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摘要: 中国的稀土元素(REE)资源丰富,矿床类型多样,其中轻稀土元素(LREE)绝大多数来自于碱性岩−碳酸岩有关的REE矿床,而重稀土(HREE)主要来自离子吸附型(或称风化壳型)REE矿床,其他稀土矿床类型还包括REE砂矿和伴生的REE矿床等。目前,中国的REE资源开发主要是针对碳酸岩−碱性岩型LREE矿床和离子吸附型HREE矿床,REE砂矿和其他矿床中伴生的REE资源尚未得到有效利用。文章在综合已有研究成果的基础上,对中国伴生的REE矿床的类型、资源潜力进行评述。结果表明,中国伴生的REE资源类型包括海相沉积磷矿床、煤矿床、铝土矿床、岩浆型磷−铁磷矿床等,其潜在的REE资源巨大,特别是海相沉积磷矿床和铝土矿床中伴生的REE资源。铝土矿床中伴生的REE以LREE为主,且其中的Sc具有重要的资源意义。沉积磷矿床中伴生的HREE(含Y)占比高,特别是产于四川德阳地区的什邡式磷矿上部层位的富硫磷铝锶型矿石,其中的REE含量明显高于磷块岩型矿石,且中、重REE占50%以上,还伴生有多种关键金属,具有重要的资源意义和经济价值。另外,岩浆型(铁)磷矿床、煤矿床、油页岩矿床、金矿床中伴生的REE资源也值得重视。但由于缺少详细的勘查数据,目前对中国伴生的REE资源家底不清,资源综合利用水平及REE回收和提取技术也有待提高。而加强中国伴生REE资源的评价和综合利用水平,充分利用生产矿山中伴生的REE资源,特别是磷矿床和铝土矿床,不仅可以有效缓解中国HREE资源供应压力,还是贯彻中国节约资源和保护环境基本国策的重要举措。Abstract:
Objective China is the largest producer of rare earth element (REE) and hosts the largest amount of REE resources. Various types of REE deposits have been reported in China, with alkaline-carbonatite related light REE deposits and ion-adsorption heavy REE deposits being the most important ones. Other REE deposit types include REE placers and deposits with REE by-products. Currently, the development of rare earth resources in China is primarily focused carbonatite-alkaline related light REE deposits and ion-adsorption type heavy REE deposits. REE in placer deposits and other REE by-products have not been effectively utilized. Methods Based on existing exploration studies and whole-rock REE geochemistry data analysis, this study provides a brief review of the types and resource potential of deposits with REE by-products in China. Results China's by-products REE resource types include marine sedimentary phosphate, coal, bauxite, and magmatic iron-phosphate deposits. These deposits, particularly marine sedimentary phosphate deposits and bauxite, contain enormous potential REE resources. REEs in bauxite are primarily light REE, with some containing high amount of scandium (Sc). In sedimentary phosphate deposits, the proportion of heavy REEs (including yttrium) is high, particularly in the S−P−Al−Sr rich ores that occur as the layers overlying the phosphorite in the Shifang-type phosphate deposits of Sichuan Province. These S−P−Al−Sr rich ores have significantly higher REE content than phosphorite, with medium and heavy REE accounting for over 50%, along with various critical metals, making these ores highly valuable