The geochemistry of trace elements in geothermal fluids,Iceland

Trace element geochemistry was studied in geothermal fluids in Iceland. The major and trace element compositions of hot springs, sub-boiling, and two-phase (liquid and vapor) wells from 10 geothermal areas were used to reconstruct the fluid composition in the aquifers at depth. Aquifer fluid temperatures ranged from 4 to 300 °C, pH values between 4.5 and 9.3, and fluids typically contained total dissolved solids <1000 ppm, except in geothermal areas that have seawater and seawater-meteoric water mixtures. Trace alkali elements Li, Rb and Cs are among the most mobile elements in aquifer fluids, with concentrations in the range of <1 ppb to 3.49 ppm Li, <0.01 to 57 ppb Cs, and <1 ppb to 3.77 ppm Rb. Their chemistry is thought to be dominated by rock leaching and partitioning into Na- and K-containing major alteration minerals. Arsenic, Sb, Mo and W are typically present in concentrations in the range of 1–100 ppb. They are relatively mobile, yet Mo may be limited by molybdenite solubility. The alkaline earth elements Ba and Sr are quite immobile with concentrations in the range of <0.1–10 ppb Ba and <1–100 ppb Sr in the dilute fluids, but up to 5.9 ppm Ba and 8.2 ppm Sr in saline fluids. These elements show a systematic relationship with Ca, possibly due to substitution for Ca in Ca-containing major alteration minerals like calcite, epidote and anhydrite. Incorporation into major Ca-minerals may also be important for Mn. Many metals including Fe, Cr, Ni, Zn, Cu, Co, Pb and Ag have low mobility and concentrations, typically <1 ppb for Ag, Cd, Co, Cr, Cu, Ni, and Pb, <10 ppb for Zn and < 100 ppb for Fe, although for some metals higher concentrations are associated with saline fluids. Based on the metals assessed, saturation is approached with respect to many sulfide minerals and in some cases oxide minerals but Cu, Ni and Pb minerals are slightly but systematically undersaturated, and Ag phases significantly undersaturated. Evaluation of mineral-fluid equilibria for these metals is problematic due to their low concentrations, problems associated with assessing the aqueous species distribution by thermodynamic calculations, and uncertainties concerning the exact minerals possibly involved in such reactions. Reaction path calculations, poor comparison of concentrations measured in the samples collected at the wellhead and published downhole data as well as boiling, cooling and mass precipitation calculations suggest removal of many metals due to changes upon depressurization boiling and conductive cooling of the aquifer fluids as they ascend in wells. These results imply that processes such as mass precipitation upon fluid ascent may be highly important and emphasize the importance of considering mass movement in geothermal systems.     

渤海湾盆地石炭-二叠系微量元素特征及其指相意义

本文采用ICP-MS测试分析技术,对渤海湾盆地4口钻井42件石炭—二叠系岩心样进行了Sr、Ba、Ga、V、Ni、Co等沉积环境敏感元素的系统测试分析,讨论6种元素含量及Sr/Ba、Ba/Ga、Ni/Co等比值的变化特征。除去5件样品中的异常点,测试元素大多数集中的变化范围:Sr(100~200)×10-6,Ba(100~700)×10-6,Ga(10~40)×10-6,V(80~200)×10-6,Co(5~30)×10-6,Ni(15~45)×10-6,Sr/Ba 0.2~0.9,Ba/Ga 2~20,Ni/Co 1~4。根据微量元素指标特点结合岩相资料,认为渤海湾盆地本溪组发育海相沉积,太原组发育过渡相沉积,山西组及其以上地层发育陆相沉积。元素指标中,Ba、Sr/Ba和Ba/Ga沉积环境指示意义显著,在判断渤海湾盆地石炭—二叠纪沉积相方面具有实用价值。     

Proton-induced X-ray emission measurements of trace elements in water samples collected from an Indiana coal mining locality

