Phase–mineral and chemical composition of composite samples from feed coals,bottom ashes and fly ashes at the Soma power station,Turkey

The phase–mineral and chemical composition of feed coals (FCs) and their bottom ashes (BAs) and fly ashes (FAs) produced in the Soma thermo-electric power station (TPS), Turkey, was characterized. FCs are high-ash Soma subbituminous coals abundant in moisture and Ca, and depleted in S. The inorganic composition (in decreasing order of significance) of FCs includes calcite, quartz, kaolinite, illite+muscovite, chlorite, plagioclase, gypsum, pyrite, montmorillonite, K-feldspar, dolomite, siderite, ankerite, opal, and volcanic glass. The results for 57 elements studied show that Ca>Nb>Cs>(V, Li) have significantly higher contents in FC ashes than the respective Clarke values for coal ashes. The water-soluble residues isolated from FCs include gypsum, calcite, inorganic amorphous matter, Ca–Mg–Na–K phase, and opal. These residues are enriched in Na>Se>S>B>Mg>Mo>Sr>Ca>K. The phase–mineral composition of BAs and FAs includes mainly glass, quartz, char, mullite, plagioclase, calcite, and portlandite; and, to a lesser extent, illite+muscovite, melilite, hematite, anhydrite, lime, cristobalite, kaolinite, and magnetite. Minor amounts of K-feldspar, dolomite, ankerite, Fe-spinel, gypsum, and Ca–K–Na phase also occur in BAs and FAs. FAs are enriched in inorganic matter, glass, cristobalite, mullite, Fe oxides, lime, and anhydrite, and depleted in mineral matter, char, quartz, clay minerals, melilite, portlandite, and carbonates in comparison with BAs. Only Se is significantly enriched in BAs and FAs compared to FC ashes. Most of the trace elements (in particular As, Bi, Cd, Ge, Pb, Sn, Tl, and W) are more abundant in FAs, while BAs are more enriched in Ca, Cs, Fe, Ho, Mn, P, Sc, Se and Tb. Significant percentages (11–59%) of elements initially present in FCs, namely S>Sb>Sn>Ta>Mo>Bi>Zn>Ni>Na>(Lu, Tm)>B, were emitted by stack emissions and not captured by the cleaning equipment in the Soma TPS. Some genetic features, properties, possible environmental concerns, and potential utilization directions related to FCs, BAs, and FAs are also discussed.     

Incorporation of U,Pb and Rare Earth Elements in Calcite through Crystallisation from Amorphous Calcium Carbonate: Simple Preparation of Reference Materials for Microanalysis

Uncertainty for elemental and isotopic measurements in calcite by LA‐ICP‐MS is largely controlled by the homogeneity of the reference materials (RMs) used for calibration and validation. In order to produce calcite RMs with homogeneous elemental and isotopic compositions, we incorporated elements including U, Pb and rare earth elements into calcite through heat‐ and pressure‐induced crystallisation from amorphous calcium carbonate that was precipitated from element‐doped reagent solution. X‐ray absorption spectra showed that U was present as U(VI) in the synthesised calcite, probably with a different local structure from that of aqueous uranyl ions. The uptake rate of U by our calcite was higher in comparison with synthetic calcite of previous studies. Variations of element mass fractions in the calcite were better than 12% 2RSD, mostly within 7%. The ²⁰⁷Pb/²⁰⁶Pb ratio in the calcite showed < 1% variations, while the ²³⁸U/²⁰⁶Pb ratio showed 3–24% variations depending on element mass fractions. Using the synthetic calcite as primary RMs, we could date a natural calcite RM, WC‐1, with analytical uncertainty as low as < 3%. The method presented can be useful to produce calcite with controlled and homogeneous element mass fractions and is a promising alternative to natural calcite RMs for U‐Pb geochronology.     

