Diamond Classification, Compositional Characteristics, and Research Progress: A Review
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摘要: 金刚石由于其独特的物理化学性质，在经济生产与科学研究中均具有重要价值.金刚石形成于地球大于150 km的深度范围内，是人类可以获得的来自地球深部地幔乃至核幔边界的最直接的样品，因此可以为研究地球深部物质组成和物理化学条件提供重要的素材.金刚石由碳元素组成，还含有微量的杂质元素（如氮、硼、氢、氧等），其中氮和硼元素对于划分金刚石的晶体结构类型发挥着重要的作用.根据金刚石的产出类型，金刚石可以划分为幔源型、超高压变质型、陨石相关型以及蛇绿岩型金刚石.全球约百分之一的幔源型金刚石含有包裹体，对这些包裹体的研究显示，金刚石主要来源于地球150~200 km深度的岩石圈地幔.这些含有包裹体的金刚石中，仅有1%的金刚石来自于地球深部的软流圈、地幔过渡带、下地幔、甚至核幔边界.我国的金刚石产出类型多样，但是，目前仅山东蒙阴、辽宁复县的金伯利岩矿床以及湖南沅水的砂矿具有经济价值.蛇绿岩型金刚石是近年来金刚石研究领域取得的重要进展，该类型金刚石分布在全球多个造山带不同时代、不同构造属性的蛇绿岩地幔橄榄岩和铬铁矿中，被认为是一种新的金刚石的产出类型.相对于其他国家和地区的金刚石的研究，我国的金刚石领域的研究程度相对较低，缺乏对金刚石结构、化学组成以及包裹体组成的系统研究，制约了对我国金刚石成因的认识，限制了我国的金刚石的找矿工作.因此，亟需结合先进的分析手段对我国的金刚石及其围岩做进一步的研究，以期揭示金刚石的形成过程，为金刚石的找矿提供理论基础.Abstract: Due to the unique physicochemical characteristics, diamonds are of great significance in economic production and scientific research. Diamonds record valuable information about the physicochemical conditions and compositions of Earth's deep mantle and even the core-mantle boundary. Diamond mainly consists of carbon, with minor impurities such as nitrogen, boron and hydrogen. Of these impurities, nitrogen and boron play important roles in the classification of diamonds. Carbon and nitrogen are vital elements for life, the cycles of which are closely related to the environment that humans live in. Diamonds can provide clues for the deep carbon and nitrogen cycle on the Earth. Studies on the mineral inclusions show that diamonds mainly form between a depth window of 150-200 km, with 1% of the diamond population forming in the asthenosphere (>200 km), the mantle transition zone, the lower mantle or even the core-mantle boundary. China hosts different types of diamonds, however, diamonds of economic significance only exist in the Shandong Province and Liaoning Province. The discovery of ophiolite-hosted diamonds (also called ophiolitic diamonds) is an important progress in the study of diamonds. Ophiolite-hosted diamonds in China have been discovered in ophiolitic peridotites and chromitites in different orogenic belts, and have been accepted as a new occurrence for diamonds. Diamond research in China is very limited, which has hampered the understanding of diamond genesis and diamond exploration. New analytical methods need to be applied on diamond and country rock research to provide new constraints on diamond formation and theoretical basis for diamond explorations.
