Non-traditional Stable Isotopes Research Articles

Ca–Zn isotope fractionation during fluid–rock interaction in subduction zones and its implication for deep carbon cycle

Subducting slabs transport Earth's surface carbon into the deep mantle, with a portion of this carbon potentially recycled through volcanic eruptions at mid-ocean ridges or ocean islands. Non-traditional stable isotopes such as calcium (Ca) and zinc (Zn) are increasingly used to trace this deep carbon cycle. However, the potential for Ca and Zn isotope fractionation in the subduction zone, critical for the successful application of these tracers, remains insufficiently explored. In this study, we investigate high-pressure carbonated metamafic rocks and enclosed vein systems from a Paleo-oceanic subduction complex (SW Tianshan) to explore the possible fractionation of Ca and Zn isotope during subduction-related metamorphism and fluid–rock interaction. The δ44/40Ca (0.77 ‰–0.90 ‰) and δ66Zn isotope compositions (0.20 ‰–0.39 ‰) of greenschist-, blueschist- and eclogite-facies metabasites are consistent with their protoliths (OIBs and MORBs). We observe no systematic fractionation of either Ca and Zn isotopes across prograde metamorphism and associated dehydration. However, the precipitation of carbonate in surrounding rock along fluid pathways leads to an increase in the δ44/40Ca of residual fluids (>0.90 ‰). More significantly, we find detectable Zn isotope fractionation (ΔA-H = ẟ66Znaltered - ẟ66Znhost of 0.06–0.10 ‰) during fluid-mediated metasomatism of some blueschists/eclogites. Light Zn isotopes are preferentially released into the infiltrating fluid, resulting in an elevated δ66Zn isotope composition in the immediate carbonated eclogites along the vein. The modified slab fluids during migration are likely charactered by heavy δ44/40Ca and light δ66Zn compositions, which may play a crucial role in determining the low δ66Zn values found in some arc lavas. However, the MORB-like δ44/40Ca compositions observed in global arc magmatic rocks suggest that the slab-released Ca (possibly along with some carbon) is probably sequestered and stored along the migration path of the fluid, thereby hindering the slab–arc carbon recycling. Our study emphasizes that intraslab fluid–rock interaction results in similar δ44/40Ca and δ66Zn signature in carbonate-bearing eclogites compared to sedimentary carbonates. Consequently, deeply subducted carbonate-bearing eclogites –not necessarily sedimentary carbonates– might carry light δ44/40Ca and heavy δ66Zn signatures into the deep mantle, potentially influencing the corresponding Ca-Zn isotope compositions of some mantle-derived basalts.

Cd–Pb isotopic characteristics within the Hehuashan carbonate-hosted Pb–Zn deposit, Middle-Lower Yangtze River Metallogenic Belt: Constraints for ore-forming metal sources and implications for exploration

The Hehuashan carbonate-hosted Pb–Zn deposit is a large-scale deposit situated in the Middle-Lower Yangtze-River Metallogenic Belt (MLYRMB) in China. It contains 0.99 million tons of Zn at an average grade of 1.5 % and 0.41 million tons of Pb at an average grade at 1.9 %, accompanied by critical metals of Cd and Ga. The ores are mainly composed of breccia-type and vein-type in the deposit. Though previous chemical compositions of sphalerite showed that Cd is enriched in both two types of mineralization and the sulfide sulfur isotopes research showed that the reduced sulfur is derived from the marine sulfate reduction, the source of ore-forming metals is still unclear. In this research, we studied the non-traditional stable isotope of Cd and the radioactive isotope Pb of the Hehuashan deposit to discuss the ore-forming metal sources and provide genesis constraints to the Hehuashan Pb–Zn deposit. The sphalerite Cd isotopic compositions are relatively concentrated but the Zn/Cd ratios are scattered in the Hehuashan deposit, of which the early-stage sphalerite δ114/110Cd values ranged from 0.21 ‰ to 0.30 ‰ with an outlier of 0.09 ‰, mean of 0.22 ‰ and a wide range of Zn/Cd ratios (78 to 430), and the late-stage sphalerite δ114/110Cd values ranged from 0.09 ‰ to 0.15 ‰ with two outliers of −0.05 ‰ and 0.52 ‰, mean of 0.17 ‰ with also a wide range of Zn/Cd ratios (50 to 286), both stages of Cd isotopic compositions are overlapped with the ranges of diorite and OIB & MORB, implying the Cd is might be derived from the dioritic intrusions of the Hehuashan deposit district, and the varied Zn/Cd ratios imply that the limestone also provided some of ore-forming metals to the both two ore-forming stages. Additionally, the Pb isotopic compositions of galena in the two mineralization stages exhibit a concentrated range (206Pb/204Pb = 18.2806 – 18.4190, 207Pb/204Pb = 15.6262 – 15.6484, and 208Pb/204Pb = 38.5710 – 38.6529) and all the Pb isotopic data points of the Hehuashan deposit are plotted in the right-hand side of the geochron and the overlapped field of marine sediments, Tongling dioritic intrusions, and Lower Triassic limestones in the Tongling area in the diagrams of (207Pb/204Pb)i vs. (206/204Pb)i and in the field (208Pb/204Pb)i vs. (206/204Pb)i, implying that the Pb is mainly derived from the magma of dioritic intrusions and marine sediments. Subsequently, the sulfide Cd–Pb isotopic compositions show that the ore-forming metals in the Hehuashan deposit are mainly originated from the dioritic intrusions and marine sediments. The plots of deposit genesis classification show that the Cd isotopic compositions in the Hehuashan deposit are unsuitable to the plots of δ114/110Cd vs. Zn/Cd ratios, but imply the metals were derived from multi sources. Finally, the Cd-Pb studies of the Hehaushan Pb–Zn deposit show that the earlier Lower Triassic carbonate formations and its contact with dioritic rocks should be ideal exploration targets for Pb–Zn and associated Cd sources in the Tongling mining area.

