Geogenic versus anthropogenic geochemical influence on trace elements contents in soils from the Milazzo Peninsula

Milazzo Peninsula soils and substrates are extremely variable, composed of acidic, mafic and ultramafic metamorphic rocks, carbonatic sedimentary rocks, and sometimes volcanic rocks, thus contributing to a mixed influence on their chemical composition. Moreover, the region is highly polluted due to atmospheric releases from anthropogenic activities, such as refinery industry. In addition, emissions of airborne particles from volcanic eruptions are also likely to fall to the ground and provide trace elements to the soils. The purpose of this study is to distinguish between anthropogenic and geogenic sources contributing to the concentrations of metals in soils by studying their distribution in major and trace elements in relation to substrates. As regards geogenic sources, the major elements composition of soils comes firstly from metamorphic rocks, secondly from carbonates, and to a minor extent from volcanic rocks. Enrichment factors calculations relative to substrate rocks, and using Th as reference element, show that the soils are enriched in As, Pb, Zn, and Ni. Rare earth elements (REEs) patterns normalized to substrate rocks exhibit enrichment in light REEs and a positive anomaly in Gd, indicating anthropogenic contributions in the soil composition. REE ratios and trace elements were plotted to investigate the relationships between anthropogenic sources and substrates in soils compositions. The graphs of La/Ni vs La/Gd and La/Ce vs La/Nd show that soils plot on a line toward substrate rocks on one side, and toward an end member which is represented by a spent catalyst and atmospheric particles emitted by refinery activities. Plots of La vs Cr, and V vs La show similar trends, whereas plots of Zn vs Ni and Pb vs V suggest that another end member, which is unidentified, contributes to soil enrichment in Zn and Pb. A binary mixing model applied to the most Zn enriched soil suggests that anthropogenic inputs from refinery emissions may have contributed to 16% of the anomalies in La/Gd. These results suggest that the trace element composition of Milazzo's peninsula soils partly bears the signature of atmospheric emissions of the refinery.     

Anthropogenic impact on sediment composition and geochemistry in vertical overbank profiles of river alluvium from Belgium and Luxembourg

The geochemical study of alluvial sediments allows to reconstruct pollution through time. Geochemical and sedimentological variations recorded in 40 vertical overbank sediment profiles from Belgium and Luxembourg can be classified in three dominant pattern types:• type 1 profiles with dominantly non-anthropogenically influenced geochemical distribution patterns. These profiles are devoid of anthropogenic particles such as charcoal, plastic, brick and slag fragments, with the exception, in some cases, of their uppermost parts. Background concentrations thus are displayed throughout the profile (subtype 1A). However, in this group, profiles displaying anomalous values caused by the presence of heavy minerals (subtype 1B) or by base metal mineralisations in the catchment (subtype 1C) also occur;• type 2 profiles displaying clear evidence of anthropogenic influences. Most of these profiles display a gradual increase in heavy metal content in their upper part, with values doubling or tripling (subtype 2A). However, other profiles display a dramatic increase in pollution-related elements caused by past or present-day heavy industrial activities in the catchment (subtype 2B). Here also the sedimentological patterns reflect the influence of the industrial activities;• type 3 profiles contain features related to pedogenetic translocations of mobile elements. Apart from classical pedogenetic features such as illuviation/eluviation, the mobility of As and Cd is of particular importance. From a sedimentological point of view, these profiles do not necessarily differ from type 1 or 2 profiles.It should be noted that in some profiles, pattern types can be superimposed. Type 2B profiles are of particular environmental concern, because the potential release of heavy metals may have consequences for agricultural activities or groundwater contamination in the catchment. Furthermore, reworking of polluted sediments temporarily stored in the alluvial plain can also have negative effects on the ecosystem.     

Mineralogy and trace element geochemistry of sulfide minerals from the Wocan Hydrothermal Field on the slow-spreading Carlsberg Ridge,Indian Ocean