A new method of simultaneous multi-elemental analysis, Proton Induced X-ray Emission (PIXE), was used to detect trace elements in waters associated with a coal strip-mining operation in southern Indiana. Stream, pond, and ground water samples were collected and analyzed monthly from, or near, Sulphur Creek in Sullivan County. The concentrations of 26 major and trace elements were determined in samples from eleven locations: K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Br, Rb, Sr, Mo, Cd, Sn, Sb, I, Ba, Hg, Pb, and U. Elemental concentrations fluctuated considerably throughout the 13-month sampling period and also among sampling sites. Nickel, Zn, As, Cd, Mn, Fe, and Ca were highest in the upstream water which was most acidic (pH = 2.9–4.0) because of old unreclaimed mining operations. The highest values recorded were Ni = 1662 ppb, Zn = 4953 ppb, As = 26 ppb, Cd = 93 ppb, Mn = 5063 ppb, Fe = 63 ppm, and Ca = 325 ppm. The concentrations of these elements decreased downstream as the pH of Sulphur Creek increased which was likely due to the influence of the calcareous glacial till cover in the area and the recent mining activity which disturbed overburden containing a high percentage of calcareous materials. Lead, I, Br, and Ti values were highest (661 ppb, 86 ppb, 70 ppb, and 45 ppb, respectively) in the ground water from the coal seam (pH approximately 7). Other elements which were relatively high in the pH 7 waters closest to the current mining operations (pond, stream, and groundwater) included K (17 ppm), Sr (3408 ppb), Ba (173 ppb), As (14 ppb), Rb (16 ppb), Sn (14 ppb), and Cu (3840 ppb). The highest Cu concentration was recorded at the point where drainage water from the mine entered Sulphur Creek. Gallium, U, Hg, and Mo were found in low (< 13 ppb for Ga and Hg; < 205 ppb for Mo and U) concentrations and only in the ponds within the mine.     

Wavelength-dispersive X-ray fluorescence spectrometric determination of Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites

Komatiites are mantle-derived ultramafic volcanic rocks. Komatiites have been discovered in several States of India, notably in Karnataka. Studies on the distribution of trace-elements in the komatiites of India are very few. This paper proposes a simple, accurate, precise, rapid, and non-destructive wavelength-dispersive x-ray fluorescence (WDXRF) spectrometric technique for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites, and discusses the accuracy, precision, limits of detection, x-ray spectral-line interferences, inter-element effects, speed, advantages, and limitations of the technique. The accuracy of the technique is excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Zr, Nb, Ba, Pb, and Th and very good (within 4%) for Y. The precision is also excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th. The limits of detection are: 1 ppm for Sc and V; 2 ppm for Cr, Co, and Ni; 3 ppm for Cu, Zn, Rb, and Sr; 4 ppm for Y and Zr; 6 ppm for Nb; 10 ppm for Ba; 13 ppm for Pb; and 14 ppm for Th. The time taken for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in a batch of 24 samples of komatiites, for a replication of four analyses per sample, by one operator, using a manual WDXRF spectrometer, is only 60 hours.     

Algal uptake of U and some other metals: Implications for global geochemical cycling

Freshwater green algae Ankistrodesmus sp, cultured in dilute solutions of metals chelated with EDTA, revealed massive uptake of U. Examination of Thames River waters and selected micro-organisms of its aquatic ecosystem revealed an average dissolved U concentration of 1.46 ppb, representing about twice the global mean riverine solute concentration of 0.6 ppb U. Suspended particulates, principally algae, contain U at 10³ to 10⁵ times that of their river habitat, averaging 28 300 ppb U. One community of the filamentous algae Spirogyra sp. contained intracellular crystals tentatively identified as the Ca-oxylate weddelite. Studies of algae from a variety of environments have shown large concentration factors for a wide range of elements. Algae from an acid U mine tailings site contain up to 2.7% U (dry weight) plus very high concentrations of other metals. Micro-organisms may act as an important sink for metal solutes in the hydrosphere.     

