THE EFFECTS OF PHOSPHATIZATION ON THE REY OF CO-RICH FE-MN CRUSTS
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摘要:
稀土(REY)是一组有效示踪物质源区和地质过程的元素，本研究利用X荧光光谱法(XRF)和电感耦合等离子光谱仪(ICP-MS)分析了马尔库斯-威克海山和中太平洋海山富钴结壳的主要元素和稀土元素，结合前人研究成果对比了磷酸盐化及未磷酸盐化富钴结壳的稀土特征。结果显示：磷(P)含量低的结壳具有相对低的稀土总量(∑REY)，北美页岩标准化后显示铈(Ce)正异常和钇(Y)负异常；磷酸盐化后的结壳具有相对高的∑REY，并表现出Ce正异常和显著Y正异常。磷酸盐化结壳中应存在“富稀土磷酸盐”组分，特别是对Y具有重要贡献。将磷酸盐化结壳视为磷酸盐组分和结壳组分的混合，模拟结果显示富稀土磷酸盐组分具有海山磷块岩的稀土配分模式，但是其∑REY达到普通磷块岩的10倍或以上。考虑到海洋中富钙沉积物丰富，大量PO43-不同程度地交代碳酸盐等钙质物质，容易形成贫稀土磷酸盐。而伴随结壳缓慢的成矿过程，部分磷酸盐的形成未受到碳酸盐的影响，容易形成富稀土磷酸盐。
Abstract:Rare earth elements and yttrium (REY) are extremely coherent in the nature. The relative abundances of them can be used to deduce their sources or subsequent geological processes. Major elements and REY of the Co-rich Fe-Mn Crusts from Marcus-Wake Seamounts and Mid-Pacific seamounts are analyzed by XRF and ICP-MS. Combined with previous studies, REY characteristic of phosphatized and non-phosphatized Fe-Mn Crusts are emphasized respectively. Fe-Mn Crusts with low P have low ΣREY and notably positive Ce anomaly, as well as negative yttrium anomaly, after normalized by the North American shale composite(NASC). While Fe-Mn Crusts with high P have relatively high ΣREY, positive Ce anomaly and notably positive yttrium anomaly normalized by NASC. There must exist REY-rich phosphate components in the phosphatized Co-rich Fe-Mn Crusts, which are especially rich in yttrium. The issue of phosphatized crusts could be regarded as a mixed model of phosphate components and Fe-Mn crust components. Mixed model simulating result indicates that REY-rich phosphate components in Fe-Mn Crusts have the same REY pattern as seamount phosphate rock, but the content could be more than 10 times over that of seamount phosphate rock. Besides REY3+ and Ca2+, other alkali-earth metal ions can also be bound to PO43- in water column, and there are numerous calcareous sediments in ocean, PO43- can replace CO32- in carbonate sediments to form REY-poor phosphate. However, the growth of the Fe-Mn Crust is so slow that REY has a better environment to compete with Ca at the time of PO43- input, forming dissemination REY-rich phosphate. Although PO43- is still mainly bound with Ca2+ in REY-rich phosphate, ΣREY/Ca ratio increases remarkably. This REY enrichment model may be a common geological process in non-calcium sediments in deep sea.
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表 1 富钴结壳浅钻岩心样品特征
Table 1. Sample information of Co-rich Fe-Mn crust from Bataza and Qianyu seamount