The basalt-hosted Wocan Hydrothermal Field (WHF), located on the NW slope of an axial volcanic ridge at a depth of ∼3000 m at 6°22′N on the slow-spreading Carlsberg Ridge, northwest Indian Ocean, was discovered in 2013 during Chinese DY28th cruise. Preliminary investigations show that the field consists of two hydrothermal sites: Wocan-1, which shows indications for recent high-temperature hydrothermal activity, is located near the peak of the axial volcanic ridge at a water depth of 2970–2990 m, and Wocan-2 site, located at a water depth of 3100 m, ∼1.7 km to the northwest of Wocan-1. The recovered hydrothermal precipitates can be classified into four groups: (i) Cu-rich chimneys; (ii) Cu-rich massive sulfides; (iii) Fe-rich massive sulfides; and (iv) silicified massive sulfides. We conducted mineral texture and assemblage observation and Laser-ablation ICP-MS analyses of the hydrothermal precipitates to study the mineralization processes. Our results show that there are distinct systematic trace element distributions throughout the different minerals in the four sample groups. In general, chalcopyrite from the group (i) is enriched in Pb, As, Mo, Ga, Ge, V, and Sb, metals that are commonly referred to as medium- to low-temperature elements. In contrast these elements are present in low contents in the chalcopyrite grains from other sample groups. Selenium, a typical high-temperature metal, is enriched in chalcopyrite from groups (ii) and (iv), whereas Ag and Sn are enriched only in some silicified massive sulfides. As with chalcopyrite, pyrite also shows distinct trace element associations in grains with different habitus. The low-temperature association of elements (Pb, Mo, Mn, U, Mg, Ag, and Tl) is typically present in colloform/framboidal pyrite, whereas the high-temperature association (Se, Co, and Bi) is enriched in euhedral pyrite. Sphalerite in the groups (i) and (iii) at Wocan-1 is characterized by high concentrations of Ga, Ge, Pb, Cd, As, and Sb, indicating that sphalerite in these sample groups likely precipitated at intermediate temperatures. Early bornite, which mainly occurs in the central part of the Cu-rich chimney, is typically enriched in Sn and In compared to the other minerals. In contrast, late bornite that likely formed during increasing interaction of hydrothermal fluids with cold, oxygenated seawater has low Sn and In, but significantly higher concentrations of Ag, Au, Mo and U. Digenite, also forming in the exterior parts of the samples during the late stages of hydrothermal fluid venting, is poor in most trace elements, except Ag and U. The notable Ag enrichment in the late-stage mineral assemblages at both Wocan-1 and Wocan-2 may therefore be related to lower temperatures and elevated pH. Our results indicate that Wocan-1 has experienced a cycle of heating with Cu-rich chimney growth and subsequent cooling, followed by late seafloor weathering, while Wocan-2 has seen intermediate- to high-temperature mineralization followed by intense silicification of sulfides. Seafloor weathering processes or mixing of hydrothermal fluids with seawater during the waning stages of hydrothermal fluid flow result in significant redistributions of trace elements in sulfide minerals.     

汉诺坝幔源橄榄岩包体的微量元素和Re-Os同位素地球化学：SCLM的性质和形成时代

本文报道了汉诺坝新生代碱性玄武岩中地幔橄榄岩包体的主量、微量元素和Re-Os同位素。14个尖晶石橄榄岩Re、Os含量分别为0.022～0.193ng/g和1.237～4.304ng/g，^187Os/^188Os比值为0.1183～0.1244，与^187Os/^188Os比值相关性不好，但与熔体亏损指标如重稀土元素Yb的含量、全岩Al2O3的百分含量有很好的线性关系，可能反映了地幔熔融后的Re或/和Os的活动。全岩Al2O3、CaO、TiO2含量均与MgO有很好的负相关性，全岩原始地幔标准化REE丰度模式呈现了LREE亏损，表明该区橄榄岩包体是由软流圈地幔经过部分熔融，亏损了玄武质组分后形成的。由Os同位素代理等时线得到该区陆下岩石圈地幔的形成年龄为1.7～2.0Ga，表明尖晶石相橄榄岩所代表的岩石圈地幔是中元古代的陆下岩石圈地幔减薄后的残留体。     

Effects of pH, alkalinity and bedrock chemistry on metal concentrations of springs in an acidified catchment (Ecker Dam, Harz Mountains, FRG)

Thirty-four springs were sampled on five different source rocks in the upper Ecker watershed of the Northern Harz Mountains (Germany) four times during the course of 1995. The analyses included 41 cations and the major anions. Approximately 90% of the rocks in the upper Ecker watershed are low in basic cations, which inhibit the neutralisation of hydrogen-ion loading. As a consequence, the concentrations of Al, Fe, Mn, Zn, Pb, Y, Ce, As, La, Nd, Cd, Be, Co, Sb, Pr, Gd, Dy, Yb, Er, Sm, U, Tl, Ho and Tb of the Ecker dam water (pH=5.1) exceed those of the nearby Söse Dam water (pH=6.5) by almost one order of magnitude or more. With the exception of the spring waters on gabbro (pH up to 7.7) all waters on the highly siliceous rocks (quartzite, granite and gneiss) are dominated by sulfate anions with a pH range of 4–6. The concentrations of major conservative ions show a progressive increase with decreasing catchment elevation and decreasing average precipitation. Trace elements such as Sr, Be, Zn, Cd, Ba, Y, La, lanthanides, U, Li, Ni, Al, Mn, Co, Cu, Pb, As, Sb and Tl are increased in the low acid neutralizing capacity (ANC_(aq)) spring waters. The behaviours of Sr, Be, Zn, Cd, Ba, Y, La, lanthanides and U resemble that of the major cations. The highest concentrations of Li and Ni are found on quartzite. Al, Mn, Co and Cu exhibit no clear correlation with catchment elevation and one particular bedrock. The concentrations of V and Cr show a distinct increase in high ANC_(aq) spring waters on gabbro. Pb, As, Sb and Tl are characterized by being found in relatively high concentrations on granite at higher altitudes. Pb, As and Sb are affected by contaminated soils. The extreme variability of trace element concentrations of low ANC_(aq) spring waters cannot be explained by the rock data. It is mainly controlled by the topography-dependent weathering rates of the different rock-types and the decreasing dilution with decreasing catchment elevation.     

