Mineralogy and Petrology

, Volume 112, Supplement 1, pp 243–257 | Cite as

Deformation-related spectroscopic features in natural Type Ib-IaA diamonds from Zimmi (West African craton)

  • Karen V. SmitEmail author
  • Ulrika F. S. D’Haenens-Johansson
  • Daniel Howell
  • Lorne C. Loudin
  • Wuyi Wang
Original Paper


Zimmi diamonds (Sierra Leone) have 500 million year mantle residency times whose origin is best explained by rapid tectonic exhumation to shallower depths in the mantle, associated with continental collision but prior to kimberlite eruption. Here we present spectroscopic data for a new suite of Zimmi sulphide-bearing diamonds that allow us to evaluate the link between their spectroscopic features and their unusual geological history. Cathodoluminesence (CL) imaging of these diamonds revealed irregular patterns with abundant deformation lamellae, associated with the diamonds’ tectonic exhumation. Vacancies formed during deformation were subsequently naturally annealed to form vacancy clusters, NV0/− centres and H3 (NVN0). The brownish-yellow to greenish-yellow colours observed in Zimmi Ib-IaA diamonds result from visible absorption by a combination of isolated substitutional nitrogen (\( {\mathrm{N}}_{\mathrm{S}}^0 \)) and deformation-related vacancy clusters. Colour-forming centres and other spectroscopic features can all be attributed to the unique geological history of Zimmi Ib-IaA diamonds and their rapid exhumation after formation.


Zimmi diamond Type Ib-IaA Spectroscopy Isolated nitrogen West African craton Deformation 



Israel Eliezri from Coldiam Ltd. is thanked for providing samples from Zimmi. Adrian Chan assisted with laser cutting and polishing the diamond plates. Phil Diggle, Mark Newton and Thomas Stachel are thanked for discussions that helped clarify some concepts. Thank you to John King for his help with the diamond colour descriptions, and Evan Smith for his comments on a previous version of this paper. Constructive reviews from Thomas Hainschwang, Eloise Gaillou, Sergey Titkov, an anonymous reviewer and the editor, Lutz Nasdala, improved the manuscript. D.H. acknowledges support from European Research Council Starting Grant 307322 awarded to Fabrizio Nestola.

Supplementary material

710_2018_587_MOESM1_ESM.pdf (2.2 mb)
ESM 1 (PDF 2212 kb)