Geochemistry of rare earth elements in the mainstream of the Yangtze River,China

Water, suspended matter, and sediment samples were taken from 8 locations along the Yangtze River in 1992. The concentration and speciation (exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter, and residual forms) of rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb, and Lu) were determined by instrumental neutron activation analysis (INAA).The contents of the soluble fraction of REEs in the river are low, and REEs mainly reside in particulate form. In the particles, the chondrite-normalized distribution patterns show significant LREE enrichment and Eu-depletion. While normalized to shales, both sediments and suspended matter samples show relative LREE enrichment and HREE depletion. REEs are relatively enriched in fine-grained fractions of the sediments.The speciation characteristics of REEs in the sediments and suspended matter are very similar. The amount of the five forms follows the order: residual>>bound to organic matter∼bound to Fe–Mn oxides>bound to carbonates>>exchangeable. About 65 to 85% of REEs in the particles exist in the residual form, and the exchangeable form is very low. High proportions of residual REEs reveal that REEs in sediments and suspended matter are controlled by their abundances in the earth's crust. Carbonate, Fe–Mn oxide and organic fractions of REEs in sediments account for 2.4–6.9%, 5.2–11.1%, and 7.3–14.0% of the total contents respectively. They are similar to those in the suspended matter. This shows that carbonates, Fe–Mn oxides and organic matter play important roles during the particle-water interaction processes. By normalization to shales, the 3 forms of REEs follow convex shapes according to atomic number with middle REE (Sm, Eu, and Tb) enrichment, while light REE and heavy REE are depleted.     

Distribution and immobilization of heavy metals in Pliocene aquifer sediments in Wadi El Natrun depression, Western Desert

The Pliocene aquifer receives inflow of Miocene and Pleistocene aquifer waters in Wadi El Natrun depression. The aquifer also receives inflow from the agricultural activity and septic tanks. Nine sediment samples were collected from the Pliocene aquifer in Wadi E1 Natrun. Heavy metal (Cu, Sr, Zn, Mn, Fe, Al, Ba, Cr, Ni, V, Cd, Co, Mo, and Pb) concentrations of Pliocene aquifer sediments were investigated in bulk, sand, and mud fractions. The determination of extractable trace metals (Cu, Zn, Fe, Mn, and Pb) in Pliocene aquifer sediments using sequential extraction procedure (four steps) has been performed in order to study environmental pathways (e.g., mobility of metals, bounding states). These employ a series of successively stronger chemical leaching reagents which nominally target the different compositional fractions. By analyzing the liquid leachates and the residual solid components, it is possible to determine not only the type and concentration of metals retained in each phase but also their potential ecological significance. Cu, Sr, Zn, Mn, Fe, and Al concentrations are higher in finer sediments than in coarser sediments, while Ba, Cr, Ni, V, Cd, Co, Mo, and Pb are enriched in the coarser fraction. The differences in relative concentrations are attributed to intense anthropogenic inputs from different sources. Heavy metal concentrations are higher than global average concentrations in sandstone, USEPA guidelines, and other local and international aquifer sediments. The order of trace elements in the bulk Pliocene aquifer sediments, from high to low concentrations, is Fe?>?Al?>?Mn?>?Cr?>?Zn?>?Cu?>?Ni?>?V?>?Sr?>?Ba?>?Pb?>?Mo?>?Cd?>?Co. The Pliocene aquifer sediments are highly contaminated for most toxic metals, except Pb and Co which have moderate contamination. The active soluble (F0) and exchangeable (F1) phases are represented by high concentrations of Cu, Zn, Fe, and Mn and relatively higher concentrations of Pb and Cd. This may be due to the increase of silt and clay fractions (mud) in sediments, which act as an adsorbent, retaining metals through ion exchange and other processes. The order of mobility of heavy metals in this phase is found to be Pb?>?Cd?>?Zn?>?Cu?>?Fe?>?Mn. The values of the active phase of most heavy metals are relatively high, indicating that Pliocene sediments are potentially a major sink for heavy metals characterized by high mobility and bioavailability. Fe–Mn oxyhydroxide phase is the most important fraction among labile fractions and represents 22% for Cd, 20% for Fe, 11% for Zn, 8% for Cu, 5% for Pb, and 3% for Mn. The organic matter-bound fraction contains 80% of Mn, 72% of Cu, 68% of Zn, 60% of Fe, 35% of Pb, and 30% of Cd (as mean). Summarizing the sequential extraction, a very good immobilization of the heavy metals by the organic matter-bound fraction is followed by the carbonate-exchangeable-bound fraction. The mobility of the Cd metal in the active and Fe–Mn oxyhydroxide phases is the highest, while the Mn metal had the lowest mobility.     

