Geochemical Characteristics and Influencing Factors of Germanium-enriched Soils in Nehe City, Heilongjiang Province
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摘要:
锗是生命的必需元素，随着近年来中国各地富锗土壤的发现，开发富锗土地逐渐得到社会的重视。本文采用电感耦合等离子体质谱/发射光谱法(ICP-MS/OES)等技术测定黑龙江讷河地区土壤，讨论该区土壤锗地球化学特征、影响因素及主要农作物富锗情况，探究富锗土地开发潜力。结果表明：①讷河地区表层土壤锗含量为0.74~1.78mg/kg，平均值为1.13mg/kg，其中富锗土壤面积约599.8km2，占全市面积的9.31%；②土壤锗元素来源为中更新统上荒山组和上更新统顾乡屯组地层，不同土壤类型土壤的锗含量以沼泽土和黑土为最高。③讷河地区主要农作物以黄豆的锗含量最高，且较外围地区作物中的锗含量高出近2倍。综合认为，讷河地区具有连片富锗土壤，锗含量与地层、土壤类型及人为活动有关，作物以黄豆最为富集锗，具有良好的开发富锗农业前景。
Abstract:BACKGROUND Germanium is an essential element for life. With the discovery of germanium-enriched soils all over China in recent years, the development of germanium-enriched agriculture has gradually gained attention.
OBJECTIVES To study the characteristics and range of germanium-enriched soil in typical black soil areas, and to analyze factors affecting soil germanium content.
METHODS Germanium content in soil was determined by inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-optical emission spectrometry (ICP-OES).
RESULTS The germanium content in the topsoil of the Nehe area was 0.74-1.78mg/kg, with an average value of 1.13mg/kg. There was a large area of concentrated and contiguous germanium-enriched soil in the Nehe area, about 599.8km2, accounting for 9.31% of the city's area. The source of germanium in the soil was the middle Pleistocene upper Huangshan Formation and the upper Pleistocene Guxiangtun Formation. The content of germanium in swamp soil and black soil was highest.
CONCLUSIONS The germanium content in the soil is related to the stratum, soil type and human activities. Soybeans have the highest germanium content in the crops. This area has good potential for the development of germanium-enriched agriculture.
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表 1 元素分析检出限
Table 1. Detection limit of elemental analysis
元素 方法检出限(mg/kg) 分析方法 元素 方法检出限(mg/kg) 分析方法 Ag 0.016 AES Hg 0.0003 AFS As 0.5 AFS I 0.3 ICP-MS Au 0.0002 ICP-MS La 0.10 ICP-MS B 1 AES Li 0.5 ICP-MS Ba 1.46 ICP-OES Mn 4 XRF Be 0.08 ICP-MS Mo 0.06 ICP-MS Bi 0.02 ICP-MS N 19 VOL Br 0.8 XRF Nb 0.3 ICP-MS Cd 0.02 ICP-MS Ni 0.80 XRF Ce 0.31 ICP-MS P 6 XRF Cl 8 XRF Pb 0.3 ICP-MS Co 0.12 XRF Rb 0.40 ICP-MS Cr 0.90 ICP-MS S 26 VOL Cu 0.29 ICP-MS Sb 0.04 AFS F 60 ISE Sc 0.3 ICP-OES Ga 0.42 ICP-MS Se 0.01 AFS Ge 0.059 ICP-MS Sn 0.70 AES Sr 1.0 XRF Al2O3* 0.02 ICP-OES Th 0.3 ICP-MS SiO2* 0.05 XRF Ti 4 ICP-OES TFe2O3* 0.02 XRF Tl 0.07 ICP-MS CaO* 0.03 XRF U 0.04 ICP-MS MgO* 0.03 XRF V 1 ICP-OES K2O* 0.02 ICP-OES W 0.3 ICP-MS Na2O* 0.03 XRF Y 0.2 ICP-MS TC* 0.08 VOL Zn 0.6 XRF Corg* 0.03 VOL Zr 0.6 XRF pH 0.10 ISE 注：标注“*”的元素计量单位为10-2。AES—发射光谱法；