Petrological Characteristics and Genesis of the Central Indian Ocean Basin Basalts

The Central Indian Ocean Basin (CIOB) basalts are plagioclase-rich, while olivine and pyroxene are very few. The analyses of 41 samples reveal high FeOT (~10–18 wt%) and TiO2 (~1.4–2.7 wt%) indicating a ferrobasaltic composition. The basalts have high incompatible elements (Zr 63–228 ppm; Nb ~1–5 ppm; Ba ~15–78 ppm; La ~3–16 ppm), a similar U/Pb (0.02–0.4) ratio as the normal mid-oceanic basalt (0.16±0.07) but the Ba/Nb (12.5–53) ratio is much larger than that of the normal mid-oceanic ridge basalt (~5.7) and Primitive Mantle (9.56). Interestingly almost all of the basalts have a significant negative Eu anomaly (Eu/Eu*=0.78–1.00) that may have been a result of the removal of feldspar and pyroxene during crystal fractionation. These compositional variations suggest that the basalts were derived through fractional crystallization together with low partial melting of a shallow seated magma.     

Organic matter-metal interactions in Recent sediments: the role of humic substances

Atomic emission spectrographic analysis of the trace inorganic constituents of marine humic substances gave the following range of concentrations: Si, 200 ppm to > 2%; Al, 400 ppm to ~ 1%; Fe, 600–3000 ppm; Ca, 600 ppm to > 2%; Mg, 20–6000 ppm; Na, 600 ppm to > 2%; Ag, < 6–600 ppm; B, < 60–1000 ppm; Cu, 600–4000 ppm; Mn, 8–100 ppm; Mo, <20–3000 ppm; Ni, 100–1000 ppm; Pb, < 40–600 ppm; Sn, 40–600 ppm; Ti, < 20–2500 ppm; V, 20–200 ppm; Zn, 350–4500 ppm; Zr, < 60–500 ppm.Humic substances contain a sizeable portion of the Cu, Mo and Zn found in sediments, but are less important for Ni, Co and Pb, and are insignificant for the Mn, V and Fe content. The metals are mostly introduced into the humates during their diagenetic formation in sediment by dissolution of metals from various mineralogical phases. A precursor of the sedimentary humates, the polymeric organic material dissolved in interstitial water, contains most of the Cu and Zn, about half of the Ni, Fe and Co, and very little of the Mn found in interstitial water. Comparison of the data on humates with that obtained by H₂O₂ treatment of sediments indicates that Cu, Zn and possibly most of the Mo are associated with organic matter, but that Ni and Co are associated with sulfides.     

Deciphering a multistage history affecting U–Cu(–Fe) mineralization in the Singhbhum Shear Zone,eastern India,using pyrite textures and compositions in the Turamdih U–Cu(–Fe) deposit

The ～200-km-long intensely deformed Singhbhum Shear Zone (SSZ) in eastern India hosts India’s largest U and Cu deposits and related Fe mineralization. The SSZ separates an Archaean cratonic nucleus to the south from a Mesoproterozoic fold belt in the North and has a complex geologic history that obscures the origin of the contained iron-oxide-rich mineral deposits. This study investigates aspects of the history of mineralization in the SSZ by utilizing new petrographic and electron microprobe observations of pyrite textures and zoning in the Turamdih U–Cu(–Fe) deposit. Mineralization at Turamdih is hosted in intensively deformed quartz–chlorite schist. Sulfides and oxides include, in inferred order of development: (a) magmatic Fe(–Ti–Cr) oxide and Fe–Cu(–Ni) sulfide minerals inferred to be magmatic (?) in origin; followed by (b) uranium, Fe-oxide, and Fe–Cu(–Co) sulfide minerals that predate most or all ductile deformation, and are inferred to be of hydrothermal origin; and (c) Fe–Cu sulfides that were generated during and postdating ductile deformation. These features are associated with the formation of three compositionally and texturally distinct pyrites. Pyrite (type-A), typically in globular–semiglobular composite inclusions of pyrite plus chalcopyrite in magnetite, is characterized by very high Ni content (up to 30,700 ppm) and low Co to Ni ratios (0.01–0.61). The textural and compositional characteristics of associated chalcopyrite and rare pyrrhotite suggest that this pyrite could be linked to the magmatic event via selective replacement of magmatic pyrrhotite. Alternatively, this pyrite and associated sulfide inclusions might be cogenetic with hydrothermal Fe-oxide. Type-B pyrite that forms elongate grains and irregular relics and cores of pyrite with high Co contents (up to 23,630 ppm) and high Co to Ni ratios (7.2–140.9) are interpreted to be related to hydrothermal mineralization predating ductile deformation. A third generation of pyrite (type C) with low Co, low Ni, and moderate Co to Ni ratios (0.19–13.93) formed during and postdating the ductile deformation stage overgrowing, replacing, and surrounding type-B pyrite. The textural evolution of pyrite parallels the tectonometamorphic evolution of the shear zone demonstrating grain elongation during progressive ductile deformation and prograde metamorphism, annealing at the peak metamorphic condition, porphyroblastic growth at the retrograde path and cataclasis following porphyroblastic growth. Compositional characteristics of hydrothermal pyrite and available geological information suggest that the U–Cu(–Fe) deposit at Turamdih might be a variant of the Fe oxide (–Cu–U–rare earth elements) family of deposits.     