Phosphorus fractions and bioavailability in relation to particle size characteristics in sediments from Lake Hongfeng, Southwest China

Information on the chemical composition of phosphorus (P) fractions in sediments is fundamental to understanding P bioavailability and eutrophication in lake ecosystems. Phosphorus fractions and its bioavailability in sediments cores of Lake Hongfeng, southwest China, were investigated using a chemical sequential extraction scheme. Relationships between P fractions, P bioavailability and particle sizes were discussed. P fractions concentrations were ranked in the order: Residual-P > NaOH–rP > NaOH–NRP > HCl–P > BD–P > NH₄Cl–P, and all of them decreased with increasing sediment depth. Statistical analysis showed that concentrations of bioavailable P (BAP) which includes the NH₄Cl–P, BD–P, NaOH–rP and NaOH–NRP fractions ranged from 404.68 to 1,591.99 mg/kg and accounted for 26.8–71.8 % of the concentrations of total phosphorus (TP) in the top 5 cm sediments, whereas in the whole sediment cores, their concentrations ranged from 239.70 to 1,591.99 mg/kg and accounted for 26.8–76.0 % of TP. The results suggested that the sediments were a large potential source of P for algae blooms in Lake Hongfeng. Phosphorus fractions and their potential bioavailability were influenced by the sediment particle sizes, especially the bioavailability of the NH₄Cl–P fraction, which was strongly affected by the presence of fine particle sizes in the sediments.     

Geochemical processes and mobilization of toxic metals and metalloids in an As-rich base metal waste pile in Zimapán,Central Mexico

The geochemistry and mineralogy of samples collected along depth profiles from an As-rich tailing deposit with abundant calcite was studied to determine the processes that influence the mobility of Fe, Zn, Cu, Ni, Cd, As, Sb, Cr and Tl. In spite of their near neutral pH, almost all of them are acid potential generators. Total concentrations decreased as: Fe > As > Zn > Pb > Cu > Sb > Cd > Cr > Ni > Tl. Soluble contents were lower and followed a slightly different order. Mobility decreased as: Tl > Cd, Zn, Cu, Sb, Ni, As > Fe, Pb > Cr. Higher soluble concentrations of Fe, Cu, Zn, As, Pb, and Ni were found in low-pH samples and of Sb and Tl in near-neutral samples. Sulfide oxidation processes are developing in the tailing’s dam. These processes do not have a trend with depth but occur mainly in acid layers. Near neutral layers formed by primary sulfides and calcite probably correspond to wastes produced from the processing of ore coming mainly from pods within the skarn, and acid layers with abundant secondary minerals from material mined from chimneys and mantos. The presence of calcite influences speciation, neutralizes acid mine drainage (AMD), and decreases the mobility of most toxic metals and metalloids (TMMs). However, a hard-pan layer was not observed in the studied profiles. Retention of TMM within tailings probably occurs through the formation of low solubility metal carbonates and from elevation of pH that promotes Fe hydroxides precipitation that may retain As, Sb and metals. Calcite occurrence promotes As, Cd, Cu, Fe, Zn, Pb, Cd and Cr retention, does not play a role on Tl and Ni mobilization, and increases Sb release.     

The effect of mineralogy on the mobility of heavy metals in mine tailings: a case study in the Samsanjeil mine,Korea

This study examined the chemical speciation and mobility of As and heavy metals in a tailings impoundment in Samsanjeil mine located in Gosung, Korea, as well as the factors affecting them. XRD, SEM, and 5-step sequential extraction were used to examine the samples at two sampling sites (NN and SN sites). The pH of the tailings decreased with increasing depth at the NN site (from 7.2 to 2.8), whereas no significant differences were observed at the SN site (8.1–8.8). The samples at the SN site showed a larger amount of calcite than those at the NN site, indicating that calcite plays an important role buffering the pH in the study sites. Jarosite was found only at the lower part of the NN site, where calcite was not found. The mineralogical observation of jarosite and calcite was also confirmed by SEM. The concentrations of As and heavy metals in the tailings were as follows: Cu > As > Zn > > Pb > Co > Cr > Ni > Cd. The total concentrations of Ni, Zn, Co, and Cd were higher at the SN site than those at the NN site. On the other hand, the concentrations of As and Cr existing as oxyanions were higher at the NN site, which can be explained by the mobility changes of those elements affected by pH variations. At the NN site, the fractions of heavy metals bound to the Fe/Mn oxides, except for As and Cr, decreased, and Cu, Zn, and Co showed an increasing fraction of exchangeable metals with increasing depth. This suggests that the pH and resulting surface charge of minerals, such as goethite and jarosite, are the dominant factors controlling the chemical speciation of metals. These results highlight the importance of mineralogy in controlling the mobility and possible bioavailability of heavy metals in tailings.     

