Global calibration of a novel,branched GDGT-based soil pH proxy

Recently, 6-methyl branched glycerol dialkyl glycerol tetraethers (brGDGTs) were separated from 5-methyl brGDGTs, which are used in brGDGT-based proxies. Here we analyzed brGDGTs in 27 soil samples along the 400 mm isoline of mean annual precipitation in China by using tandem 2D liquid chromatography. The fractional abundance of 6-methyl brGDGTs showed a positive correlation with soil pH, while that of 5-methyl brGDGTs decreased with increasing soil pH. The abundance ratio of 6-/5-methyl brGDGTs, namely the isomerization of branched tetraethers (IBT), was calculated. The correlation of IBT with pH (pH = 6.33 − 1.28 × IBT; R² 0.89; root mean squared error, RMSE, 0.24) was much stronger than that of the traditionally used cyclization index of branched tetraethers (CBT) with pH (R² 0.52; RMSE 0.49) and comparable with that of CBT′ with pH (R² 0.88; RMSE 0.25). Compiling all available data from 319 soil samples resulted in a global calibration: pH = 6.53 − 1.55 × IBT (R² 0.72; RMSE 0.65), which has a better correlation than the CBT_5ME-pH proxy (R² 0.63; RMSE 0.78), but a weaker correlation than the CBT′-pH proxy (R² 0.85; RMSE 0.52). Our result suggests that the IBT is a promising indicator for soil pH, particularly in cases when some compounds in the CBT′ index cannot be determined.     

The 6-methyl branched tetraethers significantly affect the performance of the methylation index (MBT′) in soils from an altitudinal transect at Mount Shennongjia

The methylation index (MBT or MBT′) of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in soils along altitudinal transects of some mountains, e.g. Mount (Mt.) Shennongjia and Mt. Gongga, exhibited no correlation with altitude or mean annual air temperature (MAT) alone. However, a significant correlation between MBT′, cyclization ratio (CBT) of brGDGTs and MAT for each transect could still be found. To investigate the reason, we reanalyzed the brGDGTs in soils from Mt. Shennongjia using an improved liquid chromatography method and examined whether the newly described 6-methyl brGDGTs were the main cause of the large scatter in the correlation between MBT′ and MAT. In contrast to MBT′, the MBT′_5ME, based on 5-methyl brGDGTs alone, correlated significantly with MAT (R² 0.89, p < 0.001) but had no relationship with soil pH. However, MBT′_6ME, based only on 6-methyl brGDGTs, was strongly dependent on soil pH. This suggests that pH dependent 6-methyl brGDGTs introduce large scatter in the correlation between MBT′ and MAT, which is likely to mechanistically explain the poor relationship between MBT′ and MAT, yet good correlation between MBT′, pH and MAT. A series of indices derived from 6-methyl brGDGTs, including IR_IIIa′ and IR_IIa′ (isomer ratio of structures IIIa′ and IIa′, respectively), correlated with soil pH and can be used as new paleo pH indicators to supplement the classic CBT proxy. The tetramethylated brGDGTs with 0–1 cyclopentyl rings (Ia and Ib) were found to comprise unknown isomers, whose abundances also appear to increase with soil pH. A further optimized liquid chromatography method is needed to quantify these new isomers more accurately and to determine the environmental controls on them.     

Distribution of glycerol dialkyl glycerol tetraether lipids along an altitudinal transect on Mt. Xiangpi,NE Qinghai-Tibetan Plateau,China

The distribution of glycerol dialkyl glycerol tetraethers (GDGTs) can reflect continental environmental changes. Recently, the distribution of branched GDGTs (bGDGTs) has been proposed as a novel tool for paleoelevation reconstructions. Here we report the variation in TEX₈₆ (tetraether index of 86 carbon atoms) of isoprenoidal GDGTs (iGDGTs) and MBT (methylation of branched tetraether index) of bGDGTs along an altitudinal transect on Mt. Xiangpi, NE Qinghai-Tibetan Plateau. Both TEX₈₆ and MBT values of surface soils showed significant linear decreases with altitude (TEX₈₆: R² = 0.65; n = 50; MBT: R² = 0.69; n = 24). We suggest that the apparent relationships between the two indices and altitude may be related to temperature. Our preliminary investigation suggests that the TEX₈₆ index can potentially be applied as a paleoelevation indicator in addition to the MBT index on the Qinghai-Tibetan Plateau.     