Trace elements and their variation along seam profiles of certain coal seams of Middle and Upper Barakar formations (Lower Permian) in East Bokaro coalfield,district Hazaribagh,Bihar, India

Trace-element data are presented for the first time for any coal seam in India, across a full working section, based on systematically collected channel samples of coal, together with their maceral composition. The trace-element variation curves along the seam profile are presented together with group maceral compositions of Kargali Bottom, Kargali Top, Kargali, Kathara, Uchitdih, Jarangdih Bottom, Jarangdih, and Jarangdih Top seams, East Bokaro coalfield. The Kathara and Uchitdih seams have also been sampled at two other localities and lateral variation in data in their trace-element and maceral compositions is also evaluated.The East Bokaro coals have: Ba and Sr > 1000 ppm; Mn < 450 ppm; Zr < 400 ppm; Ni and V < 250 ppm; Cr < 185 ppm; La < 165 ppm; Cu, Nb, and B < 125 ppm; Pb, Co and Y < 75 ppm; Ga, Sn, Mo, In and Yb < 15 ppm; Ag 2 ppm; and Ge 7 ppm. Petrographically, the coals are dominant in vitrinite (33–97%), rare in exinite (<15%), and semifusinite (0.8–49%) is the dominant inertinite maceral, with variable mineral and shaly matter (11–30%), graphic representation of trace elements versus vitrinite, inertinite, and coal ash indicates the affinity of (a) vitrinite with Cu, Ni, Co, V, Ga and B; (b) inertinite with Nb and B; and (c) coal ash (mineral matter) with Pb, Cu, Ni, La, Mn and Y; Ba, Cr, Sr, Zr, Cu and Ni are of organic as well as inorganic origins.The trend of the variation patterns and average compositions of the different seams are shown to be distinct and different. The variation along the same profile is inferred to be different for different seams of the coalfield.Trace-element data for certain coals of seams from different coalfields in the Gondwana basins of India are presented. There is a wide difference for each of these basins with respect to certain elements. This is suggestive of the proportions of Cu, Ni, V, Y, Ba, Sr, Cr, B, Zr and Ag, characterizing the different Gondwana Basins.     

Geochemistry of uranium in sediments of the Bohai Gulf,China

The following conclusions can be drawn from the work reported in this paper:

1. Sixteen samples were determined for uranium by spectrophotometric method. The uranium content in the sea floor sediments of the Bohai Gulf ranges from 1.6 to 6.3 ppm, with an average of 4.3 ppm.
2. Statistical data show close relationship between U concentration and grain size. Relatively larger amount of uranium was found accumulated in mud than in sand. The bulk of uranium is assumed to be derived from terrestrial detrital minerals.
3. A positive correlation between U and Fe is recognized. Similar relation also can be seen between U and Al. The plot of U concentration vs. Fe is linear, and can be expressed by the linear regression equation:Y=?0.37+1.35X. The plot of U against Al gives an equation ofY=?2.48+1.01X.
4. The average U/C_org. ratio for these sediments is 7×10^?4, and the average ratios of U/P, U/Mn, and U/CaCO₃ are 100×10^?4, 50×10^?4 and 2×10^?4, respectively.
5. Compared with the abundances of other shelf sediments, the average concentration of U in the area under consideration is close to that of sediments on the selves of Japan and the Gulf of Mexico, and the Black Sea. Uranium concentration in the Bohai Gulf sediments is comparable to that of the continental crust, but differs from that of deep-sea clay.

