogites and country rocks reveals that they did not leave the stability field of lawsonite during subduction and exhumation. The widespread preservation of lawsonite in eclogitic metabasites and eclogites can be attributed to rapid subduction and subsequent exhumation in a low geothermal gradient of the oceanic crust material without experiencing a thermal relaxation. Peak P–T conditions of lawsonite eclogites are estimated at 24 ± 1 kbar and 460 ± 25 °C. These P–T conditions indicate a remarkably low geotherm of 6.2 °C/km corresponding to a burial depth of 74 km.