AFS—原子荧光光谱法；ICP-MS—电感耦合等离子体质谱法；ICP-OES电感耦合等离子体发射光谱法；XRF—X射线荧光光谱法；ISE—离子选择性电极法；VOL—容量法。
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表 2 土壤重复样分析合格率统计(密码样)
Table 2. Statistics of qualified rate of soil repeated sample analysis (password sample)
元素 超差点数(件) 合格率(%) 元素 超差点数(件) 合格率(%) Ag 15 96.17 Pb 13 96.68 As 12 96.94 Rb 0 100.00 Au 14 96.43 S 25 93.62 B 16 95.92 Sb 6 98.47 Ba 0 100.00 Sc 2 99.49 Be 9 97.70 Se 20 94.90 Bi 13 96.68 Sn 18 95.41 Br 14 96.43 Sr 0 100.00 Cd 18 95.41 Th 9 97.70 Ce 12 96.94 Ti 0 100.00 Cl 23 94.13 Tl 14 96.43 Co 9 97.70 U 10 97.45 Cr 5 98.72 V 116 99.74 Cu 5 98.72 W 11 97.19 F 0 100.00 Y 0 100.00 Ga 7 98.21 Zn 6 98.47 Ge 16 95.92 Zr 0 100.00 Hg 24 93.88 SiO2 0 100.00 I 4 98.98 Al2O3 0 100.00 La 3 99.23 TFe2O3 0 100.00 Li 4 98.98 MgO 1 99.74 Mn 2 99.49 CaO 3 99.23 Mo 16 95.92 Na2O 1 99.74 N 0 100.00 K2O 0 100.00 Nb 4 98.98 Corg 2 99.49 Ni 14 96.43 TC 1 99.74 P 2 99.49 pH 6 98.47
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表 3 讷河地区富锗土壤54种元素平均值与中国土壤背景值对比
Table 3. Comparison of the average value of 54 elements in germanium-enriched soil in Nehe area and the background value of Chinese soils
元素 锗含量平均值(mg/kg) 变异系数 含量背景值a (mg/kg) 含量比值 元素 含量平均值(mg/kg) 变异系数 含量背景值a (mg/kg) 含量比值 Ag 0.08 0.01 0.13 0.61 Pb 26.58 1.94 26.00 1.02 As 12.55 1.10 11.20 1.12 Rb 117.74 1.80 111.00 1.06 Au 1.55 0.27 - - S 409.17 67.22 287.93 1.42 B 38.26 6.65 47.80 0.80 Sb 0.88 0.08 1.21 0.73 Ba 600.74 19.43 469.00 1.28 Sc 13.05 1.27 11.10 1.18 Be 2.66 0.20 1.95 1.36 Se 0.28 0.03 0.29 0.97 Bi 0.45 0.04 0.37 1.22 Sn 3.29 0.54 2.60 1.27 Br 6.61 0.98 5.40 1.22 Sr 182.43 23.56 167.00 1.09 Cd 0.12 0.02 0.10 1.20 Th 12.39 1.14 13.75 0.90 Ce 78.06 8.17 68.40 1.14 Ti 5080.17 63.79 3800 1.34 Cl 50.56 10.79 68.00 0.74 Tl 0.68 0.07 0.62 1.10 Co 17.66 2.03 12.70 1.39 U 2.62 0.12 3.03 0.86 Cr 72.48 2.12 61.00 1.19 V 111.74 3.80 82.40 1.36 Cu 21.50 0.90 22.60 0.95 W 2.16 0.22 2.48 0.87 F 544.89 80.68 478.00 1.14 Y 27.91 0.60 22.90 1.22 Ga 20.14 0.76 17.50 1.15 Zn 64.12 1.82 74.20 0.86 Ge 1.18 0.15 1.70 0.90 Zr 277.63 5.03 256.00 1.08 Hg 0.02 0.01 0.07 0.29 SiO2 60.05 0.52 59.90 1.00 I 3.45 0.50 3.76 0.92 Al2O3 15.01 0.21 6.62 2.27 La 35.82 3.06 39.70 0.90 TFe2O3 5.49 0.50 2.94 1.87 Li 36.19 2.83 32.50 1.11 MgO 1.33 0.10 0.78 1.71 Mn 824.63 90.70 583.00 1.41 CaO 1.40 0.10 1.54 0.91 Mo 0.74 0.10 2.00 0.37 Na2O 1.34 0.08 1.02 1.31 N 1787.40 350.02 625.60 2.86 K2O 2.42 0.04 1.86 1.30 Nb 16.73 0.25 - - OrgC 23.67 0.23 3.10 1.18 Ni 27.64 3.56 26.90 1.03 TC 2.53 0.29 - - P 647.71 57.22 836.10 0.77 pH 6.18 0.27 6.7 0.97 注：统计样品数为表层土壤共1608件，背景值a为中国土壤背景值，参考中国环境监测总站出版的《中国土壤元素背景值》[28]；