Variability of tetraether lipids in Yellow River-dominated continental margin during the past eight decades: Implications for organic matter sources and river channel shifts

Glycerol dialkyl glycerol tetraethers (GDGTs) and bulk organic geochemical parameters were examined for a short core from the Bohai Sea, a Yellow River-dominated continental margin. A three end member mixing model using branched/isoprenoid tetraethers (BIT) index, δ¹³C and C/N shows that the average fractions of soil, marine and plant organic matter (OM) during the period of 1933–2011 are 67.7% (38–92%), 26.1% (0–58%) and 6.2% (0–23%), respectively. Abrupt changes of sedimentary OM compositions around 1953, 1976 and 1996 are synchronous with the Yellow River mouth relocations. The BIT index values (0.33–0.80) present a stronger correlation with crenarchaeol abundance (R² = 0.88) than branched GDGTs abundance (R² = 0.27), suggesting that variations of marine Thaumarchaeota abundance rather than soil OM inputs is the first order factor controlling the BIT index values, although this proxy has been widely used for soil OM. The comparison between the BIT index, nutrient status and historical Yellow River sediment load indicates that the high sensitivity of the BIT index to the Yellow River channel shifts cannot be explained by a nutrient stimulation mechanism, but instead is likely caused by the restriction of Thaumarchaeota growth in highly turbid water due to the enormous sediment inputs from Yellow River. Our study demonstrates that local conditions should be considered when applying the BIT index as an environmental proxy.     

Intermediate sulfidation epithermal gold-base metal deposits in Tertiary subaerial volcanic rocks,Sahinli/Tespih Dere (Lapseki/Western Turkey)

Gold in the Sahinli and Tespih Dere intermediate sulfidation gold-base metal deposits in Western Turkey occurs in relatively deep epithermal quartz veins along with base metal minerals which have epithermal textures, including plumose quartz, vug infills, comb and cockade textures and matrix-supported milled breccias. The total sulfide content of the veins in the area is variable ranging from < 1% to 60% and is dominated by pyrite, galena, sphalerite and chalcopyrite. Sphalerite is Fe-poor (0.6 to 1.4 mol% FeS). Minor amounts of Ag-rich tetrahedrite are present. Primary hydrothermal alteration minerals include illite/muscovite, mixed-layer illite/smectite (11.6 Å) and clinochlore towards the east and, alunite, dickite/nacrite and pyrophyllite towards the west at Sahinli; major illite/muscovite and dickite occur at Tespih Dere and Sarioluk, respectively.Fluid inclusions in main-stage quartz at Sahinli are only liquid-rich, with homogenization temperatures ranging from 220 to 322 °C and the majority of T_h values between 250 and 300 °C. Salinity ranges from 4.3 to 6.9 wt.% NaCl equiv. First ice-melting temperatures (T_mf) between ?24.5 and ?19.0 °C indicate that the fluids were dominated by NaCl – H₂O during mineralization. The relatively higher average T_h at the Tespih Dere deposit (295 °C) is attributed to a relatively deeper level of exposure.Calculated δ¹⁸O values indicate that ore-forming hydrothermal fluids in the study area had δ¹⁸O_H2O ranging from + 1.1 to + 9.7‰ (average = 3.8‰), strongly ¹⁸O-enriched compared with present-day hydrothermal meteoric water in the area (δ¹⁸O = ?8.5‰). δD values of fluid inclusions in quartz range from ?58 to ?93‰ and δD values of clay minerals and alunite from ?40 to ?119‰. δD values from intermediate argillic alteration (average = ?68‰) in the study area are very similar to δD values of the present-day local geothermal system (average δD = ?54‰) whereas δD values from advanced-argillic alteration (average δD = ?33‰) are very different from the present-day local geothermal system.The δ³⁴S values in samples from the Sahinli and Tespih Dere deposits average ?2.9‰ for pyrite; ?3.3‰ for chalcopyrite; ?5.4‰ for sphalerite and ?7.6‰ for galena. These data are consistent with derivation of the sulfur from either igneous rocks or possibly from local wallrock.     

Soil n-alkane δD vs. altitude gradients along Mount Gongga, China

The altitude effect on the isotopic composition of precipitation and its application to paleoelevation reconstruction using authigenic or pedogenic minerals have been intensively studied. However, there are still no studies on variations in biomarker δD along altitude transects to investigate its potential as a paleoelevation indicator, although it has been observed that δD of higher plant lipid may record changes in precipitation δD (δD_p). Here, we present δD values of higher plant-derived C₂₇, C₂₉, and C₃₁n-alkanes from surface soil along the eastern slope of Mount Gongga, China with great changes in physical variables and vegetation over a range from 1000 to 4000 m above sea level. The weighted-mean δD values of these n-alkanes (δD_wax) show significant linear correlations with predicted δD_p values (R² = 0.76) with an apparent isotopic enrichment (ε_wax-p) of −137 ± 9‰, indicating that soil δD_wax values track overall δD_p variation along the entire altitudinal transect. Leaf δD_wax is also highly correlated with mountain altitude by a significant quadratic relationship (R² = 0.80). Evapotranspiration is found declining with altitude, potentially lowering δD_wax values at higher elevations. However, this evapotranspiration effect is believed to be largely compensated by the opposing effect of vegetation changes, resulting in less varied ε_wax-p values over the slope transect. This study therefore confirms the potential of using leaf δD_wax to infer paleoelevations, and more generally, to infer the δD of precipitation.     