Mg-Ca-Fe isotopes of post-collisional magmatic rocks record the crust-mantle interaction processes beneath southern Tibet

The non-traditional Mg, Ca and Fe isotopes have proven to be useful tools for investigating the petrogenesis of the mantle- and crust-derived rocks. Individual non-traditional isotopes in continental basalts are well-studied, particularly in subduction settings. In contrast, there is a significant lack of comprehensive research on various non-traditional stable isotopes related to magmatic processes within continental collision zones, especially during post-collisional stage. To address this knowledge gap, this study presents stable Mg-Ca-Fe isotopic data for the Miocene post-collisional magmatic rocks including ultrapotassic, potassic, and adakitic rocks from the Lhasa Terrane in southern Tibet. The ultrapotassic rocks exhibit slightly lower δ26Mg (−0.28 ± 0.07‰, 2SD, n = 18) and significantly lower δ44/40Ca (0.69 ± 0.03‰, 2SD, n = 18) values than the depleted mantle. The high CaO/Al2O3 and CaO/TiO2 ratios of the ultrapotassic rocks are typical characteristics of carbonate metasomatism, suggesting that the light Mg and Ca isotopic composition may be attributed to the involvement of recycled Ca-rich sedimentary carbonate in the mantle source. Additionally, these ultrapotassic rocks display δ56Fe values (0.026–0.163‰, 2SD, n = 18) ranging from the normal peridotite mantle to much higher values, suggesting a likely origin from a pyroxenite-bearing lithospheric mantle source. These findings imply that subducted oceanic crust and overlying Ca-rich sediments plausibly account for the formation of a mantle source characterized by distinctive Mg-Ca-Fe isotope compositions. The adakitic rocks exhibit the highest δ26Mg (−0.13 ± 0.10‰, 2SD, n = 15) and δ56Fe (up to 0.304‰) values, along with the lowest δ44/40Ca values (0.60 ± 0.07‰, 2SE, n = 15) among these post-collisional magmatic rocks. They also demonstrate strong correlations between δ56Fe and (Gd/Lu)N ratios, indicating a significant role of garnet in their source, consistent with their origin from the thickened lower crust associated with the collision between India and Asia continents. Given the consistent δ56Fe values (0.102 ± 0.067‰, 2SD, n = 5) observed in the adakitic rocks from the western Lhasa Terrane, we posit that it reflects the Fe isotopic composition of the thickened lower crust in southern Tibet. The potassic rocks display lighter Ca isotopes (δ44/40Ca = 0.67 ± 0.03‰, 2SE, n = 5) than the mantle, consistent with a carbonate metasomatized source. They exhibit varying δ26Mg (−0.31 ± 0.07‰ to −0.04 ± 0.07‰, 2SD) and relatively uniform δ56Fe (0.186 ± 0.051‰, 2SE, n = 6) values, falling within the range of nearly contemporaneous ultrapotassic and adakitic rocks. This suggests that potassic rocks may be formed through the mixing of mantle materials resembling ultrapotassic rocks and thickened crustal components resembling adakitic rocks in the lower crust. Building upon these findings, we propose that the distinctive geochemical characteristics, as well as the spatial and temporal distribution of post-collisional magmatic rocks in southern Tibet, are the outcome of partial melting within a carbonated pyroxenite-bearing lithospheric mantle, coupled with the involvement of thickened crust and their subsequent interactions.