“-”表示无此数据。
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表 4 讷河及外部地区农作物锗含量
Table 4. Germanium content in crops in Nehe area and outside area
样品位置 作物类型 样品数量(件) 锗含量范围(mg/kg) 锗含量平均值(mg/kg) 讷河地区 黄豆 7 1.6~2.38 2.45 水稻 13 1.62~2.99 2.13 玉米 12 0.99~2.96 2.13 讷河外部地区 黄豆 3 1.26~1.58 1.58 玉米 6 0.68~1.34 0.85
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表 5 不同地层和不同土壤类型锗含量特征
Table 5. Characteristics of germanium content in different strata soil and different type soil
讷河地区主要地层 样品数量(件) 锗含量极大值(mg/kg) 锗含量极小值(mg/kg) 锗含量平均值(mg/kg) Q33d(大兴屯组) 44 1.65 1.01 1.28 Q33g(顾乡屯组) 199 1.78 0.86 1.20 Q24s(上荒山组) 954 1.76 0.74 1.19 Q2x(下荒山组) 183 1.47 0.81 1.14 Q43al(冲积层) 183 1.58 0.79 1.14 Q3-4dl+pl(坡洪积层) 44 1.37 0.83 1.10 土壤类型 样品数量(件) 锗含量最大值(mg/kg) 锗含量最小值(mg/kg) 锗含量平均值(mg/kg) 暗棕壤 134 1.42 0.89 1.13 草甸土 475 1.65 0.79 1.15 黑钙土 133 1.54 0.82 1.19 黑土 863 1.78 0.74 1.20 新积土 6 1.21 0.95 1.09 沼泽土 7 1.38 1.05 1.22
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[1] 姬丙艳, 许光, 姚振, 等. 锗的研究进展及开发前景[J]. 中国矿业, 2016, 6(25): 22-24. https://www.cnki.com.cn/Article/CJFDTOTAL-ZGKA2016S1006.htm
Ji B Y, Xu G, Yao Z, et al. Research progress and development prospect of germanium[J]. China Mining Industry, 2016, 6(25): 22-24. https://www.cnki.com.cn/Article/CJFDTOTAL-ZGKA2016S1006.htm
[2] 刘元方, 石进元, 罗志福, 等. 锗对梨形四膜虫细胞和啤酒酵母菌生长的促进作用[J]. 科学通报, 1984(4): 235-237. https://www.cnki.com.cn/Article/CJFDTOTAL-KXTB198404012.htm
Liu Y F, Shi J Y, Luo Z F, et al. Effects of germanium on the growth of Tetrahymena piriformis cells and Saccharomyces cerevisiae[J]. Science Bulletin, 1984(4): 235-237. https://www.cnki.com.cn/Article/CJFDTOTAL-KXTB198404012.htm
[3] Höll R, Kling M, Schroll E. Metallogenesis of germanium—A review[J]. Ore Geology Reviews, 2007, 3(30): 145-180,
[4] 李青仁, 李会, 岳春月, 等. 微量元素锗与人体健康[J]. 世界元素医学, 2008, 15(3): 21-23. https://www.cnki.com.cn/Article/CJFDTOTAL-WYJK602.035.htm
Li Q R, Li H, Yue C Y, et al. Trace element germanium and human health[J]. World Elemental Medicine, 2008, 15(3): 21-23. https://www.cnki.com.cn/Article/CJFDTOTAL-WYJK602.035.htm
[5] 朱立贤, 林海. 锗的研究进展[J]. 饲料研究, 2000(3): 20-23. doi: 10.3969/j.issn.1002-2813.2000.03.007