Can sedimentary leaf waxes record D/H ratios of continental precipitation? Field, model, and experimental assessments

D/H ratios of leaf waxes (δD_wax) derived from terrestrial plants and preserved in lake sediments can provide important information on past continental hydrology. Ideally, δD_wax can be used to reconstruct precipitation D/H ratios (δD_P) which is a well-established paleoclimate proxy. However, many other factors, such as vegetation and relative humidity (RH), also affect δD_wax variation. How the combination of these factors affects sedimentary δD_wax is unclear. Here, we use a transect of 32 lake surface sediments across large gradients of precipitation, relative humidity, and vegetation composition in the southwestern United States to study the natural factors affecting sedimentary δD_wax. δD values of C₂₈n-alkanoic acids show significant correlation with δD_P values (R² = 0.76) with an apparent isotopic enrichment of ∼99 ± 8‰, indicating that sedimentary δD_wax values track overall δD_P variation along the entire transect. Leaf waxes produced by plants grown under controlled conditions (RH = 80%, 60%, 40%) show a small increase in D/H ratios as RH decreases, consistent with prediction from the Craig-Gordon model. However, the isotopic effect of RH on δD_wax along the natural transect is partially countered by the opposing influence of vegetation changes. The correlation between δD_wax and δD_P values is significantly higher (R² = 0.84) in the drier portions of the transect than in the wetter regions (R² = 0.64). This study suggests that D/H ratios of sedimentary leaf waxes can be used as a proxy for precipitation δD variations, with particularly high fidelity in dry regions, although more studies in other regions will be important to further test this proxy.     

Effect of plant life form on relationship between δD values of leaf wax n-alkanes and altitude along Mount Taibai, China

We present δD_wax values from different forms of plants and soils, and δD_sw values from soil water along the northern slope of Mount Taibai, China. The results show a highly negative linear correlation of the δD_wax values for soils with altitude (R² 0.74) and we observed the same correlation for δD_sw values of soil water with altitude (R² 0.68). The δD_wax of living plants behaves like the soil, but does not exhibit a significant linear correlation with altitude (R² 0.11). The δD_wax values of woody plants and grasses also show a similar trend with respect to altitude with significant and no linear correlation, respectively (R² 0.50 for woody plants and 0.17 for grass), which suggest that the “altitude effect” can not be well documented for the δD_wax values of living plants, which may be due to differences in plant type and/or evapotranspiration controlled by the plant microclimate. The ε_wax-sw values of woody plants, grasses and soil show minor fluctuations with altitude. However, the ε_wax-sw and δD_wax values of woody plants are roughly 51‰ and 50‰ more positive, respectively, than those of grasses, suggesting that an “altitude effect” could be documented in the δD_wax of woody plants and grasses, with each responding independently to changes in precipitation along the altitude transect. Additionally, the ε_wax-sw values of soil are relatively constant with altitude, suggesting that the altitudinal change in the proportions between woody plant and grass input to soils will likely change the relationship between the δD_wax values of soil n-alkanes and altitude.     

Late Quaternary behavior of the East African monsoon and the importance of the Congo Air Boundary

Both Atlantic and Indian Ocean climate dynamics exert influence over tropical African hydroclimate, producing complex patterns of convergence and precipitation. To isolate the Indian Ocean influence on African paleohydrology, we analyzed the deuterium/hydrogen ratio of higher plant leaf waxes (δD_wax) in a 25 000-year sediment record from Lake Challa (3° S, 38° E) in the easternmost area of the African tropics. Whereas both the seismic record of inferred lake level fluctuations and the Branched and Isoprenoidal Tetraether (BIT) index proxy record changes in hydrology within the Challa basin, δD_wax, as a proxy for the isotopic composition of precipitation (δD_P) is interpreted as a tracer of large-scale atmospheric circulation that integrates the history of the moisture transported to the Lake Challa area. Specifically, based on modern-day isotope–rainfall relationships, we argue that Lake Challa δD_wax reflects the intensity of East African monsoon circulation. The three hydrological proxy records show generally similar trends for the last 25 000 years, but there are important differences between them, primarily during the middle Holocene. We interpret this deviation of δD_wax from local hydrological history as a decoupling of East African monsoon intensity – which heavily influences the isotopes of precipitation in East Africa today – from rainfall amount in the Challa basin. In combination, the hydrological proxy data from Lake Challa singularly highlight zonal gradients in tropical African climate that occur over a variety of timescales, suggesting that the Congo Air Boundary plays a fundamental role in controlling hydroclimate in the African tropics.     