Mineralogy and composition of Kuroko deposits from northeastern Honshu and their possible modern analogues from the Izu-Ogasawara (Bonin) Arc south of Japan: Implications for mode of formation

The Kuroko deposits of NE Honshu are a key type deposit for the study of volcanogenic massive sulfide deposits. However, these deposits have not been studied in detail since the early 1980's and knowledge of their mode of formation is now dated. In this study, we present the analysis of 12 samples of the Kuroko deposits, 12 samples of submarine hydrothermal minerals from the Sunrise deposit and 6 samples from Suiyo Seamount, both of which are located on the Izu-Ogasawara (Bonin) Arc, for 27 elements. For the Kuroko deposit, Cd>Sb>Ag>Pb>Hg>As>Zn>Cu are highly enriched, Au>Te>Bi>Ba>Mo are moderately enriched, In>Tl are somewhat enriched and Fe is not significantly enriched relative to the average continental crust. Within each of these deposits, a similar pattern of element associations is apparent: Zn–Pb with As, Sb, Cd, Ag, Hg, Tl and Au; Fe–Cu–Ba with As, Sb, Ag, Tl, Mo, Te and Au; Si–Ba with Ag and Au; CaSO₄. The enrichment of the chalcophilic elements in these deposits is consistent with hydrothermal leaching of these elements from the host rocks which are dominantly rhyolite–dacite in the case of the Kuroko deposits, rhyolite in the case of the Sunrise deposit and dacite–rhyolite in the case of the Suiyo Seamount deposit. However, this pattern of element enrichment is also similar to that observed in fumarolic gas condensates from andesitic volcanoes. This suggests that there may be a significant magmatic contribution to the composition of the hydrothermal fluids responsible for the formation of the Kuroko deposits, although it is not yet possible to quantify the relative contributions of these two sources of elements.The compositional data show that Sunrise and Suiyo Seamount deposits are much closer compositionally to the Kuroko deposits from NE Honshu than are the submarine hydrothermal deposits from the JADE site in the Okinawa Trough which contain, on average, significantly higher concentrations of Pb, Zn, Sb, As and Ag than each of these deposits. In spite of the greater similarity in tectonic setting of the Hokuroku Basin in which the Kuroko deposits formed to the Okinawa Trough (intracontinental rifted back-arc basin) compared to Myojin Knoll and Suiyo Seamount (active arc volcanoes), it appears that submarine hydrothermal deposits from Myojin Knoll and Suiyo Seamount are closer analogues of the Kuroko deposit than are those from the Okinawa Trough. The present data are consistent with the magmatic hydrothermal model for the formation of Kuroko-type deposits as formulated by Urabe and Marumo [Urabe, T., Marumo, K., 1991. A new model for Kuroko-type deposits of Japan. Episodes 14, 246–251].     

Hydrothermal mineralization in the sandstone–hosted Hangjinqi uranium deposit,North Ordos Basin,China

Tabular–type uranium ore deposits (the Hangjinqi and Daying deposits) have recently been found in the Middle Jurassic Zhiluo Formation, north of the Ordos Basin, China. Petrographic observations, the chemical composition of U minerals determined by EMPA and fs–LA–ICP–MS, whole rock geochemistry and the microthermometric study of fluid inclusions have been integrated to characterize the genetic conditions of the U mineralization in the Hangjinqi sandstone–hosted deposit. Two different groups of U minerals have been identified. One group includes coffinite(I) associated with vanadium–rich micas. Coffinite(I) is enriched in vanadium (V) and devoid of iron (Fe) and yttrium (Y) and has a LREE–enriched chondrite–normalized REE pattern. The U minerals of this group are similar to meteoric fluid infiltration related deposits. The second group has coeval coffinite(II) and coarsely crystalline calcite cement. Coffinite(II) is enriched in Y and Fe and depleted in V and is marked by a flat chondrite–normalized REE pattern, which is compatible with typical hydrothermal genetic deposits with high–salinity mineralizing fluids. The temperature and salinity of the primary aqueous inclusions in the ore–stage calcite are 120–180 °C and 8.00–16.34% (eq. wt% NaCl), respectively. These mineral assemblages, temperatures and salinities indicate that the Hangjinqi deposit was affected by two distinct types of ore–bearing fluids: low–salinity meteoric waters and high–salinity hydrothermal fluids. The meteoric fluids event began at 97 ± 5 Ma with the titling of the northern Ordos Basin and the uplift of the Hetao region to the north. Hydrothermal U mineralization occurred since 39 ± 2 Ma with the rifting of the Hetao graben. Thus, the previous biogenic model for the U mineralization should be modified in the uraniferous region of the north Ordos Basin.     

