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The determination of arsenic content in phosphorus pentoxide by atomic fluorescence spectroscopy method was studied, and the acid medium, acidity, reducing agent concentration, pre reducing agent, and masking agent were determined. The results indicate that the method has good linearity in the range of 1.0~50.0 μg/L, the correlation coefficient is r>0.999, the detection limit is 0.06 μg/L, quantification limit is 0.21 μg/L. The relative standard deviation (RSD) of the 8 sample analysis results is 1.94%, and the spiked recovery rate are 92.87%~101.30%. The test results show no significant difference from the DDTC silver salt method, and this method is a reliable method for detecting arsenic content in phosphorus pentoxide, because it is more convenient and less reagent used.

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李少华(1971—),女,硕士,高级工程师,主要研究方向为磷化工、日用化工产品等的重金属检测及有色金属产品检测。

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李少华(1971—),女,硕士,高级工程师,主要研究方向为磷化工、日用化工产品等的重金属检测及有色金属产品检测。

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李少华(1971—),女,硕士,高级工程师,主要研究方向为磷化工、日用化工产品等的重金属检测及有色金属产品检测。

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金属元素对原子荧光法测定砷的干扰研究[J]. 环境污染与防治, 2013, 35(3):35-38., articleTitle=金属元素对原子荧光法测定砷的干扰研究, refAbstract=null), Reference(id=1176949719793283518, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172618991957852976, doi=null, pmid=null, pmcid=null, year=2017, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[24], rfOrder=23, authorNames=国家标准化管理委员会, journalName=合格评定化学分析方法确认和验证指南:GB/T27417—2017, refType=null, unstructuredReference=国家标准化管理委员会. 合格评定化学分析方法确认和验证指南:GB/T27417—2017[S]. 北京: 中国标准质检出版社, 2017., articleTitle=null, refAbstract=null), Reference(id=1176949719847809471, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172618991957852976, doi=null, pmid=null, pmcid=null, year=2020, volume=null, issue=7, pageStart=60, pageEnd=63, url=null, language=null, rfNumber=[25], rfOrder=24, authorNames=潘宇婷, 苏布德, 李金凤, journalName=中国盐业, refType=null, unstructuredReference=潘宇婷, 苏布德, 李金凤, 等. 工业用固体氢氧化钠中钾含量的测定[J]. 中国盐业, 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tableContent=
盐酸酸度/% 荧光强度
2 2 210.733
3 2 276.811
4 2 325.681
5 2 386.255
6 2 377.639
8 2 381.590
10 2 385.027
), ArticleFig(id=1176949716878242202, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172618991957852976, language=CN, label=表1, caption=

酸度对荧光强度的影响

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盐酸酸度/% 荧光强度
2 2 210.733
3 2 276.811
4 2 325.681
5 2 386.255
6 2 377.639
8 2 381.590
10 2 385.027
), ArticleFig(id=1176949716949545371, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172618991957852976, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
KBH4浓度/% 荧光强度
1.0 1 678.455
1.5 2 085.901
2.0 2 431.762
2.5 2 369.833
3.0 2 334.490
3.5 2 169.043
4.0 1 887.169
), ArticleFig(id=1176949717008265628, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172618991957852976, language=CN, label=表2, caption=

KBH4浓度对荧光强度的影响

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KBH4浓度/% 荧光强度
1.0 1 678.455
1.5 2 085.901
2.0 2 431.762
2.5 2 369.833
3.0 2 334.490
3.5 2 169.043
4.0 1 887.169
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预还原剂加入量/mL 测定值/(μg·L-1) 还原率/%
5 27.5 55.0
10 38.5 77.0
15 48.6 97.2
20 51.5 103.0
25 49.2 98.4
30 49.6 99.2
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5%硫脲+5%抗坏血酸加入量试验结果

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预还原剂加入量/mL 测定值/(μg·L-1) 还原率/%
5 27.5 55.0
10 38.5 77.0
15 48.6 97.2
20 51.5 103.0
25 49.2 98.4
30 49.6 99.2
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空白荧光强度 S b 检出限/(μg·L-1) 定量限/(μg·L-1)
12.560,13.733,10.373,
11.280,12.613,12.996,
13.093,13.227,13.600,
13.049,13.867,15.076,
16.507,15.467,14.720,
16.604,12.187,15.218,
13.867,15.698
1.651 77.21 0.064 0.21
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方法的检出限与定量限

