Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates,nicotianamine, and phytosiderophore,and new Fe isotopic measurements in higher plants

Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ～3‰ (⁵⁶Fe/⁵⁴Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ～1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate₂ and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ⁵⁶Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.     

Rb‐Sr geochronology and Sr isotopic composition of Devonian granitoids,eastern Tasmania

Biotite igneous ages and well‐defined isochron ages of plutons from the composite Blue Tier Batholith and the Coles Bay area in northeastern Tasmania range from 395 to 370 Ma. The older limit of this range, for the George River granodiorite, is considerably older than any age previously recorded for NE Tasmania. The ages of the youngest plutons (Mt Paris and Anchor granites), which host cassiterite ores, record pervasive hydrothermal alteration events. The initial ⁸⁷Sr/⁸⁰Sr ratios of the granitoids range from 0.7061 to 0.7136 and suggest different protolith compositions, consistent with mineralogical and geochemical characteristics of each pluton. The S‐type garnetbiotite granites (Ansons Bay and Booby alia granites) have initial ratios greater than 0.7119, indicative of enriched, high Rb/Sr ratio, crustal source‐rocks of Proterozoic age (1700–800 Ma). The S‐type biotite granites (Poimena and Pearson granites) have relatively high initial ⁸⁷Sr/⁸⁶Sr ratios (0.7070, 0.7105) but overlap with those of the I‐type granodiorites (George River, Scamander Tier, Pyengana and Coles Bay granodiorites) which are in the range of 0.7061 to 0.7073. The initial ratios of the enriched altered plutons are poorly constrained, and on both hand‐specimen and thin‐section scales, reveal open‐system Sr isotopic patterns.

Isochron ages for the arenite‐lutite and lutite sedimentary associations of the Mathinna Beds, which are intruded by the granitoids, reflect an approach to Sr isotopic equilibrium during regional metamorphism. The metamorphic age (401 ± 7 Ma) of the early Pragian arenite‐lutite association indicates a relatively small time interval between deposition, regional metamorphism and granitoid intrusion. The isotopic age for the lutite sedimentary association (423 ± 22 Ma) is tentatively correlated with a Benambran‐age burial metamorphic event that has not previously been recorded in Tasmania.     

陕西地区岩浆岩Nd、Sr同位素特征及其与大地构造发展的联系

岩浆岩Nd、Sr同位素特征表明,扬子地块基底有着和华北地块很不相同的早期演变历史。这意味着华北和扬子两地块在历史上曾经是相互独立的,后来才拼合在一起。Nd、Sr同位素研究还表明,华北和扬子两地块的会聚在泥盆纪以前就已经在进行中,它是通过位於两地块之间的古秦岭海洋壳俯冲消亡在华北地块之下实现;华北和扬子两陆块最终相碰撞至少发生在二叠纪以前。     

海南福基田幔源辉石结构OH与氢氧同位素

采用IR光谱和质谱技术分析了海南福基田幔源巨晶和包体中辉石的结构羟基红外光谱和氢氧同位素。测试的所有巨晶普通辉石和包体中透辉石及顽火辉石均含结构OH,对比印证了国内外同类矿物的红外光谱特征。结构水质量分数分别是:普通辉石87×10-6~389×10-6;透辉石127×10-6~273×10-6;顽火辉石69×10-6~207×10-6。包体中结构水质量分数为1 811×10-6~5 377×10-6,平均为3 133×10-6。包体中辉石的氢氧同位素特征如下:透辉石的δ(D)为-123.17‰,顽火辉石的δ(D)为-132.04‰;透辉石的δ(18O)为5.96‰,顽火辉石的δ(18O)为5.60‰。实验和对比表明,辉石是海南福基田上地幔重要的"水储库",包体未受地壳成分污染,继承和保持了上地幔"富水贫氘"的特征。上述结果为该地区上地幔研究提供了结构水和氢氧同位素的基础资料。     

硝酸盐氮氧同位素反硝化细菌法测试研究

进入21世纪,硝酸盐氮氧同位素测试技术的显著进展是反硝化细菌法测试技术的建立。反硝化细菌法具有可同时分析浓度低至μg/L的硝酸盐氮氧同位素组成、免去复杂的样品预处理、分析时间大大缩短以及从复杂溶液中只转化NO3-为N2O等优点。实验过程由细菌挑选和培养、样品NO3-转化为N2O、N2O提取纯化、同位素测试以及同位素测试结果校正等几个关键步骤组成。国外研究结果显示该技术不仅可用于海水和淡水中硝酸盐同位素测试,而且还可用于土壤样品,并得到不断的完善和应用;国内建立了这一技术,在包气带和地下水硝酸盐污染研究中取得重要进展。由于该技术诸多优点,建议大力促进这一技术在我国的研究和应用,希望有关部门加大支持力度,进一步完善该技术并推广应用。     