Constraints on the application of the MBT/CBT palaeothermometer at high latitude environments (Svalbard,Norway)

Branched glycerol dialkyl glycerol tetraethers (GDGTs) are membrane lipids of unknown bacteria that are ubiquitous in soil and peat. Two indices based on the distribution of these lipids in soils, the Cyclization of Branched Tetraethers (CBT) and the Methylation of Branched Tetraethers (MBT) indices have been shown to correlate with soil pH, and mean annual air temperature (MAT) and soil pH, respectively, and can be used to reconstruct MAT in palaeoenvironments. To verify the extent to which branched GDGTs in marine sediments reflect the distribution pattern on land and whether these proxies are applicable for palaeoclimate reconstruction in high latitude environments with a MAT of <0 °C, we compared the branched GDGT distribution in Svalbard soils and nearby fjord sediments. Although branched GDGT concentrations in the soil are relatively low (0.02–0.95 μg/g dry weight (dw)) because of the cold climate and the short growing season, reconstructed MATs based on the MBT/CBT proxy are ca. ?4 °C, close to the measured MAT (ca. ?6 °C). Concentrations of branched GDGTs (0.01–0.20 μg/g dw) in fjord sediments increased towards the open ocean and the distribution was strikingly different from that in soil, i.e. dominated by GDGTs with one cyclopentane moiety. This resulted in MBT/CBT-reconstructed MAT values of 11–19 °C, well above measured MAT. The results suggest that at least part of the branched GDGTs in marine sediments in settings with a low soil organic matter (OM) input may be produced in situ. In these cases, the application of the MBT/CBT palaeothermometer will generate unrealistic MAT reconstructions. The MBT/CBT proxy should therefore only be used at sites with a substantial input of soil OM relative to the amount of marine OM, i.e. at sites close to the mouth of rivers with a catchment area where sufficient soil formation takes place and the soil thus contains substantial amounts of branched GDGTs.     

Geochemical and isotopic approach to maturity/source/mixing estimations for natural gas and associated condensates in the Thrace Basin,NW Turkey

The Tertiary Thrace Basin located in NW Turkey comprises 9 km of clastic-sedimentary column ranging in age from Early Eocene to Recent in age. Fifteen natural gas and 10 associated condensate samples collected from the 11 different gas fields along the NW–SE extending zone of the northern portion of the basin were evaluated on the basis of their chemical and individual C isotopic compositions. For the purpose of the study, the genesis of CH₄, thermogenic C₂₊ gases, and associated condensates were evaluated separately.Methane appears to have 3 origins: Group-1 CH₄ is bacteriogenic (Calculated δ¹³C_C1–C = −61.48‰; Silivri Field) and found in Oligocene reservoirs and mixed with the thermogenic Group-2 CH₄. They probably formed in the Upper Oligocene coal and shales deposited in a marshy-swamp environment of fluvio-deltaic settings. Group-2 (δ¹³C_C1–C = −35.80‰; Hamitabat Field) and Group-3 (δ¹³C_1–C = −49.10‰; Değirmenköy Field) methanes are thermogenic and share the same origin with the Group-2 and Group-3 C₂₊ gases. The Group-2 C₂₊ gases include 63% of the gas fields. They are produced from both Eocene (overwhelmingly) and Oligocene reservoirs. These gases were almost certainly generated from isotopically heavy terrestrial kerogen (δ¹³C = −21‰) present in the Eocene deltaic Hamitabat shales. The Group-3 C₂₊ gases, produced from one field, were generated from isotopically light marine kerogen (δ¹³C = −29‰). Lower Oligoce ne Mezardere shales deposited in pro-deltaic settings are believed to be the source of these gases.The bulk and individual n-alkane isotopic relationships between the rock extracts, gases, condensates and oils from the basin differentiated two Groups of condensates, which can be genetically linked to the Group-2 and -3 thermogenic C₂₊ gases. However, it is crucial to note that condensates do not necessarily correlate to their associated gases.Maturity assessments on the Group-1 and -2 thermogenic gases based on their estimated initial kerogen isotope values (δ¹³C = −21‰; −29‰) and on the biomarkers present in the associated condensates reveal that all the hydrocarbons including gases, condensates and oils are the products of primary cracking at the early mature st age (R_eq = 0.55–0.81%). It is demonstrated that the open-system source conditions required for such an early-mature hydrocarbon expulsion exist and are supported by fault systems of the basin.     

