Determination of Organic Matter Content in Farm Land Soil by High Frequency Infrared Carbon-Sulfur Analyzer
-
摘要: 应用高频红外碳硫仪测定农用地土壤样品中的有机质，避免了传统方法中的试样液体转化环节，测定效率高，但存在土壤样品电磁感应低和基体影响较大等问题。本文通过实验优化了样品称样量、助熔剂铁和钨的添加量等测定条件，结果表明：当样品称样量为0.05g、助熔剂铁添加量为0.40g、钨添加量为1.50g时，有机质测定效果最佳。通过土壤标准物质进行验证，方法检出限为0.003%，相对标准偏差（RSD，n=7）小于4%，测定值与认定值的相对误差小于5%，且不同分析人员的测定结果间没有显著差异。采用本法与重铬酸钾容量法对甘肃省农用地土壤样品进行测定，两种方法测定值的绝对误差为-0.25%~0.28%，测定结果之间呈极显著线性正相关（R2=0.9736），表明两种方法的一致性很好。本方法的检出限、精密度、准确度均满足农用地土壤样品有机质测定要求。Abstract:
BACKGROUNDThe application of high frequency infrared carbon-sulfur analyzer to determine the organic matter in agricultural soil samples avoids the traditional method of sample liquid conversion. The method has a high measurement efficiency, but has problems such as low electromagnetic induction of soil samples and greater influence of the matrix. OBJECTIVESTo solve the problems of low electromagnetic induction and large matrix effect in the determination of organic matter in agricultural soil samples. METHODSThe iron and tungsten flux was optimized for the sample size. An accurate and efficient method for the determination of soil organic matter content was established by high frequency infrared carbon-sulfur analyzer. RESULTSWhen the conditions set for a sample size of 0.05g, the flux iron content was 0.40g, and the tungsten content was 1.50g, optimum results of organic content were obtained. The method was verified by soil standard materials. The detection limit of this method was 0.003%, the relative standard deviation (RSD, n=7) was less than 4%, and the error between the analytical result and the standard value was less than 5%. There was no significant difference between the results of different analytical staff. The proposed method and potassium dichromate volumetric method were used to analyze soil samples in farm land of Gansu Province. The absolute error ranges of this method and potassium dichromate volumetric method were from -0.25% to 0.28%. The positively linear correlation between the determination results (R2=0.9736) indicated that the two methods were in good agreement. CONCLUSIONSThe detection limit, precision and accuracy of the established method meet the requirements of the soil samples of farm land. -
Key words:
- high frequency infrared carbon-sulfur analyzer /
- farmland soil /
- organic matter /
- flux aid /
- iron /
- tungsten
-
-
表 1 铁和钨添加量对有机质含量测定的影响
Table 1. Effect of iron and tungsten addition on determination of organic matter content
项目 铁添加量(g) 钨添加量(g) 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.50 1.00 1.50 2.00 2.50 有机质含量5次测定值(%) 1.86 1.92 1.75 1.88 1.92 1.84 1.93 1.88 1.90 1.84 1.80 1.82 1.72 1.79 1.84 1.81 1.93 1.81 1.91 1.77 1.77 1.92 1.88 1.94 1.82 1.70 1.94 1.90 1.83 1.88 1.82 1.90 1.83 1.86 1.89 1.92 1.88 1.85 1.88 1.94 1.86 1.92 1.87 1.77 1.88 1.95 1.86 1.86 1.67 1.86 1.85 1.86 1.94 1.92 1.87 1.70 1.95 1.87 1.94 1.92 平均值(%) 1.79 1.82 1.85 1.88 1.89 1.87 1.88 1.80 1.86 1.89 1.88 1.89 认定值(%) 1.84 1.84 1.84 1.84 1.84 1.84 1.84 1.84 1.84 1.84 1.84 1.84 RSD(%) 5.00 4.48 3.78 2.62 2.52 2.64 2.25 4.54 3.53 2.40 2.67 2.65 