in terms of both resource and economic significance. Furthermore, REE resources in magmatic (iron) phosphate deposits, coal, oil shale, and gold deposits deserve attention. Conclusions Owing to the lack of detailed exploration data, the full extent of China's by-products REE resources remains unclear. The comprehensive utilization of resources, as well as the technology for REE recovery and extraction, requires improvement. Significance Strengthening the evaluation and comprehensive utilization of China's associated REE resources, particularly by fully utilizing the REE resources associated with phosphate and bauxite deposits, can effectively alleviate the pressure on China's HREE supply. This represents an important measure for implementing China's fundamental national policies on resource conservation and environmental protection. -
图 1 中国主要沉积磷矿床中磷块岩的REE含量统计图和配分曲线 (数据来源见表1,PAAS数据引自McLennan,1989)
a—ΣREY含量频数分布图;b—PAAS标准化稀土配分曲线
Figure 1. Rare earth elements content and partition pattern of phosphorite for major sedimentary phosphate deposits in China (data from references listed in Table 1; REE data for PAAS from McLennan, 1989)
(a) Frequency histogram of ΣREY content; (b) PAAS normalized REE partition pattern
图 2 中国主要铝土矿床中铝土矿石的中REE含量统计图(数据来源见表3)
a—镧系金属元素总量分布直方图;b—Sc含量分布直方图
Figure 2. Statisrical chart of rare earth elements content and their partition pattern of bauxite ore from major bauxite deposits in China (data from references listed in table 3)
(a) Frequency histogram of total lanthanide elements content; (b) Frequency histogram of Sc content
图 4 中国主要岩浆型磷−铁磷矿床矿石中REE含量统计图和配分曲线(数据来源于表4)
a—ΣREE含量频数分布图;b—球粒陨石标准化配分曲线(球粒陨石标准化值引自 McDonough and Sun,1995)
Figure 4. Rare earth elements content and partition pattern for phosphate ores from major magmatic phosphate-iron phosphate deposits in China (data from references listed in Table 4)
(a) Frequency histogram of ΣREEcontent; (b) Chondrite normalized REE partition pattern (REE content for chondrite from McDonough and Sun, 1995)
图 5 岩浆型磷−铁磷矿石全岩P2O5−∑REY和(TFe2O3+MnO+MgO) −∑REY 的相关图解(数据来源见表4)
a—P2O5−∑REY相关图解;b—(TFe2O3+MnO+MgO) −∑REY 相关图解
Figure 5. Correlation diagram of P2O5−∑REY and (TFe2O3+MnO+MgO) −∑REY for magmatic phosphate-iron phosphate ores (data from references listed in table 4)
(a) P2O5 − ∑REY diagram;(b) (TFe2O3+MnO+MgO) − ∑REY diagram
图 8 中国主要油页岩矿床中油页岩的REE含量和配分特征(数据来源见表6)