Zhu L X, Lin H. Research progress of germanium[J]. Feed Research, 2000(3): 20-23. doi: 10.3969/j.issn.1002-2813.2000.03.007
[6] 方益华, 杨玉爱. 微量元素锗的研究进展[J]. 广东微量元素科学, 1998, 5(1): 1-4. https://www.cnki.com.cn/Article/CJFDTOTAL-GWYS199801000.htm
Fang Y H, Yang Y A. Research progress of trace element germanium[J]. Guangdong Trace Element Science, 1998, 5(1): 1-4. https://www.cnki.com.cn/Article/CJFDTOTAL-GWYS199801000.htm
[7] 王永霞, 肖纯. 有机锗的研究概况和进展[J]. 江西医学检验, 2006, 24(3): 252-254. https://www.cnki.com.cn/Article/CJFDTOTAL-JXJL200603030.htm
Wang Y X, Xiao C. Research overview and progress of organic germanium[J]. Jiangxi Medical Laboratory Science, 2006, 24(3): 252-254. https://www.cnki.com.cn/Article/CJFDTOTAL-JXJL200603030.htm
[8] Rosenberg E. Germanium: Environmental occurrence, impor-tance and speciation[J]. Reviews in Environmental Science & Bio/Technology, 2009, 1(8): 29-57.
[9] Dobrzyński D, Boguszewska-Czubara A, Sugimori K. Hydrogeochemical and biomedical insights into germanium potential of curative waters: A case study of health resorts in the Sudetes Mountains (Poland)[J]. Environmental Geochemistry & Health, 2018, 40: 1355-1375.
[10] Wada T, Hanyu T, Nozaki K, et al. Antioxidant activity of Ge-132, a synthetic organic germanium, on cultured-mammalian cells[J]. Biological & Pharmaceutical Bulletin, 2018, 5(41): 749-753.
[11] 白明章, 耿立峰, 孙丽娟, 等. 具有生物活性的有机锗化合物及其合成方法[J]. 化学通报, 1987(11): 23-28. https://www.cnki.com.cn/Article/CJFDTOTAL-HXTB198711004.htm
Bai M Z, Geng L F, Sun L J, et al. Organic germanium compounds with biological activity and their synthesis methods[J]. Chemical Bulletin, 1987(11): 23-28. https://www.cnki.com.cn/Article/CJFDTOTAL-HXTB198711004.htm
[12] 王敬国. 生物地球化学[M]. 北京: 中国农业大学出版社, 2017: 385-388.
Wang J G. Biogeochemistry[M]. Beijing: China Agricultural University Press, 2017: 385-388.
[13] 徐德海, 李绍山. 化学元素知识简明手册[M]. 北京: 化学工业出版社, 2012: 54.
Xu D H, Li S S. A concise handbook of chemical element knowledge[M]. Beijing: Chemical Industry Press, 2012: 54.
[14] 林南琴. 青海省首次发现大面积富锗土壤[J]. 西部资源, 2015(A3): 60. https://www.cnki.com.cn/Article/CJFDTOTAL-XBZY201405055.htm
Lin N Q. The first large-scale germanium-rich soil discovered in Qinghai Province[J]. Western Resources, 2015(A3): 60. https://www.cnki.com.cn/Article/CJFDTOTAL-XBZY201405055.htm
[15] 广西南部发现大面积富锗土地[N]. 中国有色建设, 2016(4): 30-31.
Alarge area of germanium-rich land was discovered in southern Guangxi[N]. China Nonferrous Construction, 2016(4): 30-31.
