Geochemical characteristics of strontium and development potential of strontium−rich ecological industry in Chengde, Hebei
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摘要:
研究目的 厘清基岩−风化壳−土壤−特色作物体系中锶的丰度、物质来源、迁移聚集规律，对助力承德市富锶土壤标准建立，指导富锶生态产业发展具有重要意义。
研究方法 通过参比元素标准化方法厘定了承德全区和红旗—大庙小流域表层土壤的锶元素地球化学基线；采用多元统计分析与GIS方法、岩石风化元素化学损耗分数CDF、元素生物富集系数BCF，电子探针和原位微区分析等方法阐明了不同地质建造基岩、风化层和土壤，不同水体和特色作物样品的Sr元素丰度、空间分异与迁聚特征，识别了高锶特征寄主矿物类型，探讨了承德市锶元素异常的地球化学成因。系统归纳总结了国内外富锶生态产业的发展现状，结合承德市特色生态资源禀赋特征，评价了承德市富锶生态产业发展潜力。
研究结果 承德全区和红旗—大庙小流域土壤Sr地球化学基线值分别为206.87~216.49 mg/kg和241.69~260.51 mg/kg。全区表层土壤Sr平均含量为514.59 mg/kg，其中59.05%和68.10%样品Sr含量超过全区地球化学基线值和中国表层土壤Sr背景基准值。承德全区基岩Sr含量平均达546.57 mg/kg，富锶寄主矿物为辉石、橄榄石、磷灰石、钙长石和角闪石。化学风化过程中，斜长岩、斜长片麻岩和花岗岩Sr淋溶损失程度较高。基岩Sr丰度空间分异与区域构造格架具有良好的耦合关系，华北克拉通大陆地壳减薄隆起造成丰宁—隆化和大庙—娘娘庙深大断裂之间富锶的太古宇变质基底物质上涌，基性岩浆与陆壳混染、结晶分离形成的大庙斜长岩体、海西期侵入岩，火山岩和太古代变质基底建造多具富锶特征。滦河流域58.08%水样，红旗—大庙斜长岩体周边81.61%井水和53.57%泉水Sr2+浓度超过锶矿泉水标准限值，地热温泉水Sr2+浓度平均达0.78 mg/L。区内34种经济作物Sr平均含量范围为0.77~26.60 mg/kg，道地黄芩Sr含量范围为15.94~116.51 mg/kg，显著高于我国其他黄芩产区。
结论 承德市富锶水土资源禀赋优势突出，地理标志性生态产品、道地中药材锶富集明显，在饮用矿泉水、地热温泉康养、饮料饮品和酿酒，特色生态农业、绿色食品和农副产品开发，道地药材等富锶生态产业方面具有巨大的发展潜力。
Abstract:This paper is the result of hydrogeological survey engineering.
Objective It is of great significance to the establishment of strontium−rich soil standards and the development of strontium−rich ecological industries to clarify the abundance, sources, and migration patterns of strontium in the bedrock − regolith −soil−plant continuum system.
Methods The geochemical baseline values of the strontium in topsoil of the Chengde region and the Hongqi−Damiao small catchment were determined using the reference element method. Multivariate statistical analysis, GIS methods, chemical depletion fraction (CDF), bioconcentration factor (BCF), electron probe microanalysis, and in−situ microanalysis were systematically conducted to elucidate the abundance, spatial variation, migration and accumulation characteristics of strontium in bedrock−regolith−soil layers of different geological formations, different types of water and plant samples, as well as to identify the host minerals of strontium in bedrock and the causes of geochemical anomalies of strontium in Chengde City. The development potential of strontium−rich ecological industry in Chengde was evaluated combining the current research status of strontium−rich ecological industry at home and abroad with the ecological resource endowment of Chengde City.