Hydro-geochemical and isotopic fluid evolution of the Los Azufres geothermal field,Central Mexico

Hydrothermal alteration at Los Azufres geothermal field is mostly propylitic with a progressive dehydration with depth and temperature increase. Argillic and advanced argillic zones overlie the propylitic zone owing to the activity of gases in the system. The deepest fluid inclusions (proto-fluid) are liquid-rich with low salinity, with NaCl dominant fluid type and ice melting temperatures (T_mi) near zero (0 °C), and salinities of 0.8 wt% NaCl equivalent. The homogenization temperature (T_h)  = 325 ± 5 °C. The boiling zone shows T_h = ±300 °C and apparent salinities between 1 and 4.9 wt% NaCl equivalent, implying a vaporization process and a very important participation of non-condensable gases (NCGs), mostly CO₂. Positive clathrate melting temperatures (fusion) with T_h = 150 °C are observed in the upper part of the geothermal reservoir (from 0 to 700 m depth). These could well be the evidence of a high gas concentration. The current water produced at the geothermal wells is NaCl rich (geothermal brine) and is fully equilibrated with the host rock at temperatures between T = 300 and 340 °C. The hot spring waters are acid-sulfate, indicating that they are derived from meteoric water heated by geothermal steam. The NCGs related to the steam dominant zone are composed mostly of CO₂ (80–98% of all the gases). The gases represent between 2 and 9 wt% of the total mass of the fluid of the reservoir.The authors interpret the evolution of this system as deep liquid water boiling when ascending through fractures connected to the surface. Boiling is caused by a drop of pressure, which favors an increase in the steam phase within the brine ascending towards the surface. During this ascent, the fluid becomes steam-dominant in the shallowest zone, and mixes with meteoric water in perched aquifers. Stable isotope compositions (δ¹⁸O–δD) of the geothermal brine indicate mixing between meteoric water and a minor magmatic component. The enrichment in δ¹⁸O is due to the rock–water interaction at relatively high temperatures. δ¹³C stable isotope data show a magmatic source with a minor meteoric contribution for CO₂. The initial isotopic value δ³⁴S_RES = −2.3‰, which implies a magmatic source. More negative values are observed for shallow pyrite and range from δ³⁴S (FeS₂) = −4‰ to −4.9‰, indicating boiling. The same fractionation tendencies are observed for fluids in the reservoir from results for δ¹⁸O.     

Geochemical and isotopic evidence for a magmatic-hydrothermal origin of the polymetallic vein-type Zn-Pb deposits in the northwest margin of Jiangnan Orogen,South China

Polymetallic vein-type Zn-Pb deposits are located in the Xiangxi–Qiandong zinc-lead metallogenic belt (XQMB) of the northwestern margin of the Jiangnan Orogen, South China. Ores are mainly found in fault-bounded quartz veins hosted in the upper part of the Banxi Group that consists of low-grade metamorphic sandstone, siltstone with minor tuff interbeds. The Zn-Pb deposits primarily contain sphalerite, galena, chalcopyrite and pyrite, accompanied by quartz and minor calcite. Zinc, lead, copper, indium and gallium are enriched in these ores. Investigation of the ore fluid reveals low temperature (87–262 °C) with scattered salinity (range from 2.73 to 26.64 wt% NaCl_eqv.). Hydrogen and oxygen isotopic compositions of fluid inclusions in quartz indicate mixing of magmatic hydrothermal fluid and meteoric water (δ¹⁸O_{H2O SMOW} = 0.2‰ to 4.2‰; δD_{H2O SMOW} = −126‰ to −80‰). Carbon and oxygen isotopic composition of carbonate samples indicate the magmatic hydrothermal origin of CO₃²⁻ or CO₂ in ore-forming fluid (δ¹³C_PDB = −6.9‰ to −5.7‰, δ¹⁸O_SMOW = 11.3‰ to 12.7‰). Sulfur and lead isotopic compositions (δ³⁴S_VCDT = 8.8–14.2‰ and ²⁰⁶Pb/²⁰⁴Pb = 17.156–17.209, ²⁰⁷Pb/²⁰⁴Pb = 15.532–15.508, ²⁰⁸Pb/²⁰⁴Pb = 37.282–37.546) demonstrate that sulfur sources were relatively uniform, and low radiogenic lead isotopic compositions indicate that ore metals were derived from a relatively unradiogenic source, probably by mixing of mantle with crust. Therefore, polymetallic vein-type Zn-Pb mineralization in this area probably arose from a magmatic-related hydrothermal system, and the deposition of sulfides occurred in response to cooling and boiling of magmatic hydrothermal fluids (high salinity, high δ¹⁸O_H2O and δD_H2O and metal-bearing), and is mainly the result of emplacement into open space and mixing with meteoric water (low salinity, low δ¹⁸O_H2O and δD_H2O). This study provides direct evidence that magmatism was involved in the ore-forming processes of the low temperature metallogenic district, South China, and it raises awareness about the presence of polymetallic vein-type Zn-Pb deposits in the northwest margin of Jiangnan Orogen and their potential as a source of zinc, copper, indium and gallium.     