Fe–Cu Isotope Characteristics and Geological Significance of the Yushui Seafloor Massive Sulfide Deposit in the Late Paleozoic Marine Depression, Eastern Guangdong Province

The Yong’an-Meixian Late Paleozoic Hercynian depression, located in western Fujian-eastern Guangdong, is an important metallogenic belt in China. The Yushui copper-polymetallic massive sulfide deposit from the middle part of the depression, with extremely high copper grades, has attracted considerable attention and research interest from geologists for years. In most previous research, the ore-forming material source and metallogenic process were inferred from indirect evidence (i.e., using H-O-C-S isotopic systematics as geochemical tracers). In this paper, the ore-forming process of the Yushui deposit has been studied directly by using nontraditional stable (Fe–Cu) isotopes for the first time, providing new evidence for the genesis of this deposit. The results show that there is a relatively negative Fe-Cu isotopic composition in the Yushui deposit, with δ56Fe values ranging from −0.519 to −1.063‰ and δ65Cu values ranging from −1.539 to −1.609‰, respectively. The fractionation of Fe isotopes is primarily attributed to hydrothermal leaching of the basement strata by ore-forming fluids, along with rapid precipitation of sulfides during the ore-forming process. On the other hand, the fractionation of Cu isotopes is probably controlled by the relatively low temperature of ore formation, sulfide precipitation and the involvement of organic matter in mineralization. Combining our findings with previous studies, the ore-forming materials of the Yushui deposit are likely derived from the basement ore-bearing strata (pre-Devonian strata) through leaching by hydrothermal fluids. Moreover, some of the ore bodies might have been locally overprinted by late-stage hydrothermal reworking and alteration.

The mobilization of boron and lithium in the hydrothermal system of the ∼3.48 Ga Dresser caldera: A stable isotope perspective

Voluminous hydrothermal circulation in the ∼3.48 Ga Dresser caldera produced zoned alteration haloes around major fluid pathways. Specifically, in the North Star Basalt (the footwall) hydrothermal alteration decreases with increasing distance from the margins of hydrothermal silica±barite veins, changing from argillic (i.e., kaolinite-quartz) to phyllic (i.e., illite-quartz), and then to either propylitic (i.e., chlorite-albite-epidote) or actinolitic (i.e., actinolite-albite-chlorite-epidote) assemblages at distal positions. This alteration series developed through hydrolysis reactions at decreasing acidic conditions, which promoted variable degrees of mobilization of major and trace elements in the hydrothermal fluids.In this study, we characterize the B and Li concentrations and the relative stable isotope ratios of the altered North Star Basalt to provide new insights into the hydrothermal processes that generated these complex alteration patterns. In particular, we focus on the magnitude and timing of the inputs from different fluid reservoirs, the mobilization of B and Li in the hydrothermal system of the Dresser caldera and their influence on the near-surface environment where ancient stromatolites were forming.Actinolitic and propylitic samples have homogeneous δ11B and δ7Li values (−17 to −15‰ and +1 to +3‰, respectively) that are associated with lower B and Li concentrations in actinolitic (4 to 11 ppm and 46 to 128 ppm, respectively) relative to propylitic samples (9 to 25 ppm and 176 to 305 ppm for B and Li, respectively). This pattern suggests that at least the propylitic assemblage interacted with alteration fluids of largely magmatic origin, thus excluding the possibility of an early seawater contributions to the hydrothermal system. Conversely, phyllic samples have distinctly higher B contents (57 to 99 ppm) and δ7Li values (+7 to +8‰), but have much lower δ11B values (−19 to −28‰) and Li contents (5 to 6 ppm) relative to actinolitic and propylitic samples. We argue that these striking differences are attributable to mineralogical and temperature controls that promoted the preferential removal of 6Li during chlorite dissolution and incorporation of 10B into illite. Furthermore, the highly negative δ11B values in phyllic samples suggest that the additional B incorporated into the altered North Star Basalt originated from the magma chamber underlying the Dresser caldera rather than from seawater or other crustal sources. The most intensely altered (argillic) samples have moderate B and Li contents (2 to 43 ppm and 41 to 71 ppm, respectively) and highly variable δ11B and δ7Li values (−24 to −0.4‰ and −10 to +11‰, respectively). These signatures are interpreted to represent the input of ‘external’ fluids into the upper portions of the hydrothermal system during periodic crack-seal events that allowed the influx of restricted amounts of seawater and, possibly, meteoric fluids.Overall, this study provides a novel non-traditional stable isotope perspective on the evolution of the hydrothermal system of the Dresser caldera that adds richness to our understanding of this complex environment. Both B and Li stable isotopes support a prominent magmatic contribution to the hydrothermal fluid budget, reinforcing the interpretation of a hot-spring origin of the tourmaline-bearing layers associated with the stromatolites of the North Pole Chert.