Peculiarities in the zoning of primary halos

The Grigoryan-Ovchinnikov universal zoning rule in primary halos is frequently violated because of changes due to certain physico-chemical conditions prevailing during the formation of orebodies. Thus, depth changes in the formation of an orebody cause significant variations in the ore element ratios in the primary halos. For example, the As·Sb/Mo·W and As·Sb·B·W/Ag·Pb·Cu·Mo ratios change by 2–3 orders for deposits of different formation depths. To obtain a more definite interpretation of one's vertical position in a deposit the use of the characteristics of metasomatite composition and associated elements (K, Na, Rb, Sr and others) is suggested. A conjugate distribution of Au and sulphides is shown. Gold migration as hydrosulphide complexes are considered possible.     

Carbonate- and silicate-rich globules in the kimberlitic rocks of northwestern Tarim large igneous province,NW China: Evidence for carbonated mantle source

We report carbonate- and silicate-rich globules and andradite from the Wajilitage kimberlitic rocks in the northwestern Tarim large igneous province, NW China. The carbonate-rich globules vary in size from 1 to 3 mm, and most have ellipsoidal or round shape, and are composed of nearly pure calcite. The silicate-rich globules are elliptical to round in shape and are typically larger than the carbonate-rich globules ranging from 2 to several centimeters in diameter. They are characterized by clear reaction rims and contain several silicate minerals such as garnet, diopside and phlogopite. The silicate-rich globules, reported here for the first time, are suggested to be related to the origin of andradite within the kimberlitic rocks. Our results show that calcite in the carbonate-rich globules has a high X_Ca (>0.97) and is characterized by extremely high concentrations of the total rare earth elements (up to 1500 ppm), enrichment in Sr (8521–10,645 ppm) and LREE, and remarkable depletion in Nd, Ta, Zr, Hf and Ti. The calcite in the silicate-rich globules is geochemically similar to those in the carbonate-rich globules except the lower trace element contents. Garnet is dominantly andradite (And_{59.56–92.32}Grs_5.67–36.03Pyr_0.36–4.61Spe_0–0.33) and is enriched in light rare earth elements (LREEs) and relatively depleted in Rb, Ba, Th, Pb, Sr, Zr and Hf. Phlogopite in the silicate-rich globules has a high Mg^# ranging from 0.93 to 0.97. The composition of the diopside is Wo_{45.82–51.39}En_{39.81–49.09}Fs_0.88–0.95 with a high Mg^# ranging from 0.88 to 0.95. Diopside in the silicate-rich globules has low total rare earth element (REE) contents (14–31 ppm) and shows middle REE- (Eu to Gd), slight light REE- and heavy REE-enrichment with elevated Zr, Hf and Sr contents and a negative Nb anomaly in the normalized diagram. The matrix of the kimberlitic rocks are silica undersaturated (27.92–29.31 wt.% SiO₂) with low Al₂O₃ (4.51–5.15 wt.%) and high CaO (17.29–17.77 wt.%) contents. The samples are characterized by incompatible element enrichment with high (La/Yb)_N values (41–58) and remarkable negative anomalies in HFSEs (e.g. Ta, Zr, Hf). Our new data suggest that the carbonate-rich globule most likely crystallized at high-temperature and does not represent immiscible liquids, whereas the silicate-rich globules are related to carbonate-rich deuteric hydrothermal fluids during the later-stage of melt evolution. The fluids reacted with the surrounding silicate melts resulting in the formation of skarn minerals such as phlogopite, diopside and andradite. The presence of the carbonate-bearing globules indicates that the Wajilitage kimberlitic rocks are carbonate-rich and most likely derived from an enriched mantle with abundant carbonate. We correlate the carbonated mantle to metasomatism by the migration of deep-seated fluids (carbonate-rich) in response to the impingement of the early Permian mantle plume.     

Qiarbahete Sanukitoids and adakitic rocks in NW Tianshan: age and geochemical constraints on their petrogenesis and tectonic settings

The Qiarbahete complex in NW China consists of gabbroic diorite, granodiorite, and late-stage quartz diorite porphyry veins. Zircon sensitive high-resolution ion microprobe (SHRIMP) U–Pb analyses show that the gabbroic diorite and granodiorite formed at 368 ± 5.2 Ma and 354 ± 4.1 Ma, respectively, indicating that the complex was emplaced in the Late Devonian–Early Carboniferous. The gabbroic diorites, characteristic of Sanukitoids, exhibit high Mg^# (62 average), MgO (6.84% average), Cr (195 ppm average), and Ni (61.4 ppm average) contents. The rocks show moderately fractionated rare earth element (REEs) patterns and weak negative Eu anomalies (δEu: 0.83–0.89), enrichment of large ion lithophile elements (LILEs), and depletion of high field strength elements (HFSEs), with low ?_Nd(t) values (1.46–1.73). The gabbroic diorites originated from partial melting of a hydrous mantle wedge followed by assimilation of crust during ascent. The granodiorites show a geochemical affinity with adakitic rocks, e.g. SiO₂ (64.95–67.87%) > 56%, Al₂O₃ (15.88–16.56%) > 15%, MgO (1.79–2.31%) < 3%, Sr (315–375 ppm) > 300 ppm, and Yb (1.84–2.06 ppm). They are enriched in light rare earth elements (LREEs) and LILEs and depleted in HFSEs, with weak negative Eu anomalies (δEu: 0.78–0.87). The granodiorites were mainly derived by the partial melting of a subducted oceanic slab, followed by subsequent melt–mantle interaction and crustal rocks contamination. All these indicate that the Qiarbahete complex was emplaced in a continental arc setting attending the southward subduction of the Junggar Ocean during the Late Devonian–early Carboniferous, generating the lateral accretion of continental crust in NW Tianshan.     