     

Age and geochemistry of the granitoid from the Lunte area,Northeastern Zambia: Implications for magmatism of the Columbia supercontinent

The Paleoproterozoic tectonic evolution of the Bangweulu Block has long been controversial. Paleoproterozoic granites consisting of the basement complex of the Bangweulu Block are widely exposed in northeastern Zambia, and they are the critical media for studying the tectonic evolution of the Bangweulu Block. This study systematically investigated the petrography, zircon U-Pb chronology, and petrogeochemistry of the granitoid extensively exposed in the Lunte area, northeastern Zambia. The results show that the granitoid in the area formed during 2051±13–2009±20 Ma as a result of Paleoproterozoic magmatic events. Geochemical data show that the granites in the area mainly include syenogranites and monzogranites of high-K calc-alkaline series and are characterized by high SiO₂ content (72.68% –73.78%) and K₂O/Na₂O ratio (1.82–2.29). The presence of garnets, the high aluminum saturation index (A/CNK is 1.13–1.21), and the 1.27%–1.95% of corundum molecules jointly indicate that granites in the Lunte area are S-type granites. Rare earth elements in all samples show a rightward inclination and noticeably negative Eu-anomalies (δEu = 0.16–0.40) and are relatively rich in light rare earth elements. Furthermore, the granites are rich in large ion lithophile elements such as Rb, Th, U, and K and are depleted in Ba, Sr, and high field strength elements such as Ta and Nb. In addition, they bear low contents of Cr (6.31×10⁻⁶–10.8×10⁻⁶), Ni (2.87×10⁻⁶–4.76×10⁻⁶), and Co (2.62×10⁻⁶–3.96×10⁻⁶). These data lead to the conclusion that the source rocks are meta-sedimentary rocks. Combining the above results and the study of regional tectonic evolution, the authors suggest that granitoid in the Lunte area were formed in a tectonic environment corresponding to the collision between the Tanzania Craton and the Bangweulu Block. The magmatic activities in this period may be related to the assembly of the Columbia supercontinent.©2021 China Geology Editorial Office.     

Application of trace metal anomalies for recognition of petroleum prospects in surface sediments of Kutch and Saurashtra Basins, India

Seepage of hydrocarbons, either as macroseepage or microseepage, can set up near-surface oxidation-reduction zones that favour the development of a diverse array of chemical and mineralogic changes. In this study trace metal alterations were mapped that appear to be associated with hydrocarbon microseepages in the oil/gas fields. A total of 210 soil samples were collected from near surface sediments of Kutch and Saurashtra Basins, India. The soil samples were collected from a depth of 2–2.5 m. The paper reports the chemical alterations associated with trace metals in soils that are related to hydrocarbon microseepages above the Kutch and Saurashtra Basins, India. The soil samples for trace metals; Scandium (Sc), Vanadium (V), Chromium (Cr), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Barium (Ba) and Strontium (Sr) were analyzed using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). The concentrations of the trace elements ranged between for Sc (12.69 to 21.91 ppm), V (109.20 to 436.05 ppm), Cr (87.15 to 481.57 ppm), Co (18.25 to 64.31 ppm), Ni (57.55 to 263.15 ppm), Cu (44.88 to 143.96 ppm), Zn (137.60 to 502.31 ppm), Ba (149.27 to 921.46 ppm) and Sr (143.93 to 425.63 ppm) were obtained. It was observed that trace elements concentrations were tremendously increased when compared with normal concentration in the soils. The adsorbed soil gas analysis showed the presence of high concentrations of ΣC₂₊ (C₂H₆, C₃H₈ and n-C₄H₁₀) ranged between 1 to 121 ppb respectively. Integrated studies of trace elements over adsorbed light gaseous hydrocarbon (ΣC₂₊) anomalies showed good correlation. The carbon isotopic composition of δ¹³C₁ of the samples ranges between — 36.6 ‰ to ?22.7‰ (Pee Dee Belemnite) suggest thermogenic source for hydrocarbon gases. The increase in trace metal concentrations near oil/gas producing areas, suggests that soil chemical change to a reducing environment, presumably due to the influence of hydrocarbon microseepage, which could be applied with other geo-scientific data to identify areas of future hydrocarbon exploration in the frontier areas.     