a—ΣREY含量频数分布直方图; b—PAAS标准化稀土配分曲线
Figure 8. Rare earth elements content and patition pattern of oil shale for major oil shale deposits in China (data from references listed in Table 6)
(a) Frequency histogram of ΣREY content; (b) PAAS normalized REE partition pattern
表 1 海相沉积磷矿床磷矿石的全岩REE含量(×10−6 )统计结果
Table 1. Statistical results of rare earth content in the whole rock of phosphate ores in marine sedimentary phosphate deposits
矿床名称 地理位置 ΣREY范围 ΣREY平均值 HREE总量
(Gd-Y)范围HREE总量
(Gd-Y)平均值HREE含
量占比数据来源 铜仁磷矿床 贵州省铜仁市 237.8~2496.3 1116.7 125.7~1359.8 646.9 57.93% 汪宇航,2023;
杨旭, 2019;
卢正浩, 2022;
张兰, 2021开阳磷矿床 贵州省贵阳市 28.3~507.6 204.6 14.6~244.3 95.7 46.77% Yang et al.,2019a 瓮福磷矿区 贵州省瓮安县 10.2~400.3 116.0 5.0~225.6 54.6 47.07% Zhang et al.,2022;
Yang et al.,2019a;
Wang and Qiao,2024;
任海利, 2017;
梁坤萍, 2022;
杨海英等,2020织金磷矿床 贵州省毕节市 508.3~2041.0 1198.7 181.7~862.7 494.4 41.24% Zhang et al.,2022;
Gong et al.,2021;
Li et al.,2019b;
He et al.,2022;
Xing et al.,2021;
Wang and Qiao,2024;
汪宇航, 2023;
曹金鑫, 2022;
蒋权等, 2023大坪剖面 湖南省张家界 781.7~1004.1 905.1 339.9~438.8 400.5 44.25% 王文全, 2016 大浒剖面 湖南省张家界 470.6~2203.6 1344.9 275.7~1029.7 651.4 48.43% 王文全,2016 黄家坪磷矿床 四川省乐山市 85.6~113.2 99.5 36.8~60.8 50.6 50.85% 李佐强等, 2023 什邡磷矿区 四川省什邡市 184.7~5615.6 1921.7 91.6~853.3 518.3 26.97% 张跃跃,2015 白龙潭磷矿床 云南省昆明市 95.0~379.8 199.5 55.1~181.5 99.6 49.92% 曹金鑫等,2022 会泽磷矿床 云南省曲靖市 217.8~313.1 265.4 121.4~177.9 149.7 56.41% 徐凯等, 2023 昆阳磷矿床 云南省昆明市 161.5~440.8 304.9 90.2~242.4 154.6 50.71% 杨帆,2011;Zhang et al.,2022 羊场磷矿床 云南省昭通市 382.1~1181.5 619.5 136.4~474.0 241.8 39.03% 秦欢等,2022 遵义磷矿床 贵州省遵义市 142.7~1401.0 605.2 49.4~682.1 294.1 48.60% 王文全,2016 表 2 中国部分铝土矿床中伴生的REE品位和资源量
Table 2. Associated rare earth grade and resources in some bauxite deposits in China
编号 矿床名称 位置/行政区划代码 REE平均品位(REO,wt%) REE资源总量(t)
(除特别注明外均指C级以上或333以上)1 相王铝土矿床 山西省孝义市相王 / 37339.70 2 西红河矿床区铝土矿床 山西省忻州市宁武县薛家洼乡 / 6716.72 3 湍水头铝土矿床 山西省吕梁市临县湍水头镇 / 19248.00 4 后塔上铝土矿床 山西省吕梁市离石区 / 7192.60 5 铁金村铝土矿床 山西省交口县铁金村 / 36281.49 6 蒲依铝土矿床 山西省吕梁市交口县蒲依村 / 35500.00 7 石且河铝土矿床 山西省保德县 0.079 89091.00 8 曹窑煤矿床深部铝土矿床 河南渑池县 / 32500.00(未注明储量级别) 9 交口−汾西铝土矿床 山西交口−汾西地区 / 178103.00(未注明储量级别) 10 前文猛铝土矿床 山西静乐县 / 23500.20(未注明储量级别) 11 墕则村铝土矿床 山西保德县 / 16931.00(334) 12 下反里铝土矿床 山西汾西县 0.100 9370.00(334) 13 沙墕铝土矿床 山西交口县 / 19710.00(未注明储量级别) 14 桃花铝土矿床 山西交口县 / 4973.00(未注明储量级别) 15 石槽铝土矿床 山西娄烦县 / 4533.76(未注明储量级别) 16 西窑铝土矿床 山西平陆县 / 7921.20(334) 17 旋风窝铝土矿床 山西沁源县 / 16110.00(334) 18 苗家岭铝土矿床 山西襄垣县 / 8523.00(334) 19 奥家湾铝土矿床 山西兴县 0.110 21411.80(未注明储量级别) 20 范家疃铝土矿床 山西兴县 / 21191.40(334) 21 井沟铝土矿床 山西曲阳县 / 12295.00(未注明储量级别) 数据来源:全国地质资料馆“http://www.ngac.org.cn/”;“/”表示无数据或网上未提供 表 3 中国部分铝土矿床的矿石全岩REE含量(×10−6 )统计结果