Occurrence and mobility of major and trace elements in groundwater from pristine volcanic aquifers in Jeju Island,Korea

Major and trace elements in groundwater from basaltic aquifers in pristine conditions were investigated in a volcanic island to evaluate sources, sinks, and mobility of elements over a wide range of mineralization conditions with total dissolved solids from 50 mg/L to 3400 mg/L. Groundwater was highly undersaturated with respect to primary silicate minerals, indicating that dissolution of basaltic rocks may continue under conditions with precipitation of calcite and secondary silicates. Evolution of B/Cl ratio in groundwater from marine aerosols to basaltic rocks showed that the ratio could be used as a conservative tracer for interactions between water and basaltic rocks. Relative mobility (RM) of elements calculated using the concentrations of elements in the local basaltic rocks and those in groundwater showed that mobility decreased in the order of B > Rb > Na > K > Mg > Ca > Mo > V > Si > Sr > Sc > P > U > Zn > Pb > Cr > Cu > Ba > Ni > Ti > (Mn, Al, Fe, Co, Th) indicating that oxyanion-forming elements and alkali metals had the highest mobility. Compared to average RM, V had decreased mobility, and Fe and Mn had increased mobility in anoxic groundwater while V, Mo, and U had higher mobility in oxic-alkaline water. The sources of V, Cr, Cu, and Zn in rocks were estimated using the partition coefficients between minerals and basaltic melt, and the disparity between sources and mobility indicated that sinks are more important for controlling the concentrations of these elements in groundwater than the contents in the rocks. Principal component analysis (PCA) of hydrogeochemical parameters in groundwater produced three principal components (PC) which represent dissolution of basaltic rocks without significant attenuation of released solutes, higher degree of water–rock interactions resulting in oxic-alkaline conditions, and attenuation of Zn and Cu in higher pH, respectively. Spatial distribution of PCs revealed that groundwater with elevated concentrations of mobile elements was concentrated in the southwestern area and that concentrations of V and Cr were more scattered, which is likely to be controlled by pH and redox states of groundwater as well as degree of water–rock interactions.     

Occurrence of Li,B, Cu and Zn in some Egyptian Nile sediments

Lithium, boron, copper and zinc have been determined on cored and surface sediments from the delta and the drainage valley of the Nile River. The clay size fraction separated from the samples consists of montmorillonite and kaolinite as the predominant clay components, followed by illite and chlorite. Quartz and calcite are the non-clay admixtures.Lithium content varies between 7 and 48 ppm in the bulk sediments and between 28 and 61 ppm in the clay fractions, being clearly enriched in the clay material. In the clay fractions, concentration of lithium in kaolinite is indicated by a close relation between the lithium and kaolinite contents and is further supported by a close correlation with A1₂O₃.Boron in the clay fraction (62–112 ppm) appears to be concentrated in detrital illite.The concentrations of copper (26–900 ppm) and zinc (65–333 ppm) in the clay fractions correlate positively with the CO₂ percentage. Both elements tend to occur in or on the claysized grains of caleite.     

