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Comparative Cr and Mn speciation across a shore-to-reef gradient in lagoon sediments downstream of Cr-rich Ferralsols upon ultramafic rocks in New Caledonia
Journal of Geochemical Exploration ( IF 3.9 ) Pub Date : 2021-06-16 , DOI: 10.1016/j.gexplo.2021.106845
Pauline Merrot , Farid Juillot , Pierre Le Pape , Pierre Lefebvre , Jessica Brest , Isabelle Kieffer , Nicolas Menguy , Eric Viollier , Jean-Michel Fernandez , Benjamin Moreton , Olivier Radakovitch , Guillaume Morin

Ferralsols upon ultramafic rocks are among the most Cr-enriched soils at the Earth surface. Weathering and erosion of these soils represents a major source of Cr for coastal sediments downstream of ultramafic settings. Although Cr mainly occurs as Cr(III)-bearing chromite and Fe-(hydr)oxides in Ferralsols upon ultramafic rocks, several evidences of oxidized Cr(VI) in relation with Mn-oxides have been reported. Regarding the high solubility and toxicity of this latter Cr species, a thorough characterization of Cr and Mn crystal-chemistry in tropical sedimentary settings downstream of Ferralsols upon ultramafic rocks is needed to evaluate the potential threat towards the biodiversity of these coastal environments. In this study, we determined Cr and Mn speciation across a shore-to-reef gradient in lagoon sediments downstream of one of the largest lateritized ultramafic regolith in New Caledonia that contains up to 5 wt% Cr2O3. Chromium K-edge XANES data emphasized the absence of Cr(VI) and indicated a major hosting of Cr by chromite and clay minerals close to the shore, whereas Cr-bearing goethite dominated Cr speciation close to the reef. Manganese K-edge XANES data indicated a major hosting of Mn by clay minerals close to the shore, whereas Mn‑carbonates dominated Mn speciation close to the reef. The lack of Mn-oxides detection was considered to explain the absence of Cr(VI) in the studied sediments. This result thus suggests that, despite their shallow character that can favor occasional re-oxidation of the top-layer sediments upon re-suspension events, lagoon sedimentary settings downstream of Cr-rich Ferralsols upon ultramafic rocks appear rather favorable to Cr sequestration as the less mobile and less toxic Cr(III) form. However, the reverse trends observed from the shore to the reef between the chromite and goethite contributions to Cr speciation, as well as the decrease of the Cr/Ti ratio, suggest that a fraction of Cr could have been released towards the water column upon partial weathering of chromite to goethite during sediments transport across the shore-to-reef gradient. This latter point emphasizes the potential hazard that could still represent Cr for the exceptional biodiversity of tropical lagoon ecosystems downstream of Cr-rich Ferralsols, despite the absence of detectable Cr(VI). It thus calls for further studies aimed at better evaluating the stability of Cr(III)-bearing mineral phases upon early diagenesis in these shallow sedimentary settings.



中文翻译:

新喀里多尼亚超基性岩上富铬铁矿下游泻湖沉积物中的海岸到珊瑚礁梯度的比较 Cr 和 Mn 形态

超镁铁质岩石上的铁土是地球表面最富含铬的土壤之一。这些土壤的风化和侵蚀是超基性环境下游沿海沉积物的主要 Cr 来源。尽管 Cr 主要以含 Cr(III) 的铬铁矿和 Fe-(Hydro)氧化物的形式出现在超基性岩石上的 Ferralsols 中,但已经报道了与 Mn 氧化物有关的氧化 Cr(VI) 的几个证据。关于后一种 Cr 物种的高溶解度和毒性,需要对 Ferralsols 下游热带沉积环境中超基性岩上的 Cr 和 Mn 晶体化学进行彻底表征,以评估对这些沿海环境生物多样性的潜在威胁。在这项研究中,2 O 3. Chromium K-edge XANES 数据强调不存在 Cr(VI) 并表明靠近海岸的铬铁矿和粘土矿物主要承载 Cr,而含 Cr 的针铁矿在靠近礁石的位置占主导地位。锰 K 边缘 XANES 数据表明,靠近海岸的粘土矿物主要承载 Mn,而靠近礁石的 Mn 碳酸盐主导了 Mn 形态。Mn 氧化物检测的缺乏被认为可以解释所研究的沉积物中不存在 Cr(VI)。因此,该结果表明,尽管它们的浅层特征可能有利于在重新悬浮事件中偶尔重新氧化顶层沉积物,但在超基性岩上富铬铁矿下游的泻湖沉积环境似乎对 Cr 封存相当有利,因为流动性和毒性较小的 Cr(III) 形式。然而,从岸边观察到铬铁矿和针铁矿对 Cr 形态的贡献之间的反向趋势,以及 Cr/Ti 比率的降低,表明部分 Cr 可能在部分风化后向水体释放在沉积物穿过海岸到珊瑚礁梯度的过程中铬铁矿到针铁矿。后一点强调了尽管没有可检测到的 Cr(VI),但对于富含 Cr 的 Ferralsols 下游热带泻湖生态系统的特殊生物多样性来说,仍然可能代表 Cr 的潜在危害。因此,需要进一步研究以更好地评估这些浅层沉积环境中早期成岩作用中含 Cr(III) 矿物相的稳定性。以及 Cr/Ti 比值的降低,表明在沉积物穿过海岸到珊瑚礁梯度的过程中,铬铁矿部分风化成针铁矿时,一小部分 Cr 可能已经释放到水体中。后一点强调了尽管没有可检测到的 Cr(VI),但对于富含 Cr 的 Ferralsols 下游热带泻湖生态系统的特殊生物多样性来说,仍然可能代表 Cr 的潜在危害。因此,需要进一步研究以更好地评估这些浅层沉积环境中早期成岩作用中含 Cr(III) 矿物相的稳定性。以及 Cr/Ti 比值的降低,表明在沉积物穿过海岸到珊瑚礁梯度的过程中,铬铁矿部分风化成针铁矿时,一小部分 Cr 可能已经释放到水体中。后一点强调了尽管没有可检测到的 Cr(VI),但对于富含 Cr 的 Ferralsols 下游热带泻湖生态系统的特殊生物多样性来说,仍然可能代表 Cr 的潜在危害。因此,需要进一步研究以更好地评估这些浅层沉积环境中早期成岩作用中含 Cr(III) 矿物相的稳定性。后一点强调了尽管没有可检测到的 Cr(VI),但对于富含 Cr 的 Ferralsols 下游热带泻湖生态系统的特殊生物多样性来说,仍然可能代表 Cr 的潜在危害。因此,需要进一步研究以更好地评估这些浅层沉积环境中早期成岩作用中含 Cr(III) 矿物相的稳定性。后一点强调了尽管没有可检测到的 Cr(VI),但对于富含 Cr 的 Ferralsols 下游热带泻湖生态系统的特殊生物多样性来说,仍然可能代表 Cr 的潜在危害。因此,需要进一步研究以更好地评估这些浅层沉积环境中早期成岩作用中含 Cr(III) 矿物相的稳定性。

更新日期:2021-06-29
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