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空白荧光强度 S b 检出限/(μg·L-1) 定量限/(μg·L-1)
12.560,13.733,10.373,
11.280,12.613,12.996,
13.093,13.227,13.600,
13.049,13.867,15.076,
16.507,15.467,14.720,
16.604,12.187,15.218,
13.867,15.698
1.651 77.21 0.064 0.21
), ArticleFig(id=1176949717377364385, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172618991957852976, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
样品编号 样品质量/g 样品种砷质量分数/(μg·g-1) 本底值/μg 砷加标量/μg 加标后测定值/μg 加标回收率/%
1# 0.683 7 33.86 23.15 15.00 37.08 92.87
0.551 6 18.68 30.00 46.89 94.03
0.735 1 24.89 45.00 69.86 99.93
2# 0.609 8 22.23 13.56 10.00 23.69 101.30
0.885 9 19.69 20.00 38.47 93.90
0.957 7 21.29 30.00 51.45 100.53
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加标回收率的测定结果

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样品编号 样品质量/g 样品种砷质量分数/(μg·g-1) 本底值/μg 砷加标量/μg 加标后测定值/μg 加标回收率/%
1# 0.683 7 33.86 23.15 15.00 37.08 92.87
0.551 6 18.68 30.00 46.89 94.03
0.735 1 24.89 45.00 69.86 99.93
2# 0.609 8 22.23 13.56 10.00 23.69 101.30
0.885 9 19.69 20.00 38.47 93.90
0.957 7 21.29 30.00 51.45 100.53
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序号 砷(As)质量分数/(mg·kg-1) 显著性检验
二乙基二硫代氨基甲酸银分光光度法 原子荧光光谱法 d d2
1 34.86 33.33 1.530 2.341
2 33.78 35.04 -1.260 -1.588
3 35.59 32.92 2.670 7.129
4 34.36 34.28 0.080 0.006 4
5 33.08 33.69 -0.610 -0.372
6 33.28 33.90 -0.620 0.384
7 34.57 33.41 1.160 1.346
8 32.72 34.10 -1.380 1.904
平均 34.11 33.83 0.196
S 0.983 0.657 1.452
合计 272.24 270.67 d=1.570 d2=11.150
t 0.382 t(0.05,7)=2.365 t<t(0.05,7),差异不显著
), ArticleFig(id=1176949717561913764, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172618991957852976, language=CN, label=表6, caption=

方法对比和显著性检验

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序号 砷(As)质量分数/(mg·kg-1) 显著性检验
二乙基二硫代氨基甲酸银分光光度法 原子荧光光谱法 d d2
1 34.86 33.33 1.530 2.341
2 33.78 35.04 -1.260 -1.588
3 35.59 32.92 2.670 7.129
4 34.36 34.28 0.080 0.006 4
5 33.08 33.69 -0.610 -0.372
6 33.28 33.90 -0.620 0.384
7 34.57 33.41 1.160 1.346
8 32.72 34.10 -1.380 1.904
平均 34.11 33.83 0.196
S 0.983 0.657 1.452
合计 272.24 270.67 d=1.570 d2=11.150
t 0.382 t(0.05,7)=2.365 t<t(0.05,7),差异不显著
), ArticleFig(id=1176949717620634021, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172618991957852976, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
测定值/(mg·kg-1) 平均值/
(mg·kg-1)
S RSD/%
1 2 3 4 5 6 7 8
33.33 35.04 32.92 34.28 33.69 33.90 33.41 34.10 33.83 0.657 1.94
), ArticleFig(id=1176949717675159974, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172618991957852976, language=CN, label=表7, caption=

1#五氧化二磷样品中砷含量测定的重复性测试结果(n=8)

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测定值/(mg·kg-1) 平均值/
(mg·kg-1)
S RSD/%
1 2 3 4 5 6 7 8
33.33 35.04 32.92 34.28 33.69 33.90 33.41 34.10 33.83 0.657 1.94
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原子荧光光谱法测定五氧化二磷中的砷
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李少华 1, 2 , 白帆 1, 2 , 孔涛 1, 2 , 罗兰 1, 2 , 杨智蓉 1 , 寸杰 1
湿法冶金 | 分析测试 2024,43(4): 466-471
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湿法冶金 | 分析测试 2024, 43(4): 466-471
原子荧光光谱法测定五氧化二磷中的砷
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李少华1, 2, 白帆1, 2, 孔涛1, 2, 罗兰1, 2, 杨智蓉1, 寸杰1
作者信息
  • 1 云南省产品质量监督检验研究院, 云南 昆明 650032
  • 2 国家磷化工产品检验检测中心(云南), 云南 昆明 650032
  • 李少华(1971—),女,硕士,高级工程师,主要研究方向为磷化工、日用化工产品等的重金属检测及有色金属产品检测。