Geochemical behavior of stable strontium isotopes during continental weathering process: A review

Continental weathering, an important geological process that affects the formation and evolution of the earth, involves the interaction of matter and energy among the lithosphere, atmosphere, hydrosphere, and biosphere. Stable Sr isotope (δ88/86Sr) is a novel non-traditional stable isotope. It has been widely discussed in tracing continental weathering, studying marine Sr cycle, and analyzing biogeochemical behavior in recent years. Its combination with 87Sr/86Sr can indicate the source of Sr and the mass fractionation of geological processes, which has incomparable advantages over other isotopic systems, such as Li, Mg, and Ba. However, owing to the small mass difference (2%) between 86Sr and 88Sr, fractionation is not significant, which makes the measurement of the ratio δ88/86Sr difficult and limits its application to trace continental weathering.In this study, major developments and challenges in using stable Sr isotopes to trace continental weathering are reviewed, when considering high-precision testing methods, characteristics of δ88/86Sr in natural reservoirs, and geochemical behaviors. The high-precision measurement methods currently used for stable Sr isotopes mainly include multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) and thermal ionization mass spectrometry (TIMS), both of which involve chemical purification by a cation exchange column or Sr specific resin, coupled with various methods for quality discrimination correction. The present analytical precision for the determination of δ88/86Sr in geological samples is 0.02‰ ∼ 0.08‰. The δ88/86Sr varies widely in natural reservoirs. In particular, the range of δ88/86Sr values in extraterrestrial reservoirs, the biosphere, the lithosphere, and the hydrosphere are -1.73‰ to +0.66‰, -0.87‰ to +0.85‰, -0.20‰ to +0.53‰ and -0.45‰ to +0.66‰, respectively. Stable Sr isotope fractionation occurs in the processes of differential dissolution of primary minerals (Δ88/86Sr = -0.13‰), formation and adsorption of secondary minerals (Δ88/86Sr = -0.15‰), precipitation of carbonate (Δ88/86Sr = -0.20‰), and biological processes (Δ88/86Sr = -0.15‰), which causes the δ88/86Sr in fluid (solid) phase to δ88/86Sr increases (decrease). Previous research on the fractionation mechanisms and constraint conditions of stable Sr isotopes during continental weathering is insufficient. Thus, promoting a wide application of stable Sr isotopes to trace continental weathering through the combination of field profiles, laboratory experiments and theoretical calculation is urgently warranted.

Exploring diet shifts and ecology in modern sharks using calcium isotopes and trace metal records of their teeth.

Sharks occupy all living environments of the marine realm as well as some freshwater systems. They display varied and flexible feeding behaviours, but understanding their diet remains challenging due to their elusive ecology and the invasiveness of stomach content analyses in regard of their threatened status. As a potential alternative, we discuss the variability in δ44/42 Ca values recorded in the tooth enamel of size-graded individuals belonging to three species of large sharks with distinct diets (Isurus oxyrinchus, Hexanchus griseus and Carcharodon carcharias). The preliminary results highlight shifts in diet linked to ontogeny (I. oxyrinchus and H. griseus) and spatial distribution (C. carcharias) characterizing feeding behaviour in these species at individual and population level. These outcomes agree with the results of traditional stomach analyses supporting that nontraditional stable isotopes thus represent new perspectives for the study of modern and extinct shark ecology. In addition, for the first time, the Sr/Ca elemental ratios measured in H. griseus reflect sexual differences that could be interpreted in terms of spatial segregation or physiological heterogeneities.

COSMO: Double spike optimization for sample-limited analyses of isotopically anomalous materials

The double spike (DS) technique is the gold standard by which high-precision and high-accuracy mass-dependent isotope fractionations are quantified, and has played a critical role in the recent development of numerous non-traditional stable isotope systems. The democratization of the technique is in great part due to the availability of the so-called ‘DS toolbox’, a software suite that allows for the straightforward identification of optimal DS compositions. As new applications for DS measurements arise, some additional considerations must be taken into account in deciding on an optimal double spike. In particular, sample-limited investigations of combined mass-dependent and independent isotope effects (e.g., in Early Solar System materials) present an additional challenge in determining optimal spikes.Here, we describe the cosmo software package, which specifically addresses this upcoming need in cosmochemistry/isotope geochemistry to optimize DS measurements for small samples with mass-independent anomalies (e.g., nucleosynthetic anomalies, radiogenic ingrowth). These measurements are subject to additional errors from a complementary unspiked measurement, which is necessary to properly quantify mass-dependent isotope effects during the DS inversion. The software package addresses this additional complication by offering users the ability to (i) specify additional parameters relevant to practical sample-limited analyses (e.g., instrumental transmission efficiency, number of cycles of analyses), (ii) optimize how a sample is split between unspiked and spiked measurements, and (iii) identify the internal normalization scheme that leads to the lowest uncertainty on the mass-dependent fractionation factor, α, and/or the isotope anomalies, ε. These additional functionalities were designed to operate within the DS toolbox framework and expands its applicability to a wider array of samples (i.e., extraterrestrial samples) and measurement scenarios to push the limits of new and improved instrumentation.