Geology,mineralogy, and geochemistry of fault-controlled hydrothermal Cu–Au mineralization in the Shanmen Volcanic Basin,SE China

The Yukeng–Banling deposit is a typical fault-controlled hydrothermal Cu–Au deposit in the Shanmen Volcanic Basin (SVB), SE China. Ore bodies commonly occur as lodes, lenses and disconnected pods dipping SW with vertical zonation of ore minerals. Ore-related hydrothermal alteration is well developed on both sides of the veins, dominated by silicification, sericitization, chloritization and argillation with a banded alteration zonation. The mineralization can be divided into three stages (stages I, II and III). Native gold is present as veinlets in fractures of fine-grained pyrite from stage II.Zircon U–Pb and Rb–Sr isochron ages indicate that the Cu–Au mineralization is coeval with the Caomen alkaline granite and Xiaokeng quartz-diorite, both emplaced at ca. 102 Ma. Microthermometric measurements of fluid inclusions in quartz and sphalerite from stage II veins indicate that the Yukeng–Banling deposit is an epithermal deposit. Six ore-related quartz grains have δD_H2O values of − 69 to − 43‰, and δ¹⁸O_H2O values calculated using total homogenization temperatures that range from − 2.0 to 0.7‰. All samples plot in an area between the magmatic field and the meteoric line, suggesting that the ore-forming fluids are derived from a mixed source of magmatic and meteoric waters. δ³⁴S values for eight pyrite separates range from − 2.1 to + 4.1‰ with an average of + 1.7‰, and δ³⁴S values for galena and sphalerite are 2.3‰ and 2.2‰, similar to magmatic sulfur. Four alkaline granite samples have Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb)_t = 18.175–18.411, (²⁰⁷Pb/²⁰⁴Pb)_t = 15.652–15.672 and (²⁰⁸Pb/²⁰⁴Pb)_t = 38.343–38.800. Three quartz-diorite samples have ratios (²⁰⁶Pb/²⁰⁴Pb)_t, (²⁰⁷Pb/²⁰⁴Pb)_t and (²⁰⁸Pb/²⁰⁴Pb)_t of 18.277–18.451, 15.654–15.693 and 38.673–38.846, respectively. These age-calculated lead isotopic data for alkaline granite are similar to those for the analyzed sulfides. Co/Ni ratios for stage II pyrites range from 1.42 to 5.10, indicating that the Yukeng–Banling deposit records the past involvement of magmatic hydrothermal fluids. The isotope data, together with geological, mineralogical and geochronological evidence, favor a primary magmatic source for sulfur and metals in the ore fluids. Mixing of the Cu- and Au-rich fluids with meteoric water led to precipitation of the Cu–Au veins along NW-trending faults.The Yukeng–Banling deposit, the contemporaneous Caomen alkaline granite and Xiaokeng quartz-diorite in the SVB formed under an extensional setting, due to high-angle subduction of the paleo-Pacific plate. The extensional setting facilitated the formation of Cu- and Au-rich magmas which was derived from enriched mantle and lower crust.     

Crassulacean acid metabolism influences D/H ratio of leaf wax in succulent plants

This study sought to characterize hydrogen isotopic fractionation during biosynthesis of leaf wax n-alkanes in succulent plants capable of crassulacean acid metabolism (CAM). The metabolic and physiological features of CAM represent crucial strategies for survival in hot and dry climates and have been hypothesized to impact hydrogen isotope fractionation. We measured the stable carbon and hydrogen isotopic compositions (δ¹³C and δD, respectively) of individual n-alkanes in 20 species of succulent plants from a global collection of the Huntington Botanical Gardens, San Marino, California. Greenhouse conditions and irrigation with water of constant δD value enabled determination of interspecies differences in net D/H fractionation between source water and leaf wax products. Carbon isotope ratios provide constraints on the extent of CAM vs. C₃ photosynthesis and indicate a wide range of CAM use, with δ¹³C values ranging from −33.01‰ to −18.54‰ (C₂₇–C₃₃ n-alkanes) and −26.66‰ to −17.64‰ (bulk tissue). Despite the controlled growth environment, we observed ca. 90‰ interspecies range in δD values from −193‰ to −107‰. A positive correlation between δ¹³C_bulk and δD_C31 values with R² = 0.60 (δ¹³C_C31 and δD_C31 values with R² = 0.41) implicates a metabolic isotope effect as the dominant cause of interspecies variation in the hydrogen isotopic composition of leaf wax n-alkanes in CAM-intermediate plants.     