Determination of Arsenic Content in Phosphorus Pentoxide by Atomic Fluorescence Spectroscopy Method
Shaohua LI1, 2, Fan BAI1, 2, Tao KONG1, 2, Lan LUO1, 2, Zhirong YANG1, Jie CUN1
Affiliations
  • 1 Yunnan Provincial Institute of Product Quality Supervision and Inspection, Kunming 650032, China
  • 2 National Phosphorus Chemical Product Inspection and Testing Center (Yunnan), Kunming 650032, China
出版时间: 2024-08-20 doi: 10.13355/j.cnki.sfyj.2024.04.017
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研究了采用原子荧光光谱法测定五氧化二磷中的砷,确定了酸介质、酸度、还原剂浓度、预还原剂和掩蔽剂。结果表明:方法在1.0~50.0 μg/L范围内线性良好,相关系数r>0.999,检出限为0.064 μg/L,定量限为0.21 μg/L;8次样品分析结果的相对标准偏差(RSD)为1.94%,加标回收率为92.87%~101.30%,检验结果与DDTC银盐法无明显差异。该法操作更便捷,所用试剂少,是一种测定五氧化二磷中砷含量的可靠方法。
原子荧光光谱法  /  DDTC银盐法  /  五氧化二磷  /  砷  /  测定  /  分析

The determination of arsenic content in phosphorus pentoxide by atomic fluorescence spectroscopy method was studied, and the acid medium, acidity, reducing agent concentration, pre reducing agent, and masking agent were determined. The results indicate that the method has good linearity in the range of 1.0~50.0 μg/L, the correlation coefficient is r>0.999, the detection limit is 0.06 μg/L, quantification limit is 0.21 μg/L. The relative standard deviation (RSD) of the 8 sample analysis results is 1.94%, and the spiked recovery rate are 92.87%~101.30%. The test results show no significant difference from the DDTC silver salt method, and this method is a reliable method for detecting arsenic content in phosphorus pentoxide, because it is more convenient and less reagent used.

