Geochemistry of the high-PCO2 waters in Logudoro,Sardinia, Italy

A geochemical study of the high-PCO₂ waters in Logudoro, northern Sardinia, was carried out starting from regional hydrogeochemical prospecting for geothermal energy, based on the major dissolved components and some minor elements. This preliminary investigation led to the identification of five different lithologies marking the different aquifers. The high-PCO₂ waters can be divided into the less saline (TDS < 1g/l) with high tritium unit (T.U.) values and the more saline ones (TDS= 1–3.5 g/l) with T.U. values close to zero. The water-rock interaction process affecting the major components is shown to be the result of interaction between CO₂-rich waters and aluminosilicates; the process takes place at different degrees depending on the depth at which CO₂ interacts with different aquifers while migrating upward from the mantle. Consideration of the SO₄/Cl and F/Cl ratios in the solution allowed the deep ciruits of S. Martino and Abbarghente in the Oligo-Miocene volcanic rocks and S. Lucia in the carbonate-schistose-granitic basement of the Goceano Mountains to be located.     

Geochemistry of trace and minor elements in sediments and manganese micronodules from the Angola Basin

Indicator role of trace elements in sedimentation and ore formation is considered for sediments from Station 2182 in the Angola Basin. It is shown that pelagic sediments were formed from two main sources: biogenic calcium carbonate and lithogenic sediment component compositionally similar to the miopelagic clay. Increase of the Mn/Al ratio, Ce anomaly in the REE composition, Co/Ni and Mo/W ratios, and anomalous accumulation of Tl, Pb, Bi and other microelements indicate that sediments from horizons 15–20 and 30–35 cm contain significant amounts of hydrogenic material as Fe-Mn oxyhydroxides. Manganese micronodules (MN) were extracted from different horizons (10–15, 15–20, and 30–35 cm) and analyzed to study the hydrogenic component. Their development is related to retardation of biogenic and lithogenic sedimentation. The studied manganese micronodules are represented by the hydrogenic-diagenetic formations >100 μm in size with Mn/Fe = 2.0–2.8, Co/Ni = 0.2–0.4, Ce an = 4.2–5.7, and Mo/W = 5.2–7.9. The MN content is too low to affect the major and trace element composition of sediments. The main part of Fe and Mn is confined to fraction <10 μm.     

煤矸石中微量元素的地球化学行为

以兖州矿煤矸石中微量元素的淋滤作用及析出含量为例,分析了微量元素在洗选过程和淋滤作用下的分布、迁移规律等地球化学行为。在用不同的pH值酸性溶液作淋滤实验时发现,pH值对微量元素的析出影响很大。研究还发现土壤中微量元素的富集量随着距矸石堆距离的增加呈明显的下降趋势。     

Geochemistry of the Adamello massif (northern Italy)

The Tertiary Adamello massif, outcropping over an area of more than 550 km² in the southern Alps (northern Italy) is composed mainly of granitoid rocks (granodiorite, tonalite, quartz diorite) with minor amounts of diorite and gabbro. The major and trace element composition of these rocks is comparable to calc-alkaline volcanic rocks of continental margins. The granitoid rocks display spatial and temporal variations in their composition, particularly in Na, P, Sr, La, Nb and Y contents and ⁸⁷Sr/⁸⁶Sr ratios. The variations were probably produced by concurrent contamination/wall-rock assimilation and fractional crystallization of high-alumina basaltic magma.     

