Diamond-forming media through time – Trace element and noble gas systematics of diamonds formed over 3 billion years of Earth’s history
Introduction
Rare macroscopic mineral inclusions in gem-quality (clear) monocrystalline diamonds (hereafter GMC diamonds), such as clinopyroxenes and garnets, have been used to determine the P-T conditions, growth environment and formation ages of diamonds (e.g., Pearson and Shirey, 1999, Stachel and Harris, 2008). Complimentary to this information, sub-micron fluid inclusions in fibrous diamonds directly provide information on the origin of the diamond-forming fluid (Navon et al., 1988). Abundant fluid inclusions in fibrous diamonds have made it possible to determine trace element concentrations by Instrumental Neutron Activation Analysis (INAA; Schrauder et al., 1996) and via online laser ablation- Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) techniques (Rege et al., 2005, Rege et al., 2010) on small pits (<100 µm in diameter). Trace element data for fluid-rich growth zones of diamonds show two main different trace element patterns; ribbed (elevated Ba-U-Th-Light Rare Earth Elements, depleted Nb-Ta) and planed (flat from Cs to Pr, without large anomalies) patterns (terminology of Weiss et al., 2013), which are observed in all fluid end-members (Schrauder et al., 1996, Rege et al., 2005, Tomlinson et al., 2005, Zedgenizov et al., 2007, Weiss et al., 2008, Tomlinson and Müller, 2009, Weiss et al., 2009, Klein-BenDavid et al., 2010, Rege et al., 2010, Weiss et al., 2011, Klein-BenDavid et al., 2014).
Fluid inclusions within GMC diamonds are scarce (Jablon and Navon, 2016). Rege et al. (2010) showed that although cloudy monocrystalline diamonds sometimes have trace element concentrations above the detection limit of “online” laser ablation ICP-MS, clear diamonds, without abundant fluid inclusions, have concentrations too low to permit quantitative measurement via this method. McNeill et al. (2009) developed an “offline” laser ablation and solution mode ICP-MS technique to sample larger quantities of GMC diamond, concentrating the analytes by ablations lasting between 20 minutes and several hours, such that analyte levels were above the limit of quantification by solution-mode ICP-MS. This approach also avoids the problems inherent to the lack of a matrix-matched reference material for direct ablation diamond analysis. The data available using the off-line ablation approach (Rege et al., 2010, Melton et al., 2012, Krebs et al., 2019) suggest that the trace element patterns of GMC diamonds are similar to those of fibrous diamonds, showing LREE enrichment over HREE, negative Sr anomalies, enriched Th, U, and both ribbed and planed patterns. In contrast, most GMC diamonds analysed by Melton et al. (2012) showed trace element patterns different to those of fibrous diamonds and the authors suggested that trace elements in these GMC diamonds may be present in ‘complex and variable mixtures of mineral inclusions’.
Like trace elements, noble gases are probably primarily located in fluid inclusions (e.g., Johnson et al., 2000, Broadley et al., 2018) and noble gas isotopic compositions and elemental abundances may thus possibly be related to trace element ratios and contents. As with trace elements, noble gas data for GMC diamonds are scarce. For a better understanding of the structure, volatile cycles, and evolution of the mantle, samples of different ages need to be investigated for both trace elements and noble gases (as 4He and 40Ar are decay products of the trace elements U-Th-Sm and K). The present-day noble gas compositions of the convecting upper mantle and a deeper mantle source contaminated by subducted material have been characterised by studying fresh basaltic glasses from mid-ocean-ridge (MORBs) and ocean islands (OIBs) (e.g., McDougall and Honda, 1998). Diamonds, on the other hand, could shed light on the noble gas composition of the sub-continental lithospheric mantle in the past. Diamond is an ideal mineral to study noble gases over time, as diamonds have a wide range in formation ages (0.07–3.5 Ga; Pearson and Shirey, 1999, Shirey et al., 2013), are physically and chemically inert, and have extremely low He diffusion rates (4He ∼ 4 × 10−21 cm2/s; Shelkov et al., 1998). Thus, diamonds can preserve trapped noble gas compositions over long timescales. Noble gases analysed from polycrystalline diamonds with minimum age constraints that are greater than or equal to the kimberlite eruption age, suggest heterogeneity in the mantle or evolution of the composition over time (Honda et al., 2011). However, no GMC diamonds with better age constraints have been studied for noble gases so far.