Multi-collector Inductively Coupled Plasma Mass Spectrometry: New Developments and Basic Concepts for High-precision Measurements of Mass-dependent Isotope Signatures

Due to the development of multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) around 25 years ago, the isotopes of a large range of elements (masses from Li to U) are now analyzed with high enough precision and accuracy to resolve subtle natural variations. These so-called 'non-traditional stable isotope systems' opened many new research avenues and are applied at an increasing rate in research and industry projects and in a broad range of different disciplines, including archeology, biology, physics, cosmochemistry and geology. Here, we briefly summarize the most basic concepts of MC-ICP-MS, introduce new technical developments and address important points on how to acquire accurate high-precision isotope measurements of non-traditional stable isotopes.

Mercury Isotopes in Shale Gas From Wufeng-Longmaxi Shale Formation of Sichuan Basin, Southern China: A Preliminary Investigation

A series of investigations have been conducted concerning the study of traditional stable isotopes and rare gas stable isotopes in natural gas. However, little is known regarding non-traditional stable isotopes of mercury in natural gas, especially in the development and utilization of shale gas in recent years. In fact, the presence of mercury in natural gas (including shale gas) provides a basis for research on mercury isotopes. Mercury was extracted from shale gas at the Wufeng-Longmaxi Formation in the YS108 block of the Zhaotong National shale gas demonstration area in the Sichuan Basin by using an acid potassium permanganate solution, followed by the analysis of mercury content and stable isotope composition. The mercury content in the marine shale gas at the Wufeng-Longmaxi Formation ranged from 171 to 2,906 ng/m3, with an average of 1,551.08 ± 787.08 ng/m3 (n = 37, 1 SD). The Δ199Hg values of mercury stable isotopes range from 02‰ to 0.39‰, with an average of 22‰ ± 0.08‰ (n = 37, 1 SD); the δ202Hg values range from −1.68‰ to −0.04‰, with an average of −0.87‰ ± 0.31‰ (n = 37, 1 SD), which are significantly different from the Δ199Hg and δ202Hg information of coalbed gas, but similar to the Δ199Hg and δ202Hg information of terrestrial oil-type gas and the Δ199Hg in the main hydrocarbon-forming organic matter of lower organisms such as algae (t-test, p > 0.05). This indicates that terrestrial target strata with abundant algae or strata with positive Δ199Hg are the target strata for the exploration of terrestrial oil and gas.

Diffusive fractionation of K isotopes in molten basalts

The 41K/39K isotope ratio profiles in diffusion couple experiments have been measured by Secondary Ion Mass Spectrometry (SIMS). One goal of this research is to push the use of SIMS in measuring non-traditional stable isotope ratios. The second, more important goal, is to quantify for the first time diffusive fractionation of K isotopes and its dependence on temperature and different counter-diffusion elements. The data show that the precision in a single day-night session of SIMS measurements can reach 0.2‰ (1σ hereafter) with effort, and the long-term accuracy without using any isotope ratio standard is about 2.5‰. At an initial concentration contrast (ratio of high concentration to low concentration) of about 70 in a diffusion couple, the total 41K/39K fractionation (maximum minus minimum) is about 10‰. The 41K/39K ratio profiles were initially fit by assuming constant effective binary diffusivity (D) of K2O, which led to minor misfits and more importantly, to large disagreement between diffusivities based on chemical diffusion and isotope diffusion profiles. It was found that D for K2O varies with its concentration. The profiles were then fit by assuming D for K2O increases exponentially with K2O concentration, which resolved the misfits and disagreements. That is, combining concentration and isotope ratio profiles enables distinguishing subtle concentration-dependent diffusivity. For the SiO2-K2O interdiffusion couples, the empirical diffusive isotope fractionation parameter β increases slightly with temperature from 0.104 ± 0.003 at 1260°C to 0.116 ± 0.003 at 1500°C. For the MgO-K2O interdiffusion couples, excluding an outlier point at 1260°C, β increases from 0.090 ± 0.005 at 1350°C to 0.100 ± 0.003 at 1500°C. These β values are roughly consistent with a diffusion mechanism of NaKO exchanging with SiO2 in the SiO2-K2O interdiffusion couples, or NaKO exchanging with MgO in the MgO-K2O interdiffusion couples. Applying the obtained β value to model diffusive isotope fractionation in nature, diffusive K isotope fractionation during magma mixing is expected to be large enough to be resolvable by SIMS. When collecting samples for K-Ar or K-Ca dating, it is important to correct for the effect of possible K isotope fractionation by measuring K isotope ratio in the sample. When diffusive and convective-diffusive modeling was applied to evaluate isotope fractionation during volatile loss through diffusion and evaporation, it is found that a loss of 80% potassium would lead to an increase of δ41K by 6.3‰ to 8.9‰, more than 10 times greater than the enrichment of δ41K in the Moon relative to the Earth. Hence, the depletion of K and the associated enrichment of δ41K in the Moon relative to the Earth are unlikely diffusion controlled.

