Acta Geochimica (v.37, #1)

Heterogeneous Mg isotopic composition of the early Carboniferous limestone: implications for carbonate as a seawater archive by Haoran Ma; Yihe Xu; Kangjun Huang; Yuanlin Sun; Shan Ke; Yang Peng; Xianguo Lang; Zhen Yan; Bing Shen (1-18).
Carbonate precipitation and hydrothermal reaction are the two major processes that remove Mg from seawater. Mg isotopes are significantly (up to 5‰) fractionated during carbonate precipitation by preferential incorporation of 24Mg, while hydrothermal reactions are associated with negligible Mg isotope fractionation by preferential sequestration of 26Mg. Thus, the marine Mg cycle could be reflected by seawater Mg isotopic composition (δ26Mgsw), which might be recorded in marine carbonate. However, carbonates are both texturally and compositionally heterogeneous, and it is unclear which carbonate component is the most reliable for reconstructing δ26Mgsw. In this study, we measured Mg isotopic compositions of limestone samples collected from the early Carboniferous Huangjin Formation in South China. Based on petrographic studies, four carbonate components were recognized: micrite, marine cement, brachiopod shell, and mixture. The four components had distinct δ26Mg: (1) micrite samples ranged from −2.86‰ to −2.97‰; (2) pure marine cements varied from −3.40‰ to −3.54‰, while impure cement samples containing small amount of Rugosa coral skeletons showed a wider range (−3.27‰ to −3.75‰); (3) values for the mixture component were −3.17‰ and −3.49‰; and (4) brachiopod shells ranged from −2.20‰ to −3.07‰, with the thickened hinge area enriched in 24Mg. Due to having multiple carbonate sources, neither the micrite nor the mixture component could be used to reconstruct δ26Mgsw. In addition, the marine cement was homogenous in Mg isotopes, but lacking the fractionation by inorganic carbonate precipitation that is prerequisite for the accurate determination of δ26Mgsw. Furthermore, brachiopod shells had heterogeneous C and Mg isotopes, suggesting a significant vital effect during growth. Overall, the heterogeneous δ26Mg of the Huangjin limestone makes it difficult to reconstruct δ26Mgsw using bulk carbonate/calcareous sediments. Finally, δ26Mgsw was only slightly affected by the faunal composition of carbonate-secreting organisms, even though biogenic carbonate accounts for more than 90% of marine carbonate production in Phanerozoic oceans and there is a wide range (0.2‰–4.8‰) of fractionation during biogenic carbonate formation.
Keywords: Seawater Mg isotopic composition; Limestone; Fossil; Micrite; Cement

Diffusion in garnet: a review by Bowen Li; Jianhua Ge; Baohua Zhang (19-31).
With improvements on high-pressure experimental techniques in multi-anvil apparatus and the development of new analytical tools, major progress has been made on diffusion in garnets in the past several decades. The data obtained in the experimental determination of diffusion coefficients in garnets are of fundamental importance for diffusion modeling and timescales of geological and planetary processes. In this review, we have compiled experimental data on self-diffusion (Si, O, cations), trace element diffusion (Li, Y, Ga, Cr, Sr, REEs), and interdiffusion (Ca–Fe/Mg, Si–Al) in garnet in the light of new advances and recent applications. In addition, some empirical relationships among diffusion parameters (pre-exponential factor D 0, activation energy E, ionic radius) are also discussed. We hope that this review can provide a useful data digest and guide to future study of diffusion in garnet.
Keywords: High temperature and high pressure; Diffusion; Garnet; Point defects