Heavy metals contamination in road dust in Delhi city,India

Road dust samples were collected from four different areas having different landuse patterns: industrial, heavy traffic, residential and mixed use in Delhi city of India. The samples were analyzed for Ba, Co, Cr, Cu Fe, Mn, Ni, Pb and Zn by ICP-AES. Results indicate high levels of Co, Cr, Cu, Mn and Ni in samples collected from industrial area. Ba, Pb and Zn showed higher concentration levels in heavy traffic area while Fe did not show any discernible variation between the localities. The concentrations of Fe, Mn, Ba, Zn, Cr, Cu, Pb, Ni and Co showed a decreasing trend. The content of heavy metals was comparable to those in other cities in the world. A multivariate statistical approach which includes Pearson’s correlations and principal component analysis was used to identify the possible sources of metals in the road dust. Enrichment factors were estimated for further confirming the sources of contamination. Significant positively correlations between road dust metals Cu–Mn–Co–Cr–Ni suggest that major common source of origin is industrial activities. A meaningful correlation between Ba and Zn, and a moderate positive correlation between Pb and Ba indicate the influence of traffic activities. Enrichment factors calculation indicated that Pb, Cu, Cr and Zn are moderately enriched whereas Co, Ni and Mn are less enriched while Ba exhibited very low enrichment in the dust samples. The results indicate that industrial and vehicular traffic are the two major sources. Traffic appears to be responsible for the high levels of Zn, Cu and Ba. High concentration of Co, Cr, Cu and Mn may be due to industrial sources.     

岩石中低量稀土和其他痕量元素的X-荧光光谱测定

用X-荧光光谱测定岩石中低量稀土元素的仪器参数和测定条件,文[1]已作过讨论。本文介绍样品分析所采用的基本校正,谱线重叠校正和背景处理方法,并将这些方法应用于其他少量和痕量元素的测定。基体的吸收校正岩石样品中最重的主元素是铁,镧系元素La～Er的La线和Ti,Sc,Cr,Mn,Fe,     

宁芜云台山黄铁矿矿床中黄铁矿矿物的初步研究

宁芜云台山黄铁矿矿床中黄铁矿矿物以自形晶为主 ,次为他形粒状 ;黄铁矿晶胞参数为 5 .415 2 3～ 5 .41843× 10 -10 m ,晶体化学式为 (Fe0 .9968Co0 .0 0 0 6Ni0 .0 0 2 6) 1.0 0 0 0 S2 .0 597;黄铁矿红外吸收光谱主吸收峰值为 34 8cm-1,最小透过率为 30 .0 0 %～ 48.80 % ,透过率极差为 31.13～ 47.5 1;黄铁矿中Fe平均含量为 45 .44 % ,S平均含量 5 3.91% ,具有富S特征 ;Co/Ni平均值为 0 .2 1;稀土元素总量平均为2 1.84× 10 -6,具有明显负铈异常 (δCe :0 .76～ 0 .93)和负铕异常 (δEu :0 .72～ 0 .90 ) ;硫同位素组成δ3 4S为 7.0 0‰～ 2 3.0 0‰ ,黄铁矿是含矿热液以堆积、充填和交代方式形成 ,黄铁矿床为火山热水沉积矿床。     