扩散法——EA-IRMS测定天然水体铵态氮同位素实验条件研究

稳定氮同位素是研究氮循环和氮污染源示踪的一个有效手段。然而目前国内对水体中铵态氮同位素测定方法研究较少,限制了水体氮循环和污染机理的深入探讨。本文采用改进的扩散法(EA-IRMS)测定水中铵态氮同位素,探讨了样品制备过程中扩散溶液的体积、浓度和扩散时间对回收率及氮同位素测定值的影响。实验得出最佳扩散条件为:1.50 mg/L氯化铵溶液400 mL扩散14天,回收率大于95%,且不会产生氮同位素分馏。本研究为高精度测定天然水体中铵态氮同位素提供了更可靠的实验条件。     

Geochemistry and Petrogenesis of Intracontinental Basaltic Volcanism on the Northwest Arabian Plate,Gaziantep Basin,Southeast Anatolia,Turkey

Volcanism along the northwest boundary of the Arabian Plate found in the Gaziantep Basin, southeast Turkey, is of Miocene age and is of alkaline and calc-alkaline basic composition. The rare earth element data for both compositional series indicates spinel–peridotite source areas. The rare earth and trace elements of the alkaline lavas originate from a highly primitive and slightly contaminated asthenospheric mantle; those of the calc-alkaline lavas originate from a highly heterogeneous, asthenospheric, and lithospheric mantle source. Partial melting and magmatic differentiation processes played a role in the formation of the petrological features of these volcanics. These rocks form two groups on the basis of their ~(87) Sr/~(86) Sr and ~(143) Nd/~(144) Nd isotopic compositions in addition to their classifications based on their chemical compositions(alkaline and calc-alkaline). These isotopic differences indicate a dissimilar parental magma. Therefore, high Nd isotope samples imply a previously formed and highly primitive mantle whereas low Nd isotope samples may indicate comparable partial melting of an enriched heterogeneous shallow mantle. Other isotopic changes that do not conform to the chemical features of these lavas are partly related to the various tectonic events of the region, such as the Dead Sea Fault System and the Bitlis Suture Zone.     

Petrogenesis of plio-quaternary intra-plate continental alkaline lavas from the İskenderun Gulf (Southern Turkey): Evidence for metasomatized lithospheric mantle

The Quaternary alkaline volcanic field of Southern Turkey is characterized by intra-continental plate-type magmatic products, exposed to the north of the ?skenderun Gulf along a NE-SW trending East Anatolian Fault, to the west of its intersection with the N–S trending Dead Sea Fault zone. The ?skenderun Gulf alkaline rocks are mostly silica-undersaturated with normative nepheline and olivine and are mostly classified as basanites and alkaline basalts with their low-silica contents ranging between 43 and 48?wt.% SiO₂. They display Ocean Island Basalt (OIB)–type trace element patterns characterized by enrichments in large-ion-lithophile elements (LILE) and light rare earth element (LREE), and have (La/Yb)_N?=?8.8–17.7 and (Hf/Sm)_N?=?0.9–1.6 similar to those of basaltic rocks found in intraplate suites. The basanitic rocks have limited variations Sr-Nd isotopic ratios (⁸⁷Sr/⁸⁶Sr?=?0.70307–0.70324, ¹⁴³Nd/¹⁴⁴Nd?=?0.512918–0.521947), whereas the alkali basalts display more evolved Sr-Nd isotopic ratios (⁸⁷Sr/⁸⁶Sr?=?0.70346-0.70365, ¹⁴³Nd/¹⁴⁴Nd?=?0.512887–0.521896). The ?skenderun Gulf alkaline rocks also display limited Pb isotopic variations with ²⁰⁶Pb/²⁰⁴Pb?=?18.75–19.09 ²⁰⁷Pb/²⁰⁴Pb?=?15.61–15.66 and²⁰⁸Pb/²⁰⁴Pb?=?38.65–39.02, indicating that they originated from an enriched lithospheric mantle source. Calculated fractionation vectors indicate that clinopyroxene and olivine are the main fractionating mineral phases. Similarly, based on Sr-Nd isotopic ratios, the assimilation and fractional crystallization (AFC) modeling shows that the alkali basalts were affected by AFC processes (r?=?0.2) and were slightly contaminated by the upper crustal material.The high TiO₂ contents, enrichments in Ba and Nb, and depletions in Rb can likely be explained by the existence of amphibole in the mantle source, which might, in turn, indicate that the source mantle has been affected by metasomatic processes. The modeling based on relative abundances of trace elements suggests involvement of amphibole-bearing peridotite as the source material. ?skenderun Gulf alkaline rocks can thus be interpreted as the products of variable extent of mixing between melts from both amphibole-bearing peridotite and dry peridotite.     