Early Cambrian highly metalliferous black shale in South China: Cu and Zn isotopes and a short review of other non-traditional stable isotopes

Early Cambrian black shales on the Yangtze Platform host a regionally distributed highly metalliferous sulfide-rich carbonaceous unit which has been the subject of extensive debate. This marker unit, with a few centimeters or tens of centimeters in thickness, displays extreme enrichment in Mo and Ni (wt% range), and in a broad spectrum of other metals such as As, Au, PGE, Re, Cu, Zn, Cd, Ag, Sb, Se, Tl, and Hg, and occurs discontinuously along the western passive margin of the Yangtze Platform. It grades laterally in stratigraphically equivalent meter-thick vanadium-rich shale and tens-of-meter-thick sapropelite (combustible shale). New Cu and Zn isotope data, combined with existing Cd, Cr, Ni, Mo, Hg, and Se isotope and other chemical data, allow to attempt an integrated view on the formation of this intriguing unit of hyper-enriched metalliferous black shale. The authigenic Cu enrichment in the 1000-ppm range has produced no or little Cu isotope fractionation (0.03 ± 0.26 ‰ δ65Cu) beyond the lithogenic background. Heavy zinc and cadmium isotope enrichment in the sulfidic samples (1.11 ± 0.18 ‰ δ66Zn, 0.31 ± 0.10 ‰ δ114Cd) is controlled by sulfide fractionation and contrasts with V-rich and barren shale (0.60 ± 0.18 ‰ δ66Zn, 0.00 ± 0.14 ‰ δ114Cd). The distinctly negative Ni isotope composition of the metalliferous unit (−0.84 ± 0.05 ‰ δ60Ni) with Ni in the percent range has been interpreted as due to hydrothermal activity related to the leaching of mafic rocks and their sulfides. Sorption processes (Fe-oxyhydroxides) and redox cycling in the water column and the bottom sediment with microbial activity could be an alternative interpretation. The extreme metal enrichment can be understood as due to a process chain, from high biological productivity in the oxic photic zone to sulfate reduction in the deeper sulfidic water column and upper sediment layer. Key to the metal enrichment seems to be extremely low clastic sedimentation and advanced carbon destruction by anaerobic oxidation. Hydrothermal input of basinal brines along the rifted margin of the Yangtze Platform was likely a part of this scenario.

Isotopic geochemical characteristics and identification indexes of shale gas hydraulic fracturing flowback/produced water

China is rich in shale gas resources, which are mainly distributed in densely populated southern marine carbonate areas. The geological and surface conditions are complex, the ecological environment is fragile, and water resources are scarce or unevenly distributed. Therefore, large-scale fracturing mining has high pressure of water resources utilization and serious risk of water environment pollution. In this paper, the geochemical characteristics of traditional and non-traditional stable isotopes such as hydrogen, oxygen, boron, lithium, strontium in shale gas hydraulic fracturing flowback/produced water (FP water) were comprehensively analyzed. The results show that, the hydrogen and oxygen isotopic composition of the FP water in Sichuan Basin, China has similar evolution trend with the produced water of conventional wells from Cambrian, Permian and Triassic Xujiahe, Jialingjiang and Leikoupo formations, but different from that of the Sinian conventional produced water. It indicates that the FP water in Sichuan Basin is a mixture of fracturing injected fluid and formation brine retained in Silurian shale. The saline end member is close to the formation water of Cambrian, but with higher δ11B values. The FP water in Sichuan Basin has δ11B values close to that of the Marcellus FP water, and both are derived from the evaporated seawater. The δ11B values of FP water in Sichuan Basin have overlap with that of the conventional produced water from different strata, so it can not be precisely distinguished. However, the δ11B and B/Cl values of the FP water in Sichuan Basin can be clearly distinguished from the river and the FP water from non-marine facies shale in Qaidam Basin. The FP water in Sichuan Basin has slightly higher δ7Li values than that of the Marcellus FP water, but has overlap with that of the Yangtze River. The average value of 87Sr/86Sr of FP water is 0.7197 in Weiyuan and 0.7193 in Changning, which is much higher than that of the produced water from conventional wells in different formations. This is because the Silurian shale is affected by terrestrial siliceous sediments and the underlying Sr-rich fluids. As a result, 87Sr/86Sr values measured in the Silurian strata in southern Sichuan Basin are high, which makes 87Sr/86Sr values become an effective index to distinguish shale gas fracturing FP water from conventional gas well produced water and shallow groundwater in Sichuan Basin.