Trace metals (Cd,Pb, Cu,Zn and Ni) in sediment of the submarine pit Dragon ear (Soline Bay,Rogoznica, Croatia)

Vertical profiles of trace metal (Cd, Pb, Zn, Cu, Ni) concentrations, organic matter content, carbonate content and granulometric composition were determined in two sediment cores from the submarine pit Dragon Ear (Middle Adriatic). Concentrations of the analyzed metals (Cd: 0.06–0.12 mg kg⁻¹, Pb: 28.5–67.3 mg kg⁻¹, Zn: 17.0-65.4 mg kg⁻¹, Cu: 21.1–51.9 mg kg⁻¹, Ni: 27.8–40.2 mg kg⁻¹) were in usual range for Adriatic carbonate marine sediments. Nevertheless, concentrations of Cu, Zn, and especially Pb in the upper layer of sediments (top 12 cm) were higher than in bottom layer, while Cd and Ni concentration profiles were uniform. Regression analysis and principal component analysis were used to interpret distribution of trace metals, organic matter and carbonate content in sediment cores. Results of both analysis showed that concentrations of all trace metals in the core below the entrance to the pit were significantly positively correlated with organic matter and negatively correlated with carbonate, while in the core more distant from the entrance only Pb showed significant positive correlation with organic matter. Obtained results indicated that, except for lead which was enriched in surface sediment, in the time of sampling (before the building of the nautical marina) investigated area belonged to unpolluted areas.     

Natural and anthropogenic influences on the geochemistry of Quaternary lake sediments from Holzmaar, Germany

 The accumulation of heavy metals and trace elements has been investigated in a well laminated sequence of Holocene and late Pleistocene lake sediments composed of diatomaceous gyttja, tuff and silt and clay sediments. Varve chronology of the annually deposited gyttja yielded a continuous high-resolution time sequence and allowed the absolute age dating of the sediment. Fluxes of elements remained largely uniform from the late Pleistocene into the Holocene (12 867–2 364 VT years ago; VT: varve time, years before 1950). Higher trace element and heavy metal fluxes occur from 2 322 to 862 VT years ago and reached their maxima in the uppermost sediments (<845 VT years ago). These increasing element fluxes correlate with increasing inputs of clastic material. The changing accumulation rates are the result of elevated soil erosion in the lake catchment caused by human settlement, deforestation and agricultural activities. Thus disturbances of the natural geochemical cycles of the Holzmaar region have occurred since the beginning of the Iron Age and especially since the beginning of the Middle Ages. Received: 29 May 1996 · Accepted: 19 August 1996     

Recognition of environmental trace metal contamination using pine needles as bioindicators. The urban area of Palermo (Italy)

Pinus pinea L., collected in and around the city of Palermo were analysed for major and trace elements by INAA and ICP-MS. The chemical composition of pine needles suggests that the presence of Pb, Sb and Br in excess with respect to soil composition is due to anthropogenic emissions. The anomalously high values of these elements observed in the urban area decrease outside town. Lead isotope data confirm the anthropogenic origin of lead. The origin of Zn and Cu excess remains uncertain at the moment, although wholly-crustal origin appears doubtful. Morphological alterations attributable to phenol accumulation, such as modifications in the length of mesophyll cells and the appearance of lacunae in the distal portions, were observed in needles. The accumulation of phenols, linked to the presence of lead, gives rise to a specific pattern of metabolites providing mechanisms of detoxification and protection, so that the accumulation degree may be proposed as a marker of environmental pollution. Received: 4 June 1999 · Accepted: 24 June 1999     

Major, trace element and isotope geochemistry (Sr-Nd-Pb) of interplinian magmas from Mt. Somma-Vesuvius (Southern Italy)