下载: 导出CSV
表 2 高频红外碳硫仪分析方法的检出限
Table 2. Detection limit of the method with high frequency infrared carbon-sulfur analyzer method
测定次数 有机质含量(%) 1 0.006 2 0.008 3 0.007 4 0.006 5 0.005 6 0.008 7 0.007 8 0.007 9 0.005 10 0.006 11 0.007 平均值 0.0065 标准偏差(s) 0.0010 检出限(3s) 0.003
下载: 导出CSV
表 3 两种方法测定有机质含量的准确度和精密度对比
Table 3. Comparison of accuracy and precision of organic matter content determined with the two methods
标准物质编号 有机质含量认定值(%) 测定方法 分析人员 有机质含量测定值(%) 平均值(%) RSD(%) 相对误差(%) GBW07401 3.10±0.28 高频红外碳硫仪 甲 3.06
3.053.05
3.173.10
3.223.23
3.13 2.55 0.97 乙 3.17
3.203.19
3.153.23
3.073.04
3.15 2.22 1.61 重铬酸钾容量法 甲 3.07
3.063.16
3.043.20
3.193.17
3.13 2.17 0.97 GBW07404 1.07±0.14 高频红外碳硫仪 甲 1.13
1.041.10
1.141.16
1.061.11
1.11 3.90 3.74 乙 1.07
1.171.08
1.151.15
1.091.14
1.12 3.58 4.67 重铬酸钾容量法 甲 1.16
1.151.08
1.111.09
1.051.06
1.10 3.86 2.80 GBW07425 1.84±0.10 高频红外碳硫仪 甲 1.79
1.911.80
1.821.82
1.841.77
1.82 2.48 -1.09 乙 1.94
1.891.85
1.821.92
1.901.80
1.87 2.79 1.63 重铬酸钾容量法 甲 1.80
1.831.78
1.771.78
1.901.89
1.82 2.96 -1.09
下载: 导出CSV
表 4 两种方法测定农用地土壤样品有机质含量结果对比
Table 4. Comparison of the analytical results of organic matter content in farm land soil samples measured with the two methods
实际样品编号 有机质含量测定平均值(%) 绝对误差(%) 高频红外碳硫仪 重铬酸钾容量法 1 1.62 1.54 0.08 2 1.75 1.85 -0.10 3 0.90 0.85 0.05 4 3.10 3.35 -0.25 5 3.51 3.23 0.28 6 3.68 3.46 0.22 7 0.60 0.64 -0.04 8 1.61 1.50 0.11 9 1.13 1.07 0.06 10 2.31 2.44 -0.13 11 1.97 1.80 0.17 12 2.60 2.69 -0.09 13 1.61 1.46 0.15 14 1.40 1.51 -0.11 15 1.69 1.59 0.10
下载: 导出CSV
-
[1] 窦森.土壤有机质[M].北京:科学出版社, 2010.
Dou S.Soil organic matter[M].Beijing:Science Press, 2010.
[2] 杨帆, 徐洋, 崔勇, 等.近30年中国农田耕层土壤有机质含量变化[J].土壤学报, 2017, 54(5):1047-1056. https://xueshu.baidu.com/usercenter/paper/show?paperid=e67e141945c0fe2c2cb27f7a40a6bb85&site=xueshu_se
Yang F, Xu Y, Cui Y, et al.Variation of soil organic matter content in croplands of China over the last three decades[J].Acta Pedologica Sinica, 2017, 54(5):1047-1056. https://xueshu.baidu.com/usercenter/paper/show?paperid=e67e141945c0fe2c2cb27f7a40a6bb85&site=xueshu_se
[3] 汪景宽, 徐英德, 丁凡, 等.植物残体向土壤有机质转化过程及其稳定机制的研究进展[J].土壤学报, 2019, 56(3):528-540. http://www.zhangqiaokeyan.com/academic-journal-cn_acta-pedologica-sinica_thesis/0201272581190.html
Wang J K, Xu Y D, Ding F, et al.Process of plant residue transforming into soil organic matter and mechanism of its stabilization:A review[J].Acta Pedologica Sinica, 2019, 56(3):528-540. http://www.zhangqiaokeyan.com/academic-journal-cn_acta-pedologica-sinica_thesis/0201272581190.html
[4] 徐明岗, 卢昌艾, 张文菊, 等.我国耕地质量状况与提升对策[J].中国农业资源与区划, 2016, 37(7):8-14. http://www.cnki.com.cn/Article/CJFDTotal-ZGNZ201607003.htm
Xu M G, Lu C A, Zhang W J, et al.Situation of the quality of arable land in China and improvement strategy[J].Chinese Journal of Agricultural Resources and Regional Planning, 2016, 37(7):8-14. http://www.cnki.com.cn/Article/CJFDTotal-ZGNZ201607003.htm
[5] 郑昊楠, 王秀君, 万忠梅, 等.华北地区典型农田土壤有机质和养分的空间异质性[J].中国土壤与肥料, 2019(1):55-61. http://www.cnki.com.cn/Article/CJFDTotal-TRFL201901010.htm