重庆石柱二叠纪栖霞组地球化学特征及其环境意义

在对重庆市石柱县二叠纪栖霞组地层野外露头沉积特征研究的基础上,结合室内薄片观察,根据碳酸盐岩样品的元素含量、比值及相关性,探讨了栖霞组沉积地球化学特征与古环境意义.用于古环境分析的10件栖霞组样品SiO₂、MgO含量低,且两者具有较好的正相关性,Sr含量高,平均为1 751×10-6,Mn/Sr<0.1,Fe/Sr<1,δ18O_PDB>-10‰,表明成岩过程中样品几乎不受硅化及白云岩化作用的影响,未发生化学性质上的改变,可作为古环境分析的可靠对象.栖霞组碳酸盐岩CaO含量高,平均为53.81%,接近纯灰岩的理论化学组成,陆源元素Al₂O₃、TiO₂含量很低,平均值分别为0.17%与0.012%,表明其形成于陆源碎屑影响微弱的稳定古海洋环境.古气候指标MgO/CaO比值极低,平均为0.026,古盐度指标100×(MgO/Al₂O₃)比值高,平均为1 241,古水深判别指标Sr/Ba、1000×(Sr/Ca)比值高,平均值分别为286和4.54,指示了栖霞组碳酸盐岩为潮湿气候下的陆表海(远岸)沉积.古氧相地球化学指标U/Al、V/Al、Mo/Al、Cr/Al、Co/Al、V/(V+Ni)和U/Th特征一致表明栖霞组碳酸盐岩沉积于贫氧—缺氧环境.垂向上,陆源元素∑(Al₂O₃+TiO₂)含量逐渐降低,古水深指标Sr/Ba、1000×(Sr/Ca)比值逐渐增大,表明栖霞组沉积过程中离岸渐远、陆源供给逐步减少、水体持续加深.     

Statistical assessment of geochemical pattern in overbank sediments of the river Sava,Croatia

Four overbank profiles from the three terraces of different age were sampled in 10 to 20 cm intervals for the bulk content of major and minor (Ca, Mg, Fe, Ti, Al, Na, K and P) and trace (Mo, Cu, Pb, Zn, Ni, Co, Mn, As, U, Th, Sr, Cd, Sb, V, La, Cr, Ba, W, Zr, Ce, Sn, Y, Nb, Ta, Sc, Li, Rb and Hf) elements in the minus 0.125 mm fraction. Univariate statistics together with analysis of variance discriminated between the lower-lying carbonate (CA) population dominantly composed of carbonates and the overlying silicate (SI) population being dominantly of silicate mineralogy. This stratified pattern resulted from the intensive erosive action of melting glaciers exerted on limestones and dolomites in the alpine region, followed by local inputs mainly of silicate composition. Elements exhibiting the greatest between-population variability are Ca and Mg being enriched in the CA population and Fe, Mn, P, Sr, Al, Na, K, Li, Rb, Y, Zr, Ni, Cr and Ti being enriched in the SI population. Anomalously high Hg, Pb and Ba concentrations (maximum values: 6,500±2,860 ppb, 225±13 ppm and 1,519±91 ppm, respectively) in the lowermost part of the profile S7, which is nearest to the Croatian-Slovenian border, derive from the mineralized Slovenian catchment area. This profile also contains trimodal frequency distributions of Fe, Mn and P whose highest concentrations coincide with increased values of Zn and Cu which are bimodally distributed. Geochemical patterns of majority of elements in all four profiles consistently reflect the average compositions of the upstream drainage basins.     

浙江八面山萤石矿床稀土元素地球化学特征及成因探讨

对浙江八面山萤石矿床中不同类型萤石矿石和围岩样品的稀土元素的系统分析表明,细粒萤石矿石的ΣREE〈39×10-6,LREE为14.36×10-6～34.24×10-6,HREE0.96×10-6～2.04×10-6,Y〈3×10-6;巨晶萤石矿石中的ΣREE3.62×10-6～20.81×10-6,LREE2.71×10-6～17.67×10-6,HREE0.24×10-6～1.49×10-6;而围岩花岗岩的ΣREE460.29×10-6,LREE225.97×10-6,HREE91.32×10-6,Y＆gt;140×10-6;沉积岩中的ΣREE20.22×10-6、LREE16.11×10-6、HREE1.61×10-6。矿石与围岩中沉积岩的稀土总量、轻稀土、重稀土和Y的含量接近,与花岗岩的稀土总量、轻稀土、重稀土和Y元素含量相差悬殊。萤石矿石的稀土分布型式主要为轻稀土富集型,（La/Yb）N通常多数大于8,在8.07～17.26间,δEu值在0.45～1.30,δCe在0.89～1.14间,Ce、Eu基本不显异常。矿石与围岩的稀土地球化学研究显示,八面山萤石矿床为受地层、岩体与断裂共同控制＂三位一体＂的低温热液型矿床。     

Concentration and distribution of elements in Late Permian coals from western Guizhou Province,China