atomic fluorescence spectroscopy method  /  DDTC silver salt method  /  phosphorus pentoxide  /  arsenic  /  determination  /  analyzation
李少华, 白帆, 孔涛, 罗兰, 杨智蓉, 寸杰. 原子荧光光谱法测定五氧化二磷中的砷. 湿法冶金, 2024 , 43 (4) : 466 -471 . DOI: 10.13355/j.cnki.sfyj.2024.04.017
Shaohua LI, Fan BAI, Tao KONG, Lan LUO, Zhirong YANG, Jie CUN. Determination of Arsenic Content in Phosphorus Pentoxide by Atomic Fluorescence Spectroscopy Method[J]. Hydrometallurgy of China, 2024 , 43 (4) : 466 -471 . DOI: 10.13355/j.cnki.sfyj.2024.04.017
云南省磷矿资源丰富[1],是黄磷的主产区,产能产量居全国前列[2-3]。五氧化二磷是以黄磷为原料生产的化工产品,在精细化工产品的生产中应用广泛。五氧化二磷主要用于制造高纯度磷酸、多聚磷酸、聚磷酸铵、医药中间体、有机磷酸酯等[4],也用作气体和液体干燥剂、有机合成的脱水剂、糖的精制剂等[5-6]。但其中含有的砷是一种有毒的金属元素,可引起人体内脏器官损伤,破坏神经、造血及免疫系统,诱发多种癌症[7-8],因此,严格控制五氧化二磷中的砷含量,采用可靠便捷的测定方法,对加强生产过程控制、提高产品质量、拓宽应用领域具有重要意义。
目前,有关砷的测定方法主要有DDTC银盐法、石墨炉原子吸收法、原子吸收法(带氢化物发生器)、ICP-OES法、ICP-MS法及原子荧光光谱法等[9-15]。DDTC银盐法操作步骤繁琐,所用试剂较多,费时较长;同时所用吸收液吡啶或三氯甲烷均为有机挥发物,具有一定毒性,散发恶臭气味,会对检测人员的健康造成伤害[9,16]。石墨炉法记忆效应严重,精密度低,背景干扰大,须进行基体改进及背景矫正[15]。原子吸收法敏感度低,检出限高[14]。ICP法测砷基体干扰大,雾化效率低,灵敏度低,检出限高,且ICP及ICP-MS仪器价格较高,维护费用较高,不利于在中小企业普及推广[17]。五氧化二磷中的砷含量可依据《化工产品中砷含量测定的通用方法》(GB/T 7686—2016)[16]测定,但其中未明确样品制备规定和检出限等,使其操作性和应用领域受到限制。目前,有关五氧化二磷中砷含量的测定方法研究尚未见报道。原子荧光光谱法测定砷具有基体干扰小、线性范围宽、灵敏度高、检出限低、操作便捷、适合批量检测等优点,且原子荧光光度计价格较低,因此,试验研究了采用原子荧光光谱法测定五氧化二磷中砷含量,并分析了该法的准确度和可靠性。
主要试剂:砷单元素标准溶液(GSB 04-1714—2004),质量浓度1 000 μg/mL,国家有色金属及电子材料分析测试中心生产;盐酸溶液(1+1),5%盐酸载流溶液,2.0%硼氢化钾和0.5%氢氧化钾混合溶液,均为分析纯;5%硫脲+5%抗坏血酸混合溶液;高纯氩气,纯度≥99.99%。
试验仪器:AFS-9561型原子荧光光度计,北京海光仪器公司生产;METTLER-TOLEDO MS-S精密电子天平;艾柯Exceed-Cb-30实验室超纯水机。
灯电流:40 mA;负高压270 V;原子化温度200 ℃;原子化器高度:8 mm;载气:高纯氩气;载气压力:0.2~0.3 MPa;载气流量:300 mL/min,屏蔽气流量:800 mL/min;读数时间:12 s;读数方式:峰面积;延迟时间2.0 s;测定方式为标准曲线法。
用浓度为5%的盐酸将1 000 μg/mL的砷标准溶液稀释至1 μg/mL的砷标准储备液;移取5.0 mL的1 μg/mL砷标准储备液至100 mL容量瓶中,加入20 mL 5%的硫脲-抗坏血酸溶液及5 mL盐酸,定容至刻度,放置30 min,即为50 μg/L砷标准工作溶液。将原子荧光仪器软件中自动进样方式设置为自动配标模式,设置砷标准工作溶液质量浓度为0.0、10.0、20.0、30.0、40.0、50.0 μg/L。以砷标液的浓度为横坐标,荧光强度为纵坐标,根据1.2仪器工作条件得到线性回归方程。
快速称取试样1 g(精确至0.1 mg)于200 mL烧杯中,将烧杯置于沸腾的水浴锅上,充分吸湿后,缓慢加水溶解试样,加水稀释至约100 mL;冷却,分次用水转入250 mL容量瓶中,用水稀释至刻度,反复摇匀,作为待测样品溶液。在制备待测样品溶液的同时,制备样品空白溶液,除了不加试样外,其他操作和加入的试剂量与待测样品溶液制备时相同。
移取适量上述待测样品溶液,放入100 mL容量瓶中,加入10 mL(1+1)盐酸、20 mL 5%硫脲-抗坏血酸溶液,用水稀释至刻度,反复摇匀,作为待测样品测定溶液,使其中砷质量浓度在1~50 μg/L范围内,放置30 min以上。按照1.2仪器工作条件,用原子荧光光度计测定待测样品溶液和空白溶液的荧光强度,通过工作曲线回归方程计算得到待测样品溶液和空白溶液中的砷质量浓度。
氢化物发生的效率是本方法的关键环节,三价砷发生氢化物反应的速率远高于五价砷[18],因此,一般不以硝酸为酸介质。硝酸是氧化性酸,其氧化性可将三价砷氧化为五价砷,降低氢化物发生的效率,从而降低荧光强度[19]。因此,选择具有还原性的盐酸作为介质[20]
酸度条件对氢化物发生反应影响较大:酸度过低时,氢化物发生反应不充分,荧光强度较低;酸度过高时,氢化物发生反应太过剧烈,导致传数不稳定,相应的信号值也不稳定。因此,样品酸度选择十分重要。酸度对荧光强度的影响结果见表1。可以看出,盐酸酸度在5%~10%(体积分数,下同)范围内,砷荧光强度值变化不大,这与文献[19]结论一致。因此,选择盐酸酸度为5%。