Dilatant plasticity in high-strain experiments on calcite–muscovite aggregates

Torsion experiments were performed on synthetic aggregates of calcite with a 50% volume of muscovite. The tests were performed at 627–727 °C with a confining pressure of 300 MPa at constant shear strain rates of 3 × 10^?5–3 × 10^?4 s^?1 on cylindrical samples with the starting foliation parallel and perpendicular to the cylinder axis. Both the foliation parallel and the foliation perpendicular experiments show similar stress–strain patterns, with an initial hardening stage followed by significant strain weakening (>60%) before a catastrophic rupture. Microstructural analysis shows that in low-strain experiments calcite grains are intensely twinned while muscovite grains appear slightly bent and kinked. Higher strains promote a segregation of the two phases with calcite forming thin layers of fine, dynamically recrystallized grains, which act as localized shear bands, while muscovite grains keep their original size and rotate assuming a strong shape preferred orientation. This strain localization of the calcite from an initially homogeneous rock produced catastrophic failure at moderate bulk shear strains (γ ～ 3). Localization of the strain first involved ductile deformation to produce a new calcite layering with fine dynamically recrystallized grains along which cavities nucleated. The orientation and kinematics of the cavities are comparable to R1 Riedel structures. All experiments on calcite–muscovite mixtures resulted in heterogeneous strain. In these torsion experiments chemical changes and crystallization of new phases (anorthite and kalsilite) are observed at 627 °C. Whereas, samples hot pressed or deformed in compression at 670 °C did not show such reactions or any localization. The effect of stress-field geometry and pore pressure upon mineral reactions is discussed. It is concluded that deformation-induced heterogeneous phase distributions caused local strength differences initiating strain localization in the calcite–muscovite mixtures, eventually leading to plastic failure.     

Environmental assessment of the arsenic-rich,Rodalquilar gold–(copper–lead–zinc) mining district,SE Spain: data from soils and vegetation

The Rodalquilar mineral deposits (SE Spain) were formed in Miocene time in relation to caldera volcanic episodes and dome emplacement phenomena. Two types of ore deposits are recognized: (1) the El Cinto epithermal, Au–As high sulphidation vein and breccia type; and (2) peripheral low sulphidation epithermal Pb–Zn–Cu–(Au) veins. The first metallurgical plants for gold extraction were set up in the 1920s and used amalgamation. Cyanide leaching began in the 1930s and the operations lasted until the mid 1960s. The latter left a huge pile of ~900,000–1,250,000 m³ of abandoned As-rich tailings adjacent to the town of Rodalquilar. A frustrated initiative to reactivate the El Cinto mines took place in the late 1980s and left a heap leaching pile of ~120,000 m³. Adverse mineralogical and structural conditions favoured metal and metalloid dispersion from the ore bodies into soils and sediments, whereas mining and metallurgical operations considerably aggravated contamination. We present geochemical data for soils, tailings and wild plant species. Compared to world and local baselines, both the tailings and soils of Rodalquilar are highly enriched in As (mean concentrations of 950 and 180 μg g⁻¹, respectively). Regarding plants, only the concentrations of As, Bi and Sb in Asparagus horridus, Launaea arborescens, Salsola genistoides, and Stipa tenacissima are above the local baselines. Bioaccumulation factors in these species are generally lower in the tailings, which may be related to an exclusion strategy for metal tolerance. The statistical analysis of geochemical data from soils and plants allows recognition of two well-differentiated clusters of elements (As–Bi–Sb–Se–Sn–Te and Cd–Cu–Hg–Pb–Zn), which ultimately reflect the strong chemical influence of both El Cinto and peripheral deposits mineral assemblages.     

“Dedolomitization reactions” driven by anthropogenic activity on loessy sediments,SW Hungary

In the Szigetvár area, SW Hungary, shallow groundwaters draining upper Pleistocene loess and Holocene sediments are considerably contaminated by domestic effluents and leachates of farmland fertilizers. The loess contains calcite and dolomite, but gypsum was not recognized in these sediments. The anthropogenic inputs contain significant amounts of Ca and SO₄. The Ca from these anthropogenic inputs is promoting calcite growth, with concomitant consumption of carbonate alkalinity, undersaturation of the system with respect to dolomite, and dolomite dissolution; in brief, is driving “dedolomitization reactions”. Geochemical arguments supporting the occurrence of “dedolomitization reactions” in the area are provided by the results of mass balance and thermodynamic analyses. The mass balances predicted the weather sequence dolomite > calcite > plagioclase > K-feldspar, at odds with widely accepted sequences of weatherability where calcite is the first mineral in the weathering sequence. The exchange between calcite and dolomite can be a side effect of “dedolomitization reactions” because they cause precipitation of calcite. The thermodynamic prerequisites for “dedolomitization reactions” are satisfied by most local groundwaters (70%) since they are supersaturated (or in equilibrium) with respect to calcite, undersaturated (or in equilibrium) with respect to dolomite, and undersaturated with respect to gypsum. The Ca vs. SO₄ and Mg vs. SO₄ trends are also compatible with homologous trends resulting from “dedolomitization reactions”.     