样品编号 海山区 结壳厚度/cm 结壳描述 下伏基岩描述 BA02 9 黑色结壳具有三层结构，底部2 cm，为致密亮煤状；中部6 cm疏松多孔；上部1 cm具豆状突起 蚀变的灰黑色玄武岩和灰白色灰岩 BA04 7 黑色结壳为单层结构，较致密，表面粗糙，有豆状凸起 基岩为浅黄色碳酸盐岩，较疏松，遇盐酸冒泡，为风化的碳酸盐 BA05 1.5 黑色结壳为单层结构，致密，表面粗糙 基岩为浅黄色至灰白色的礁灰岩，可见脉状方解石充填，含有贝壳等生物化石 BA06 20 黑色结壳为单层结构，致密 未获取基岩 BA08 7 黑色结壳为单层结构，较致密，表层有豆状突起 上部深灰色礁灰岩，可见较多的生物化石；下部为灰白色礁灰岩，多孔疏松，有较多的生物化石 BA10A 马尔库斯-威克海山区 4.15 3个黑色结核状结壳，球状，表面光滑。中型2个，粒径4~5 cm；小型粒径2 cm 基岩为黄白色-浅粉色生物碎屑灰岩，表面有少量黑色的微结核，岩石中有大量贝壳，螺壳，有孔虫等 BA10 5.5 黑色结壳具有三层结构，上层较致密，局部有鲕状突起；中层深褐色，可见浅色的碳酸盐充填在孔洞和裂隙中；下层致密亮煤状 未获取基岩 BA11 9 黑色结壳具有三层结构，上层4 cm，较致密，有葡萄状或者瘤状突起；中层3 cm，疏松多孔；下层2 cm，致密亮煤状 基岩上部为灰白色到浅黄色礁灰岩，局部可见生物化石；下部为灰白色钙质胶结的生物碎屑灰岩，疏松多孔 BA14 12 黑色结壳具有三层结构，上层2 cm，较致密；中层5 cm，较疏松多孔；下层5 cm，致密亮煤状 浅黄色至灰白色的礁灰岩，可见脉状方解石充填，含有生物化石 BA15 8 黑色结壳具有三层结构，上层2 cm，较致密，表面平坦；中层2 cm，较疏松多孔；下层4 cm，致密亮煤状 基岩为灰白色角砾岩，角砾为玄武岩，砾径为0.2~4 cm，分选差 QY01 2 黑色结壳单层结构，较致密 灰白色，主要由老结壳碎块组成，粒径最大可达数厘米，棱角状，分选性差，基质主要由钙质组成，部分发生磷酸盐化 QY03 中太平洋海山区 8 黑色结壳具有三层结构，上层2 cm黑色，较致密，表面有豆状突起；中层2 cm，疏松多孔；下层4 cm，致密亮煤状 上部为浅黄色风化壳灰岩，中间夹杂黄色灰岩团块，钙质胶结；下部为灰白色-肉红色生物碎屑角砾岩，棱角状，局部有空洞发育和生物碎屑颗粒 QY06 2 黑色结壳为单层结构，较致密，表层有豆状突起 白色的生物碎屑礁灰岩，无分层，可见大量的生物壳体，最大者达2~3 cm 
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表 2 富钴结壳主量元素和稀土元素分析结果
Table 2. Composition of major and rare earth elements in Co-rich Fe-Mn crusts from Bataza and Qianyu seamounts
样号 单位 BA02 BA04 BA04 BA05 BA06 BA08 BA10A BA10 BA10 BA11 BA14 BA14 BA15 QY01 QY03 QY03 QY06 GSMC-1 GSMC-1 层位 上层 下层 上层 下层 上层 下层 参考值 测试值 Mn % 23.50 23.28 16.46 19.04 26.59 24.98 24.10 22.49 21.53 19.97 25.24 26.17 18.66 25.98 24.87 24.37 19.92 23.2 23.35 Fe 14.21 17.74 6.03 18.45 11.39 13.06 16.15 17.46 11.87 10.04 14.96 11.90 12.25 9.99 17.41 15.26 17.82 17.1 17.08 P2O5 1.33 1.00 23.06 1.24 4.24 0.99 1.36 1.65 11.09 12.96 1.00 6.57 11.74 7.70 1.52 3.41 1.01 1.59 1.54 CaO 4.25 3.41 35.45 3.85 9.25 4.41 4.19 4.28 18.72 21.32 3.67 12.56 19.65 14.74 3.71 7.08 3.5 4.6 4.73 MgO 2.43 2.21 0.78 2.24 2.25 2.55 2.25 2.16 1.26 1.36 2.38 1.57 1.40 1.70 2.16 2.00 2.11 1.85 1.96 Al2O3 2.69 2.10 1.32 3.41 1.50 2.68 2.08 2.35 1.26 1.78 2.13 0.95 1.68 1.05 1.52 1.46 2.95 2.1 2.14 SiO2 11.35 11.99 3.70 17.59 5.66 10.17 10.21 12.57 4.39 6.48 10.10 2.90 5.88 3.39 9.20 6.84 14.94 10.3 10.24 K2O 0.95 0.67 0.51 0.81 0.72 0.95 0.68 0.68 0.51 0.65 0.80 0.57 0.52 0.61 0.57 0.64 0.77 0.76 0.74 TiO2 2.14 1.57 0.97 1.79 1.85 2.02 1.77 1.58 1.46 1.37 1.85 1.47 1.64 1.53 1.45 2.00 2.33 2.2 2.20 Cu 0.25 0.09 0.03 0.13 0.18 0.26 0.14 0.09 0.10 0.11 0.20 0.10 0.11 0.11 0.06 0.10 0.25 0.14 0.14 Co 0.67 0.58 0.21 0.55 0.62 0.63 0.64 0.58 0.29 0.32 0.62 0.38 0.30 0.50 0.86 0.58 0.61 1.3 1.27 Ni 0.54 0.48 0.30 0.36 0.66 0.67 0.50 0.42 0.34 0.40 0.59 0.39 0.31 0.54 0.39 0.46 0.38 0.44 0.43 Y 10-6 144.4 200.4 781.2 193.1 251.9 176.9 200.0 212.6 300.7 584.3 187.9 355.5 1 468.2 251.5 205.3 225.2 93.6 239 241 La 200.9 293.9 438.0 314.5 232.4 230.4 295.3 297.2 313.6 377.2 268.4 392.8 970.1 257.2 264.8 261.3 199.5 352 347 Ce 1 344 728.4 746.8 702.4 1210 1169 918.4 822.4 2484 1 098 1 089 2 976 1 423 1 391 1 023 1 284 1 281 1 320 1 290 