Isotopic-geochemical evidence for crustal contamination of eclogites in the Kokchetav subduction-collision zone

This paper reports isotopic and geochemical studies of eclogites from the western ultrahigh pressure (UHP) and eastern high-pressure (HP) blocks of the Kokchetav subduction-collision zone. These HP and UHP eclogites exhumed in two stages: (1) The rocks of the western block metamorphosed within the field of diamond stability (e.g., Kumdy-Kol and Barchy); (2) In contrast, the metamorphic evolution of the eastern block reached the pressure peak within the stability field of coesite (e.g., Kulet, Chaglinka, Sulu-Tyube, Daulet, and Borovoe). The eclogites vary widely in the ratios of incompatible elements and in the isotope ratios of Nd (¹⁴³Nd/¹⁴⁴Nd = 0.51137-0.513180) and Sr (⁸⁷Sr/⁸⁶Sr = 0.703930.78447). The Sulu-Tyube eclogites display isotope-geochemical features close to N-MORB, while those from the other sites are compositionally similar to E-type MORB or island arc basalts (IAB). The model ages T_Nd(DM) of eclogites vary between 1.95 and 0.67 Ga. The Sulu-Tyube eclogite yields the youngest age; it has the values of ε_Nd(T) (7.2) and ⁸⁷Sr/⁸⁶Sr (0.70393) close to the depleted mantle values. The crustal input to the protolith of the Kokchetav eclogites is evident on the ε_Nd(T)-⁸⁶Sr/⁸⁷Sr and ε_Nd(T)-T plots. The eclogites make up a trend from DM to country rocks. Some eclogites from the Kulet, Kumdy-Kol, and Barchy localities display signs of partial melting, such as high Sm/Nd (0.65-0.51) and low (La/Sm)_N (0.34-0.58) values. The equilibrium temperatures of these eclogites are higher than 850 °C. The geochemical features of eclogites testify to the possibility of the eclogite protolith formation in the tectonic setting of passive continental rift margin subducted to depths over 120 km.     

湘南王仙岭花岗岩体的锆石U-Pb年代学、地球化学、锆石Hf同位素特征及其地质意义

湘南王仙岭岩体由主体电气石黑云母花岗岩和侵入其内部的黑云母二长花岗岩组成,LA-MC-ICPMS锆石U-Pb定年显示电气石黑云母花岗岩形成于印支期(235.0±1.3Ma),黑云母二长花岗岩形成于燕山期(155.9±1.0Ma),表明该岩体是两期岩浆活动的产物。这两期岩石均为高钾钙碱性系列,A/CNK值为1.07～1.66,属过铝-强过铝质花岗岩类。稀土元素显示LREE富集,HREE亏损,Eu负异常明显(0.01～0.38)的特征。早期电气石黑云母花岗岩和晚期黑云母二长花岗岩的εHf(t)值分别为-7.92～+4.61和-10.66～-5.35;两阶段Hf模式年龄(tDM2)分别为1758～967Ma和1875～1538Ma。两期花岗岩均来自于古中元古代地壳物质重熔,其中早期电气石黑云母花岗岩在侵位上升过程中捕获了部分幔源老锆石,成岩过程中有少量地幔物质参与,且其源区具有高εHf(t)值的特点。综合前人研究成果,本文认为华南中生代印支期和燕山期均有钨锡矿化作用,印支期花岗质岩浆形成于碰撞挤压作用间隙伸展环境,而燕山期花岗质岩浆可能形成于大陆边缘弧后伸展环境。