Recently measured high gamma ray values in the Yanchang Formation of the Upper Triassic in the Ordos Basin have added an interesting and controversial twist to the study of the formation’s uranium enrichment and genesis. High uranium and thorium contents in the tuffaceous layer cause high gamma ray values in the Yanchang Formation. Petrographic studies, major elements, rare earth elements (REEs), and trace elements have been systematically analyzed to determine the composition, geochemical environment, and diagenetic processes of the layer. The observed color of the tuffaceous layer in the study area varies from yellow to yellowish brown. The tuff consists of matrix supported with sub-rounded to sub-angular lithic fragments. These lithic fragments probably derived from pre-existing rocks and incorporated into the tuffaceous layer during volcanic eruption. Quartz, plagioclase, and biotite were observed in well to poorly sorted form, in addition to framboidal pyrite and organic laminae. Measured ratios of SiO2/Al2O3 ranged from 3.277 to 6.105 with an average of 3.738. The ratio of TiO2/Al2O3 varied from 0.037 to 0.201 with an average of 0.061, indicating that the sediments of the tuffaceous layer originated from an intermediate magma. REE distribution patterns show sharp negative Eu anomalies, indicating a reducing environment, which is suitable for uranium deposition. A reducing environment was confirmed by black shale in the base of the Yanchang Formation. Such black shale has high organic matter content that can take kerogene from mudstone and provide a reducing environment for uranium enrichment in the tuffaceous layer. Moreover, negative Eu anomalies and the REE patterns indicate a subduction-related volcanic arc environment as the magma source of the tuffaceous layers. High values of Rb, Ba, and Sr might be the result of fluid phase activities; low values of Hf and Eu indicate the involvement of crustal material during diagenesis of the tuff. Discrimination diagrams (Th/Yb vs Ta/Yb, Th/Hf vs Ta/Hf) suggest an active continental margin as the tectonic setting of source volcanoes. Plots of Nb versus Y, Rb versus Y + Nb, TiO2 versus Zr, and Th/Yb versus Nb/Yb of the tuffaceous content point to calc-alkaline continental arc-related magmatism. We concluded that uranium enrichment in the tuffaceous layer was supported by oxidation–reduction.
Keywords: Tuffaceous layer; Gamma ray values; Uranium enrichment; Yanchang Formation; Ordos Basin

The Kukaazi Pb–Zn–Cu–W polymetallic deposit, located in the Western Kunlun orogenic belt, is a newly discovered skarn-type deposit. Ore bodies mainly occur in the forms of lenses and veins along beddings of the Mesoproterozoic metamorphic rocks. Three ore blocks, KI, KII, and KIII, have been outlined in different parts of the Kukaazi deposit in terms of mineral assemblages. The KI ore block is mainly composed of chalcopyrite, scheelite, pyrrhotite, sphalerite, galena and minor pyrite, arsenopyrite, and molybdenite, whereas the other two ore blocks are made up of galena, sphalerite, magnetite and minor arsenopyrite and pyrite. In this study, we obtained a molybdenite isochron Re–Os age of 450.5 ± 6.4 Ma (2σ, MSWD = 0.057) and a scheelite Sm–Nd isochron age of 426 ± 59 Ma (2σ, MSWD = 0.49) for the KI ore block. They are broadly comparable to the ages of granitoid in the region. Scheelite grains from the KI ore block contain high abundances of rare earth elements (REE, 42.0–95.7 ppm) and are enriched in light REE compared to heavy REE, with negative Eu anomalies (δEu = 0.13–0.55). They display similar REE patterns and Sm/Nd ratios to those of the coeval granitoids in the region. Moreover, they also have similar Sr and Nd isotopes [87Sr/86Sr = 0.7107–0.7118; εNd(t) = −4.1 to −4.0] to those of such granitoids, implying that the tungsten-bearing fluids in the Kukaazi deposit probably originate from the granitic magmas. Our results first defined that the Early Paleozoic granitoids could lead to economic Mo–W–(Cu) mineralization at some favorable districts in the Western Kunlun orogenic belt and could be prospecting exploration targets.
Keywords: Molybdenite Re–Os; Scheelite Sm–Nd; REE; Kukaazi Pb–Zn–Cu–W polymetallic deposit; Western Kunlun orogenic belt