Zheng H N, Wang X J, Wan Z M, et al.Spatial heterogeneity of soil organic matter and nutrients in typical farmland in the North China Plain[J].Soil and Fertilizer Sciences in China, 2019(1):55-61. http://www.cnki.com.cn/Article/CJFDTotal-TRFL201901010.htm
[6] 夏家淇.农用地块土壤污染分类标准制订方法探讨[J].生态与农村环境学报, 2019, 35(3):405-408. http://www.cnki.com.cn/Article/CJFDTotal-NCST201903019.htm
Xia J Q.Methods for derivation of site specific standard for management of contaminated agricultural soil[J].Journal of Ecology and Rural Environment, 2019, 35(3):405-408. http://www.cnki.com.cn/Article/CJFDTotal-NCST201903019.htm
[7] 于洋, 刘文清, 许人骥, 等.典型地区农用地污染调查及风险管控标准探讨[J].中国环境监测, 2019, 35(3):1-7. http://www.cnki.com.cn/Article/CJFDTotal-IAOB201903027.htm
Yu Y, Liu W Q, Xu R J, et al.Investigation of agricultural land pollution in typical areas and discussion on risk control standards[J].Environmental Monitoring in China, 2019, 35(3):1-7. http://www.cnki.com.cn/Article/CJFDTotal-IAOB201903027.htm
[8] 陈卫平, 谢天, 李笑诺, 等.中国土壤污染防治技术体系建设思考[J].土壤学报, 2018, 55(3):557-568. http://www.cnki.com.cn/Article/CJFDTotal-TRXB201803003.htm
Chen W P, Xie T, Li X N, et al.Thinking of construction of soil pollution prevention and control technology system in China[J].Acta Pedologica Sinica, 2018, 55(3):557-568. http://www.cnki.com.cn/Article/CJFDTotal-TRXB201803003.htm
[9] Salehi M H, Beni O H, Harchegani H B, et al.Refining soil organic matter determination by loss-on-ignition[J].Pedosphere, 2011, 21(4):473-482. doi: 10.1016/S1002-0160(11)60149-5
[10] 吴才武, 夏建新, 段峥嵘.土壤有机质测定方法述评与展望[J].土壤, 2015, 47(3):453-460. http://www.cnki.com.cn/Article/CJFDTotal-TURA201503004.htm
Wu C W, Xia J X, Duan Z R.Review on detection methods of soil organic matter[J].Soils, 2015, 47(3):453-460. http://www.cnki.com.cn/Article/CJFDTotal-TURA201503004.htm
[11] 徐虎, 申华平, 周世伟, 等.铝模块消解仪加热法测定土壤中有机质含量[J].中国土壤与肥料, 2016(3):140-144. http://d.wanfangdata.com.cn/Periodical/tr201603023
Xu H, Shen H P, Zhou S W, et al.Determination of soil organic matter content by heating method with an aluminum module digesting device[J].Soil and Fertilizer Sciences in China, 2016(3):140-144. http://d.wanfangdata.com.cn/Periodical/tr201603023
[12] 邱灵佳, 黄国林, 帅琴, 等.灼烧法中有机质与总有机碳换算关系的重建及其在页岩分析中的应用[J].岩矿测试, 2015, 34(2):218-223. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2015.02.011
Qiu L J, Huang G L, Shuai Q, et al.Reconstruction of the conversion relationship between organic matter and total organic carbon in calcination method and its application in shale analysis[J].Rock and Mineral Analysis, 2015, 34(2):218-223. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2015.02.011
[13] 胡彩莉, 马玉贞, 郭超, 等.烧失量法测定土壤有机质含量的实验条件探究[J].地球与环境, 2016, 44(1):110-118. http://d.wanfangdata.com.cn/Periodical/dzdqhx201601015
Hu C L, Ma Y Z, Guo C, et al.Optimization of the experiment conditions for estimating organic matter content with loss-on-ignition method[J].Earth and Environment, 2016, 44(1):110-118. http://d.wanfangdata.com.cn/Periodical/dzdqhx201601015
[14] Schumacher B A.Methods for the determination of total organic carbon (TOC) in soils and sediments[R].US Environmental Protection Agency, 2002.