  1. Boyd SR, Kiflawi I, Woods GS (1994) The relationship between infrared absorption and the A defect concentration in diamond. Philos Mag B 69(6):1149–1153CrossRefGoogle Scholar
  2. Brookes A, Daniel R (2001) Influence of nitrogen content on the mechanical properties of diamond. In: Neves AJ, Nazare M (eds) Properties, growth and applications of diamond. INSPEC, The Institution of Electrical Engineers, London, pp 142–148Google Scholar
  3. Bulanova GP, Varshavsky AV, Kotegov VA (2005) A venture into the interior of natural diamond: genetic information and implications for the gem industry. J Gemmol 29(7/8):377–386CrossRefGoogle Scholar
  4. Chrenko RM, Strong HM, Tuft RE (1971) Dispersed paramagnetic nitrogen content of large laboratory diamonds. Philos Mag 23(182):313–318CrossRefGoogle Scholar
  5. Clark CD, Ditchburn RW, Dyer HB (1956) The absorption spectra of irradiated diamonds after heat treatment. P Roy Soc A-Math Phy 237(1208):75–89CrossRefGoogle Scholar
  6. Collins AT (1979) High temperature annealing of colour centres in Type I diamond. Diamond Research 1979 (De Beers Industrial Diamond Division) 7–12Google Scholar
  7. Collins AT (1980) Vacancy enhanced aggregation of nitrogen in diamond. J Phys C Solid State 13:2641–2650CrossRefGoogle Scholar
  8. Collins AT (1982a) Colour centres in diamond. J Gemmol 18(1):37–75CrossRefGoogle Scholar
  9. Collins AT (1982b) A spectroscopic survey of naturally-occurring vacancy-related colour centres in diamond. J Phys D Appl Phys 15:1431–1438CrossRefGoogle Scholar
  10. Collins AT (1992) The characterisation of point defects in diamond by luminescence spectroscopy. Diam Relat Mater 1:457–469CrossRefGoogle Scholar
  11. Collins AT, Woods GS (1982) An anomaly in the infrared absorption spectrum of synthetic diamond. Philos Mag B B 46:77–83CrossRefGoogle Scholar
  12. Dale MW (2015) Colour centres on demand in diamond. PhD thesis, University of WarwickGoogle Scholar
  13. Davies G, Hamer MF (1976) Optical studies of the 1.945 eV vibronic band in diamond. P Roy Soc A 348:285–298CrossRefGoogle Scholar
  14. de Vries RC (1975) Plastic deformation and “work-hardening” of diamond. Mater Res Bull 10(11):1193–1199CrossRefGoogle Scholar
  15. Dobrzhinetskaya LF, Eide EA, Larsen RB, Sturt BA, Trønnes RG, Smith DC, Taylor WR, Posukhova TV (1995) Microdiamond in high-grade metamorphic rocks of the Western Gness region, Norway. Geology 23(7):597–600CrossRefGoogle Scholar
  16. Evans T, Qi Z (1982) The kinetics of aggregation of nitrogen in diamond. P Roy Soc A 361:109–127Google Scholar
  17. Fedortchouk Y, Zhang Z (2011) Diamond resorption: link to metasomatic events in the mantle or record of magmatic fluid in kimberlitic magma? Can Mineral 49:707–719CrossRefGoogle Scholar
  18. Fisher D, Sibley SJ, Kelly CJ (2009) Brown colour in natural diamond and interaction between the brown related and other colour-inducing defects. J Phys-Condens Mat 21:364213CrossRefGoogle Scholar
  19. Gaillou E, Post JE, Bassim ND, Zaitsev AM, Rose T, Fries MD, Stroud RM, Steele A, Butler JE (2010) Spectroscopic and microscopic characterizations of color lamellae in natural pink diamonds. Diam Relat Mater 19:1207–1220CrossRefGoogle Scholar
  20. Gaillou E, Post JE, Rose T, Butler JE (2012) Cathodoluminescence of natural, plastically deformed pink diamonds. Microsc Microanal 18:1292–1302CrossRefGoogle Scholar
  21. Goss JP, Briddon PR, Hill V, Jones R, Rayson MJ (2014) Identification of the structure of the 3107 cm−1 H-related defect in diamond. J Phys-Condens Mat 26:145801CrossRefGoogle Scholar
  22. Graham RJ, Moustakas TD, Disko MM (1991) Cathodoluminescence imaging of defects and impurities in diamond films grown by chemical vapor deposition. J Appl Phys 69(5):3212–3218CrossRefGoogle Scholar
  23. Hainschwang T, Fritsch E, Notari F, Rondeau B (2012) A new defect center in type Ib diamond inducing one phonon infrared absorption: the Y center. Diam Relat Mater 12:120–126CrossRefGoogle Scholar
  24. Hainschwang T, Fritsch E, Notari F, Rondeau B, Katrusha A (2013) The origin of color in natural C center bearing diamonds. Diam Relat Mater 39:27–40CrossRefGoogle Scholar
  25. Hanley PL, Kiflawi I, Lang AR (1977) On topographically identifiable sources of cathodoluminescence in natural diamonds. P Roy Soc 284:329–368Google Scholar