Summary Major, trace element and isotopic (Sr, Nd, Pb) data are reported for representative samples of interplinian (Protohistoric, Ancient Historic and Medieval Formations) activity of Mt. Somma-Vesuvius volcano during the last 3500 years. Tephra and lavas exhibit significant major, trace element and isotopic variations. Integration of these data with those obtained by previous studies on the older Somma suites and on the latest activity, allows to better trace a complete petrological and geochemical evolution of the Mt. Somma-Vesuvius magmatism. Three main groups of rocks are recognized. A first group is older than 12.000 yrs, and includes effusive-explosive activity of Mt. Somma. The second group (8000–2700 yrs B.P.) includes the products emitted by the Ottaviano (8000 yrs. B.P.) and Avellino (3550 yrs B.P.) plinian eruptions and the interplinian activity associated with the Protohistoric Formation. Ancient Historic Formation (79–472 A.D.), Medieval Formation (472–1139 A.D.) and Recent interplinian activity (1631–1944 A.D.) belong to the third group of activity (79–1944 A.D.). The three groups of rocks display distinct positive trends of alkalis vs. silica, which become increasingly steeper with age. In the first group there is an increase in silica and alkalis with time, whereas an opposite tendency is observed in the two younger groups. Systematic variations are also evident among the incompatible (Pb, Zr, Hf, Ta, Th, U, Nb, Rb, Cs, Ba) and compatible elements (Sr, Co, Cr). REE document variable degrees of fractionation, with recent activity displaying higher La/Yb ratios than Medieval and Ancient Historic products with the same degree of evolution. N-MORB normalized multi-element diagrams for interplinian rocks show enrichment in Rb, Th, Nb, Zr and Sm (> ^*10 N-MORB). Sr isotope ratios are variable, with Protohistoric rocks displaying ⁸⁷Sr/⁸⁶Sr =  0.70711–0.70810, Ancient Historic ⁸⁷Sr/⁸⁶Sr = 0.70665–0.70729, and Medieval ⁸⁷Sr/⁸⁶Sr = 0.70685–0.70803. Neodymium isotopic compositions in the interplinian rocks show a tendency to become slightly more radiogenic with age, from the Protohistoric (¹⁴³Nd/¹⁴⁴Nd = 0.51240–0.51247) to Ancient Historic (¹⁴³Nd/¹⁴⁴Nd = 0.51245–0.51251). Medieval interplinian activity (¹⁴³Nd/¹⁴⁴Nd: 0.51250–0.51241) lacks meaningful internal trends. All the interplinian rocks have virtually homogeneous compositions of ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb in acid-leached residues (²⁰⁷Pb/²⁰⁴Pb ∼15.633 to 15.687, ²⁰⁸Pb/²⁰⁴Pb ∼38.947 to 39.181). Values of ²⁰⁶Pb/²⁰⁴Pb are very distinctive, however, and discriminate among the three interplinian cycles of activity (Protohistoric: 18.929–18.971, Ancient Historic: 19.018–19.088, Medieval: 18.964–19.053). Compositional trends of major, trace element and isotopic compositions clearly demonstrate strong temporal variations of the magma types feeding the Somma-Vesuvius activity. These different trends are unlikely to be related only to low pressure evolutionary processes, and reveal variations of parental melt composition. Geochemical data suggest a three component mixing scheme for the interplinian activity. These involve HIMU-type and DMM-type mantle and Calabrian-type lower crust. Interaction between these components has taken place in the source; however, additional quantitative constraints must be acquired in order to better discriminate between magma characteristics inherited from the sources and those acquired during shallow level evolution. Received May 5, 2000; revised version accepted June 19, 2001     

Enrichment of redox-sensitive trace metals (U,V, Mo,As) associated with the late Hauterivian Faraoni oceanic anoxic event

The Faraoni Level is a short-lived oxygen-deficient event that took place during the latest Hauterivian. In order to improve our understanding of the palaeoenvironmental conditions that occurred during this event, we have analysed the contents of several redox-sensitive trace elements (U, V, Mo, As, Co, Cd, Cu, Zn, Ni, Pb, Cr) from bulk limestone samples of late Hauterivian–early Barremian age from three reference sections. U, V, Mo and As show consistent and significant enrichments during the Faraoni event whereas the other redox-sensitive trace elements analysed here are not systematically enriched. In order to explain this discrepant behaviour, we propose that the Faraoni Level was deposited during a period of anoxic conditions near the sediment–water interface. The distinctive peaks in U, V, Mo and As contents are traceable throughout the three studied sections and represent a good correlation tool which helps to identify the Faraoni Level and its equivalents in the western Tethyan realm and outside of the Tethys. For example, a peak in U contents in upper Hauterivian sediments of the northwestern Pacific realm (ODP leg 185, site 1149) may well be an expression of the Faraoni event in this particular basin.     