Three-dimensional stability analysis of a longitudinally inclined shallow tunnel face

The tunnel inclination angle (δ) generally exists in urban and cross-river (sea) tunnels; hence, its effect should be considered in the stability analysis of a tunnel face. However, the influence of this tunnel inclination angle is rarely studied. In this paper, considering the effects of the tunnel inclination angle and the tunneling length (L), the optimal upper-bound solutions of the active and passive failure pressures were obtained using sequential quadratic programming (SQP) based on the upper-bound limit analysis. The effects of the dimensionless parameters on the pressures and failure modes were investigated. The results show that the tunnel inclination angle δ and the dimensionless parameter L/D (D is the section diameter of the tunnel) significantly affect active and passive stabilities. The difference in the results between δ = −10° and δ = 10° is mostly greater than 10% and reaches 80% when the internal friction angle (φ) is large. When the value of δ is zero, L/D does not affect on the result. The maximum difference in the results between L/D = 0 and L/D = 5 are 92.5% (passive failure) and 36.3% (active failure). For the active failure mode, with increasing of φ, the curves, which have δ values of −10°, 0° and 10°, intersect at a particular point when φ reaches a specific value.     

Measuring the effective diffusion coefficient of dissolved hydrogen in saturated Boom Clay

Boom Clay is studied as a potential host formation for the disposal of high-and intermediate level long-lived radioactive waste in Belgium. In such a geological repository, generation of gases (mainly H₂ from anaerobic corrosion) will be unavoidable. In order to make a good evaluation of the balance between gas generation vs. gas dissipation for a particular waste form and/or disposal concept, good estimates for gas diffusion coefficients of dissolved gases are essential. In order to obtain an accurate diffusion coefficient for dissolved hydrogen in saturated Boom Clay, diffusion experiments were performed with a recently developed through-diffusion set-up for dissolved gases. Due to microbial activity in the test set-up, conversion of hydrogen into methane was observed within several experiments. A complex sterilisation procedure was therefore developed in order to eliminate microbiological disturbances. Only by a combination of heat sterilisation, gamma irradiation and the use of a microbial inhibitor, reliable, reproducible and accurate H₂(g) diffusion coefficients (measured at 21 °C) for samples oriented parallel (D_eff = 7.25 × 10⁻¹⁰ m²/s and D_eff = 5.51 × 10⁻¹⁰ m²/s) and perpendicular (D_eff = 2.64 × 10⁻¹⁰ m²/s) to the bedding plane were obtained.     

Hydrochemistry,mineralogy and sulfur isotope geochemistry of acid mine drainage at the Mt. Morgan mine environment,Queensland, Australia

Mineralogical, hydrochemical and S isotope data were used to constrain hydrogeochemical processes that produce acid mine drainage from sulfidic waste at the historic Mount Morgan Au–Cu mine, and the factors controlling the concentration of SO₄ and environmentally hazardous metals in the nearby Dee River in Queensland, Australia. Some highly contaminated acid waters, with metal contents up to hundreds of orders of magnitude greater than the Australia–New Zealand environmental standards, by-pass the water management system at the site and drain into the adjacent Dee River.Mine drainage precipitates at Mt. Morgan were classified into 4 major groups and were identified as hydrous sulfates and hydroxides of Fe and Al with various contents of other metals. These minerals contain adsorbed or mineralogically bound metals that are released into the water system after rainfall events. Sulfate in open pit water and collection sumps generally has a narrow range of S isotope compositions (δ³⁴S = 1.8–3.7‰) that is comparable to the orebody sulfides and makes S isotopes useful for tracing SO₄ back to its source. The higher δ³⁴S values for No. 2 Mill Diesel sump may be attributed to a difference in the source. Dissolved SO₄ in the river above the mine influence and 20 km downstream show distinctive heavier isotope compositions (δ³⁴S = 5.4–6.8‰). The Dee River downstream of the mine is enriched in ³⁴S (δ³⁴S = 2.8–5.4‰) compared with mine drainage possibly as a result of bacterial SO₄ reduction in the weir pools, and in the water bodies within the river channel. The SO₄ and metals attenuate downstream by a combination of dilution with the receiving waters, SO₄ reduction, and the precipitation of Fe and Al sulfates and hydroxides. It is suggested here that in subtropical Queensland, with distinct wet and dry seasons, temporary reducing environments in the river play an important role in S isotope systematics.     