  26. Harlow GE (1998) The nature of diamonds. Cambridge University Press. 278 ppGoogle Scholar
  27. Hounsome L, Jones R, Martineau PM, Fisher D, Shaw MJ, Briddon PR, Oberg S (2006) Origin of brown coloration in diamond. Phys Rev B 73:125203(8)CrossRefGoogle Scholar
  28. Howell D, O’Neill CJ, Grant KJ, Griffin WL, O’Reilly SY, Pearson NJ, Stern RA, Stachel T (2012a) Platelet development in cuboid diamonds: insights from micro-FTIR mapping. Contrib Mineral Petrol 64:1011–1025CrossRefGoogle Scholar
  29. Howell D, O’Neill CJ, Grant KJ, Griffin WL, Pearson NJ, O’Reilly SY (2012b) micro-FTIR mapping: distribution of impurities in different types of diamond growth. Diam Relat Mater 29:29–36CrossRefGoogle Scholar
  30. Howell D, Stern RA, Griffin WL, Southworth R, Mikhail S, Stachel T (2015) Nitrogen isotope systematics and origins of mixed-habit diamonds. Geochim Cosmochim Ac 157:1–12CrossRefGoogle Scholar
  31. Hull D, Bacon DJ (1984) Introduction to dislocations. Pergamon Press, Oxford, p 257Google Scholar
  32. Janak M, Ravna EJK, Kullerud K, Yoshida K, Milovsky R, Hirajima T (2013) Discovery of diamond in the Tromsø Nappe, Scandinavian Calenonides (N. Norway). J Metamorph Geol 31:691–703CrossRefGoogle Scholar
  33. Jones R, Goss JP, Pinto H, Palmer DW (2015) Diffusion of nitrogen in diamond and the formation of A-centres. Diam Relat Mater 53:35–39CrossRefGoogle Scholar
  34. Khan RUA, Cann BL, Martineau PM, Samartseva J, Freeth JJP, Sibley SJ, Hartland CB, Newton ME, Dhillon HK, Twitchen DJ (2013) Colour-causing defects and their related optoelectronic transitions in single crystal CVD diamond. J Phys-Condens Mat 25:275801CrossRefGoogle Scholar
  35. Kiflawi I, Lang AR (1976) On the correspondence between cathodoluminescence images and X-ray diffraction contrast images of individual dislocations in diamond. Philos Mag 33:697–701CrossRefGoogle Scholar
  36. Kiflawi I, Mayer AE, Spear PM, van Wyk JA, Woods GS (1994) Infrared absorption by the single nitrogen and A defect centres in diamond. Philos Mag B 69(6):1141–1147CrossRefGoogle Scholar
  37. Kiflawi I, Mainwood A, Kanda H, Fisher D (1996) Nitrogen interstitials in diamond. Phys Rev B 54(23):16719–16726CrossRefGoogle Scholar
  38. Kiflawi I, Kanda H, Mainwood A (1998) The effect of nickel and the kinetics of the aggregation of nitrogen in diamond. Diam Relat Mater 7:327–332CrossRefGoogle Scholar
  39. King JM, Shigley JE, Gelb TH, Guhin SS, Hall M, Wang W (2005) Characterization and grading of natural-color yellow diamonds. Gems Gemol 41(2):88–115CrossRefGoogle Scholar
  40. Lawson SC, Fisher D, Hunt DC, Newton ME (1998) On the existence of positively charged single-substitutional nitrogen in diamond. J Phys-Condens Mat 10:6171–6180CrossRefGoogle Scholar
  41. Lifshitz IM, Slyozov VV (1961) The kinetics of precipitation from supersaturated solid solutions. J Phys Chem Solids 19:35–50CrossRefGoogle Scholar
  42. Liggins S (2010) Identification of point defects in treated single crystal diamond. PhD thesis, University of WarwickGoogle Scholar
  43. Lytwyn J, Burke K, Culver S (2006) The nature and location of the suture zone in the Rokelide orogen, Sierra Leone: geochemical evidence. J Afr Earth Sci 46:439–454CrossRefGoogle Scholar
  44. Majka J, Rosen A, Janak M, Froitzheim N, Klonowska I, Manecki M, Sasinkova V, Yoshida K (2014) Microdiamond discovered in the Seve Nappe (Scandinavian Caledonides) and its exhumation by the “vacuum-cleaner” mechanism. Geology 42(12):1107–1110CrossRefGoogle Scholar
  45. Massi L, Fritsch E, Collins AT, Hainschwang T, Notari F (2005) The “amber centres” and their relation to the brown colour in diamond. Diam Relat Mater 14:1623–1629CrossRefGoogle Scholar
  46. Mineeva RM, Titkov SV, Speransky AV (2009) Structural defects in natural plastically deformed diamonds: evidence from EPR spectroscopy. Geol Ore Deposit 51:233–242CrossRefGoogle Scholar
  47. Orlov YL (1977) The mineralogy of diamond. John Wiley and Sons, Hoboken, pp 248Google Scholar
  48. Petts DC, Stern RA, Chacko T, Stachel T, Heaman LM (2015) A nitrogen isotope fractionation factor between diamond and its parental fluid derived from detailed SIMS analysis of a gem diamond and theoretical calculations. Chem Geol 410:188–200CrossRefGoogle Scholar