Due to the important scientific significance of the interaction between alkaline feldspar and high-temperature and high-pressure fluids. We have conducted a series of autoclave experiments of feldspar dissolution and secondary mineral precipitation in conditions of 250–500 °C, 8–50 MPa, and pH = 3.0 and 5.5. Based on the interaction experiments between alkaline feldspar and fluid of high-temperatures and high-pressures, we get the main results as follows: (1) The law that people have grasped below the critical point about the influence of temperature, pressure, and pH value on the alkaline feldspar dissolution behavior is still held above the critical point. (2) Due to the experimental techniques of autoclave flip 180°—sharp quenching and based on electron microprobe analysis of mineral new formed, theoretical analysis has determined that the new altered minerals distributed on the island dissolution surface of feldspar are products of precipitation on a feldspar surface after saturation of the relative ion concentration in water fluid.
Keywords: Alkaline feldspar; Autoclave; High-temperature and high-pressure experiments

Identification of bacterial fossils in marine source rocks in South China by Baojian Shen; Jianzhong Qin; Borjigin Tenger; Anyang Pan; Yunfeng Yang; Lizeng Bian (68-79).
Based on the results of conventional geochemistry analysis including thin sections and SEM observations, different shapes of bacterial fossils, with size ranging from dozens of nanometers to several microns, were discovered in the low-mature marine source rocks and coal seams in South China, of which the Permian source rocks were dominated by the bacterial fossils derived from symbiotic sulphur bacteria with gypsum, and the Chengkou section in the Cambrian strata were occupied by abundant nanoscale bacterial fossils with rod and bar shapes. In contrast, a large quantity of possible bacterial fossils found in the high-mature Permian, Silurian, and Cambrian source rocks using SEM need to be further explored. Despite this, this study has indicated that bacterial fossils were prevalent in the source rocks, such as mudstone, siliceous rock and gypsum-bearing coal seams in South China, which has been ignored before. It also suggests that the bacterial fossils may play an important role in the formation and accumulation of shale gas in the geological history.
Keywords: South China; Excellent marine source rocks; Bacterial fossil; Sedimentary environment

Timing of mineralization at the Shihu gold deposit in the middle segment of the Taihang Mountain, China by Chao Chen; Shuyin Niu; Fang Wang; Fuxiang Zhang; Qinglian Zhang; Baojun Ma; Aiqun Sun; Jianzhen Zhang; Yaqi Cao; Xiaoqing Zhang (80-89).
The Shihu gold deposit, located in the middle-south section of the core of the Fuping mantle branch structure, is hosted in the Archean Fuping Group and adjacent to the quartz diorite porphyrite. The gold deposit is the only large gold deposit with reserves of more than 30 tons gold discovered in western Hebei Province so far. In order to constrain the timing of mineralization of this ore deposit, this paper focuses on the isotopic dating of zircon and pyrite. Zircons in gold-bearing quartz veins are magmatic in origin and no hydrothermal zircon has been found in such quartz veins, indicating that zircons were derived from the wall rocks. U–Pb ages of zircons fall mainly in the two domains: 2492 ± 82 and 136 ± 4 Ma, respectively, indicative of the contribution of the Fuping-Group TTG gneiss and Yanshanian igneous rocks, respectively. The Re–Os isotopic compositions of pyrites in the gold-bearing quartz veins yield an isochron age of 127 ± 31 Ma. Combined with other dating results, we suggest that the main metallogenic age of the Shihu gold deposit is 120–127 Ma.
Keywords: Mantle branch structure; Shihu gold deposit; Zircon U–Pb dating; Pyrite Re–Os dating; Gold-bearing quartz vein