Isotope and fluid inclusion geochemistry and genesis of the Qiangma gold deposit,Xiaoqinling gold field,Qinling Orogen,China

The Qiangma gold deposit is hosted in the > 1.9 Ga Taihua Supergroup metamorphic rocks in the Xiaoqinling terrane, Qinling Orogen, on the southern margin of the North China Craton. The mineralization can be divided as follows: quartz-pyrite veins early, quartz-polymetallic sulfide veinlets middle, and carbonate-quartz veinlets late stages, with gold being mainly introduced in the middle stage. Three types of fluid inclusions were identified based on petrography and laser Raman spectroscopy, i.e., pure carbonic, carbonic-aqueous (CO₂–H₂O) and aqueous inclusions.The early-stage quartz contains pure carbonic and CO₂–H₂O inclusions with salinities up to 12.7 wt.% NaCl equiv., bulk densities of 0.67 to 0.86 g/cm³, and homogenization temperatures of 280−365 °C. The early-stage is related to H₂O–CO₂ ± N₂ ± CH₄ fluids with isotopic signatures consistent with a metamorphic origin (δ¹⁸O_water = 3.1 to 5.2‰, δD = − 37 to − 73‰). The middle-stage quartz contains all three types of fluid inclusions, of which the CO₂–H₂O and aqueous inclusions yield homogenization temperatures of 249−346 °C and 230−345 °C, respectively. The CO₂–H₂O inclusions have salinities up to 10.9 wt.% NaCl equiv. and bulk densities of 0.70 to 0.98 g/cm³, with vapor bubbles composed of CO₂ and N₂. The isotopic ratios (δ¹⁸O_water = 2.2 to 3.6‰, δD = − 47 to − 79‰) suggest that the middle-stage fluids were mixed by metamorphic and meteoric fluids. In the late-stage quartz only the aqueous inclusions are observed, which have low salinities (0.9−9.9 wt.% NaCl equiv.) and low homogenization temperatures (145−223 °C). The isotopic composition (δ¹⁸O_water = − 1.9 to 0.5‰, δD = − 55 to − 66‰) indicates the late-stage fluids were mainly meteoric water.Trapping pressures estimated from CO₂–H₂O inclusions are 100−285 MPa for the middle stage, suggesting that gold mineralization mainly occurred at depths of 10 km. Fluid boiling and mixing caused rapid precipitation of sulfides and native Au. Through boiling and inflow of meteoric water, the ore-forming fluid system evolved from CO₂-rich to CO₂-poor in composition, and from metamorphic to meteoric, as indicated by decreasing δ¹⁸O_water values from early to late. The carbon, sulfur and lead isotope compositions suggest the hostrocks within the Taihua Supergroup to be a significant source of ore metals. Integrating the data obtained from the studies including regional geology, ore geology, and fluid inclusion and C–H–O–S–Pb isotope geochemistry, we conclude that the Qiangma gold deposit was an orogenic-type system formed in the tectonic transition from compression to extension during the Jurassic−Early Cretaceous continental collision between the North China and Yangtze cratons.     

Effect of precipitation regime on δD values of soil n-alkanes from elevation gradients - Implications for the study of paleo-elevation

We measured δD values of long chain n-alkanes isolated from 30 surface soil samples along two elevation transects on the Tibetan Plateau differing in precipitation regime and water source. The East Asian Monsoon precipitation dominates the wetter regime on the eastern slope (from 1230 to 4300 m) of Gongga Shan on the eastern Tibetan Plateau. Precipitation from the Polar Westerlies dominates the drier region on the slope from 1900 to 5000 m in the West Kunlun Shan on the northwestern Tibetan Plateau. The decrease in δD value with elevation in the wetter region greatly exceeded that in drier region by, −1.9 ± 0.1‰/100 m and −1.4 ± 1.0‰/100 m respectively. The apparent fractionation between leaf wax and precipitation ε_wax-p values in the wetter region (ca. −164‰) were more negative than those in drier region (ca. −125‰ above 3200 m).We also measured δD values in leaves of six common living trees (values from −287‰ to −193‰) from Gongga Shan, ranging from about 2900-4200 m. The abundance-weighted average values of the n-alkanes (δD_wax) show a strong reverse correlation with sample source elevation (R² 0.78 for soils from Gongga Shan; R² 0.85 for soils from West Kunlun Shan above 3200 m), suggesting that n-alkane δD_wax faithfully records the precipitation δD and that the isotopic altitude effect of precipitation controls δD_wax altitudinal gradients in the mountains. The data show a fairly strong monotonic dependency of n-alkane δD values on elevation for the eastern Plateau, but a complex relationship between n-alkane δD values and elevation for the northwestern Plateau. The δD_wax values at sites below 3200 m from the Kunlun Shan area exhibit an unexpected positive correlation with elevation. The study confirms the potential for using sediment δD_wax values to reconstruct paleo-elevation in wetter regions, but suggests caution in applying the approach to dry regions. Our results also show it is essential to consider the intricacy of the pattern of atmospheric circulation and water sources and their influence on the lapse rate of δD values with elevation.