[15] 张明杰, 戴雪峰, 陆荣, 等.高频燃烧-红外碳硫仪用于农用地土壤质量调查样品中碳硫的快速测定[J].岩矿测试, 2010, 29(2):139-142. http://www.ykcs.ac.cn/article/id/ykcs_20100211
Zhang M J, Dai X F, Lu R, et al.Rapid determination of carbon and sulfur in farm land soil samples by high frequency infrared carbon sulfur analyzer[J].Rock and Mineral Analysis, 2010, 29(2):139-142. http://www.ykcs.ac.cn/article/id/ykcs_20100211
[16] 顾涛, 王迪民, 杨梅, 等.高频红外碳硫仪测定土壤/沉积物中总有机碳研究[J].华南地质与矿产, 2015, 31(3):306-310. http://www.cnki.com.cn/Article/CJFDTOTAL-HNKC201503011.htm
Gu T, Wang D M, Yang M, et al.Determination of total organic carbon in soil and sediment by high frequency infrared carbon sulfur analyzer[J].Geology and Mineral Resources of South China, 2015, 31(3):306-310. http://www.cnki.com.cn/Article/CJFDTOTAL-HNKC201503011.htm
[17] 廖漓文, 董震堃.红外碳硫仪测定土壤中碳含量的探讨[J].价值工程, 2015(11):181-182. http://www.cnki.com.cn/Article/CJFDTotal-JZGC201511072.htm
Liao L W, Dong Z K.New application of high frequency infrared ray carbon sulphur analyser[J].Value Engineering, 2015(11):181-182. http://www.cnki.com.cn/Article/CJFDTotal-JZGC201511072.htm
[18] 李国栋, 解成岩, 赵永哲.土样制备对土壤有机质测定的影响[J].黑龙江环境通报, 2018, 42(3):16-18. http://d.old.wanfangdata.com.cn/Periodical_hljhjtb201803005.aspx
Li G D, Xie C Y, Zhao Y Z.Influence of soil sample preparation on soil organic matter determination[J]. Heilongjiang Environmental Journal, 2018, 42(3):16-18. http://d.old.wanfangdata.com.cn/Periodical_hljhjtb201803005.aspx
[19] 钱宝, 刘凌, 肖潇.土壤有机质测定方法对比分析[J].河海大学学报(自然科学版), 2011, 39(1):34-38. http://www.cqvip.com/Main/Detail.aspx?id=36731726
Qian B, Liu L, Xiao X.Comparative tests on different methods for content of soil organic matter[J].Journal of Hohai University (Natural Sciences), 2011, 39(1):34-38. http://www.cqvip.com/Main/Detail.aspx?id=36731726
[20] 鲁如坤.土壤农业化学分析方法[M].北京:中国农业科技出版社, 2000.
Lu R K.Analytical method of soil agricultural chemistry[M].Beijing:China Agriculture Science and Technique Press, 2000.