柴北缘鱼卡河花岗质片麻岩的地球化学特征和锆石 LA-ICPMS定年

岩石地球化学研究表明,柴北缘鱼卡河超高压榴辉岩围岩花岗质片麻岩的SiO2、Al2O3、K2O和Na2O含量较高,而TiO2、FeOt、MgO、MnO和CaO含量较低,里特曼指数为1.93～2.36,铝饱和指数ACNK值为1.07～1.17,显示出明显的壳源S型花岗岩的特点。在微量元素方面,岩石富集大离子亲石元素,亏损高场强元素,具有轻稀土元素富集和中等的Eu负异常,也显示了壳源S型花岗岩的特征。阴极发光(CL)图像显示该花岗质片麻岩的锆石具有核-幔(边)结构,核部为原岩残留、幔部显示弱的变质重结晶。LA-ICPMS锆石原位微量元素研究显示,本区锆石经历了弱的变质重结晶作用,且可能遭受到后期热液蚀变作用的改造;参考锆石的微量元素组成特征,挑选受变质重结晶和热液改造较弱的锆石的同位素进行测试,结果获得鱼卡河花岗质片麻岩的原岩形成时代为(952±19)Ma左右的新元古代,是地壳重熔作用的产物;同时获得该片麻岩的可能变质年龄为424～480Ma,表明该片麻岩的原岩可能与榴辉岩的原岩共同经历了早古生代加里东期的变质作用,但由于片麻岩的变质程度较低,应是在榴辉岩的折返过程中构造叠置在一起的。利用LA-ICPMS对具有多阶段演化历史的变质锆石定年时,必须同时进行锆石CL图像和原位微量元素分析,才可能对所获年龄给出合理的解释。     

Geochemistry and origin of rare earth elements (REEs) in the Shengli River oil shale, northern Tibet, China

The Shengli River-Changshe Mountain oil shale zone, located in the North Qiangtang depression, northern Tibet plateau, represents a potentially large marine oil shale resource in China. Twenty-eight samples including oil shale, micritic limestone and marl were collected from the Shengli River area to determine the contents and distribution patterns of rare earth elements (REEs) in marine oil shale. Oil shale samples from the Shengli River area have high ash yield (61.86–67.48%) and TOC content (8.02–13.67%) with low total sulfur (S_t,d) content (0.76–1.39%) and intermediate shale oil content (3.60–16.30%). The total rare earth element (ΣREE) content in oil shale samples is notably depleted (46.79–67.90 μg/g), approximately one third of the mean value of the North American Shale Composite (NASC), and lower than that of world-wide black shales and Chinese coals, but higher than that of world-wide coals and micritic limestone samples (29.21 μg/g) from the Shengli River area. The oil shale samples from the Shengli River area exhibit shale-like Chondrite or NASC-normalized REE patterns similar to those of micritic limestone and marl samples from this area, indicating that REEs of these different lithological samples may have been derived from a similar terrigenous source.REE contents of oil shale samples are highly positive correlated with ash yield and show a positive correlation with Fe and a weakly positive correlation with organic sulfur, and the vertical variations of REEs mainly follow those of Si, Al, K and Ti. All these facts indicate that the REE contents in oil shale seams are mainly controlled by clay minerals and, to a lesser extent, by pyrite, as well as partly associated with oil shale organic constituents. Rare earth elements in the Shengli River oil shale have originated from two sources: a felsic volcanic rock source and a clastic or/and limestone source.     

Geochemistry of surface waters in the vicinity of open pit mines at the Cay Cham deposit, Thai Nguyen province, northern Vietnam

This study provides an assessment of the environmental impact of open pit mining operations at the Cay Cham titanomagnetite-ilmenite deposit (northern Vietnam). The results of surface water sampling indicate the formation of acid mine drainage and contamination of adjacent areas by heavy metals (Cu, Zn, Ni, and Mn). The acid mine drainage is produced by oxidation leaching of sulfide minerals associated with primary mineralization owing to the low neutralization potential of the natural waters in the humid environment of tropical rainforest. The study showed that alternating dry and wet seasons typical of this climatic region promote the generation of stored acidity leading to a sharp decrease in pH of drainage water during the wet season and result in the negative impacts of this mine on both flowing and stagnant surface waters.     

