Element Migration and Accumulation Characteristics of Bedrock-Regolith-Soil-Fruit Plant Continuum of the Earth's Critical Zone in Chengde Almond Producing Area
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摘要: 特色经济作物品质与生态地球化学条件密切相关，查明山区地球关键带基岩-风化壳-土壤-作物BRSPC系统元素迁移富集规律，对农业种植布局优化具有重要意义.选取承德冀北山区仁用杏产区为研究区，结合多元统计分析采用多种化学风化指数、元素化学损耗分数CDF、质量迁移系数法、生物富集系数BCF法分碎屑岩建造区和火山岩建造区定量评价BRSPC体系中元素迁聚特征.结果表明：研究区土壤TK和TFe2O3含量丰富，Se元素含量适量，Cu和Ge含量中等-较丰富，TP、S和B元素含量较缺乏.区内基岩-土壤总体处于初等化学风化阶段，火山岩建造区土壤风化程度总体高于碎屑岩区.土壤S、B、Se、Ti、MgO和Fe2O3含量在基岩风化过程相对富集，基岩风化过程中Se、S、B、Ni和V为质量迁移强活动元素.全区85.71%的杏果肉样品Se含量达到富硒标准，25%杏仁达到含硒-富硒标准；碎屑岩区杏果实Se含量高于火山岩区.基岩风化过程中的元素富集亏损特征与土壤-作物吸收过程中的元素迁聚密切相关，BRSPC系统元素传导具有较好的继承性.土壤Cu、Zn、TP、Se、B、CaO和TFe2O3含量是制约研究区杏果实品质的主要地化因素，火山岩基岩风化过程中Cu和Zn元素淋滤流失程度大于碎屑岩区，碎屑岩区土壤TP、Se、B、CaO和TFe2O3含量高于火山岩建造区，相对更适宜于仁用杏种植.Abstract: Eco-geochemical conditions have an important impact on the quality of characteristic crops. It is of great significance to carry out investigation of the element migration and accumulation characteristics of the bedrock-regolith-soil-plant continuum of the Earth's critical zone for the adaptive evaluation on agricultural planting and the optimization of utilization of agricultural land. Taking the almond producing area in Chengde, Hebei Province as the study area, the quantitative evaluation of element migration in BRSPC was calculated by multiple chemical weathering index, chemical depletion fraction, mass transfer coefficient and bioconcentration factor in clastic rock and volcanic rock formation area combining multiple statistical methods. The results indicate that the element geochemical grade of TK and TFe2O3 were categorized as rich level, Se categorized as moderate level, Cu and Ge categorized as moderate-rich level and TP, TS, B as insufficient level. The bedrock-regolith-soil samples in the study area are generally at the elementary chemical weathering stage while the weathering intensity of soil ofvolcanic rock formation area is relatively higher than that of clastic rock formation area. The TS, B, Se, Ti, MgO and Fe2O3 contents are relatively enriched in soil during the weathering process of bedrocks, and the Se, S, B, Ni, and V are strong active elements for mass migration. The Se content of 85.71% of the almond pulp samples belong to the selenium-rich fruit, with 25% of the almond samples being above the selenium-enriched level. Meanwhile, The Se content in both of almond pulp and almond samples located in clastic rock formation are relatively higher than that in volcanic rock formation. The characteristics of element enrichment and loss in weathering process are closely related to the element migration in the soil-plant absorption process, and the bedrock-regolith-soil-plant continuum has a good inheritance on element conduction. The contents of Cu, Zn, TP, Se, B, Cao and TFe2O3 in soil were the main geochemistry factors restricting the quality of almond and pulp in the study area. The leaching loss of Cu and Zn elements in the weathering process of volcanic bedrock is greater than that in clastic rock area, while the contents of TP, Se, B, Cao and TFe2O3 in the soil of clastic rock formation area are higher than those in the volcanic rock formation area, which leads to the conclusion that the clastic rock formation area is more suitable for almond apricot planting.