Results The geochemical baseline value of the strontium in topsoil from the Chengde region and the Hongqi−Damiao catchment was 206.87−216.49 mg/kg, and 241.69−260.51 mg/kg, respectively. The average Sr content in the topsoil of Chengde was 514.59 mg/kg, with 59.05% and 68.10% of topsoil samples exceeding the geochemical baseline value of the entire region and the Sr background value of Soil Layer A in China. The average Sr content in the bedrock of the Chengde region was 546.57 mg/kg, and the Sr−rich host minerals were identified as pyroxene, olivine, apatite, calcium feldspar, and hornblende. The leaching−loss intensity of strontium during the chemical weathering process of anorthosite, plagioclase gneiss, and granite was relatively higher than that of other geological formations. The spatial variation of strontium abundance in bedrock exhibited good spatial coupling with regional tectonic framework. The uplifting and thinning of the continental crust in the North China Craton led to the upwelling of Sr−rich Archean metamorphic basement materials between the Fengning−Longhua and the Damiao−Niangniangmiao deep faults. Consequently, the Damiao anorthosite rock mass, Hercynian intrusive rocks, volcanic rocks, and Archean metamorphic basement formed by the mixing and crystallization separation of basic magma and continental crust along the deep fault belt are enriched in strontium. The water samples in the Luanhe River Basin, well and spring water samples in Hongqi−Damiao catchment with Sr2+concentration higher than 0.4 mg/L accounted for 58.08%, 81.61% and 53.57% respectively, and the average Sr2+concentration of geothermal water and hot spring samples was 0.78 mg/L. The average Sr content of 34 economic crops ranged from 0.77 to 26.60 mg/kg, of particular note was that the Sr content of Scutellaria baicalensis was 15.94−116.51 mg/kg, which was significantly higher than other producing areas in China.
Conclusions Chengde possesses prominent advantages in strontium−rich water and soil resources, and its geographical−indication products and authentic Chinese herbal medicines exhibit distinct strontium−rich characteristics. The strontium−rich ecological industry in Chengde—including drinking mineral water, geothermal health industries, beverage and wine production, characteristic ecological agriculture, organic green foods, agricultural and sideline products, and authentic Chinese herbal medicine derivatives—holds significant development potential.
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表 1 承德市锶元素地球化学岩（土）与植物样品采集类型与数量
Table 1. Collection types and quantities of strontium geochemical rock (soil) and plant samples in Chengde City
