Quantification of photosynthetic inorganic carbon utilisation via a bidirectional stable carbon isotope tracer

The amount of bicarbonate utilised by plants is usually ignored because of limited measurement methods. Accordingly, this study quantified the photosynthetic assimilation of inorganic carbon (CO₂ and HCO₃ ^?) by plants. The net photosynthetic CO₂ assimilation (P _N), the photosynthetic assimilation of CO₂ and bicarbonate (P _N’), the proportion of increased leaf area (f _LA) and the stable carbon isotope composition (δ¹³C) of Orychophragmus violaceus (Ov) and Brassica juncea (Bj) under three bicarbonate levels (5, 10 and 15 mm NaHCO₃) were examined to determine the relationship among P _N, P _N’ and f _LA. P _N’, not P _N, changed synchronously with f _LA. Moreover, the proportions of exogenous bicarbonate and total bicarbonate (including exogenous bicarbonate and dissolved CO₂-generated bicarbonate) utilised by Ov were 2.27 % and 5.28 % at 5 mm bicarbonate, 7.06 % and 13.28 % at 10 mm bicarbonate, and 8.55 % and 17.31 % at 15 mm bicarbonate, respectively. Meanwhile, the proportions of exogenous bicarbonate and total bicarbonate utilised by Bj were 1.77 % and 3.28 % at 5 mm bicarbonate, 2.11 % and 3.10 % at 10 mm bicarbonate, and 2.36 % and 3.09 % at 15 mm bicarbonate, respectively. Therefore, the dissolved CO₂-generated bicarbonate and exogenous bicarbonate are important sources of inorganic carbon for plants.     

The effect of slight to minor biodegradation on C<Subscript>6</Subscript> to C<Subscript>7</Subscript> light hydrocarbons in crude oils: a case study from Dawanqi Oilfield in the Tarim Basin,NW China

Light hydrocarbons (LHs) are one of the main petroleum fractions in crude oils, and carry much information regarding the genetic origin and alteration of crude oils. But secondary alterations—especially biodegradation—have a significant effect on the composition of LHs in crude oils. Because most of the LHs affected in oils underwent only slight biodegradation (rank 1 on the biodegradation scale), the variation of LHs can be used to describe more the refined features of biodegradation. Here, 23 crude oils from the Dawanqi Oilfield in the Tarim Basin, NW China, eleven of which have been biodegraded to different extents, were analyzed in order to investigate the effect of slight to minor biodegradation on C₆–C₇ LHs. The study results showed that biodegradation resulted in the prior depletion of straight-chained alkanes, followed by branched alkanes. In slight and minor biodegraded oils, such biodegradation scale could not sufficiently affect C₆–C₇ cycloalkanes. For branched C₆–C₇ alkanes, generally, monomethylalkanes are biodegraded earlier than dimethylalkanes and trimethylalkanes, which indicates that branched alkanes are more resistant to biodegradation, with the increase of substituted methyl groups on parent rings. The degree of alkylation is one of the primary controlling factors on the biodegradation of C₆–C₇ LHs. There is a particular case: although 2,2,3-trimethylbutane has a relative higher alkylation degree, 2,2-dimethylpentane is more resistant to biodegradation than 2,2,3-trimethylbutane. 2,2-Dimethylpentane is the most resistant to biodegradation in branched C₆–C₇ alkanes. Furthermore, the 2-methylpentane/3-methylpentane and 2-methylhexane/3-methylhexane ratios decreased steadily with increasing biodegradation, which implies that isomers of bilateral methyl groups are more prone to bacterial attack relative to mid-chain isomers. The position of the alkyls on the carbon skeleton is also one of the critical factors controlling the rate of biodegradation. With increasing biodegradation, Mango’s LH parameters K1 values decrease and K2 values increase, the values of n-heptane and isoheptane decrease, and the indices of methylcyclohexane and cyclohexane increase. LH parameters should be applied cautiously for the biodegraded oils. Because biodegraded samples belong to slight or minor biodegraded oils, the values of n-heptane and isoheptane from Dawanqi Oilfield can better reflect and determine the “Biodegraded” zone. When the heptane value is 0–21 and the isoheptane value is 0–2.6, the crude oil in Dawanqi Oilfield is defined as the “Biodegraded” zone.     