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Key words:
- Earth's critical zone /
- geochemistry /
- weathering mechanism /
- element migration /
- BRSPC /
- almond /
- Chengde
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图 2 研究区不同建造采样剖面与典型基岩样品镜下特征显微照片(正交偏光镜下)
a.火山岩建造采样剖面；b.杏果实样品；c.流纹质凝灰岩；d.杏仁状粗安岩；e.碎屑岩建造与采样剖面；f.砂砾岩标本；h.变质粗粒岩屑长石砂岩；i.变质细粒岩屑砂岩；Pl.斜长石；K.钾长石；Q.石英；Hb. 角闪石；Bi.黑云母；Mu.白云母
Fig. 2. Sampling profile and microtextures of typical rock samples in different formation(PLM)
图 4 原岩类型判别基岩-风化层-土壤CIA、IOL、MIA风化指数三元图
a.原岩类型判别图；b.SiO2-Al2O3-Fe2O3 (Saf)砖红壤化指数IOL；c.Al2O3-CaO+Na2O-K2O (A-CN-K)化学蚀变指数CIA图；d.A-CNK-FM还原镁铁质蚀变指数MIAR；e.A-CNKM-F氧化镁铁质蚀变指数MIAo；f.AF-CNK-M氧化镁铁质蚀变指数MIAo；SS.碎屑岩区土壤；RS. 碎屑岩区风化层；BS.碎屑岩区基岩；SV.火山岩区土壤；RV.火山岩区风化层；BV.火山岩区基岩
Fig. 4. Discrimination of protolith and the CIA, IOL and MIA weathering index of bedrock-regolith-soil samples
图 5 基岩风化CIA值与Na/K关系
SS.碎屑岩区土壤；RS.碎屑岩区风化层；BS.碎屑岩区基岩；SV.火山岩区土壤；RV.火山岩区风化层；BV.火山岩区基岩
Fig. 5. Relationships of CIA versus Na /K
图 6 不同建造区基岩-土壤元素化学损耗分数CDF箱线图
Fig. 6. Statistical boxplot of chemical depletion fraction in different geological formations
图 7 不同建造区基岩-土壤元素质量迁移系数τTi箱线图
Fig. 7. Statistical boxplot of mass transfer coefficient in different geological formations
图 8 基岩-土壤元素主成分载荷与系统聚类树状图
Fig. 8. Factor loading analysis and systematic clustering dendrogram of rock and soil samples
图 9 杏果实样品微量元素与稀土元素含量
Fig. 9. Trace element and rare earth element content in almond and pulp samples
图 10 基岩-风化层-土壤与杏果实样品稀土元素
Fig. 10. Curve of distribution of REE in the bbedrock-regolith-soil-almond and pulpcontinuum
图 11 杏果实根系土-作物生物微量元素富集系数
Fig. 11. Statistical boxplot of bioconcentration factor in soil-almond and pulpcontinuum
图 12 岩土样品Cu、Zn元素含量与CIA相关关系及土壤-杏果实系统Cu、Zn元素含量相关关系
SS.碎屑岩区土壤；RS.碎屑岩区风化层；BS.碎屑岩区基岩；SV.火山岩区土壤；RV.火山岩区风化层；BV.火山岩区基岩
Fig. 12. Relationship of CIA versus Cu and Zn contentof bedrock-regolith-soil samples, and Cu and Zn content relationship in soil-crop system
图 13 杏果实元素主成分因子载荷
Fig. 13. Factor loading analysis of element content inalmond and pulp
表 1 研究区土壤-风化层-基岩元素地球化学含量统计
Table 1. Statistics of geochemical element content of bedrock-regolith-soil samples
分层 土壤 风化层 基岩 全国浅层土壤背景 碎屑岩 Min Max Mean CV Min Max Mean CV Min Max Mean CV TN(mg/kg) 450.20 1 964.00 1 168.73 0.375 112.00 2 674.00 531.95 1.290 101.00 536.00 183.00 0.709 707.00 TP(mg/kg) 202.70 1 794.00 658.65 0.541 367.40 1 589.00 709.65 0.431 233.10 3 113.00 818.20 0.800 570.00 S(mg/kg) 109.70 615.30 242.13 0.448 48.65 361.10 106.49 0.829 48.63 180.20 83.79 0.558 245.00 B(mg/kg) 11.69 94.03 38.83 0.476 8.54 116.600 