The lunar regolith: Chemistry and petrology of Luna 24 grain size fractions

Chemical data are reported for the first time for lunar soil size fractions smaller then 2 μm. We report chemical data for 30 elements by INAA in eight size fractions (370−200, 200−94, 94−74, 74−40, 40−10, 10−5, 5−2 and <2 μm) and petrology of five size fractions (down to 40−10 μm) in two Luna 24 soils, 24176 and 24214. Consistent with our previous results for lunar soils, the compositions of coarser fractions (>10 μm) are quite similar to each other but quite different from the fine fractions (<10 μm). The finer fractions (10–5, 5–2, <2 μm) become increasingly feldspathic and enriched in large-ion lithophile elements (LILE) with decreasing grain size. Chemical data for the finer fractions provide direct evidence in favor of efficient comminution of rock mesostasis and feldspar leading to their preferential incorporation into the finer fractions. High concentrations of meteoritic indicator elements (Ni, Au, Ir) in the finer fractions are consistent with the comminution process by micrometeorite impacts. The chemical data strongly support the F³ (fusion of the finest fraction) model for agglutinate formation.Based on grain size distribution, petrology, and LILE patterns of size fractions, the Luna 24 soils are less reworked than most lunar soils. The Luna 24 regolith appears to have formed as a result of mixing more mature and fine grained material with less mature coarse material in different proportions at different depth intervals.     

The origin of enriched mantle beneath São Miguel, Azores

Lavas from the island of São Miguel, Azores Archipelago have long been known to display large radiogenic isotopic variability, that ranges from “depleted” isotopic signatures (e.g. high ε_Nd ∼ +5) in the west, typical of many ocean island basalts, to more “enriched” compositions (e.g. low ε_Nd ∼ +1) in the east. Here, we further characterise the geochemistry of lavas from this remarkable locality, focussing on the nature and origin of the enriched source. Our new isotope data define a striking, linear array in Nd and Hf isotope space that points towards an unusual, enriched composition below the mantle array. This distinctive Hf-Nd isotope signature is associated with elevated values of all three radiogenic Pb isotope ratios. Although the enriched component has certain geochemical similarities to both terrigenous sediments and some samples of the continental mantle lithosphere, such comparisons do not stand closer examination. In the absence of a clear, modern analogue we explore the isotope evolution of some simple, model melt compositions to investigate plausible means of producing an appropriate enriched component. Nd-Hf isotope characteristics provide the tightest constraints and can be reproduced by an ancient (∼3 Ga), modest-degree melt (∼2%) from a garnet peridotite source. Currently, modest-degree melts from garnet-bearing sources are found forming some major oceanic islands. Subduction, isolation and later mixing of small amounts (<5%) of such basaltic material with more ubiquitous ambient mantle can account for the isotopic characteristics of the enriched São Miguel source. Yet the incompatible element ratios of the enriched São Miguel lavas do not show “recycled” signatures of near-surface alteration nor subduction zone dehydration. Thus, we infer that the enriched component was originally under-plated basalt, intruded into oceanic mantle lithosphere rather than forming the island edifice itself. Since the extreme isotope compositions of São Miguel reflect unextraordinary, albeit ancient, magmatic fractionation, the general rarity of such signatures indicates the efficiency of mantle processes in homogenising or hiding similar sources.     

Omphacite-bearing calcite marble and associated coesite-bearing pelitic schist from the meta-ophiolitic belt of Chinese western Tianshan

In the meta-ophiolitic belt of Chinese western Tianshan, marble (5–50 cm thick) is found interlayered with pelitic schist. The marble is mainly composed of calcite (>90% in volume) and accessory phases include omphacite, quartz, dolomite, albite, phengite, clinozoisite and titanite with or without rutile core. This is the first omphacite (Jd_35–50) reported from marble of Chinese western Tianshan. It mainly occurs in the calcite matrix, rarely as inclusion in albite. The presence of omphacite suggests that the layered marble was subjected to eclogite-facies metamorphism, consistent with the occurrence of high-Si phengite (Si a.p.f.u. up to 3.7) and aragonite relic in albite. The associated pelitic schist consists of quartz, white mica (phengite + paragonite), garnet, albite, amphibole (barroisite ± glaucophane) and rutile/titanite, as well as minor amounts of dolomite, tourmaline and graphite. Coesite is optically recognized within porphyroblastic pelitic garnet and is further confirmed via Raman spectroscopy. Thermodynamic models support the UHP metamorphism of calcite marble, similar to the associated pelitic schist. Shared UHP-LT history of calcareous and pelitic rocks in Chinese western Tianshan suggests that the supracrustal carbon-rich sediments have been carried to depths of >90 km during fast subduction and thus are potential sources for carbon recycled into arc crust.