Nd-Sr isotopic and trace element study of rocks and fluids from the continental deep drilling Project (KTB), Germany

Geochemical analyses were interpreted on the dominant lithological units and on a deep crustal fluid from the Continental Deep Drilling Project (KTB) Pilot Hole, situated at the western margin of the Variscan Bohemian Massif. The biotite gneiss (from 384 m depth) shows a rare earth element pattern very similar to the European shale composite with Nd model ages of 940 Ma (CHUR) and 1.4 Ga (DM). The lamprophyre dike in the upper profile (1549 m), a nepheline and olivine normative basalt, is geochemically and isotopically similar to rocks from the Tertiary Central European Volcanic Province. The lower metabasite sequence (3575–4000 m), with an intrusion age of approximately 500 Ma, is made up primarily of highly metamorphosed subalkalic olivine basalts. The geochemical characteristics of the metabasites are a (La/Yb)_N of 5–10, an La concentration of 20–50 times chondrite as well as (⁸⁷Sr/⁸⁶Sr)_i of 0.7035–0.7038 and _Nd(T) of 4–6. These values suggest a depleted mantle source for the igneous precursors, evolving by assimilation-fractional crystallization processes with up to 25% of upper crust into the ultramafic, basaltic, and intermediate rock types of the metabasite sequence. The strong geochemical and chronological similarities between the KTB metabasites and rocks from the Münchberg Massif suggest that these units belong to the same lithological complex. The high salinity as well as the radiogenic ⁸⁷Sr/⁸⁶Sr ratio of 0.709413 in the KTB fluid from 4000 m depth might be the result of migrating fluids reacting with the regional Permo-Mesozoic evaporite deposits, followed by extensive Sr isotopic exchange with the upper crust.     

Genesis of the Bianjiadayuan Pb-Zn polymetallic deposit,Inner Mongolia,China:Constraints from in-situ sulfur isotope and trace element geochemistry of pyrite

The Southern Great Xing'an Range(S(GXR)which forms part of the eastern segment of the Central Asian Orogenic Belt(CAOB)is known as one of the most important Cu-Mo-Pb-Zn-Ag-Au metallogenic belts in China,hosting a number of porphyry Mo(Cu),skarn Fe(Sn),epithermal Au-Ag,and hydrothermal veintype Ag-Pb-Zn ore deposits.Here we investigate the Bianjiadayuan hydrothermal vein-type Ag-Pb-Zn ore deposit in the southern part of the SGXR.Porphyry Sn± Cu± Mo mineralization is also developed to the west of the Ag-Pb-Zn veins in the ore field.We identify a five-stage mineralization process based on field and petrologic studies including(i)the early porphyry mineralization stage,(ii)main porphyry mineralization stage,(iii)transition mineralization stage,(iv)vein-type mineralization stage and(v)late mineralization stage.Pyrite is the predominant sulfide mineral in all stages except in the late mineralization stage,and we identify corresponding four types of pyrites:Pyl is medium-grained subhedral to euhedral occurring in the early barren quartz vein;Py2 is medium-to fine-grained euhedral pyrite mainly coexisting with molybdenite,chalcopyrite,minor sphalerite and galena;Py3 is fine-grained,subhedral to irregular pyrite and displays cataclastic textures with micro-fractures;Py4 occurs as euhedral microcrystals and forms irregularly shaped aggregate with sphalerite and galena.LA-ICP-MS trace element analyses of pyrite show that Cu,Pb,Zn,Ag,Sn,Cd and Sb are partitioned into pyrite as structurally bound metals or mineral micro/nano-inclusions,whereas Co,Ni,As and Se enter the lattice via isomorphism in all types of pyrite.The Cu,Zn,Ag,Cd concentrations gradually increase from Pyl to Py4,which we correlate with cooling and mixing of ore-forming fluid with meteoric water.Py2 contains the highest contents of Co,Ni,Se,Te and Bi,suggesting high temperature conditions for the porphyry mineralization stage.Ratios of Co/Ni(0.03-10.79,average 2.13)and sulphur isotope composition of sulfide indicate typical hydrothermal origin for pyrites.The δ~(34)S_(cDT) values of Pyl(0.42‰-1.61‰,average1.16‰),Py2(-1.23‰to 0.82‰,average 0.35‰),Py3(—0.36‰to 2.47‰average 0.97‰).Py4(2.51‰--3.72‰,average 3.06‰),and other sulfides are consistent with those of typical porphyry deposit(-5‰to 5‰),indicating that the Pb-Zn polymetallic mineralization in the Bianjiadayuan deposit is genetically linked to the Yanshanian(Jurassic-Cretaceous)magmatic-hydrothermal events.Variations of δ~(34) S values are ascribed to the changes in physical and chemical conditions during the evolution and migration of the ore-forming fluid.We propose that the high Sn content of pyrite in the Bianjiadayuan hydrothermal vein-type Pb-Zn polymetallic deposit can be used as a possible pathfinder to prospect for Sn mineralization in the surrounding area or deeper level of the ore field in this region.     