氢化物原子荧光光谱法通常采用(KBH4+KOH)作为还原剂[16-20],由于KBH4水溶液易分解,通常溶于0.5%~2%的KOH溶液才能保持稳定;但KOH溶液浓度高于2%,则易降低反应酸度,影响氢化物发生的反应效果[16,18-20]。KBH4起到还原待测元素、提供氢原子与待测元素离子生成氢化物,并为氩氢火焰提供氢气等作用。KBH4浓度对荧光强度的影响试验结果见表2。可以看出,KBH4浓度对测定结果影响很大[17]:KBH4用量不足(低于2.0%)时,因氢化物发生反应不彻底,荧光信号较低;KBH4用量过大(高于2.0%)时,由于大量氢气的产生对氢化物起到稀释作用,导致测定灵敏度降低,荧光信号也较低,此时还会造成气液溢出,污染石英管。综合考虑,选择KBH4浓度为2.0%、KOH浓度为0.5%。
由于五价砷发生氢化物反应速率远低于三价砷,因此须将五价砷预还原为三价砷[21]。单独的抗坏血酸没有还原作用,单独的硫脲还原作用和硫脲、抗坏血酸混合溶液相当[22],在现行国内有关标准和文献中多采用5%硫脲+5%抗坏血酸作为预还原剂[16-22]。另外,在测定过程中,消除共存元素的干扰十分重要。常用的掩蔽剂有EDTA、硫氰化钾、铁氰化钾、枸橼酸钠、硫脲、抗坏血酸等。5%硫脲+5%抗坏血酸混合溶液在一定酸性条件下,既有还原作用,又有掩蔽干扰元素的效果[22-23]。因此,选择5%硫脲+5%抗坏血酸混合溶液作为预还原剂和掩蔽剂。
由于本方法中标准曲线的最高点质量浓度为50 μg/L,因此,对100 mL质量浓度为50 μg/L的五价砷标准溶液进行预还原剂加入量试验,结果见表3。可以看出:预还原剂5%硫脲+5%抗坏血酸混合溶液加入量超过15 mL时,50 μg/L的五价砷标准溶液还原率即可超过97.0%,综合考虑,选择预还原剂加入量为20 mL。
在1.2仪器工作条件下绘制的标准曲线y=77.210x+12.614(y代表荧光强度,x代表砷质量浓度,下同),相关系数r=0.999 9。对样品空白溶液连续测定20次,得荧光强度,再以3倍荧光强度标准偏差(S)除以斜率(b)计算砷检出限,以10倍荧光强度标准偏差除以斜率计算溶液中砷的定量限,结果见表4。可以看出:方法检出限为0.064 μg/L,定量限为0.21 μg/L。
采用加标回收率试验和显著性检验对方法的准确度进行验证。
试验所用2个五氧化二磷样品分别由云南省某2家磷化工生产企业提供,编号分别为1#、2#,按照上述方法测定其中砷含量。分别加入从10~45 μg的三水平砷标准物进行加标回收率的测定,线性方程为y=78.147x+26.749,相关系数r=0.999 6。测定结果见表5。回收率(η)计算公式为
$\eta =\frac{{m}_{1}-mw}{{m}_{0}}\times 100\%$。
式中:m1—加标后测定值,μg;m—样品质量,g;w—样品中砷质量分数,μg/g;m0—砷加标量,μg。
分别采用二乙基二硫代氨基甲酸银分光光度法和原子荧光光谱法,对1#工业五氧化二磷样品中砷含量进行8次重复测定,线性方程为y=75.699x+3.747,相关系数r=1.000 0。采用t检验法对2种方法测定数据进行显著性检验,并通过SPSS软件计算得t=0.382,查t检验界值表可得到t(0.05,7)=2.365,可见,t<t(0.05,7),说明2种方法没有显著性差异。结果见表6
通过对上述数据进行分析和归纳可知,加标回收率在92.87%~101.30%之间,能达到《合格评定化学分析方法确认和验证指南》(GB/T 27417—2017)(附录A)中方法回收率偏差范围的要求[24-25];同时,通过方法对比进行显著性检验可知,2种方法差异不显著,说明本方法具有较高的准确度,能够满足测定要求。
在重复性条件下,对1#工业五氧化二磷样品中砷含量进行8次重复测定,线性方程为y=75.699x+3.747,相关系数r=1.000 0。测定结果见表7,可以看出,标准偏差S为0.657,相对标准偏差RSD为1.94%,达到了《合格评定化学分析方法确认和验证指南》(GB/T 27417—2017)附录B中实验室内变异系数范围的要求[24-25]
建立了用原子荧光光谱法测定五氧化二磷中砷含量的方法。在该方法中砷可以形成气态的氢化物,不但可以和基体分离,消除基体干扰,而且可将目标元素充分预富集,从而使进样效率大大提高。该方法灵敏度高,检出限较低,精密度和加标回收率高,其检验结果与DDTC银盐法无显著差异,且操作更简便,快速,是一种测定五氧化二磷中砷含量的理想方法。
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2024年第43卷第4期
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doi: 10.13355/j.cnki.sfyj.2024.04.017
  • 接收时间:2024-04-15
  • 首发时间:2025-09-10
  • 出版时间:2024-08-20
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  • 收稿日期:2024-04-15
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    1 云南省产品质量监督检验研究院, 云南 昆明 650032
    2 国家磷化工产品检验检测中心(云南), 云南 昆明 650032
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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