Global trends in novel stable isotopes in basalts: Theory and observations

The geochemistry of global mantle melts suggests that both mid-ocean ridge basalts (MORB) and ocean island basalts (OIB) sample lithological and temperature heterogeneities originating in both the upper and lower mantle. Recently, non-traditional stable isotopes have been suggested as a new tool to complement existing tracers of mantle heterogeneity (e.g., major and trace elements, radiogenic isotopes), because mineral- and redox-specific equilibrium stable isotope fractionation effects can link the stable isotope ratios of melts to their source mineralogy and melting degree. Here, we investigate five stable isotope systems (Mg-Ca-Fe-V-Cr) that have shown promise in models or natural samples as tracers of mantle temperature and/or lithological heterogeneity. We use a quantitative model, combining thermodynamically self-consistent mantle melting and equilibrium isotope fractionation models, to explore the behaviour of the isotope ratios of these elements during melting of three mantle lithologies (peridotite, and silica-excess and silica-deficient pyroxenites), responding to changes in mantle mineralogy, oxygen fugacity, temperature and pressure. We find that, given current analytical precision, the stable isotope systems examined here are not predicted to be sensitive to mantle potential temperature variations through equilibrium isotope fractionation processes. By contrast, source lithological heterogeneity is predicted to be detectable in some cases in the stable isotope ratios of erupted basalts, although generally only at proportions of >10% MORB-like pyroxenite in the mantle source, given current analytical precision. Magnesium and Ca stable isotopes show most sensitivity to a garnet-bearing source lithology, and Fe and Cr stable isotopes are potentially sensitive to the presence of MORB-like pyroxenite in the mantle source, although the behaviour of Cr isotopes is comparatively under-constrained and requires further work to be applied with confidence to mantle melts. When comparing the magnitude and direction of predicted equilibrium isotopic fractionation of peridotite and pyroxenite melts to natural MORB and OIB data, we find that aspects of the natural data (including the mean Mg-Ca-Fe-V isotopic composition of MORB, the range of Mg-Ca isotopic compositions seen in MORB data, the mean Mg-Ca-Cr isotopic composition of OIB, and the range of Mg-V-Cr isotopic compositions in OIB data) can be matched by equilibrium isotope fractionation during partial melting of peridotite and pyroxenite sources – with pyroxenite required even for some MORB data. However, even when considering analytical uncertainty on natural sample measurements, the range in stable isotope compositions seen across the global MORB and OIB datasets suggests that kinetic isotope fractionation, or processes modifying the isotopic composition of recycled crustal material such that it is distinct from MORB, may be required to explain all the natural data. We conclude that the five stable isotope systems considered here have potential to be powerful complementary tracers to other geochemical tracers of the source lithology of erupted basalts. However, continued improvements in analytical precision in conjunction with experimental and theoretical predictions of isotopic fractionation between mantle minerals and melts are required before these novel stable isotopes can be unambiguously used to understand source heterogeneity in erupted basalts.

Forming Earth’s Continental Crust: A Nontraditional Stable Isotope Perspective

The formation of continental crust via plate tectonics strongly influences the physical and chemical characteristics of Earth’s surface and may be the key to Earth’s long-term habitability. However, continental crust formation is difficult to observe directly and is even more difficult to trace through time. Nontraditional stable isotopes have yielded significant insights into this process, leading to a new view both of Earth’s earliest continental crust and of what controls modern crustal generation. The stable isotope systems of titanium (Ti), zirconium (Zr), molybdenum (Mo), and thallium (Tl) have proven invaluable. Processes such as fractional crystallization, partial melting, geodynamic setting of magma generation, and magma cooling histories are examples of processes illuminated by these isotope systems.

Hydrogeochemical mineral exploration in deeply weathered terrains: An example from Mumbwa, Zambia

Locating mineral deposits in areas of thick or transported overburden is notoriously difficult. Post-mineral cover is prevalent in many parts of the globe and has led to prospective geological sequences being missed by traditional methods of exploration. Hydrogeochemistry is particularly applicable for the exploration of Iron Oxide Copper Gold (IOCG) deposits because, when compared to larger porphyry or sediment-hosted systems, IOCG deposits tend to be smaller and high-grade with a limited lateral footprint to intersect with grid-drilling; groundwater interactions and ion dispersion tend to produce a much larger anomaly target than regolith geochemistry alone and require fewer samples. As a case study, we examine the hydrogeochemistry of the Kitumba IOCG deposit, located in the Mumbwa district of west-central Zambia. We present physicochemical data (Eh, pH, TDS, conductivity), major and trace element concentrations, and isotopic compositions (δ98Mo, 87Sr/86Sr, and δ65Cu) from groundwaters interacting with the Kitumba deposit and surrounding prospects. A hydrogeochemical footprint of As, Mo, Fe, Mn, and Zn is dispersed from the deposit. Groundwater 87Sr/86Sr values (0.708832 to 0.731807) reflect the mixing in varying proportions of waters that have interacted with distinct lithological endmembers in the Mumbwa area, corresponding to a complicated tectonic and metamorphic history. We report fractionation of 1.34 to 1.60‰ (∆65Cugroundwater – chalcopyrite) between proximal groundwater and primary chalcopyrite, which we postulate may be related to the oxidative dissolution of primary sulfide minerals. The δ98Mo3134 values of groundwaters proximal to known ore bodies are isotopically distinct (−1.08 ± 0.18‰ 2SE to 0.64 ± 0.08‰ 2 SE) from background aquifers (2.08 ± 0.12‰ 2SE). The trace element and isotopic hydrogeochemical patterns described in this study document water-rock and water-deposit interactions and demonstrate the potential of non-traditional stable isotopes to be employed in district-scale reduction of exploration ground and vectoring towards undisturbed ore deposits similar to Kitumba.