[16] 李绍铜, 王美玉. 鸡东县土壤锗元素富集特征调查与分析[J]. 水利科学与寒区工程, 2021, 4(2): 61-64. https://www.cnki.com.cn/Article/CJFDTOTAL-SLTD202102014.htm
Li S T, Wang M Y. Investigation and analysis on enrichment characteristics of germanium element in soil in Jidong County[J]. Water Science and Cold Region Engineering, 2021, 4(2): 61-64. https://www.cnki.com.cn/Article/CJFDTOTAL-SLTD202102014.htm
[17] 段轶仁, 杨忠芳, 杨琼, 等. 广西北部湾地区土壤锗分布特征、影响因素及其生态环境评价[J]. 中国地质, 2020, 47(6): 1826-1837. https://www.cnki.com.cn/Article/CJFDTOTAL-DIZI202006019.htm
Duan Y R, Yang Z F, Yang Q, et al. Distribution characteristics, influencing factors and ecological environment assessment of germanium in soil in Beibu Gulf, Guangxi[J]. Geology of China, 2020, 47(6): 1826-1837. https://www.cnki.com.cn/Article/CJFDTOTAL-DIZI202006019.htm
[18] 游桂芝, 鲍大忠, 李丕鹏. 贵州安龙县耕地土壤富锗含量特征及成因探讨[J]. 贵州大学学报(自然科学版), 2020, 37(5): 35-39. https://www.cnki.com.cn/Article/CJFDTOTAL-GZDI202005006.htm
You G Z, Bao D Z, Li P P. Characteristics and causes of germanium-rich soil in cultivated land in Anlong County, Guizhou[J]. Journal of Guizhou University (Natural Science Edition), 2020, 37(5): 35-39. https://www.cnki.com.cn/Article/CJFDTOTAL-GZDI202005006.htm
[19] 曾妍妍, 周金龙, 郑勇, 等. 新疆若羌县绿洲区富锗土壤地球化学特征及成因分析[J]. 土壤通报, 2017, 48(5): 1082-1086. https://www.cnki.com.cn/Article/CJFDTOTAL-TRTB201705009.htm
Zeng Y Y, Zhou J L, Zheng Y, et al. Geochemical characteristics and genetic analysis of germanium-rich soils in the oasis area of Ruoqiang County, Xinjiang[J]. Chinese Journal of Soil Science, 2017, 48(5): 1082-1086. https://www.cnki.com.cn/Article/CJFDTOTAL-TRTB201705009.htm
[20] 黑龙江省地质矿产局. 黑龙江区域地质志[M]. 北京: 地质出版社, 1993: 510.
Heilongjiang Provincial Bureau of Geology and Mineral Resources. Heilongjiang regional geology[M]. Beijing: Geological Publishing House, 1993: 510.
[21] 张哲寰, 宋运红, 赵君, 等. 黑龙江省讷河市土壤某些元素地球化学特征[J]. 地质与资源, 2019, 28(4): 378-382. https://www.cnki.com.cn/Article/CJFDTOTAL-GJSD202001005.htm
Zhang Z H, Song Y H, Zhao J, et al. Geochemical characteristics of some elements in soil of Nehe City, Heilongjiang Province[J]. Geology and Resources, 2019, 28(4): 378-382. https://www.cnki.com.cn/Article/CJFDTOTAL-GJSD202001005.htm
[22] 张哲寰, 赵君, 戴慧敏, 等. 黑龙江讷河市土壤-农作物系统Se元素地球化学特征[J]. 地质与资源, 2019, 29(1): 38-43. https://www.cnki.com.cn/Article/CJFDTOTAL-GJSD202001005.htm
Zhang Z H, Zhao J, Dai H M, et al. Geochemical characteristics of Se elements in the soil-crop system in Nehe, Heilongjiang[J]. Geology and Resources, 2019, 29(1): 38-43. https://www.cnki.com.cn/Article/CJFDTOTAL-GJSD202001005.htm
[23] 赵君, 张哲寰, 贺鹏飞, 等. 黑龙江省平原及丘陵区1∶25万土地质量地球化学调查报告[R]. 沈阳: 中国地质调查局沈阳地质调查中心, 2019: 45.