29.25 1.063 5.88 45.43 16.49 0.711 43.00 Cu(mg/kg) 15.23 68.50 25.56 0.453 9.34 46.63 22.57 0.496 10.73 91.94 26.76 0.710 20.00 Zn(mg/kg) 42.19 140.40 77.54 0.250 47.89 112.00 76.19 0.257 50.50 154.70 78.20 0.298 66.00 Mo(mg/kg) 0.483 1.136 0.747 0.206 0.328 1.406 0.659 0.366 0.393 2.658 0.731 0.686 0.70 Se(mg/kg) 0.107 0.574 0.224 0.410 0.040 0.405 0.121 0.979 0.032 0.084 0.047 0.353 0.17 Ge(mg/kg) 1.082 1.897 1.349 0.113 0.939 1.498 1.158 0.158 0.836 1.933 1.175 0.252 1.30 Mn(mg/kg) 499.90 1 527.00 698.08 0.273 104.00 1 238.00 629.84 0.436 318.600 1347.00 647.86 0.467 569.00 V(mg/kg) 9.533 204.200 85.908 0.304 22.550 116.600 76.393 0.356 33.370 127.900 62.638 0.419 70.00 Ti(mg/kg) 2 922.3 5 687.2 3 938.488 0.169 1 123.2 4 685.6 3 286.344 0.312 2 063.8 7 427.1 3 188.819 0.455 3 498 pH 5.27 8.420 7.15 0.132 5.91 9.08 7.64 0.100 6.60 9.10 7.99 0.102 8.00 Corg(%) 1.061 3.553 2.170 0.359 0.211 3.251 1.093 1.184 0.113 0.986 0.443 0.966 0.26 SiO2(%) 60.635 71.029 65.758 0.043 53.560 75.133 66.306 0.072 56.775 77.024 68.465 0.095 66.70 Al2O3(%) 11.763 15.351 13.344 0.076 3.718 14.684 13.362 0.184 9.489 20.138 13.495 0.173 11.90 K2O(%) 1.432 3.480 2.706 0.148 0.364 5.065 3.126 0.278 2.442 4.244 3.342 0.166 2.36 Na2O(%) 1.132 3.257 2.679 0.227 0.116 3.977 2.778 0.448 0.870 5.156 3.443 0.294 1.75 CaO(%) 0.528 5.052 1.759 0.525 1.035 19.420 2.929 1.400 1.161 11.864 3.066 1.092 2.74 MgO(%) 1.353 7.125 2.438 0.545 0.694 4.156 1.492 0.522 0.587 2.308 1.323 0.333 1.43 TFe2O3(%) 3.236 23.350 5.325 0.584 1.234 7.546 4.321 0.331 1.789 6.660 3.791 0.330 2.80 LREE(μg/kg) 162.139 166.605 164.834 0.014 98.645 159.850 134.261 0.237 79.936 298.602 174.005 0.646 139.20 HREE(μg/kg) 41.366 41.753 41.533 0.005 17.705 28.436 24.367 0.239 16.163 85.277 43.181 0.856 40.70 REE(μg/kg) 203.618 208.358 206.367 0.012 116.350 188.286 158.628 0.237 96.099 383.879 217.186 0.687 179.90 L/HREE 3.909 4.007 3.969 0.013 5.352 5.621 5.515 0.026 3.502 5.105 4.518 0.196 3.42 TN(mg/kg) 146.00 2 523.00 1 250.88 0.431 79.00 960.00 328.97 0.655 48.00 225.00 123.76 0.321 381.00 TP(mg/kg) 145.95 1 373.00 495.80 0.528 112.20 1 741.00 565.79 0.819 77.84 1 847.00 651.940 0.770 517.00 S(mg/kg) 68.91 1 562.00 240.93 0.918 31.83 592.800 117.18 0.914 21.12 1 557.00 148.06 2.028 142.00 B(mg/kg) 10.81 53.25 33.24 0.238 3.97 49.63 17.88 0.807 3.23 39.29 8.89 0.797 52.00 Cu(mg/kg) 11.13 88.20 25.13 0.560 1.76 64.33 24.86 0.629 6.55 390.20 56.53 1.216 23.00 Zn(mg/kg) 55.30 142.00 83.91 0.220 46.67 204.36 96.05 0.318 38.69 361.70 117.22 0.488 62.00 Mo(mg/kg) 0.408 8.849 