In this study, we present trace element and noble gas data for ten Southern-African GMC diamonds. Trace element abundances were determined using offline laser ablation followed by ICP-MS, He-Ne-Ar data was obtained utilising a high temperature furnace for graphitisation. The combined trace element and He-Ar data can provide new insights in the location of trace elements and noble gases in gem diamond, U-Th-Sm/He dating, diffusion and fractionation between trace elements and noble gases. The ten samples are of known parageneses (E-type n = 9, P-type n = 1) and have Re-Os or Sm-Nd mineral inclusion ages that range from 2.3 Ga to 0.09 Ga (Pearson et al., 1998, Gress et al., 2017, Timmerman et al., 2017). In addition, fragments of diamonds from Finsch and DeBeers Pool were measured for noble gases. These samples are remnants of many peridotitic monocrystalline diamonds that were broken open to extract inclusions (∼500 garnets for Finsch and ∼600 garnets for DeBeers Pool) for Sm-Nd and Rb-Sr dating, and yielded inclusion isochron ages of 3.2–3.3 Ga (Richardson et al., 1984). The wide range in mineral inclusion ages of the GMC diamonds in this study provides the unique opportunity to investigate the temporal changes of trace elements and He and Ar isotope compositions in the sub-continental lithospheric mantle.
Section snippets
Methods
Ten GMC diamonds from Koffiefontein (n = 3), Orapa (n = 4) and Letlhakane (n = 3) were analysed for trace elements and noble gases. The diamonds were selected based on homogeneous carbon isotope values and nitrogen concentrations and aggregation states. Descriptions and available N data are provided in Pearson et al., 1998, Timmerman et al., 2017. Carbon isotope values for the Koffiefontein diamonds were measured in this study, using the standard set-up for in-situ C analyses by SHRIMP as
Trace elements
Concentrations of trace elements in the studied GMC diamonds are extremely low, ranging from a few ppt up to 10 s of ppb, except for a few hundred ppb for Zr and for La and Nd in the Orapa samples (Table 3). Due to the low concentrations, the uncertainties on the element concentrations are large. The element Ce was not present above detection limit (blank plus 3σ) and is therefore not plotted or shown. In the Orapa samples the La/Nd and Nd/Pr ratios are not chondritic and appear to be
Constraining the location of trace elements and noble gases in GMC diamonds
The Orapa diamonds have on average lower trace element concentrations in their garnet and clinopyroxene mineral inclusions than the mineral inclusions in Letlhakane diamonds (Timmerman et al., 2017). In contrast, the bulk diamonds (lattice + micro-inclusions) of the same Orapa samples have higher concentrations than bulk diamonds of the Letlhakane samples. Therefore, the concentrations in the diamond are possibly highly dependent on the amount of micro-inclusions and/or number of twinning
Conclusions
Changes in the trace element and noble gas compositions in GMC diamonds over >3 billion years of Earth’s history were investigated in previously dated diamonds (3.4–0.09 Ga; 3P-type and 9 E-type diamonds), to track changes in gem-diamond forming fluid compositions and source regions through geological time. This study shows that trace element patterns of GMC diamonds are similar to fibrous diamonds and that the processes that produce variations in fluid trace element systematics, from planed
Acknowledgements
We thank Yannick Bussweiler for help with the laser, Sarah Woodland for assistance with the ICP-MS and Xiaodong Zhang for help with the Helix-MC Plus. Diamond samples from Botswana were provided by Prof. Dr. GR Davies and Dr. IL Chinn through the Debswana Diamond Company and the Finsch, DeBeers Pool, and Koffiefontein samples were provided by Prof. Dr. JW Harris through the De Beers Consolidated Mines. Both companies are members of the De Beers Group of Companies. Without this support this
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