Patterns of rare earth and other trace elements in different size fractions of clays of Campanian–Maastrichtian deposits from the Portuguese western margin (Aveiro and Taveiro Formations)

The Upper Cretaceous (Campanian–Maastrichtian) Taveiro and Aveiro Formations belong to the northern sector of the Lusitanian basin (Portuguese western margin). The Taveiro Formation was deposited in alluvial fans, including mud flow beds, lakes and sinuous rivers. The Aveiro Formation was deposited in a flat region with low hydrodynamics channels, with the formation of a barrier island-tidal system. The reconstruction of this sedimentary basin may be difficult due to its complex architecture. This work aims a methodology to be used in the reconstruction of Cretaceous sedimentary environments of the Lusitanian basin, through the establishment of geochemical patterns of different size fractions of those deposits. Chemical analysis was performed by instrumental neutron activation analysis (INAA), and the mineralogical composition obtained by X-ray diffractometry (XRD). The whole rock and different size fractions (? ≥ 125 μm, 63–125 μm, 20–63 μm, 2–20 μm and ? < 2 μm) of selected samples were studied aiming the rare earth elements (REE) and other trace elements distribution and its correlation with the grain size and mineralogy.The results obtained for the studied Cretaceous sediments showed that REE patterns and other trace elements distribution in the different size fractions may be used as a tool to differentiate deposits within and between sedimentary formations. Within the Taveiro Formation, REE are concentrated in the silt fractions (20–63 μm and 2–20 μm) of the Reveles deposit, and in the clay size fraction of S. Pedro deposit, which is richer in kaolinite. The 1st transition elements, particularly Zn, are correlated with the presence of smectite in the clay fraction of Reveles deposit. In the sand and silt size fractions (>2 μm) of samples from Taveiro Formation correlations were found between: Ga and 1st transition elements, and phyllosilicates; Cs and mica; and Rb and Ba, and K–feldspars.The Bustos deposit (Aveiro Formation) samples are very fine-grained and with a high proportion of the fine silt fraction where REE are concentrated, especially the heavy ones. Incorporation of MREE, Co and U in carbonates of the coarser fraction appears to occur. The abundances of the 1st transition elements, Ga and As, are correlated with phyllosilicates.Significant differences were found in the trace elements patterns of the various analysed size fractions of the Lusitanian basin of Cretaceous sediments, between and even within formations, which can be used as a methodological approach for a fine paleogeographic reconstruction.     

Genesis,evolution and tectonic significance of K-rich volcanics from the Alban Hills (Roman comagmatic region) as inferred from trace element geochemistry

Trace element data are reported in 21 lava samples from the Alban Hills, one of the most important volcanic complexes of the Roman comagmatic region. The samples consist mostly of tephritic leucitites with minor phonolitic tephrites and tephritic phonolites emplaced during two distinct phases of activity, separated by a caldera collapse. The ferromagnesian element contents are variable (Ni=93-26 ppm; Co=37-20 ppm; Cr=359-5 ppm; Sc=35-6 ppm) and tend to have higher values in the post-caldera rocks. Rb, Cs, Th, Sr, and LREE are extremely enriched in all the samples analyzed, with the pre-caldera rocks displaying a lower content of Rb and Cs and a higher abundance of Th, light REE and La/Yb ratio. Ta and Hf are not so high and are more enriched in the pre-caldera samples. Sr displays comparable values in the two groups of rocks. The trace element variation indicates that the rocks from the Alban Hills represent two distinct series of liquids formed by crystal/liquid fractionation processes starting from two parental magmas. The genesis of the primary melts is hypothesized as due to a low degree of partial melting of a mantle peridotite enriched in incompatible elements. All of the studied samples have distribution patterns of incompatible elements normalized against a hypothetical primordial mantle composition, which are similar to that displayed by the aeolian calc-alkaline and leucite-tephritic products and distinctively different from those of typical K-rich volcanics from an intraplate rift environment. This strongly supports the hypothesis that there is a close genetic connection between Roman magmatism and subductionrelated processes.     