云南省临沧市勐托新近系褐煤的微量元素地球化学特征

为研究云南临沧勐托新近系褐煤的微量元素地球化学特征,共采集了11个褐煤样品,采用ICP MS和ICP CCT MS(As和Se)对煤中微量元素进行了测试。结果表明：与中国煤相比,勐托褐煤中Rb(96.1 mg/kg)、Sb(15.3 mg/kg)和Cs(25.9 mg/kg)显著富集,W(10.6 mg/kg)和U(20.2 mg/kg)富集,Be(7.84 mg/kg)、Ga(16.1 mg/kg)、As(11.6 mg/kg)、Cd(0.67 mg/kg)、Sn(6.66 mg/kg)、Pb(34.6 mg/kg)、Bi(3.86 mg/kg)和Th(28.2 mg/kg)稍富集,微量元素组成与大寨富锗煤不同,与酸性花岗岩物源供应有关。勐托褐煤中REY含量范围为121~420 mg/kg,平均251 mg/kg,均较大寨富锗褐煤高,且以Ce显著正异常和Eu显著负异常为特征,明显区别于大寨褐煤,Eu负异常和上陆壳标准化的REY分配模式均表明勐托褐煤中稀土元素受盆地周边花岗岩风化陆源碎屑供应影响。     

Geochemistry and isotope geochemistry of the Monfalcone thermal waters (northern Italy): inference on the deep geothermal reservoir

Geochemical investigations were carried out to define the origin of the low- to moderate-temperature thermal waters feeding the Monfalcone springs in northern Italy. Chemical data indicate that waters approach the composition of seawater. Mixing processes with cold low-salinity waters are highlighted. The δ¹⁸O and δD values are in the range ?5.0 to ?6.4 ‰, and ?33 to ?40 ‰, respectively, suggesting the dilution of the saline reservoir by karst-type freshwaters. A surplus of Ca²⁺ and Sr²⁺ ions with respect to a conservative mixing is ascribed to diagenetic reactions of the thermal waters with Cretaceous carbonates at depth. The measured Sr isotopic composition (⁸⁷Sr/⁸⁶Sr ratio) ranges between 0.70803 and 0.70814; after correction for the surplus Sr, a ⁸⁷Sr/⁸⁶Sr ratio indicating Miocene paleo-seawater is obtained. The dissolved gases indicate long-lasting gas–water interactions with a deep-originated gas phase of crustal origin, dominated by CO₂ and marked by a water TDIC isotopic composition in the range ?5.9 to?8.8 and helium signature with 0.08?<?R/Ra?<?0.27, which is a typical range for the crust. A possible scenario for the Monfalcone thermal reservoir consists of Miocene marine paleowaters which infiltrated through the karstic voids formed within the prevalently Cretaceous carbonates during the upper Eocene emersion of the platform, and which were entrapped by the progressive burial by terrigenous sediments.     

云南白秧坪银多金属矿床微量元素地球化学特征

云南白秧坪银多金属矿床是滇西兰坪盆地内新发现的矿床,属东特提斯喜马拉雅成矿域的一部分。矿床主要产于下白垩统景星组石英砂岩、粉砂岩中。本文从微量元素地球化学研究入手,与滇西喜马拉雅期富碱岩体相比较,它们具有相同的物质来源区,这种源区被认为是壳幔物质混合的一种"EMⅡ型"富集地幔源。     

南疆阿克苏河流域水文地球化学特征

干旱、半干旱地区的地下水资源是重要的供水水源,阿克苏地区地处塔里木盆地北部,天山山脉中段南麓,人类活动密集,中部及东部荒漠的土壤盐渍化严重,地下水水质出现恶化,广泛分布着微咸水和咸水,为了合理开发利用地下水资源,需要深入地认识阿克苏河流域地下水的水化学特征和演化规律,对此,在收集阿克苏地区气象、水文、地质、水文地质等资料的基础上,系统采集了不同位置和深度的地下水样品,对水化学组分进行测定,确定了地下水水化学类型;结合水文地质调查结果,分析了阿克苏地区地下水化学组分的空间特征,推断其水文地球化学演化过程。结果显示,浅层地下水在径流区的阳离子以Na⁺、Ca+、Ca⁽²⁺⁾为主,阴离子以Cl(2+)为主,阴离子以Cl^-、SO_4-、SO_4^(2-)为主,至排泄区阳离子变成以Na(2-)为主,至排泄区阳离子变成以Na⁺为主,阴离子以Cl+为主,阴离子以Cl^-、SO_4-、SO_4^(2-)为主;中深层地下水在径流区的阳离子以Na(2-)为主;中深层地下水在径流区的阳离子以Na⁺、Ca+、Ca⁽²⁺⁾为主,阴离子以Cl(2+)为主,阴离子以Cl^-、SO_4-、SO_4^(2-)为主,至排泄区优势阳离子转为Na(2-)为主,至排泄区优势阳离子转为Na⁺,优势阴离子转为Cl+,优势阴离子转为Cl^-。阿克苏地区地下水中发生的主要水文地球化学作用为水-岩相互作用,同时也受人为因素和混合作用的影响。     