Zhao J, Zhang Z H, He P F, et al. 250000 land quality geochemical survey report of plain and hilly area in Heilongjiang Province[R]. Shenyang: Shenyang Center, China Geological Survey, 2019: 45.
[24] 阳国运, 唐裴颖, 张洁, 等. 电感耦合等离子体质谱法测定地球化学样品中的硼碘锡锗[J]. 岩矿测试, 2019, 38(2): 154-159. http://www.ykcs.ac.cn/cn/article/doi/10.15898/j.cnki.11-2131/td.201805070055
Yang G Y, Tang P Y, Zhang J, et al. Determination of boron, iodine, tin and germanium in geochemical samples by inductively coupled plasma-mass spectrometry[J]. Rock and Mineral Analysis, 2019, 38(2): 154-159. http://www.ykcs.ac.cn/cn/article/doi/10.15898/j.cnki.11-2131/td.201805070055
[25] 陈波, 刘洪青, 邢应香. 电感耦合等离子体质谱法同时测定地质样品中锗硒碲[J]. 岩矿测试, 2014, 33(2): 192-196. http://www.ykcs.ac.cn/cn/article/id/230dfc09-9aed-48e1-b479-fbd429e9bb9b
Chen B, Liu H Q, Xing Y X. Simultaneous determination of germanium, selenide and tellurium in geological samples by inductively coupled plasma-mass spectrometry[J]. Rock and Mineral Analysis, 2014, 33(2): 192-196. http://www.ykcs.ac.cn/cn/article/id/230dfc09-9aed-48e1-b479-fbd429e9bb9b
[26] 孔祥瑞. 锗的医学地理分布——论"浅井数据"的不可靠性[J]. 医学地理分册, 1994(2): 49-52. https://www.cnki.com.cn/Article/CJFDTOTAL-GONE402.000.htm
Kong X R. Medical geographical distribution of germanium—On the unreliability of "shallow well data"[J]. Medical Geography, 1994(2): 49-52. https://www.cnki.com.cn/Article/CJFDTOTAL-GONE402.000.htm
[27] 肖广全, 木志坚, 魏世强, 等. 重庆地区紫色土锗的背景含量及分布特征[J]. 水土保持学报, 2009, 23(5): 171-214.
Xiao G Q, Mu Z J, Wei S Q, et al. Background content and distribution characteristics of germanium in purple soil in Chongqing area[J]. Journal of Soil and Water Conservation, 2009, 23(5): 171-214.
[28] 中国环境监测总站. 中国土壤元素背景值[M]. 北京: 中国环境科学出版社, 1990: 87.
China National Environmental Monitoring Station. China soil element background value[M]. Beijing: China Environmental Science Press, 1990: 87.
[29] 张立春, 邵景力, 李慈君, 等. 华北平原地下水生态环境水位研究[J]. 吉林大学学报(地球科学版), 2003, 33(3): 323-326. https://www.cnki.com.cn/Article/CJFDTOTAL-CCDZ200303013.htm
Zhang L C, Shao J L, Li C J, et al. Research on the water level of groundwater ecological environment in the North China Plain[J]. Journal of Jilin University (Earth Science), 2003, 33(3): 323-326. https://www.cnki.com.cn/Article/CJFDTOTAL-CCDZ200303013.htm
[30] 张汪寿, 李晓秀, 黄文江, 等. 不同土地利用条件下土壤质量综合评价方法[J]. 农业工程学报, 2010, 26(12): 311-318. https://www.cnki.com.cn/Article/CJFDTOTAL-NYGU201012054.htm
Zhang W S, Li X X, Huang W J, et al. Comprehensive evaluation method of soil quality under different land use conditions[J]. Transactions of the Chinese Society of Agricultural Engineering, 2010, 26(12): 311-318. https://www.cnki.com.cn/Article/CJFDTOTAL-NYGU201012054.htm
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