A hydrochemical study of the Hammam Righa geothermal waters in north-central Algeria

This study focuses on the hydrochemical characteristics of 47 water samples collected from thermal and cold springs that emerge from the Hammam Righa geothermal field, located in north-central Algeria. The aquifer that feeds these springs is mainly situated in the deeply fractured Jurassic limestone and dolomite of the Zaccar Mount. Measured discharge temperatures of the cold waters range from 16.0 to 26.5 °C and the hot waters from 32.1 to 68.2 °C. All waters exhibited a near-neutral pH of 6.0–7.6. The thermal waters had a high total dissolved solids (TDS) content of up to 2527 mg/l, while the TDS for cold waters was 659.0–852.0 mg/l. Chemical analyses suggest that two main types of water exist: hot waters in the upflow area of the Ca–Na–SO₄ type (Hammam Righa) and cold waters in the recharge zone of the Ca–Na–HCO₃ type (Zaccar Mount). Reservoir temperatures were estimated using silica geothermometers and fluid/mineral equilibria at 78, 92, and 95 °C for HR4, HR2, and HR1, respectively. Stable isotopic analyses of the δ¹⁸O and δD composition of the waters suggest that the thermal waters of Hammam Righa are of meteoric origin. We conclude that meteoric recharge infiltrates through the fractured dolomitic limestones of the Zaccar Mount and is conductively heated at a depth of 2.1–2.2 km. The hot waters then interact at depth with Triassic evaporites located in the hydrothermal conduit (fault), giving rise to the Ca–Na–SO₄ water type. As they ascend to the surface, the thermal waters mix with shallower Mg-rich groundwater, resulting in waters that plot in the immature water field in the Na–K–Mg diagram. The mixing trend between cold groundwaters from the recharge zone area (Zaccar Mount) and hot waters in the upflow area (Hammam Righa) is apparent via a chloride-enthalpy diagram that shows a mixing ratio of 22.6 < R < 29.2 %. We summarize these results with a geothermal conceptual model of the Hammam Righa geothermal field.     

Improvement of saponification extraction method for fatty acids separation from geological samples

The conventional saponification method could result in lower recoveries and artificial changes of long-chain fatty acids. The main reason is the error judgment of the intermediate layer suspended between the aqueous and organic layer during the liquid–liquid extraction process. This study shows that the intermediate layer consists of lots of medium- to long-chain carboxylic salts for their special physical and chemical properties. An improved saponification extraction method is also developed and the results show that the carboxylic salts distributed in the intermediate layer could be obtained completely, which greatly enhances the authenticity and accuracy of fatty acid analysis. Additionally, the possible reasons of formation of the intermediate layer are also discussed.     

An optimized sequential extraction scheme for molybdenum association in environmental samples

By comparing three sequential extraction procedures, a new optimized extraction scheme for the molybdenum association in environmental samples was proposed. Five operational steps were described as exchangeable (KH₂PO₄ + K₂HPO₄: including water-soluble), associated with organic matter (NaOH), Fe–Mn oxides and/or carbonates (HCl), sulfides (H₂O₂) and residue (HNO₃ + HF + H₂O₂). An optimized extraction scheme was compared with Tessier’s procedure and the Commission of European Communities Bureau of Reference (BCR) was applied to black shales. Results showed Tessier’s procedure gave the lowest concentration values for exchangeable molybdenum and the highest values for the residual molybdenum, which could not present the efficiency of the extraction reagents. BCR’s procedure showed the highest values in oxidizable molybdenum and presented four fractions of molybdenum, which did not demonstrate the fractions of molybdenum in the black shales in detail. The optimized extraction scheme demonstrated a certain improvement on extraction efficiency over Tessier’s procedure for the lowest residual molybdenum, and revealed more featured fraction information of molybdenum in black shales than BCR’s. Therefore, after a comparison with other two extraction procedures, the optimized extraction scheme proved suitable for the molybdenum in black shales and it also showed an accurate determination of the molybdenum in the fractions and source of bioavailable Mo.     

Ra’s Abdah of the north Eastern Desert of Egypt: the role of granitic dykes in the formation of radioactive mineralization,evidenced by zircon morphology and chemistry

Syenogranitic dykes in the north of Egypt’s Eastern Desert are of geological and economic interest because of the presence of magmatic and supergene enrichment of radioactive mineralization. Zircon crystal morphology within the syenogranitic dykes allows precise definition of sub-alkaline series granites and crystallized at mean temperature of about 637 °C. The growth pattern of the zircons suggest magmatic and hydrothermal origins of radioactive mineralization. Hydrothermal processes are responsible for the formation of significant zircon overgrowth; high U-zircon margins might have occurred contemporaneously with the emplacement of syenogranitic dykes which show anomalous uranium (eU) and thorium (eTh) contents of up to 1386 and 7330 ppm, respectively. Zircon chemistry revealed a relative increase of Hf consistent with decreasing Zr content, suggesting the replacement of Zr by Hf during hydrothermal activity. Visible uranium mineralization is present and recognized by the presence of uranophane and autunite.     