1.217 1.296 0.045 13.560 1.242 1.776 0.218 56.000 2.414 3.599 0.52 Se(mg/kg) 0.035 0.338 0.180 0.400 0.030 0.218 0.082 0.612 0.002 0.182 0.039 0.800 0.07 Ge(mg/kg) 0.908 2.427 1.363 0.182 0.734 1.765 1.258 0.199 0.538 1.905 1.226 0.256 1.40 Mn(mg/kg) 343.75 1542.00 782.69 0.333 40.460 2742.00 824.93 0.653 20.95 1 572.00 577.74 0.548 705.00 V(mg/kg) 32.880 745.100 91.951 1.102 7.714 489.800 67.159 1.162 4.659 202.500 51.895 1.004 82.00 Ti(mg/kg) 2 669.3 5 716.3 4 142.194 0.164 0.767 5 780.6 3 426.388 0.413 863.1 6 589.941 3 336.515 0.484 3 844 pH 4.82 8.29 6.84 0.114 5.23 9.35 6.96 0.127 5.97 8.79 7.41 0.102 8.61 Corg (%) 0.076 4.008 1.705 0.557 0.031 1.500 0.325 0.920 0.054 0.220 0.096 0.331 0.60 SiO2(%) 54.054 75.683 64.956 0.066 54.380 77.039 65.891 0.070 57.054 85.290 68.601 0.095 64.87 Al2O3(%) 11.114 16.141 13.870 0.091 11.950 18.243 15.060 0.113 7.724 17.611 14.734 0.127 12.84 K2O(%) 1.970 5.872 2.988 0.238 1.410 7.628 3.486 0.379 0.614 9.900 4.431 0.455 2.34 Na2O(%) 1.364 3.255 2.110 0.173 0.276 6.700 2.811 0.419 0.413 5.980 3.299 0.384 1.70 CaO (%) 0.633 3.471 1.515 0.403 0.375 6.271 1.641 0.812 0.050 5.254 1.774 0.837 4.10 MgO(%) 0.716 2.653 1.570 0.271 0.153 2.576 1.307 0.452 0.181 3.401 1.152 0.724 1.88 TFe2O3(%) 3.559 9.414 4.935 0.222 1.445 8.349 4.629 0.328 1.344 8.072 4.293 0.441 3.71 LREE(μg/kg) 62.602 212.656 178.360 0.229 95.557 367.279 226.217 0.347 123.603 291.264 215.978 0.247 128.72 HREE(μg/kg) 9.538 77.431 44.266 0.314 12.266 79.066 50.313 0.347 19.522 68.319 45.308 0.331 41.00 REE(μg/kg) 72.140 290.087 222.626 0.239 107.823 446.345 276.529 0.344 148.411 351.823 261.286 0.252 169.72 L/HREE 2.746 6.563 4.232 0.190 3.370 7.790 4.711 0.251 3.017 7.041 4.995 0.188 3.14 注: Min表示最小值；Max表示最大值；Mean表示均值；CV表示变异系数；pH和L/HREE无量纲. 
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表 2 风化指数计算方法一览表
Table 2. Calculation formula of weathering Index
指标 计算公式 参考文献 Sa [SiO2/Al2O3] Price et al.(2003) Saf [SiO2/(Al2O3+Fe2O3)] Qiu et al.(2014) IOL [(Al2O3+Fe2O3)/(Al2O3+Fe2O3+SiO2)]×100 Babechuk et al.(2014) CIA [Al2O3/(Al2O3+CaO*+Na2O+K2O)]×100 Nesbitt and Young(1982, 1984) MIAo [Al2O3/(Al2O3+Fe2O3+MgO+CaO*+Na2O+K2O)]×100 Babechuk et al.(2014) MIOr [(Al2O3+Fe2O3)/(Al2O3+Fe2O3+MgO+CaO*+Na2O+K2O)]×100 Babechuk et al.(2014) CIX [Al2O3/(Al2O3+Na2O+K2O)]×100 Garzanti et al.(2014) ICV [(Fe2O3+MgO+CaO*+Na2O+K2O+MnO+TiO2)/Al2O3] Cox et al.(1995) 注: IOL指标运用氧化物的质量分数计算，其余风化指标均运用氧化物的分子摩尔数计算；CaO*为硅酸盐矿物中的摩尔含量，不包括碳酸盐和磷酸盐矿物中的CaO含量；由于硅酸盐中的CaO与Na2O通常以1∶1的摩尔比例存在，所以当CaO的摩尔数大于Na2O时，CaO*的分子摩尔等于Na2O的分子摩尔，而小于Na2O时则有m(CaO*)=m(CaO).