With the aim of better understanding geochemistry of coal, 71 Late Permian whole-seam coal channel samples from western Guizhou Province, Southwest China were studied and 57 elements in them were determined. The contents of Al, Ca, Co, Cr, Cu, Fe, Ga, Hf, K, Li, Mn, Mo, Nb, Ni, Sn, Ta, Ti, Th, U, V, Zr, and REEs in the Late Permian coals from western Guizhou Province are higher than the arithmetic means for the corresponding elements in the US coals, whereas As, Ba, Br, F, Hg, P, Se, and Tl are lower. Compared to common Chinese coals, the contents of Co, Cr, Cu, Ga, Hf, Li, Mn, Mo, Ni, Sc, Sn, Ti, U, V, Zn, and Zr in western Guizhou coals are higher, and As, F, Hg, Rb, Sb, Tl, and W are lower. Five groups of elements may be classified according to their mode of occurrence in coal: The first two, Group A, Tm–Yb–Lu–Y–Er–Ho–Dy–Tb–Ce–La–Nd–Pr–Gd–Sm, and Group B, As–Sr–K–Rb–Ba–F–Ash–Si–Sn–Ga–Hf–Al–Ta–Zr–Be–Th–Na, have high positive correlation coefficients with ash yield and they show mainly inorganic affinity. Some elements from Group B, such as Ba, Be, Ga, Hf, and Th, are also characterized by significant aluminosilicate affinity. In addition, arsenic also exhibits high sulfide affinity (r_S–Fe>0.5). The elements, which have negative or lower positive correlation coefficients with ash yield (with exceptions of Bi, Cs, Nb, Mn, Se, and Ti), are grouped in other four associations: Group C, Cr–V–Mo–U–Cd–Tl; Group D, Hg–Li–Sc–Ti–Eu–Nb–Cs–W; Group E, Bi–Sb; and Group F, Co–Ni–Cu–Pb–Zn–Mg–Se–Ca–Mn–S–Fe. The correlation coefficients of some elements, including Co, Cr, Cu, Fe, Hg, Li, Mo, Ni, P, S, Sc, U, V, and Zn, with ash yield are below the statistically significant value. Only Cr and Cu are negatively correlated to ash yield (−0.07 and −0.01, respectively), showing intermediate (organic and inorganic) affinity. Manganese and Fe are characterized by carbonate affinity probably due to high content of epigenetic veined ankerite in some coals. Phosphorus has low correlation coefficients with any other elements and is not included in these six associations. There are five possible genetic types of enrichment of elements in coal from western Guizhou Province: source rock, volcanic ash, low-temperature hydrothermal fluid, groundwater, and magmatic hydrothermal inputs.     

Diverse Dietary Responses by Saltmarsh Consumers to Chronic Nutrient Enrichment

We examined the effect of whole-ecosystem nutrient enrichment on herbivory in saltmarsh creek-wall habitats in the Plum Island Estuary (Massachusetts, USA). Located between the macrophyte-dominated high marsh and adjoining mudflats, creek walls are steep vertical habitats vegetated with productive filamentous algae and associated epiphytes. Annual nitrate and phosphate loading rates were increased approximately ×10–15 in creeks mimicking short-term (2-month) and chronic (6-year) eutrophication. We assessed the diets of epifaunal invertebrates (three gastropods and one amphipod species) that potentially graze on benthic algae using natural isotope abundance data and per capita grazing rate measurements derived from ¹³C prelabeled algae. Substantial dietary contributions from benthic algae were observed in all consumers even though previous research has indicated most rely on Spartina detritus as the principal food resource. The amphipod Orchestia grillus and the snail Melampus bidentatus grazed benthic algae in excess of 500 μg algal C g C^?1 h^?1, whereas the snail Nassarius obsoletus and hydrobiid snails grazed at lower rates. Few dietary changes were detected with short-term enrichment. Algal grazing rates of N. obsoletus and M. bidentatus increased with chronic enrichment probably as a functional response to increased algal productivity. O. grillus grazed at a high rate and parasitic infection did not affect its consumption of benthic algae. The abundance and frequency of occurrence of O. grillus on creek-wall habitats increased with chronic nutrient enrichment suggesting amphipods contribute to top–down control on benthic algae and slow algal growth as nutrient enrichment occurs.