Table 3. Statistical results of rare earth element content in the whole rock of some bauxite deposits in China
矿床名称 地理位置 REE总量范围 REE总量
平均值HREE总量
范围HREE总量
平均值HREE含量
占比数据来源 务正道矿区 贵州省遵义市 61.0~1815.2 419.2 16.9~143.8 44.1 10.51% Wang et al.,2013 三合铝土矿床 广西省白色市 226.0~1460.0 626.3 41.7~172.2 74.3 11.86% 李普涛和张起钻,2008 比例坝铝土矿床 贵州省贵阳市 401.0~1495.8 851.5 34.8~152.5 85.3 10.02% 张明等,2018 新民铝土矿床 贵州省遵义市 17.8~2329.8 320.3 6.1~166.2 34.3 10.70% 龙克树等,2019 高家山铝土矿床 山西省长治市 350.1~1262.6 828.5 29.6~91.9 56.5 6.82% 叶枫等,2015b 王润-西崖底铝土矿床 山西省吕梁市 286.5~1205.5 765.8 29.1~81.9 53.0 6.92% 叶枫等,2015a 小山坝铝土矿床 贵州省贵阳市 16.1~411.2* 213.7* 8.1~63.0* 35.5* 16.63%* Ling et al.,2018 林歹铝土矿床 贵州省清镇市 228.7~286.1* 257.4* 56.6~88.7* 72.7* 28.23%* Ling et al.,2017 松桂铝土矿床 云南省大理白族自治州 671.0~2300.7* 1148.6* 56.1~161.4* 97.8* 8.52%* 王行军等,2017 金龙铝土矿床 广西省崇左市 163.5~427.5* 302.7* 31.5~165.1* 91.6* 30.26%* 王岩等,2015 兴县铝土矿床 山西省吕梁市 2963.0~10711.5* 4645.8* 300.1~1154.3* 609.4* 13.12%* 董挨管等,2017;
张尚清等,2018平果矿区 广西省百色市 303.9~1001.0* 697.6* 111.4~348.0* 209.2* 29.98%* 戴塔根等,2003 靖西矿区 广西省百色市 161.3~420.8* 291.0* 94.4~139.2* 116.8* 40.13%* 戴塔根等,2003 山西某铝土矿区 山西省 441.4~1006.8* 724.1* 120.3~131.8* 126.0* 17.41%* 真允庆和王振玉,1991 黔中-川南矿区 黔中-川南地区 299.9~429.0* 374.8* 95.4~106.2* 101.7* 27.13%* 刘平,1999 贯沟铝土矿床 河南省三门峡市 107.4~1524.2** 679.6** 43.1~165.5** 74.3** 10.93%** Liu et al.,2013;
袁爱国,2010边庄铝土矿床 河南省平顶山市 197.2~2789.0** 797.6** 42.8~158.0** 89.5** 11.22%** 康微,2013;
袁爱国,2010夹沟铝土矿床 河南省偃师市 94.7~2011.0** 536.8** 27.9~135.7** 67.6** 12.59%** 袁爱国,2010 坡池村铝土矿床 河南省汝州市 222.7~807.7** 449.3** 56.0~101.5** 70.1** 15.60%** 袁爱国,2010 石寺铝土矿床 河南省洛阳市 211.9~963.9** 531.8** 46.9~91.0** 65.9** 12.38%** 冯跃文,2013 关岭铝土矿床 河南平顶山市 272.5~1432.2*** 652.3*** 137.0~233.4*** 165.2*** 25.32%*** Yang et al.,2019b 边庄铝土矿床 河南省平顶山市 191.7~2873.8*** 625.5*** 105.6~242.8*** 129.4*** 20.69%*** Yang et al.,2019b 小山坝铝土矿床 贵州省贵阳市 32.5~778.8*** 296.2*** 9.9~234.1*** 72.5**** 24.47%*** Ling et al.,2018 林歹铝土矿床 贵州省清镇市 308.6~424.6*** 353.9*** 117.1~188.9*** 144.1*** 40.71%*** Ling et al.,2013 扶绥铝土矿床 广西省崇左市 105.3~1612.1*** 608.4*** 40.4~229.4*** 119.4*** 19.63%*** Yu et al.,2014 新圩铝土矿床 广西省百色市 27.4~76.7*** 52.2*** 