样品类型 数量 总计 样品类型 数量 总计 岩石风化剖面
BRS体系斜长岩—辉长岩 17 1145 其他岩土样品 红旗小流域深层土壤 26 418 斜长片麻岩—变粒岩 24 坝上地区风沙土 140 钾长片麻岩 15 全区黄土 24 花岗岩 201 钒钛磁铁矿—铁磷矿石 50 变质闪长岩 36 铅锌矿石 15 玄武岩 196 钒钛磁铁矿尾矿砂 68 安山岩 154 水系沉积物 95 流纹岩—凝灰岩 167 水质样品 滦河流域浅层地下水 167 892 陆源碎屑砂砾岩 98 承德全区地热温泉 40 长石石英砂岩 15 红旗—大庙小流域井 223 泥页岩 34 红旗—大庙小流域泉 28 白云岩 168 红旗—大庙矿山废水 28 灰岩 20 红旗—大庙河水 83 表层土壤
（0~20 cm）承德全区 376 557 滦平盆地等浅层地下水 323 承德滦河流域 351 植物样品 道地药材—黄芩 66 135 红旗—大庙小流域 181 其他植物样品 69 
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表 2 标准化方法确定的土壤Sr元素化学基线（mg/kg）
Table 2. Geochemical baseline value of soil strontium determined by standardization method (mg/kg)
元素 承德全区（n=541） 红旗—大庙钒钛磁铁矿矿集区流域（n=71） 回归方程 R2 P 基线值 回归方程 R2 P 基线值 Sr Sr = 7.741Sc+127.76 0.153 0.01 206.871 Sr = 1.604Sc+242.64 0.624 0.01 260.513 Sr =19.746Fe2O3+113.87 0.192 0.01 209.243 Sr = 4.277Fe2O3+218.94 0.012 0.01 241.693 Sr = 1.452La+159.16 0.039 0.01 210.473 Sr =−1.554La+312.37 0.026 0.01 257.996 Sr = 89.620Eu+96.40 0.185 0.01 216.494 Sr =−22.200Eu+393.48 0.004 0.01 353.298
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表 3 承德地区不同地质建造成土母质区典型剖面岩石—风化层—土壤系统及其他环境介质Sr丰度统计特征
Table 3. Strontium abundance of bedrock−regolith−soil samples in typical weathering profiles of different geological formations and other environmental medias in Chengde area
分层 土壤 风化层 基岩 CDF 华北克拉通 岩性 Min Max Mean Cv Min Max Mean Cv Min Max Mean Cv S−P R−P Mean Baseline 斜长岩—辉长岩 196.10 1301.00 536.40 0.815 237.30 1594.00 672.25 0.593 447.50 3289.00 1289.13 0.692 −1.40 −0.92 486.0 305.0 斜长片麻岩—变粒岩 57.67 949.90 354.52 0.533 67.40 1364.00 388.20 0.651 27.72 1354.00 493.21 0.612 −0.39 −0.27 319.0~432.0 288.0~411.0 钾长片麻岩 265.80 698.60 469.17 0.464 163.50 929.70 564.62 0.514 148.00 884.10 372.60 0.839 0.21 0.34 432.0 411.0 安山岩类 32.86 1000.00 386.69 0.667 21.79 1598.00 662.62 0.645 22.27 1638.00 658.32 0.742 −0.70 0.01 614.0 614.0 流纹岩—凝灰岩类 27.53 584.30 186.74 0.407 14.62 1976.00 221.66 1.560 14.10 8621.00 401.18 2.820 −1.15 −0.81 211.0~293.0 195.0~205.0 变质闪长岩 171.90 1077.00 594.67 0.473 125.00 1477.00 738.29 0.446 97.31 1527.00 891.55 0.463 −0.50 −0.21 721.0 568.0 花岗岩类 100.30 1365.00 357.61 0.698 57.10 3977.00 513.78 0.985 28.18 1966.00 472.49 0.897 −0.32 0.08 298.0 263.0 陆源碎屑岩 69.60 790.10 268.74 0.582 39.49 980.80 322.07 0.776 10.02 928.00 395.45 0.700 −0.47 −0.23 391.0 283.0 长英质砂岩 130.70 511.30 255.97 0.570 75.30 618.30 296.27 0.854 89.96 711.20 312.19 1.109 −0.22 −0.05 284.0 233.0 泥页岩 32.52 251.90 130.80 0.488 35.29 161.80 71.56 0.558 41.03 157.70 95.16 0.466 0.27 −0.33 169.0 142.0 玄武岩 132.70 994.80 276.60 0.560 119.30 2087.00 471.33 0.700 28.90 3016.00 643.13 0.736 −1.33 −0.36 602.0 548.0 白云岩 48.78 