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硼是土壤和水系沉积物关键元素，其含量测定对环境评估、农业生产意义重大。电感耦合等离子体发射光谱法(ICP-OES)虽具备多元素同步分析优势，但硼元素检测仍受制于前处理与光谱干扰双重因素：酸消解过程易造成硼组分损失，且Fe等多种元素与B的分析谱线存在重叠，导致检测精度与稳定性显著降低。本研究建立了电热板消解-电感耦合等离子体发射光谱(ICP-OES)法测定土壤和水系沉积物全硼的分析方法。采用HF-HNO3-HCl三元酸体系消解，引入H_3PO4作为硼的络合稳定剂，抑制挥发性硼化合物逸失。系统优化了磷酸添加量(0.5 mL)、消解温度(180℃)、消解时间(3 h)及赶酸温度(180℃)等关键参数。通过评估各干扰元素的发射强度贡献率，最终选定208.959 nm为B分析谱线。硼的质量浓度在0.05～2 mg/L线性良好(R=0.9999)，检出限低(MDL=0.30 mg/kg)，优于现有电感耦合等离子体质谱法；标准样品测定值均符合认定值不确定度范围，相对标准偏差(RSD)为1.2%～5.7%。本方法具有回收率高、稳定性好、抗干扰、灵敏度高和准确度好等优点，适用于大批量检测土壤和水系沉积物中极低含量的硼元素，为环境样品痕量硼测定提供可靠检测手段，对环境质量评估有重要应用价值。
Abstract：Boron(B) is a key element in environmental geochemistry,and its accurate determination is crucial for environmental assessment of soil and stream sediments,as well as for agricultural applications. Although inductively coupled plasma optical emission spectrometry(ICP-OES) enables simultaneous multi-element analysis,the determination of boron still faces dual challenges of pre-treatment loss and spectral interference:during high-temperature digestion/evaporation in concentrated acid media,boric acid readily reacts with fluoride ions(F ~-) or chloride ions(Cl ~-) to form volatile boron compounds(BF3 and BCl3),leading to significant loss of the target element;concurrently,spectral lines from coexisting elements(e.g.,Fe) overlap with boron's analytical lines,severely affecting detection precision and stability. This study established a method for determining trace boron in soil and stream sediments using hotplate digestion combined with ICP-OES. To address pre-treatment loss,a ternary mixed acid system(HF,HNO3,HCl) was employed for sample digestion,and phosphoric acid(H3 PO4) was introduced as a complexing stabilizer for boron,effectively suppressing the formation and volatilization loss of volatile boron compounds. Key pre-treatment parameters,including the ratio of the digestion acid system,phosphoric acid addition amount,digestion temperature,digestion time,and acid removal temperature, were systematically optimized. The optimal conditions were determined as follows:total mixed acid volume(HF ∶ HNO3∶ HCl=3∶3∶1) 7 mL,phosphoric acid addition 0. 5 mL,digestion temperature 180 ℃, digestion time 3 hours,and acid removal temperature 180 ℃. During the ICP-OES analysis stage,to overcome matrix effects,a matrix-matching calibration method was used to construct the calibration curve for correcting systematic errors. The optimized instrumental parameters were:RF power 1 150 W,plasma and auxiliary gas argon(Ar),nebulizer gas flow rate 0. 5 L/min,and axial view observation mode to enhance sensitivity. By systematically evaluating the spectral interference intensity and contribution rates of coexisting elements on potential boron analytical lines,the line least affected by interference,B 208. 959 nm,was ultimately selected. Systematic method validation demonstrated:Excellent linearity within the concentration range of 0. 05-2 mg/L(calibration curve equation:y=605. 935x+31. 436,correlation coefficient R=0. 9999);Method detection limit(MDL) as low as 0. 30 mg/kg,superior to some reported values for inductively coupled plasma mass spectrometry(ICP-MS); Relative standard deviations(RSD) for six replicate determinations of GBW series soil and stream sediment certified reference materials ranged from 1. 2% to 5. 7%,with all measured values falling within the uncertainty ranges of the certified values,indicating good precision and trueness;Spike recovery tests for real samples with different matrices yielded average boron recoveries ranging from 91. 5% to 97. 8%,confirming the method's strong anti-interference capability,high and stable recovery. In summary,the established hot plate digestion-ICP-OES method,based on phosphoric acid complexation stabilization,significantly enhances the accuracy,precision,and sensitivity for determining trace boron in soil and stream sediments by effectively suppressing boron volatilization loss,optimizing digestion conditions,implementing matrix matching,and selecting the optimal analytical line. This method offers comprehensive advantages including relatively simple operation,cost-effectiveness,high and stable recovery rates,and low detection limits. It is suitable for high-throughput and highly reliable analysis of trace boron in large quantities of environmental samples,providing robust technical support for environmental quality assessment and geochemical research.
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基本信息:
DOI：10.20236/j.CJIAC.2025.12.007
中图分类号:X830;O657.31
引用信息:
[1]方小满,洪碧圆,王晨凯,等.电感耦合等离子体发射光谱(ICP-OES)法测定土壤和水系沉积物全硼[J].中国无机分析化学,2025,15(12):1959-1968.DOI:10.20236/j.CJIAC.2025.12.007.
基金信息:
国家重点研发计划项目（2023YFF0713900）