The mid-subtropical forest is one of the biggest sections of subtropical forest in China and plays a vital role in mitigating climate change by sequestering carbon. Studies have examined carbon storage density (CSD) distribution in temperate forests. However, our knowledge of CSD in subtropical forests is limited. In this study, Jiangle County was selected as a study case to explore geographic variation in CSD. A spatial heterogeneity analysis by semi-variogram revealed that CSD varied at less than the mesoscale (approximately 2000–3000 m). CSD distribution mapped using Kriging regression revealed an increasing trend in CSD from west to east of the study area. Global spatial autocorrelation analysis indicated that CSD was clustered at the village level (at 5% significance). Some areas with local spatial autocorrelation were detected by Anselin Local Moran’s I and Getis-Ord G*. A geographically weighted regression model showed different impacts on the different areas for each determinant. Generally, diameter at breast height, tree height, and stand density had positive correlation with CSD in Jiangle County, but varied substantially in magnitude by location. In contrast, coefficients of elevation and slope ranged from negative to positive. Based on these results, we propose certain measures to increase forest carbon storage, including increasing forested area, improving the quality of the current forests, and promoting reasonable forest management decisions and harvesting strategies. The established CSD model emphasizes the important role of mid-subtropical forest in carbon sequestration and provides useful information for quantifying mid-subtropical forest carbon storage.
Keywords: Carbon storage density; Geostatistics; Mid-subtropical forests; Spatial autocorrelation; Spatial heterogeneity

Application of K-means and PCA approaches to estimation of gold grade in Khooni district (central Iran) by Neda Mahvash Mohammadi; Ardeshir Hezarkhani; Abbas Maghsoudi (102-112).
Grade estimation is an important phase of mining projects, and one that is considered a challenge due in part to the structural complexities in mineral ore deposits. To overcome this challenge, various techniques have been used in the past. This paper introduces an approach for estimating Au ore grades within a mining deposit using k-means and principal component analysis (PCA). The Khooni district was selected as the case study. This region is interesting geologically, in part because it is considered an important gold source. The study area is situated approximately 60 km northeast of the Anarak city and 270 km from Esfahan. Through PCA, we sought to understand the relationship between the elements of gold, arsenic, and antimony. Then, by clustering, the behavior of these elements was investigated. One of the most famous and efficient clustering methods is k-means, based on minimizing the total Euclidean distance from each class center. Using the combined results and characteristics of the cluster centers, the gold grade was determined with a correlation coefficient of 91%. An estimation equation for gold grade was derived based on four parameters: arsenic and antimony content, and length and width of the sampling points. The results demonstrate that this approach is faster and more accurate than existing methodologies for ore grade estimation.
Keywords: K-means method; Clustering; Principal component analysis (PCA); Estimation; Gold; Khooni district

Estimation of soil organic carbon storage and its fractions in a small karst watershed by Zhenming Zhang; Yunchao Zhou; Shijie Wang; Xianfei Huang (113-124).
With few available soil organic carbon (SOC) profiles and the heterogeneity of those that do exist, the estimation of SOC pools in karst areas is highly uncertain. Based on the spatial heterogeneity of SOC content of 23,536 samples in a karst watershed, a modified estimation method was determined for SOC storage that exclusively applies to karst areas. The method is a “soil-type method” based on revised calculation indexes for SOC storage. In the present study, the organic carbon contents of different soil types varied greatly, but generally decreased with increasing soil depth. The organic carbon content decreased nearly linearly to a depth of 0–50 cm and then varied at depths of 50–100 cm. Because of the large spatial variability in the karst area, we were able to determine that influences of the different indexes on the estimation of SOC storage decreased as follows: soil thickness > boulder content > rock fragment content > SOC content > bulk density. Using the modified formula, the SOC content in the Houzhai watershed in Puding was estimated to range from 3.53 to 5.44 kg m−2, with an average value of 1.24 kg m−2 to a depth of 20 cm, and from 4.44 to 14.50 kg m−2, with an average value of 12.12 kg m−2 to a depth of 100 cm. The total SOC content was estimated at 5.39 × 105 t.
Keywords: Bare rock rate; Estimation method; Soil organic carbon storage; Small watershed; Karst