Geochemistry of sedimentary rocks from Permian–Triassic boundary sections of Tethys Himalaya: implications for paleo-weathering,provenance, and tectonic setting

The geochemical characteristics of two sections—the Permian–Triassic boundary (PTB) Guryul Ravine section, Kashmir Valley, Jammu and Kashmir, India; and the Attargoo section, Spiti Valley, Himachal Pradesh, India—have been studied in the context of provenance, paleo-weathering, and plate tectonic setting. These sections represent the siliciclastic sedimentary sequence from the Tethys Himalaya. The PTB siliciclastic sedimentary sequence in these regions primarily consists of sandstones and shales with variable thickness. Present studied sandstones and shales of both sections had chemical index of alteration values between 65 and 74; such values reveal low-to-moderate degree of chemical weathering. The chemical index of weathering in studied samples ranged from 71 to 94, suggesting a minor K-metasomatism effect on these samples. Plagioclase index of alteration in studied sections ranged from 68 to 92, indicating a moderate degree of weathering of plagioclase feldspars. The provenance discriminant function diagram suggests that the detritus involved in the formation of present studied siliciclastic sedimentary rocks fall in quartzose sedimentary and felsic igneous provenances. These sediments were deposited in a passive continental margin plate tectonic setting according to their location on a Si₂O versus K₂O/Na₂O tectonic setting diagram.     

Nuclear field shift effects on stable isotope fractionation: a review

An anomalous isotope effect exists in many heavy element isotope systems (e.g., Sr, Gd, Zn, U). This effect used to be called the “odd–even isotope effect” because the odd mass number isotopes behave differently from the even mass number isotopes. This mass-independent isotope fractionation driving force, which originates from the difference in the ground-state electronic energies caused by differences in nuclear size and shape, is currently denoted as the nuclear field shift effect (NFSE). It is found that the NFSE can drive isotope fractionation of some heavy elements (e.g., Hg, Tl, U) to an astonishing degree, far more than the magnitude caused by the conventional mass-dependent effect (MDE). For light elements, the MDE is the dominant factor in isotope fractionation, while the NFSE is neglectable. Furthermore, the MDE and the NFSE both decrease as temperatures increase, though at different rates. The MDE decreases rapidly with a factor of 1/T², while the NFSE decreases slowly with a factor of 1/T. As a result, even at high temperatures, the NFSE is still significant for many heavy element isotope systems. In this review paper, we begin with an introduction of the basic concept of the NSFE, including its history and recent progress, and follow with the potential implications of the inclusion of the NFSE into the kinetic isotope fractionation effect (KIE) and heavy isotope geochronology.     

Fractionation characteristics of rare earth elements (REEs) linked with secondary Fe,Mn, and Al minerals in soils

Soil secondary minerals are important scavengers of rare earth elements (REEs) in soils and thus affect geochemical behavior and occurrence of REEs. The fractionation of REEs is a common geochemical phenomenon in soils but has received little attention, especially fractionation induced by secondary minerals. In this study, REEs (La to Lu and Y) associated with soil-abundant secondary minerals Fe-, Al-, and Mn-oxides in 196 soil samples were investigated to explore the fractionation and anomalies of REEs related to the minerals. The results show right-inclined chondrite-normalized REE patterns for La–Lu in soils subjected to total soil digestion and partial soil extraction. Light REEs (LREEs) enrichment features were negatively correlated with a Eu anomaly and positively correlated with a Ce anomaly. The fractionation between LREEs and heavy REEs (HREEs) was attributed to the high adsorption affinity of LREEs to secondary minerals and the preferred activation/leaching of HREEs. The substantial fractions of REEs in soils extracted by oxalate and Dithionite-Citrate-Bicarbonate buffer solutions were labile (10 %–30 %), which were similar to the mass fraction of Fe (10 %–20 %). Furthermore, Eu was found to be more mobile than the other REEs in the soils, whereas Ce was less mobile. These results add to our understanding of the distribution and geochemical behavior of REEs in soils, and also help to deduce the conditions of soil formation from REE fractionation.     

阿根廷米纳毕戈塔地区水系沉积物采样粒度试验研究

中国地质调查局与阿根廷地质矿产调查局合作在阿根廷西北部米纳毕戈塔地区进行1︰25万水系沉积物测量,该区属于干旱-半干旱高寒山区,为突出找矿效果,消除或减少风积物干扰,需要确定适合于该区的水系沉积物采样粒度。为此,在该区选择一个有已知矿床的1︰5万图幅进行采样粒度试验,分别选择10~60目、-60目、60~80目、-80目4个粒度级进行粒度试验;根据我国区域地球化学勘查规范,每个粒度分析39种元素。结果表明,大部分元素在4种粒度水系沉积物中的分布形态基本一致,都能够较好地反映出区内已知矿床,说明采用的采样方法可以有效地避免风成砂干扰;金、银、铜、锡等成矿元素在4种粒度中的分布略有差异,10~60目的金、铜和锡异常对已知矿体的反应更清晰准确。因此,本区水系沉积物地球化学测量的最佳采样粒度是10~60目。根据本次试验结果,中-阿地调局在本区联合开展1︰25万水系沉积物地球化学测量时采用了10~60目水系沉积物作为采样介质,取得了很好的效果。这是本区第一次进行水系沉积粒度试验,对本区将来的地球化学调查和研究具有指导意义。