中国大陆科学钻探工程主孔石榴石单辉橄榄岩的岩石化学研究

中国大陆科学钻探工程主孔石榴石橄榄岩产出于603.20～683.53m之间,主要为石榴石单辉橄榄岩,内部还见有巨晶状角闪石岩(曾经是岩脉)和榴辉岩与橄榄岩之间厘米级的方辉辉石岩.石榴石橄榄岩多数含有钛斜硅镁石.从其内部所夹的榴辉岩条带可知,橄榄岩发生过褶皱等构造变形作用.其围岩和内部夹层榴辉岩中的锆石中舍柯石英的事实可能表明岩体经历过超高压变质作用.石榴石橄榄岩的主要造岩矿物橄榄石的Fo端员低(0.82～0.86)、全岩岩石化学的低Mg#值(77.26～85.07)和高易熔元素以及低于典型阿尔卑斯型橄榄岩的(Mg Ni)/(Fe Mn)比值,意味着该石榴石橄榄岩体的原岩为岩浆固结成因.石榴石橄榄岩的稀土元素总量低,配分型式有LREE富集型((La/Lu)N比值为9～16.6)、LREE适度富集型((La/Lu)N比值为1.47～8.22)和LREE亏损型或平坦型((La/Lu)N比值为0.62、1.19～1.92)三种,并构成从亏损或平坦型到富集型的韵律,反映了结晶分异的特点.微量元素蛛网图上,石榴单辉橄榄岩微量元素的丰度总体上低于N-MOBB的丰度.Cu、Ni和MgO的判别图表明,石榴石橄榄岩的原岩岩浆的固结成岩时期主要为镁铁质矿物的分离结晶作用而硫化物不是重要的矿物相.Ti和P的剧烈变化表明了有磁铁矿和磷灰石的堆积作用.微量元素判别图表明岩体受到了明显的地壳物质混染作用.铂族元素丰度总量低,其丰度分布型式图表明原岩岩浆的部分熔融程度高,而且元素的判别图表明岩浆具有S不饱和特点.硫化物残留在地幔中而使得岩浆中PGE相对Cu、Ni亏损,在Ni-PGE-Cu图上呈总体上的凹形分布.同属PPGE的Pt比Pd所显示的更高的相容性也表明了岩浆中S的不饱和特点.而Ir的负异常可能说明原始岩浆在侵入前的分离结晶作用其间发生了Ir的结晶析出,或者是在地幔部分熔融时Ir残留在地幔残留体中.因此,主孔石榴石橄榄岩的原始岩浆是上地幔适当部分熔融程度的产物((Pd/Ir)N≥1),可能在源区有硫化物的残余而造成了PGE相对Cu、Ni亏损而在Ni-PGE-Cu图上呈总体上的凹形分布.后S不饱和的岩浆经历分离结晶作用而造成了Pt相时于Pd亏损的特点.     

Constraints from geochemistry and Sr–Nd isotopes for the origin of albitite deposits from Central Sardinia (Italy)

Major- and trace-element contents and Sr–Nd isotope ratios were determined in albitite, albitized and unaltered late-Variscan granitoid samples from the world-class Na-feldspar deposits of central Sardinia, Italy. The albite deposit of high economic grade has geological, textural, and chemical features typical of metasomatic alteration affecting the host granitoids. Albitization, locally accompanied by chloritization and epidotization, was characterized by strong leaching of Mg, Fe, K, and geochemically similar trace elements, and by a significant increase of Na. Ca, and P were moderately leached in the most metasomatized rocks. Other major (Si, Ti, Ca) and trace elements (U, Th, Y, and Zr), along with light (LREE) and middle (MREE) rare-earth elements, behaved essentially immobile at the deposit scale. The Nd-isotope ratios (0.512098 to 0.512248) do not provide information on the emplacement age of the unaltered late-Variscan granitoids. On the other hand, their Sr-isotope ratios fit an errorchron of 274±29 Ma (1σ error), in fair agreement with all published ages of Sardinian Variscan granitoids. The very low Rb content of albitized rocks precludes application of the Rb–Sr radiometric system to determine the age of albitization. The Sm–Nd system is not applicable either, because the ¹⁴³Nd/¹⁴⁴Nd ratios of albitized rocks and unaltered granitoids overlap. The overlap confirms that Sm and Nd were substantially immobile during albitization. On the other hand, the measured ⁸⁷Sr/⁸⁶Sr ratios of the albitized rocks are appreciably lower than those of the unaltered host granitoids, whereas, their initial Sr-isotope ratios are higher. This seems to suggest that a) albitization was induced by non-magmatic fluids rich in radiogenic Sr, and b) albitization occurred shortly after the granitoid emplacement. This conclusion is supported by Nd isotopes, because unaltered granitoids and albitites fit the same reference isochron at 274 Ma. The fluids acquired radiogenic Sr by circulation through the Lower Paleozoic metasedimentary basement. Specifically, it is estimated that Sr supplied by the non-carbonatic basement represents about 22 wt% of total Sr in albitite.     

Origin of facies zonation in microbial carbonate platform slopes: Clues from trace element and stable isotope geochemistry (Middle Triassic,Dolomites, Italy)