The effect of zinc (Zn) deficiency and excessive bicarbonate on the allocation and exudation of organic acids in plant organs (root, stem, and leaf) and root exudates of two Moraceae plants (Broussonetia papyrifera and Morus alba) were investigated. Two Moraceae plants were hydroponically grown and cultured in nutrient solution in four different treatments with 0.02 mM Zn or no Zn, combined with no or 10 mM bicarbonate. The variations of organic acids in different plant organs were similar to those of root exudates in the four treatments except B. papyrifera, which was in a treatment that was a combination of 0.02 mM Zn and no bicarbonate. The response characteristics in the production, translocation, and allocation of organic acids in the plant organs and root exudates varied with species and treatments. Organic acids in plant organs and root exudates increased under Zn-deficient conditions, excessive bicarbonate, or both. An increase of organic acids in the leaves resulted in an increase of root-exuded organic acids. B. papyrifera translocated more oxalate and citrate from the roots to the rhizosphere than M. alba under the dual influence of 10 mM bicarbonate and Zn deficiency. Organic acids of leaves may be derived from dark respiration and photorespiration. By comparison, organic acids in stems, roots, and root exudates may be derived from dark respiration and organic acid translocation from the leaves. These results provide evidence for the selective adaptation of plants to environments with low Zn levels or high bicarbonate levels such as a karst ecosystem.
Keywords: Adaptation; Excessive bicarbonate; Organic acids; Organs; Root exudates; Zn deficiency

Elemental characteristics and paleoenvironment reconstruction: a case study of the Triassic lacustrine Zhangjiatan oil shale, southern Ordos Basin, China by Delu Li; Rongxi Li; Zengwu Zhu; Xiaoli Wu; Futian Liu; Bangsheng Zhao; Jinghua Cheng; Baoping Wang (134-150).
Using trace elements to reconstruct paleoenvironment is a current hot topic in geochemistry. Through analytical tests of oil yield, ash yield, calorific value, total sulfur, major elements, trace elements, and X-ray diffraction, the quality, mineral content, occurrence mode of elements, and paleoenvironment of the Zhangjiatan oil shale of the Triassic Yanchang Formation in the southern Ordos Basin were studied. The analyses revealed relatively high oil yield (average 6.63%) and medium quality. The mineral content in the oil shale was mainly clay minerals, quartz, feldspar, and pyrite; an illite–smectite mixed layer comprised the major proportion of clay minerals. Compared with marine oil shale in China, the Zhangjiatan oil shale had higher contents of quartz, feldspar, and clay minerals, and lower calcite content. Silica was mainly in quartz and Fe was associated with organic matter, which is different from marine oil shale. The form of calcium varied. Cluster analyses indicated that Fe, Cu, U, V, Zn, As, Cs, Cd, Mo, Ga, Pb, Co, Ni, Cr, Sc, P, and Mn are associated with organic matter while Ca, Na, Sr, Ba, Si, Zr, K, Al, B, Mg, and Ti are mostly terrigenous. Sr/Cu, Ba/Al, V/(V + Ni), U/Th, AU, and δU of oil shale samples suggest the paleoclimate was warm and humid, paleoproductivity of the lake was relatively high during deposition of the shale—which mainly occurred in fresh water—and the paleo-redox condition was dominated by reducing conditions. Fe/Ti ratios of the oil shale samples suggest clear hydrothermal influence in the eastern portion of the study area and less conspicuous hydrothermal influence in the western portion.
Keywords: Trace elements; Occurrence mode; Paleoenvironment; Zhangjiatan oil shale; Yanchang Formation; Ordos Basin

Erratum to: The oceanic cycles of the transition metals and their isotopes by Derek Vance; Corey Archer; Susan H. Little; Michael Köbberich; Gregory F. de Souza (151-151).