9.5~22.4*** 16.9*** 32.38%*** 刘枝刚,2005 高洞铝土矿床 贵州省福泉市 133.1~267.2*** 209.4*** 51.4~101.6*** 69.3*** 33.12%*** 金中国等,2018 教美铝土矿床 广西省百色市 352.7~1090.1*** 680.2*** 111.4~287.6*** 191.6*** 28.16%*** 章颖等,2015 渑池铝土矿床 河南省三门峡市 121.5~1732.5*** 676.3*** 52.7~291.5*** 153.0*** 22.62%*** 王燕茹等,2012 务正道矿区 贵州省遵义市 107.7~201.6*** 163.0*** 85.8~152.4*** 114.3*** 70.14%*** 张莹华等,2013 庞家庄铝土矿床 山西省吕梁市 373.0~1407.2*** 874.6*** 106.3~211.1*** 150.4*** 17.19%*** 孟健寅等,2011 宽草坪铝土矿床 山西省忻州市 146.3~1298.0*** 797.8*** 73.1~581.1*** 203.6*** 25.52%*** 孙思磊,2011 上务头村铝土矿床 山西省长治市沁源县 96.7~1714.4*** 423.7*** 49.8~267.8*** 109.1*** 25.75%*** 杨中华,2011 石墙区铝土矿床 山西省原平市 576.9~1314.5*** 987.1*** 102.5~330.5*** 196.7*** 19.93%*** 孙思磊等,2012 东门-柳桥矿区 广西省崇左市 121.4~1093.0*** 322.9*** 15.2~158.9*** 55.5*** 17.19%*** 乔龙,2016 古美矿区 广西省崇左市 333.8~1156.0*** 821.5*** 138.0~420.1*** 244.1*** 29.71%*** 乔龙,2016 太平矿区 广西省崇左市 24.7~279.5*** 142.9*** 14.2~125.8*** 62.6*** 43.78%*** 乔龙,2016 天生桥铝土矿床 云南省文山县 170.3~529.5*** 332.5*** 103.2~334.9*** 170.6*** 51.31%*** 田茂军,2013 南川-武隆铝土矿床洪官渡矿区 重庆市南川区 42.6~251.2*** 150.8*** 28.6~172.4*** 104.7*** 69.43%*** 李再会等,2012 南川-武隆铝土矿床大佛岩矿区 重庆市南川区 60.9~110.3*** 85.6*** 35.3~63.3*** 49.3*** 57.60%*** 李再会等,2012 南川-武隆铝土矿床申基坪矿区 重庆市武隆区 90.7~179.2*** 134.9*** 64.6~68.6*** 66.6*** 49.37%*** 李再会等,2012 蔡家坝铝土矿床 贵州省清镇市 425.4~907.7*** 611.0*** 88.6~152.5*** 125.9*** 20.60%*** 陈晓甫等,2022 注:***表示REE总量数据为ΣREE+Y+Sc,HREE 总量数据为Gd-Lu+Y+Sc;**表示REE总量数据为ΣREE+Sc,HREE总量数据为Gd-Lu+Sc;*表示REE总量数据为ΣREY,HREE总量数据为Gd-Lu+Y;其余无*标表示REE总量数据为ΣREE,HREE总量数据为Gd-Lu 表 4 岩浆型磷-铁磷矿床矿石的全岩REE含量(×10−6 )统计结果
Table 4. Statistical results of rare earth content in the whole rock ores of magmatic phosphate-iron phosphate deposits
矿床名称 地理位置 REE总量范围 REE总量平均值 HREE总量范围 HREE总量平均值 HREE含量占比 数据来源 枣庄沙沟杂岩体 山东省枣庄市 1790.0~2900.0 2345.0 / / / 夏学惠和刘昌涛, 1986 天山成矿带 新疆 808.7~1365.4 1087.0 / / / 夏学惠等, 2012 矾山磷铁矿床 河北省张家口市 3202.8~4182.6* 3638.4* 186.2~322.0* 273.1* 7.51%* 程春, 2001;
Hou, et al., 2015上庄磷铁矿床 青海省西宁市 329.0~1160.1* 725.8* 41.9~176.4* 87.4* 12.04%* Wang et al., 2017b 大庙杂岩体 河北省承德市 92.5~888.2* 358.0* 26.3~226.0* 83.9* 23.44%* He, et al., 2016;
Wang et al., 2017a;
路智等,2022;
Li, et al., 2015大西沟磷铁矿床 新疆和静县 183.1~226.5* 203.4* 26.7~33.2* 31.1* 15.28%* 夏学惠等, 2009;