Limestones containing radiaxial fibrous cements were sampled along the southern slope of the late Anisian (Middle Triassic) Latemar carbonate platform in the Dolomites, northern Italy. The Latemar upper slopes comprise massive microbial boundstone, whereas lower slopes are made of clinostratified grainstone, rudstone and breccia. Samples are representative of a seawater column from near sea‐level to an aphotic zone at about 500 m water depth. Radiaxial fibrous cements were analyzed for carbon (δ¹³C) and oxygen (δ¹⁸O) stable isotopic composition, as well as major and trace element content, to shed light on the origin of the slope facies zonation. The δ¹³C vary between 1·7‰ and 2·3‰ (Vienna Pee‐Dee Belemnite), with lowest values at palaeo‐water depths between 70 m and 300 m. Radiaxial fibrous cements yielded seawater‐like rare earth element patterns with light rare earth element depletion (Nd_SN/Yb_SN ≈ 0·4), superchondritic yttrium/holmium ratios (≈55) and negative cerium anomalies. Cadmium reaches maximum values of ca 0·5 to 0·7 μg/g at palaeo‐water depths between 70 m and 300 m; barium contents (0·8 to 1·8 μg/g) increase linearly with depth. The downslope patterns of δ¹³C and cadmium suggest increased nutrient and organic matter contents at depths between ca 70 m and 300 m and point to an active biological pump. The peak in cadmium and the minimum of δ¹³C mark a zone of maximum organic matter respiration and high nutrient and organic matter availability. The base of this zone at ca 300 m depth corresponds with the transition from massive microbial boundstone to clinostratified grainstone, rudstone and breccia. The microbial boundstone facies apparently formed only in seawater enriched in organic matter, possibly because this organic matter sustained benthic microbial communities at Latemar. The base of slope microbialites on high‐relief microbial carbonate platforms may be a proxy for the depth to maximum respiration zones of Palaeozoic and Mesozoic periplatform basins.     

Organic petrology and geochemistry of the Carboniferous coal seams from the Central Asturian Coal Basin (NW Spain)

This paper presents for the first time a petrological and geochemical study of coals from the Central Asturian Coal Basin (North Spain) of Carboniferous (Pennsylvanian), mainly of Moscovian, age. A paleoenvironmental approach was used, taking into account both petrographic and organic geochemical studies. Vitrinite reflectance (R_r) ranges from 0.5% to 2.5%, which indicates a high volatile bituminous to semianthracite and anthracite coal rank. The coal samples selected for paleoenvironmental reconstruction are located inside the oil–gas-prone phase, corresponding to the interval between the onset of oil generation and first gas generation and efficient expulsion of oil. This phase is represented by coals that have retained their hydrocarbon potential and also preserved biomarker information. Paleodepositional reconstruction based on maceral and petrographic indices points to a swamp environment with vitrinite-rich coal facies and variable mineral matter content. The gelification index (GI) and groundwater influence index (GWI) indicate strong gelification and wet conditions. The biomarkers exhibit a high pristane/phytane ratio, suggesting an increase in this ratio from diagenetic processes, and a high diterpanes ratio. This, in turn, would seem to indicate a high swamp water table and a humid climate. The maximum point of coal accumulation occurred during the regressive part of the Late Moscovian sequence and in the most humid climate described for this period of time in the well-known coal basins of Europe and North America.     

Chemical and mineralogical composition of fluvial sediments (Bistrita River,Romania): Geogenic vs. anthropogenic input into rivers on its way through mining areas

The upper reaches of the Bistrita drainage system were selected as a natural test site to determine the geogenic and anthropogenic input into fluvio-lacustrine systems in humid mid-latitude morphoclimatic zones. The reason for this selection lies in the complex geology and its metallogenic evolution leading to a great variety of Fe, Mn, U, and polymetallic sulfides ore deposits. It sparked an intense mining activity during the past centuries with a strong impact on the drainage system similar to many mineralized sites in the world which are still under exploitation. Sediment samples from Bistrita River were analyzed by means of X-ray fluorescence spectrometry (XRF), X-ray diffraction (XRD), near-infrared (NIR) and micro-Raman spectroscopy (μ-Raman).Our results revealed that the chemical and mineralogical built-up of the stream sediments is mainly geogenic, with most of the trace elements accumulated in the river sediments derived from the source rocks exposed in catchment area of the River Bistrita. A strong input by man has been detected in the drainage system near abandoned mining sites. The trace elements are mainly accommodated in the structure of detrital minerals representative of the clastic aureole around the source rocks, and to a lesser extent adsorbed onto the surface of clay minerals. The REE incorporated into muscovite furnish evidence of having derived from the source rocks, prevalently mica schists exposed by supergene processes in the provenance area and rule out a neoformation of clay minerals on transport and deposition.     

The influence of the limestone-quarry Čertovy schody (Czech Republic) on the precipitation chemistry and atmospheric deposition

Atmospheric precipitation samples were collected in the Bohemian Karst (30 km SW from Prague, Czech Republic) at six localities in the vicinity of the limestone-quarry Čertovy schody during years 1996–2003. Samples were analyzed for major components (Na⁺, K⁺, Mg²⁺, Ca²⁺, F⁻, Cl⁻, NO₃⁻, HCO₃⁻, SO₄²⁻) and trace metals (Cu, Mn, Fe, Zn, Pb, Be, As, Sr, Cd, Al, Cr). Deposition fluxes were calculated from more than 10 000 elemental analyses of samples collected monthly. The fluxes of monitored substances show temporal and spatial variability. The most marked attribute is the strong affection by local emission sources confirmed by the investigation of seasonal variability, temporal trend and correlation analysis.