  49. Shigley J, Breeding CM (2013) Bright yellow diamonds from Sierra Leone. Gems Gemol 49(4):259–260Google Scholar
  50. Shirey SB, Richardson SH (2011) Start of the Wilson Cycle at 3 Ga shown by diamonds from subcontinental mantle. Science 333:434–436CrossRefGoogle Scholar
  51. Skinner EMW, Apter DB, Morelli C, Smithson NK (2004) Kimberlites of the Man craton, West Africa. Lithos 76:233–259CrossRefGoogle Scholar
  52. Smit KV, Shirey SB, Wang W (2016) Type Ib diamond formation and preservation in the West African lithospheric mantle: Re-Os age constraints from sulphide inclusions in Zimmi diamonds. Precambrian Res 286:152–166CrossRefGoogle Scholar
  53. Smith EM, Helmstaedt HH, Flemming RL (2009) Survival of the brown colour in diamond during storage in the subcontinental lithospheric mantle. Can Mineral 48:571–582CrossRefGoogle Scholar
  54. Smith EM, Shirey SB, Nestola F, Bullock ES, Wang J, Richardson SH, Wang W (2016) Large gem diamonds from metallic liquid in Earth’s deep mantle. Science 354(6318):1403–1405CrossRefGoogle Scholar
  55. Sparks RSJ, Baker L, Brown RJ, Field M, Schumacher J, Stripp G, Walters A (2006) Dynamical constraints on kimberlite eruption. J Volcanol Geotherm Res 155:18–48CrossRefGoogle Scholar
  56. Stachel T, Harris JW (2008) The origin of cratonic diamonds - constraints from mineral inclusions. Ore Geol Rev 34(1–2):5–32CrossRefGoogle Scholar
  57. Stachel T, Harris JW, Hunt L, Muehlenbachs K, Kobussen A, EIMF (2018) Argyle diamonds - how subduction along the Kimberley craton edge generated the world’s biggest diamond deposit. SEG - Spec Pub, in pressGoogle Scholar
  58. Steeds JW, Davis TJ, Charles SJ, Hayes JM, Butler JE (1999) 3H luminescence in electron-irradiated diamond samples and its relationship to self-interstitials. Diam Relat Mater 8:1847–1852CrossRefGoogle Scholar
  59. Sumida N, Lang AR (1981) Cathodoluminescence evidence of dislocation interactions in diamond. Philos Mag A 43(5):1277–1287CrossRefGoogle Scholar
  60. Taylor WR, Canil D, Milledge HJ (1996) Kinetics of Ib to IaA nitrogen aggregation in diamond. Geochim Cosmochim Ac 60(23):4725–4733CrossRefGoogle Scholar
  61. Titkov SV, Shigley JE, Breeding CM, Mineeva RM, Zudin NG, Sergeev AM (2008) Natural-color purple diamonds from Siberia. Gems Gemol 44:56–64CrossRefGoogle Scholar
  62. Titkov SV, Krivovichev SV, Organova NI (2012) Plastic deformation of natural diamonds by twinning: evidence from X-ray diffraction studies. Mineral Mag 76:143–149CrossRefGoogle Scholar
  63. Titkov SV, Mineeva RM, Zudina NN, Sergeev AM, Ryabchikov ID, Shiryaev AA, Speransky AV, Zhikhareva VP (2014) The luminescent nature of orange coloration in natural diamonds: optical and EPR study. Phys Chem Miner 42(2):131–141Google Scholar
  64. Titkov SV, Shiryaev AA, Zudina NN, Zudin NG, Solodova YP (2015) Defects in cubic diamonds from the placers in the northeastern Siberian platform: results of IR microspectrometry. Russ Geol Geophys 56:354–362CrossRefGoogle Scholar
  65. van Enckevort WJP, Visser EP (1990) Photoluminescence microtomography of diamond. Philos Mag B 62:597–614CrossRefGoogle Scholar
  66. Welbourn CM, Cooper M, Spear PM (1996) De Beers natural versus synthetic diamond verification instruments. Gems Gemol 32(3):156–169CrossRefGoogle Scholar
  67. Wilson L, Head JW (2007) An integrated model of kimberlite ascent and eruption. Nature 447:53–57CrossRefGoogle Scholar
  68. Zudina NN, Titkov SV, Sergeev AM, Zudin NG (2013) Features of photoluminescence centers in cubic diamonds of various coloration from placers in the north-east of Siberian platform. Proceedings of the Russian Mineralogical Society 142(4):57–72Google Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2018

Authors and Affiliations

  • Karen V. Smit
    • 1
    Email author
  • Ulrika F. S. D’Haenens-Johansson
    • 1
  • Daniel Howell
    • 2
    • 3
  • Lorne C. Loudin
    • 1
  • Wuyi Wang
    • 1
  1. 1.Gemological Institute of AmericaNew York CityUSA
  2. 2.Dipartimento di GeoscienzeUniversità degli Studi di PadovaPadovaItaly
  3. 3.Diamond Durability LaboratoryNew York CityUSA

Personalised recommendations