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Key words:
- diamond /
- carbon isotope /
- nitrogen isotope /
- inclusion /
- ophiolite-hosted diamond /
- petrology
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图 1 不同类型金刚石的全球分布
1.Diavik, Ekati, Snap Lake, Jericho, Gahcho Kue, DO-27; 2. Fort a la Corne; 3.Buffalo Hills; 4.State Line; 5.Prairie Creek; 6.Wawa; 7.Victor; 8.Renard; 9.Guaniamo; 10.Juina/Sao Luis; 11.Arenapolis; 12.Coromandel, Abaete, Canasta; 13.Chapad Daimantina; 14.Boa Vista; 15.Koidu; 16.Kankan; 17.Akwatia; 18.Tortiya; 19.Aredor; 20.Bangui; 21.Mbuji-Mayi; 22.Camafuca, Cuango, Catoca; 23.Mavinga; 24.Mwadui; 25.Luderitz, Oranjemund, Namaqualand; 26.Orapa/Damtshaa, Lhetlakane, Jwaneng, Finsch; 27.Murowa, Venetia, The Oaks, Marsfontein, Premier, Dokolwayo, Roberts Victor, Letseng-laTerae, Jagersfontein, Koffefontein, Monastery, Kimberley (Bultfontein, Kimberley, DeBeers, Dutoitspan, Kamfersdam, Wesselton); 28. Kollur; 29.Majhgawan/Panna; 30.Momeik; 31.Theindaw; 32.Phuket; 33.West Kalimantan; 34.South Kalimantan; 35.Springfeld Basin, Eurelia/Orroro, Echunga; 36.Argyle, Ellendale, Bow River; 37.Merlin; 38.Copetown/Bingara; 39.Mengyin; 40.Fuxian; 41.Mir, 23rd Party Congress, Dachnaya, Internationalskaya, Nyurbinskaya; 42.Aykhal, Yubileynaya, Udachnaya, Zarnitsa, Sytykanskaya, Komsomolskaya; 43.Ural Mts.; 44.Arkhangelsk; 45.Kaavi-Kuopio; 46.WAlps; 47.Moldanubian; 48.Norway; 49.Rhodope; 50.Urals; 51.Kokchetav; 52.Qinling; 53.Dabie; 54.Sulu; 55.Kontum; 56.Java; 57.New England Fold Belt; 58.Canadian Cordillera; 59.Lappajarvi; 60.Reis; 61.Zapadnaya; 62.Popigai; 63.Sudbury; 64.Chixculub.据Shirey et al. (2013)
Fig. 1. Global distribution of diamonds of different types
图 2 幔源型金刚石在地球内部的分布据
Fig. 2. Distribution of mantle-derived diamonds in Earth's mantle
图 3 不同地区超高压变质岩中的原位显微金刚石
a.德国Erzgebirge片麻岩中的金刚石(Stö ckhert et al., 2001)；b.希腊的Rhodope地体中变质沉积岩中的微粒金刚石(Mposkos and Kostopoulos, 2001)；c.中国北秦岭地区的榴辉岩和片麻岩中锆石中的微粒金刚石包裹体(Yang et al., 2003)；d.奥地利的东阿尔卑斯的Pohorje地区的变质沉积岩中石榴石中的金刚石包裹体(Janák et al., 2015).Phl.金云母；Ap.磷灰石；Qtz.石英；Dia.金刚石；Grt.石榴石
Fig. 3. Microdiamonds in ultrahigh pressure metamorphic rocks
图 4 含有金刚石的蛇绿岩的全球分布
Fig. 4. Distribution of diamond-bearing ophiolites on Earth
图 5 不同地区蛇绿岩型金刚石特征
a.土耳其Pozantı-Karsantı铬铁矿中金刚石(Lian et al., 2017)；b.罗布莎铬铁矿中饿铱合金中的原位金刚石(Yang et al., 2007)；c.俄罗斯Ray-Iz铬铁矿中的原位金刚石(Yang et al., 2015); d.印度Nidar蛇绿岩地幔橄榄岩中的原位金刚石(Das et al., 2017).Sil.硅酸盐矿物；Dia.金刚石；OsIr.锇铱合金；Chr.铬尖晶石；Ol.橄榄石；Opx.斜方辉石
Fig. 5. Ophiolitic diamonds from different ophiolites
图 6 蛇绿岩型金刚石单晶(a，b)，多晶(c)以及骸晶(d)二次电子图像；蛇绿岩型金刚石不同生长区阴极发光图像(e，f)
Fig. 6. Secondary electron images for single-crystal(a, b), polycrystal(c) and skeletal-crystal (d) of ophiolitic diamond; cathodoluminescence images showing different growth sectors of ophiolitic diamond(e, f)