299.10 127.51 0.428 18.97 304.70 69.70 0.768 17.25 317.70 60.37 1.026 0.53 0.13 67.0 63.0 灰岩 97.20 124.30 111.67 0.077 97.00 253.90 137.68 0.563 169.20 374.50 251.80 0.430 −1.25 −0.83 286.0 271.0 其他 钒钛磁铁矿矿石（n=50） 钒钛磁铁矿尾矿砂（n=68） 哈叭沁—铁马支流包气带（n=26） 地壳 480.0 64.11 4486.00 811.59 1.263 110.60 1049.00 457.21 0.411 179.60 368.90 233.74 0.165 中国东部大陆地壳 350.0 黄土（n=24） 风成沙（n=140） 全国土壤背景值 197.0 23.24 315.80 186.97 0.347 92.47 1138.00 152.93 0.732 黄淮海平原土壤 177.0 水系沉积物 滦河干流 伊逊河干流 哈叭沁—铁马支流 水系沉积物 146.0 247.60 251.30 249.48 0.006 161.40 985.40 327.69 0.462 360.50 778.10 586.07 0.203 浅海沉积物 230.0 水环境 承德滦河
流域坝上高原孔隙裂隙水（n=35） 燕山山地滦河中上游裂隙水（n=68） 滦河中游孔隙岩溶裂隙水（n=64） 地热温泉（n=40） 0.04 2.28 0.30 1.460 0.07 0.98 0.46 0.540 0.07 3.42 0.59 0.850 0.15 3.81 0.78 1.026 红旗—大庙
流域井（n=223） 泉（n=28） 地表水（n=83） 矿山废水（n=28） 0.09 9.49 0.82 1.227 0.13 1.69 0.58 0.734 0.09 2.39 0.61 0.610 0.44 5.99 1.85 0.843 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；CDF—Chemical Depletion Fraction，化学损耗分数；S−P（Soil−Parent material）表示土壤相对于成土母质化学损耗分数；R−P（Regolith−Parent material）表示风化层相对于成土母质化学损耗分数；Sr含量单位为mg/kg。
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表 4 常见食品锶含量及富锶食品研究开发现状（mg/kg）
Table 4. Strontium content in common foods, research and development status of strontium-rich foods (mg/kg)
项目 Sr含量 项目 Sr含量/ 项目 Sr含量 综合 谷类及谷类制品a 1.82 酒类 赤霞珠干红葡萄酒j 0.10~5.00 大田粮食作物 薯类（牙买加）n 0.71~16.70 水果和蔬菜a 1.31 酱香型白酒k 0.00537~0.01437 土豆（神农架）i 0.132~0.268 坚果b 9.759 ±5.181 锶泉白酒l 0.75~1.30 红薯（神农架）i 0.138~1.540 饮料a 0.62 锶泉黄酒m >0.05 富锶水稻i 0.524~0.533 食用油a 0.11 蔬菜水果 水果（牙买加）n 0.48 富锶大米s 0.65 淡水鱼类与海鲜类a 7.17~9.56 叶类蔬菜（牙买加）n 0.15~0.42 富锶小米r 38.2 海州湾水产c 1.14~3.33 根茎类蔬菜（牙买加）n 0.35~2.05 小麦 3.0 肉类及内脏a 0.18~1.20 水果（丹麦）o 0.79 小麦 1.742~3.693 乳及乳制品a 0.54 叶类蔬菜（丹麦）o 1.60 筛分后小麦精粉 0.78±0.05 蛋及蛋制品a 0.52 根茎类蔬菜（丹麦）o 1.30 麦麸 2.97±0.15 盐、香料等调味品a 1.12 葫芦科（神农架）i 0.32 完整小麦颗粒 1.42±0.07 富锶酱d ≥0.30 茄科（神农架）i 0.36 荞麦 2.70~6.80 中药材（105种）e 23.50 苋科（神农架）i 2.47 燕麦 1.30 茶叶 埃及洋甘菊f 36.8 ± 1.5 十字花科（神农架）i 2.25 黑麦 7.8~70.2 葡萄牙狭叶松果菊f 32.6 ± 1.3 山楂果肉p 0.406 大麦 43.20 西班牙阔叶薰衣草f 75.8 ± 2.1 山楂叶p 1.14 玉米 0.0008~0.02 保加利亚药葵f 53.1 ± 1.6 山楂种子p 0.19 玉米（河南固始）s 0.431~0.629 绿薄荷g 122.07±2.68 富锶苹果q 1.36~1.66 玉米（神农架）i 0.132~0.274 波耳多叶g 90±1.20 苹果（神农架）i 0.132 大豆（鲜重）i 0.268 洋甘菊g 79.50±1.30 富锶葡萄q 0.34 大豆（干重） 138.0 绿茶g 45.42±1.88 葡萄（神农架）i 0.132 其他 牛肝（标准物质）e 0.53±0.03 红茶g 27.90±0.78 富锶草莓q 1.72 对虾（标准物质）e 40.6±1.7 白茶g 14.70±0.50 富锶猕猴桃q 1.10 贻贝（标准物质）e 12.8±0.6 道真绿茶h 2.5~10.0 富锶山药r 1.73~10.6 牛肝（标准物质）e 0.138 菊花（承德） 4.46 坚果类 富锶大榛子q 1.06 牡蛎肉（标准物质）e 10.36 木鱼茶叶（神农架）i 0.524 花生（河南固始）s 2.493~7.747 豆腐a 2.71 茶叶（标准物质）e 15.2±0.7 杏仁（土耳其）t 150.61 高锶金针菇 0.35~6.7 茶叶（标准物质）e 10.8±1.8 野核桃仁（神农架）i 1.018 富锶豆芽 0.50~2.5 茶树叶（标准物质） 52.4±5.6 板栗（神农架）i 0.044 富锶粉条/淀粉 ≥12.73 