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表 3 不同地质建造土壤-风化层-基岩风化指数统计
Table 3. Statistics on weathering index of bedrock-regolith-soil samples in different geological formations
建造 采样层 项目 Sa Saf IOL CIA MIAO MIOR PIA CIX ICV 碎屑岩 土壤 Min 6.71 0.96 16.73 52.14 41.48 51.01 53.12 59.24 1.20 Max 10.27 0.99 26.05 66.25 46.59 57.81 70.27 77.18 1.49 Mean 8.40 0.98 21.38 56.13 43.95 53.17 58.26 64.83 1.34 CV 0.119 0.007 0.141 0.066 0.029 0.040 0.08 0 0.076 0.051 风化层 Min 7.31 0.96 17.01 9.37 7.28 8.82 8.55 56.74 1.06 Max 9.95 0.99 24.14 64.55 49.49 59.72 72.58 86.42 1.74 Mean 8.44 0.98 21.00 52.96 42.61 50.95 54.97 63.66 1.34 CV 0.086 0.006 0.092 0.182 0.174 0.174 0.207 0.094 0.107 基岩 Min 6.71 0.96 15.66 27.38 23.86 28.05 23.59 54.54 1.18 Max 10.99 1.00 26.70 59.06 47.57 53.29 64.21 72.11 2.59 Mean 9.00 0.98 19.94 48.06 39.79 46.79 47.99 58.98 1.53 CV 0.156 0.008 0.161 0.151 0.147 0.196 0.085 0.217 0.161 火山岩 土壤 Min 6.28 0.94 16.26 52.72 38.14 49.65 53.82 58.99 0.99 Max 11.58 0.98 30.35 68.28 51.16 62.02 74.98 74.07 1.70 Mean 8.05 0.97 22.52 59.33 45.55 55.78 62.93 67.47 1.26 CV 0.140 0.009 0.131 0.058 0.069 0.051 0.073 0.055 0.128 风化层 Min 5.67 0.95 15.36 41.58 34.15 42.97 40.23 51.64 0.84 Max 10.90 0.99 29.94 67.48 55.38 64.12 85.45 74.34 2.00 Mean 7.56 0.97 22.99 57.47 46.48 55.43 61.51 64.42 1.23 CV 0.159 0.010 0.234 0.146 0.099 0.110 0.089 0.148 0.071 基岩 Min 6.01 0.89 9.61 37.69 21.40 38.54 37.18 50.13 0.84 Max 11.26 1.00 29.44 62.94 55.32 62.07 84.45 71.14 2.11 Mean 7.95 0.97 21.54 52.11 43.55 51.64 54.56 59.13 1.32 CV 0.178 0.022 0.208 0.206 0.094 0.154 0.093 0.154 0.076
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表 4 土壤-作物系统元素质量迁移系数τREE
Table 4. Mass transfer coefficient τREE in soil-plant system
迁移系数 B Ni Cu Zn Mo Se 杏仁 Min -0.010 -0.870 -0.180 1.250 -0.050 -0.890 Max 2.440 -0.560 3.890 5.300 12.230 0.260 Mean 0.970 -0.740 1.410 2.610 3.020 -0.640 CV 0.915 -0.149 0.973 0.508 1.251 -0.526 杏果肉 Min -0.960 -0.990 -0.990 -0.990 -0.970 -0.990 Max -0.510 -0.970 -0.830 -0.810 0.450 -0.930 Mean -0.794 -0.980 -0.920 -0.930 -0.760 -0.960 CV -0.153 -0.010 -0.065 -0.063 -0.477 -0.020
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