图 7 金刚石中的不同类型的矿物包裹体
a.金刚石中的单斜辉石包裹体(Stachel and Harris, 2008)；b.金刚石中的石榴石包裹体(Stachel and Harris, 2008)；c.金刚石中的硫化物包裹体(Smit et al., 2016)；d.金刚石中的铬尖晶石包裹体(Miller et al., 2014)；e.金刚石中的铁方镁石(fPer)和钙钛矿包裹体(mPv) (Harte, 2010)；f.正方铁铝榴石镁铝榴石相包裹体(TAPP) (Harte, 2010).Cpx.单斜辉石；Dia.金刚石；Grt.石榴石；Sul.硫化物；Chr.铬尖晶石；mPv.钙钛矿；fPer.铁方镁石；TAPP.正方铁铝榴石镁铝榴石相包裹体
Fig. 7. Different mineral inclusions in diamond
图 8 变质地幔橄榄岩和变质基性岩在100~1 500 km深度范围内的矿物组成
据Harte(2010).其中Cf结构矿物相是一种化学式为[Na, Ca, Mg, Fe]1[Al, Si, Fe, Mg]2O4的高压矿物相；含Na-Al矿物相是一种化学式为[K, Na, Ca]1[Mg, Fe]2[Si, Al, Fe]6O12的高压矿物相
Fig. 8. Mineral propotions in average metaperidotite and metabasite bulk compositions at depth ranging from 100 to 1 500 km
图 9 不同类型的幔源型金刚石的相对比例
据Stachel and Harris(2008, 2009). a.幔源型金刚石划分为岩石圈型、下地幔型、深部榴辉岩型以及深部地幔橄榄岩型；b.岩石圈型金刚石进一步划分为地幔橄榄岩型、榴辉岩型以及二辉辉石岩型；c.地幔橄榄岩型进一步划分为方辉橄榄岩型、二辉橄榄岩型以及异剥橄榄岩型
Fig. 9. The relative abundance of different types of mantle-derived diamonds according to the mineral assemblages
图 10 不同类型金刚石判别图解
据Grütter et al.(2004)和Stachel and Harris(2008). a.不同类型的金刚石中石榴子石的Cr2O3与CaO含量相关图解；b.不同类型金刚石中单斜辉石Mg#值与Cr#值相关图解.Mg#=Mg/(Mg+FeTotal)×100; Cr#=Cr/(Cr+Al)×100; Cpx.单斜辉石；Garnet.石榴子石
Fig. 10. Discrimination diagrams for different types of diamond
图 11 蛇绿岩型金刚石中的常见包裹体
a.中国西藏罗布莎蛇绿岩金刚石中的不规则Ni-Mn-Co合金(来自Howell et al., 2015a)；b.俄罗斯Ray-Iz蛇绿岩金刚石中的纳米级Ni-Mn-Co合金和柯石英包裹体(来自Yang et al., 2015)；c.土耳其Pozantı-Karsantı蛇绿岩金刚石中的纳米级Ni-Mn-Co合金、(Ca, Mn)SiO3和流体包裹体(来自Lian et al., 2018).Coe.柯石英；Dia.金刚石；Ni-Mn-Co. Ni-Mn-Co合金
Fig. 11. Common mineral inclusions in ophiolitic diamond
图 12 不同类型的金刚石的内部原子的排布特征
Fig. 12. Diamonds of different types showing different arrangements of carbon and impurity atoms
图 13 不同类型金刚石和沉积物碳同位素、氮同位素以及氮含量频率分布直方图
地幔橄榄岩型金刚石、榴辉岩型金刚石、变质型金刚石、纤维型/复合型金刚石、再循环碳以及变质沉积物的数据来自Cartigny (2005)和Shirey et al. (2013)，蛇绿岩型金刚石数据来自Yang et al.(2014, 2015)，Howell et al. (2015a), Lian et al. (2018), Lian and Yang(2019)
Fig. 13. Comparative frequency histograms of δ13C, δ15N, and nitrogen contents of diamonds, recycled carbon and metasediment
图 14 不同变质等级的区域变质岩中氮含量与氮同位素δ15N值的相关性图解
Fig. 14. Correlation between nitrogen content and δ15N values in regional metamorphism
图 15 幔源型金刚石δ13C-δ15N (a)以及δ13C-N (b)含量相关性图解
高δ13C和低δ13C型金刚石数据来自Boyd and Pillinger (1994)，地幔橄榄岩和榴辉岩型金刚石数据来自Cartigny et al. (1998)；N-δ13C相关性图解引自Cartigny et al. (2001)
Fig. 15. Correlation diagrams of δ15N values (a), N (b) against δ13C values of mantle-derived diamond
图 16 蛇绿岩型金刚石及相关铬铁矿和地幔橄榄岩的不同成因模型
图a据Arai (2013)；图b据Zhou et al. (2014)；图c据Yang et al. (2015)
Fig. 16. Different models for the origin of ophiolitic diamond and the hosting peridotite and podiform chromitite
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