注：a—Millour et al., 2012；b—González et al., 2013；c—王雪莲等, 2022；d—席雪瑶等, 2023；e—管竞环和李恩宽, 1998；f—Fernandes et al., 2022；g—Martins et al., 2015；h—DB 52/T 1219—2017；i—卜怡然等, 2020；肖潇等, 2022；j—韩深等, 2014；k—姜涛, 2013；l—沈阳市锶泉酒厂, 1995, 1996; m—余亚芳, 2014；n—Howe et al., 2005；o—Danish Veterinary and Food Administration, 2002；p—Cindrić et al., 2005；q—韩娟和郭燕枝, 2022；r—杨思宇, 2019；s—王东晓等, 2023；t—Kamar et al., 2018；u—罗军强等, 2019。
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表 5 承德地区与国内外典型药材产区根系土、栽培黄芩、野生黄芩及其他常见药材锶含量（mg/kg）
Table 5. Strontium content in root soil samples, cultivated and wild Scutellaria baicalensis, and other common medicinal materials in Chengde and typical domestic and foreign medicinal material production areas (mg/kg)
黄芩种类 项目 Sr含量 承德药材 鲜重Sr含量 常见药材Sr含量 产地 Min Max Mean 黄芪 11.90 47.00 辽宁（干重）b 野生黄芩
（大庙—红旗）土壤 100.50 4613.0 1106.5 桔梗 9.89 11.60 湖北（干重）b 根 15.93 116.51 45.74 苦参 18.10 7.56 河北b 茎叶 24.68 153.93 67.62 山楂 11.20 9.84 河南（干重）c 栽培黄芩
（五道岭—金沟屯）土壤 141.70 687.40 228.94 柴胡 11.39 18.80 湖北（干重）b 根 17.19 36.00 25.16 郁李仁 2.75 3.08 内蒙古（干重）b 茎叶 22.19 66.74 32.24 华北大黄 44.56 60.13 恩施（干重）d 金沟屯栽培黄芩 土壤 141.70 687.40 240.71 射干 10.49 0.57 神农架（鲜重）e 根 20.10 36.00 28.41 土贝母 7.27 2.31 恩施（干重）d 茎叶 27.36 66.74 39.55 紫苏叶 10.40 3.74 神农架（鲜重）e 五道岭栽培黄芩 土壤 146.80 455.50 220.38 当归根茎 3.59 18.70 甘肃（根干重）b 根 17.19 27.61 22.79 当归叶 12.80 32.10 恩施（根干重）d 茎叶 22.19 34.90 28.25 党参根 20.50 46.20 湖北（根干重）b 采样位置 Sr含量与生物富集系数 党参茎 52.00 51.86 恩施（根干重）d 土壤 黄芩 BCF 党参叶 61.70 18.00 山西潞党参b 承德滦平
（以鲜重计）所有样品 616.08 34.24 0.118 何首乌根 11.80 1.91 神农架（鲜重）e 野生黄芩 1106.46 45.74 0.106 何首乌茎 12.20 0.40 俄罗斯（鲜重）f 栽培黄芩 228.94 25.16 0.128 甘草 21.21 294.0 内蒙古（干重）b 金沟屯黄芩 240.71 28.41 0.112 荆芥叶 23.00 11.70 意大利（鲜重）g 五道岭黄芩 220.38 22.79 0.150 板蓝根 4.51 连翘 8.30 湖北b 河北围场a 41.46 211.16 5.09 苍术 13.26 11.40 克罗地亚h 河北赤城a 33.53 156.14 4.66 知母 8.97 丹参 43.30 湖北b 黑龙江呼玛a 181.08 48.56 0.27 地榆 25.11 6.52 山东b 黑龙江杜尔伯特a 92.07 23.08 0.25 藿香茎 8.38 葛根 5.46 广西b 吉林白城a 156.01 27.42 0.18 藿香叶 18.43 104.3 恩施d 吉林延吉a 105.39 17.19 0.16 穿山龙 119.00 黄柏 94.30 湖北b 内蒙古林西a 88.41 24.16 0.27 威灵仙根 15.90 99.69 恩施d 内蒙古赤峰a 38.97 19.31 0.50 威灵仙茎 21.00 百合 0.39 恩施d 内蒙古额尔古纳a 70.44 15.32 0.22 威灵仙叶 52.20 菊花 14.30 湖北b 甘肃合水a 58.86 17.11 0.29 马鞭草茎 21.60 神农香菊 13.07 恩施d 北京延庆a 120.90 16.77 0.14 马鞭草叶 74.20 桃仁 11.50 陕西b 陕西延安a 71.40 14.69 0.21 瞿麦茎 15.30 杏仁 7.92 陕西b 陕西太白a 32.95 10.16 0.31 瞿麦叶 26.40 明党参 14.20 安徽b 陕西山阳a 27.22 9.24 0.34 千屈菜 9.83 太子参 12.00 山东b 山西五台a 39.16 13.49 0.34 藁本根 14.82 温热药 40.03 总计105种中药材b 山西汾阳a 32.14 12.15 0.38 鸡冠花叶 23.18 寒凉药 56.73 注：a—王升等, 2014；b—管竞环和李恩宽, 1998；c—Xu, 2009；d—汪丹等, 2022；e—卜怡然等, 2020；肖潇等, 2022；f—Dyakova, 2023；g—Zeinera et al., 2015；h—Bonari et al., 2019。
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