[21] 张长均, 王蓬, 张之果.影响高频红外碳硫仪分析结果稳定性因素的探讨[J].冶金分析, 2006, 26(6):90-91. http://www.cnki.com.cn/Article/CJFDTotal-YJFX200606028.htm
Zhang C J, Wang P, Zhang Z G.Discussion on the factors affecting the stability of high frequency infrared carbon and sulfur analyzer[J].Metallurgical Analysis, 2006, 26(6):90-91. http://www.cnki.com.cn/Article/CJFDTotal-YJFX200606028.htm
[22] 于汀汀, 王玮, 许俊玉, 等.红外碳硫仪测定矿石中高含量硫[J].分析试验室, 2016, 35(6):695-699. http://www.cnki.com.cn/Article/CJFDTOTAL-FXSY201606018.htm
Yu T T, Wang W, Xu J Y, et al.Determination of high-content sulfur in ore by IR-absorption spectrometer[J].Chinese Journal of Analysis Laboratory, 2016, 35(6):695-699. http://www.cnki.com.cn/Article/CJFDTOTAL-FXSY201606018.htm
[23] 龚仓, 付桂花, 黄艳波.高频燃烧-红外碳硫仪测定岩心钻探样品中碳硫[J].黄金, 2016, 37(12):77-80. http://d.wanfangdata.com.cn/Periodical/huangj201612019
Gong C, Fu G H, Huang Y B.Determination of carbon and sulfur in drilling core samples by high frequency combustion-infrared carbon and sulfur analyzer[J].Gold, 2016, 37(12):77-80. http://d.wanfangdata.com.cn/Periodical/huangj201612019
[24] 黄启华, 徐志强, 杨玮玮.高频红外碳硫仪测定重晶石和黄铁矿中的硫[J].岩矿测试, 2017, 36(2):130-135. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2017.02.006
Huang Q H, Xu Z Q, Yang W W.Determination of sulfur in barite and pyrite by high infrared carbon-sulfur spectrometer[J].Rock and Mineral Analysis, 2017, 36(2):130-135. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2017.02.006
[25] 陈伟锐.高频红外碳硫仪测定土壤和水系沉积物中的硫实验条件改进[J].岩矿测试, 2019, 38(1):123-128. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.201804160045
Chen W R.Improvement of experimental conditions for the determination of sulfur in soil and stream sediments by high frequency infrared carbon and sulfur analyzer[J].Rock and Mineral Analysis, 2019, 38(1):123-128. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.201804160045
[26] 和振云, 段九存, 张旺强, 等.干燥箱烘焙加热法测定土壤有机质的方法改进[J].甘肃地质, 2013, 22(3):77-81. http://www.cnki.com.cn/Article/CJFDTotal-GSDZ201303013.htm
He Z Y, Duan J C, Zhang W Q, et al.Improved process on drying oven torrefaction heating method to determine soil organic matter[J].Gansu Geology, 2013, 22(3):77-81. http://www.cnki.com.cn/Article/CJFDTotal-GSDZ201303013.htm
[27] Li G A, Yan L, Chen Z H, et al.Determination of organic carbon in soils and sediments in an automatic method[J].Journal of Groundwater Science and Engineering, 2017, 5(2):124-129. http://www.cnki.com.cn/Article/CJFDTotal-DXSG201702004.htm
[28] 杨艳明, 李美玉, 赵毅华.高频燃烧-红外吸收法测定石墨中的固定碳含量[J].分析测试技术与仪器, 2018, 24(1):52-56. http://d.old.wanfangdata.com.cn/Periodical/fxcsjsyyq201801009
Yang Y M, Li M Y, Zhao Y H.Determination of fixed carbon content in graphite by high frequency combustion-infrared absorption method[J].Analysis and Testing Technology and Instruments, 2018, 24(1):52-56. http://d.old.wanfangdata.com.cn/Periodical/fxcsjsyyq201801009
[29] 陈宗定, 许春雪, 安子怡, 等.土壤碳赋存形态及分析方法研究进展[J].岩矿测试, 2019, 38(2):233-244. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.201709270148
Chen Z D, Xu C X, An Z Y, et al.Research progress on fraction and analysis methods of soil carbon[J].Rock and Mineral Analysis, 2019, 38(2):233-244. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.201709270148
-
图(1)
表(4)
计量
- 文章访问数: 3193
- PDF下载数: 127
- 施引文献: 0