Pr 45.62 55.81 67.32 55.79 47.59 46.62 59.98 59.98 45.19 59.98 55.31 59.72 82.00 44.90 45.90 48.20 42.40 72 72.2 Nd 181.3 229.3 286.6 226.3 191.8 182.0 236.1 235.0 171.8 244.2 215.4 225.8 349.8 173.5 187.6 191.0 160.6 289 291 Sm 38.43 46.32 55.92 46.55 39.85 40.26 52.96 51.43 31.78 49.24 47.00 42.26 64.10 35.20 38.80 38.80 35.70 61 60.9 Eu 9.37 11.02 13.77 11.03 9.71 9.60 12.27 11.93 7.94 12.17 11.06 10.38 16.10 8.70 9.50 9.60 8.40 14 14.2 Gd 47.03 52.20 68.60 49.84 48.47 46.27 55.01 54.16 47.38 61.57 52.29 60.42 87.10 44.70 47.70 48.90 41.50 65 66.9 Tb 6.23 7.97 10.48 7.70 6.60 6.37 8.11 8.14 5.71 8.77 7.44 7.63 12.50 6.00 6.90 6.60 5.30 9.4 9.57 Dy 37.64 52.12 71.96 48.57 42.40 39.59 51.34 52.07 37.71 60.02 47.92 48.77 86.40 39.00 44.70 42.50 32.00 58 59.8 Ho 7.05 10.26 16.60 9.73 8.47 8.27 10.16 10.51 8.75 13.86 9.46 10.89 20.00 8.40 9.70 8.90 6.10 11.3 11.7 Er 19.91 30.36 51.61 27.65 24.96 23.45 27.99 28.72 26.29 41.36 27.13 31.75 60.80 24.90 27.40 25.70 16.60 32 32.6 Tm 2.98 4.45 7.43 4.10 3.67 3.36 4.28 4.21 3.96 6.03 4.01 4.79 8.40 3.70 4.20 3.80 2.30 4.4 4.78 Yb 18.45 28.19 48.96 25.92 22.91 22.50 27.90 28.34 26.59 39.77 26.87 30.23 58.10 25.00 26.90 24.90 16.10 31 30.6 Lu 2.75 4.21 7.95 3.94 3.52 3.41 4.11 4.27 4.21 6.60 3.83 4.58 9.40 3.90 4.20 3.90 2.40 4.5 4.47 ∑REY 2 106 1 755 2 673 1 727 2 144 2 008 1 964 1 881 3 516 2 663 2 053 4 262 4 716 2 317 1 946 2 224 1 944
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表 3 磷酸盐与结壳二元混合模拟数据
Table 3. Virtual data of digital simulation mixing model between Cobalt-rich crust and phosphate
×10-6 元素 磷酸盐 结壳 4% 8% 15% 元素 磷酸盐 结壳 75% 50% 25% Y 7 000.0 134.1 408.7 683.3 1 164.0 Y 500.0 134.1 408.5 317.0 225.5 La 2 160.0 297.4 371.9 446.4 576.8 La 151.2 297.4 187.7 224.3 260.8 Ce 1 944.0 1 600.0 1 613.8 1 627.5 1 651.6 Ce 136.1 1 600.0 502.1 868.0 1 234.0 Pr 408.1 59.5 73.4 87.4 111.8 Pr 28.6 59.5 36.3 44.0 51.7 Nd 1 756.7 253.0 313.2 373.3 478.6 Nd 123.0 253.0 155.5 188.0 220.5 Sm 372.6 52.4 65.2 78.0 100.4 Sm 26.1 52.4 32.7 39.3 45.8 Eu 97.6 13.1 16.5 19.9 25.8 Eu 6.8 13.1 8.4 10.0 11.5 Gd 514.6 58.5 76.7 95.0 126.9 Gd 36.0 58.5 41.6 47.2 52.9 Tb 80.7 9.1 11.9 14.8 19.8 Tb 5.7 9.1 6.5 7.4 8.2 Dy 505.7 51.4 69.6 87.8 119.6 Dy 35.4 51.4 39.4 43.4 47.4 Ho 115.3 9.8 14.0 18.2 25.6 Ho 8.1 9.8 8.5 8.9 9.4 Er 328.3 28.2 40.2 52.2 73.2 Er 23.0 28.2 24.3 25.6 26.9 Tm 51.5 4.1 6.0 7.9 11.2 Tm 3.6 4.1 3.7 3.9 4.0 Yb 292.8 25.2 35.9 46.6 65.3 Yb 20.5 25.2 21.7 22.8 24.0 Lu 42.9 3.6 5.2 6.7 9.5 Lu 3.0 3.6 3.2 3.3 3.5 ∑REE 8 670.8 2 465.2 2 713.5 2 961.7 3 396.1 ∑REE 607.0 2 465.2 1 071.5 1 536.1 2 000.7 ∑REY 15 670.8 2 599.3 3 122.2 3 645.0 4 560.0 ∑REY 1 107.0 2 599.3 1 480.0 1 853.1 2 226.2 注：4%等表示二元模拟中磷酸盐组分的含量。
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