Theory and Calculation of Nontraditional Stable Isotope Fractionation

This paper conducts processing on isotope anharmonic effect with molecular dynamics method and Monte Carlo method based on path integration. It introduces the theoretical calculation method of pressure effect, and finally the nuclear volume effect and its theoretical calculation method, stressing that the nuclear volume effect is an important part of isotopic studies of heavy metals in the future. This paper makes an analysis on the equilibrium fractionation theory based on simple harmonic approximation.

Application of molybdenum and thallium isotopes as indicators of paleoredox conditions and genesis of hyper-enriched black shale deposits, Peel River, Yukon, Canada

ABSTRACT Hyper-enriched black shale (HEBS) deposits in northern Yukon, consist of thin (<10 cm), laterally extensive (tens of thousands of km2) stratiform sulfide mineralization layer(s) that are hyper-enriched in Ni, Mo, Zn, platinum group elements, Re, and Au. The genesis of HEBS deposits and the ambient paleoenvironment in which they formed are the subject of vigorous debate. Non-traditional stable isotopes, particularly molybdenum and thallium, are robust paleoredox indicators and we have employed these isotope systems in this study of Yukon HEBS. Systematic sampling and Mo and Tl isotopic analysis of a continuous 200 m stratigraphic section through the Yukon HEBS mineralization and footwall and hanging-wall strata at the Peel River north and south bank showings (spaced five km apart) give δ98Mo –1.24 to –0.53‰ and –8.1 to –5.2 ε-units for the mineralization and –0.70 to 0.60‰ and –6.5 to –2.0 ε-units for the unmineralized strata. These values preclude a hydrothermal origin and strongly suggest that redox processes were responsible for the Yukon HEBS mineralization. The isotopic compositions, together with rare earth element (REE) systematics (REE profile, Y positive anomalies, Ce negative anomalies, and Y/Ho values) and other bulk geochemical redox indicators (Mo, V, Re/Mo, Ni/Co, U/Th, and V/Cr) indicate that the Peel River HEBS mineralization formed because of metal scavenging from seawater in a quiescent, euxinic basinal paleoenvironment.

Non-traditional stable isotope signatures in geological matrices as a tool for interpreting environmental changes – a review

The development of new analytical techniques enabled the precise determination of the expanded set of stable isotopes and provided new insight into the existing geological issues. This review outlines recent studies of non-traditional isotope signatures in geological matrices, summarizing in one place new data for stable isotopes of Ca, Mg, Sr, Li, Ni, Cr, and Cu and their application in the interpretation of environmental processes. Although some of them, such as δ44Ca and δ26Mg, have been previously used to track changes in seawater chemistry throughout geological history, recent studies report their application as geochemical proxies of post-depositional processes. Similarly, isotopic signatures of strontium, previously used in radioactive isotope chronology, and δ7Li, used in tracing plate subduction and crust/mantle material cycling, found a new application in studies of weathering patterns. The use of δ53Cr and δ 65Cu isotope signatures, on the other hand, reflects their fractionation under different redox conditions, whereas δ60Ni, due to its co-precipitation with sulfide species and Fe-Mn phases, is used in interpreting the contributions of different material sources. And while the isotopic signatures of all these elements indicate certain environmental conditions and processes (e.g., post-depositional processes, redox conditions, organic matter input, the contribution of sources, etc.), combining them a more comprehensive insight into the investigated environment can be achieved.

Development of an Automatic Column Chromatography Separation Device for Metal Isotope Analysis Based on Droplet Counting.

A novel, simple, cost-effective, reliable, and practical automatic column chromatography separation device capable of simultaneously purifying samples for radiogenic and non-traditional stable isotope analysis has been developed. The device avoids the use of any pump and features eluent driving by the siphon effect (gravity) and quantitative control by infrared droplet counting. Several factors affecting the control of droplets were investigated, including types and concentrations of eluents and the height of the liquid level. Results showed that accurate dripping of the eluent could be readily achieved by controlling the number of droplets under selected conditions. The separation performance of the device was first demonstrated by the elution of Sr and Cd in synthetic matrix solutions. The recoveries of Sr and Cd samples were better than 87.6 and 95.0%, respectively, and the whole procedure blank was about 0.3 ng for Sr and 0.1 ng for Cd. Finally, the reliability of the device was further validated by the purification of Sr and Cd from different geological reference materials (NIST 2711a, Nod-A-1, BCR-2, and BHVO-2). The determined Cd and Sr isotope values agree well with their reference values within the uncertainty range. All these results clearly demonstrate the reliability and practicability of the proposed device, which provides a promising method for the automated purification of isotope samples.