Impact of ancient metal smelting on arsenic pollution in the Pecora River Valley,Southern Tuscany,Italy

A significant As anomaly has been reported in the literature for stream sediments and unlithified Quaternary deposits of the Pecora River valley in Southern Tuscany, extending from the “Colline Metallifere” pyrite-base metals district to the Tyrrhenian Sea. The As anomaly spreads over several square kilometers around a core that exceeds 500 ppm. Several source contributions (from natural to anthropogenic) have been invoked to explain the observed As distribution in the Pecora Valley, including the metal-working industry which was active in this area, particularly in Etrusco-Roman times and in the Middle Ages. In order to evaluate the contribution of ancient mining and metallurgical activities in the Pecora Valley to elevated As concentrations in the environment, a detailed mineralogical and geochemical survey of metallurgical slags and smelted ore minerals was undertaken from six different sites through the Pecora Valley: Poggio Butelli (Etrusco-Roman iron slags); Sata Creek, Arialla, Marsiliana, Forra and Cascata sites (all Medieval base metals slags). The As content of Etrusco-Roman slags is relatively low (few tens of ppm), whereas Medieval slags show variable, but higher amounts of base metals (±Ag) (ranging from tens to tens of thousands ppm) and As (up to 267 ppm, with average contents of about 40 ppm). Arsenic is mostly partitioned in sulfides disseminated through the glassy groundmass rather than in solid solution with the glassy matrix. Remnants of the ore used for base metal and Ag smelting during the Middle Ages had the highest As contents (up to about 1000 ppm).     

Rare earth elements in waters from the albitite-bearing granodiorites of Central Sardinia, Italy

With the aim of contributing to the knowledge of the geochemical behaviour and mobility of the rare earth element (REE) in the natural water systems, the ground and surface waters of the Ottana-Orani area (Central Sardinia, Italy) were sampled. The study area consists of albititic bodies included in Hercynian granodiorites. The waters have pH in the range of 6.0-8.6, total dissolved solid (TDS) of between 0.1 and 0.6 g/l, and major cation composition dominated by Ca and Na, whereas predominant anions are Cl and/or HCO₃.The pH and the major-element composition of the waters are the factors affecting the concentration of REE in solution. The concentrations of ∑REE+Y in the samples filtered at 0.4 μm vary between 140 and 1600 ng/l, with La of between 14 and 314 ng/l, and Yb of between <6 and 12 ng/l. A negative Ce anomaly, especially marked at high pH, is observed in the groundwaters. The surface waters show lower REE concentrations, which are independent of pH, and negligible Ce anomaly.Speciation calculations, carried out with the EQ3NR computer program, showed that the complexes with the CO₃²⁻ ligand are the dominant REE species at pH in the range of 6.7-8.6. The REE³⁺ ions dominate the speciation at pH <6.7 and only in the light REE (LREE).The relative concentrations of REE in water roughly reflect those in the aquifer host rocks. However, when concentrations of REE in water are normalised relative to the parent rocks, a preferential fractionation of heavy REE (HREE) into the water phase can be observed, suggesting the greater mobility and stability of HREE in aqueous solution.     

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.     