夏学惠等, 2010卡乌留克塔格铁磷矿床 新疆尉犁县 254.1~381.7* 317.9* 31.4~62.7* 47.1* 14.81%* 夏学惠等,2011a 瓦吉尔塔格磷铁矿床 新疆巴楚县 1167.3~1993.3* 1600.8* 113.3~191.6* 157.9* 9.86%* 夏学惠等,2009 奥尔塘铁磷矿床 新疆尉犁县 470.1~325.7* 397.9* 51.8~70.3* 61.1* 15.34%* 袁家忠等, 2010 招兵沟铁磷矿床 河北省丰宁县 156.1~372.2* 261.6* 51.2~114.2* 84.8* 32.42%* 王亿等,2024 注:*表示REE总量数据为ΣREY,HREE总量数据为Gd-Lu+Y;无*标表示REE总量数据为ΣREE,HREE总量数据为Gd-Lu 表 5 中国主要煤矿的全岩REE含量(×10−6 )统计结果
Table 5. Statistical results of rare earth element content in the whole rock of major coal deposits in China
矿床名称 地理位置 ΣREY(La-Lu+Y)
范围ΣREY(La-Lu+Y)
平均值HREE(Gd-Lu+Y)
含量范围HREE(Gd-Lu+Y)
含量平均值HREE含量
占比数据来源 渭北煤田 陕西省渭南市 32.2~412.6 141.1 8.3~70.8 29.3 20.73% 车青松,2021;
刘贝等,2015吕家坨煤矿床 河北省唐山市 48.6~876.8 374.1 3.3~34.5 15.3 4.09% 张华等,2024 大同煤田 山西省 73.8~596.9 165.8 18.6~216.9 65.8 39.70% 刘东娜等,2015 鄂尔多斯盆地西缘煤田 鄂尔多斯盆地 5.6~314.5 115.2 1.3~74.3 23.1 20.01% 秦国红等,2016 万福煤矿床 广西省南宁市 88.7~1028.3 362.1 23.2~382.6 146.5 40.46% 朱士飞等,2020 峰峰矿区 河北省邯郸市 22.7~454.1 99.9 11.0~110.3 25.7 25.77% 魏迎春等,2020 北皂煤矿床 山东省烟台市 14.8~42.5 32.8 3.7~13.2 7.4 22.60% 马小敏,2019 梁家煤矿床 山东省烟台市 37.9~222.8 114.4 5.5~33.8 18.9 16.50% 马小敏,2019 洼里煤矿床 山东省烟台市 48.7~62.4 55.6 12.7~12.1 12.4 22.32% 马小敏,2019 鱼洞煤矿床 云南省凯里市 388.3~1378.8 961.0 149.4~373.5 273.6 28.47% 吴艳艳等,2010 聚乎更矿区 青海省天峻县 5.2~55.8 21.9 1.9~14.3 5.2 23.48% 霍婷等,2020 陈家山煤矿床 陕西省铜川市 12.8~517.0 112.4 3.3~93.2 25.1 22.35% 杨磊等,2008 芦塘煤矿床 重庆市彭水县 120.7~320.5 194.2 35.3~151.3 66.1 34.02% 邹建华等,2022 黑岱沟煤矿床 内蒙古鄂尔多斯市 63.7~604.3 267.8 12.3~78.3 41.6 15.52% 刘大锐等,2018 表 6 中国主要油页岩中REE含量(×10−6 )统计结果
Table 6. Statistical results of rare earth element content in the whole rock of major oil shale deposits in China
矿床名称 地理位置 ΣREY范围 ΣREY平均值 HREE(Gd-Lu+Y)
总量范围HREE(Gd-Lu+Y)
总量平均值HREE含量
占比数据来源 银额盆地油页岩矿区 内蒙古乌拉特后旗 94.8~178.1 126.2 27.3~54.5 34.6 27.44% Liu et al.,2015a 黄县盆地油页岩矿区 山东省烟台市 17.1~163.3 100.1 4.2~34.2 19.8 19.82% Zheng et al.,2020 胜利河−长蛇山油页岩带 西藏羌塘盆地 10.3~498.6 63.9 3.6~34.1 14.5 22.71% Fu et al.,2010;
Fu et al.,2011a;
Fu et al.,2011b;
Fu et al.,2015a;
Fu et al.,2015b大黄山油页岩矿区 新疆准噶尔盆地 39.7~132.3 93.7 13.2~40.1 26.3 28.06% Tao et al.,2013 吉木萨尔凹陷和石树沟凹陷油页岩带 新疆准噶尔盆地 95.9~361.9 166.1 28.4~106.5 52.6 31.67% Zhao et al.,2023 抚顺盆地油页岩矿区 辽宁省抚顺市 118.3~412.4 233.0 23.5~57.0 37.9 16.26% Liu et al.,2015b 伦坡拉盆地油页岩矿区 西藏班戈县 125.1~176.4 154.0 26.4~37.8 32.7 21.24% Fu et al.,2012 石长沟油页岩矿区 新疆准噶尔盆地 107.7~163.4 129.7 30.4~51.6 41.4 31.92% Tao et al.,2016 鄂尔多斯盆地油页岩矿区 山西省彬州市-铜川市 126.8~205.6 169.8 34.3~56.0 40.7 23.98% 马中豪等,2016 桦甸盆地 吉林省吉林市桦甸市 91.5~356.0 162.6 9.7~40.5 15.5 9.53% 孟庆涛,2010 -
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