陈家山矿煤中微量元素和稀土元素地球化学特征

通过对陈家山煤矿中下侏罗统延安组4^#主采煤层中微量元素和稀土元素的测试分析,发现煤中富集亲花岗岩的钨钼族元素W、Mo、Bi、Sn、Ba、Sr和Li,说明该区煤系形成期间的陆源碎屑主要来自花岗岩和花岗片麻岩等中、酸性岩石。4^#煤中ΣREE平均值为98.2×10^-6,稀土元素分布模式十分相似,呈左高右低的宽缓“V”型曲线,Eu负异常明显,反映出稀土元素与陆源碎屑岩关系密切,成煤期间稀土元素来源一致,陆源物质的供应相对稳定。     

Geochemistry of heavily exploited aquifers in the Emilia-Romagna region (Po Valley, northern Italy)

 More than 5 800 chemical analyses on water samples collected during 1987–1995 from 528 monitoring wells located in the southernmost part of the Po Valley (Emilia-Romagna region, northern Italy), one of the most urbanized, industrialized and agriculturally developed areas of Italy, have been processed. The analysis of data showed that: (1) waters are discharging from both confined and unconfined aquifers; (2) the water in the unconfined aquifer(s) is Ca(Mg)-HCO₃ in composition while confined ones are Na-Cl and/or Na-(HCO₃); (3) both confined and unconfined aquifer samples have δ¹⁸O and δD isotopic values of meteoric signature; (4) waters from both the aquifers are at least 40 years old; (5) the pumping rate has caused subsidence, particularly where the aquifer(s) is (are) unconfined; (6) the unconfined aquifer(s) is exposed to the risk of NO₃ pollution; (7) considering the present "pressure" (i.e. pumping rate) on this natural environment by human activity, care must be taken in the future to preserve this "strategic" resource. Received: 27 October 1997 · Accepted: 12 March 1998     

Late Quaternary multiple incised valley systems: An unusually well‐preserved stratigraphic record of two interglacial valley‐fill successions from the Arno Plain (northern Tuscany,Italy)

Un‐fragmented stratigraphic records of late Quaternary multiple incised valley systems are rarely preserved in the subsurface of alluvial‐delta plains due to older valley reoccupation. The identification of a well‐preserved incised valley fill succession beneath the southern interfluve of the Last Glacial Maximum Arno palaeovalley (northern Italy) represents an exceptional opportunity to examine in detail evolutionary trends of a Mediterranean system over multiple glacial–interglacial cycles. Through sedimentological and quantitative meiofauna (benthic foraminifera and ostracods) analyses of two reference cores (80 m and 100 m long) and stratigraphic correlations, a mid‐Pleistocene palaeovalley, 5 km wide and 50 m deep, was reconstructed. Whereas valley filling is chronologically constrained to the penultimate interglacial (Marine Isotope Stage 7) by four electron spin resonance ages on bivalve shells (Cerastoderma glaucum), its incision is tentatively correlated with the Marine Isotope Stage 8 sea‐level fall. Above basal fluvial‐channel gravels, the incised valley fill is formed by a mud‐prone succession, up to 44 m thick, formed by a lower floodplain unit and an upper unit with brackish meiofauna that reflects the development of a wave‐dominated estuary. Subtle meiofauna changes towards less confined conditions record two marine flooding episodes, chronologically linked to the internal Marine Isotope Stage 7 climate‐eustatic variability. After the maximum transgressive phase, recorded by coastal sands, the interfluves were flooded around 200 ka (latest Marine Isotope Stage 7). The subsequent shift in river incision patterns, possibly driven by neotectonic activity, prevented valley reoccupation guiding the northward formation of the Last Glacial Maximum palaeovalley. The applied multivariate approach allowed the sedimentological characterization of the Marine Isotope Stage 7 and Marine Isotope Stage 1 palaeovalley fills, including shape, size and facies architecture, which revealed a consistent river‐coastal system response over two non‐consecutive glacial–interglacial cycles (Marine Isotope Stages 8 to 7 and Marine Isotope Stages 2 to 1). The recurring stacking pattern of facies documents a predominant control exerted on stratigraphy by Milankovitch and sub‐Milankovitch glacio‐eustatic oscillations across the late Quaternary period.