Determination of Trace Heavy Metal Elements in Sewage by Total Reflection X-Ray Fluorescence Spectrometry

doi:10.19894/j.issn.1000-0518.220210

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (3): 404-412.DOI: 10.19894/j.issn.1000-0518.220210

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Determination of Trace Heavy Metal Elements in Sewage by Total Reflection X-Ray Fluorescence Spectrometry

Lei WU¹(), Ling-Yun LI², Yong-Zhen PENG¹()

^1.National Engineering Laboratory for Advanced Municipal Wastewater Treatment and Reuse Technology Engineering，Beijing University of Technology，Beijing 100124，China
^2.Beijing Enterprises Water Group Limited，Beijing 100102，China

Received:2022-06-12 Accepted:2022-12-12 Published:2023-03-01 Online:2023-03-27
Contact: Lei WU,Yong-Zhen PENG
About author:wulei@bjut.edu.cn
pyz@bjut.edu.cn；
Supported by:
the Creative Research Groups of National Natural Science Foundation of China(62021003)

Abstract

Abstract:

In this work， Ga is used as the internal standard to explore the feasibility of rapid determination of multi-mass concentration gradient of multi-element heavy metal solution by Total Reflection X-ray Fluorescence （TXRF） Spectrometry， e.g. Mn， Fe， Co， Ni， Cu， Zn， As， Cd， Sn， Sb， and Pb， and the effects of three pretreatment methods on the determination of heavy metal elements in actual domestic sewage are compared and analyzed. The experimental results show Mn， Fe， Co， Ni， Cu， Zn， As， Pb are more suitable for the direct analysis with TXRF； Overlapping of Lα Line of Pb and Kα Line of As results in a slightly higher recovery of As than other elements， which does not affect Pb； Cd， Sn and Sb can be used for trend analysis because the recovery and precision can not meet the quantitative requirements in most cases. When the mass concentrations are 40 and 4 mg/L， Mn， Fe， Co， Ni， Cu， Zn and Pb show high accuracy and precision. The recovery rates are 99%~117% and the RSDs are between 1.4%~2.7%. With the gradual decrease of concentration， the accuracy and precision of each element decreases. When the mass concentration is at the lowest level of 4 μg/L in this experiment， the recovery rate and RSD of most element exceed the required range. Through the comparison of three pretreatment methods， it is found that the concentration of each element in the sewage after centrifugation and filter membrane filtration and is significantly lower than that of raw water and acid digestion water samples， and the raw water is slightly lower than that of acid digestion water samples， which indicates that the heavy suspended particles of sewage also carry some metal elements. After digestion， the accuracy and precision of the six elements Mn， Fe， Co， Ni， Cu and Zn are the best. The concentration range is 36~152 μg/L， and the recovery rates are higher than 95% with RSD lower than 5%. In summary， TXRF can directly achieve rapid and accurate quantitative analysis of sewage samples， and its accuracy and accuracy depend largely on the type of elements， sample preparation procedures and the concentration of elements to be measured. For low concentration samples， preconcentration technology can be combined to improve the accuracy.

Key words: Total reflection X-ray fluorescence spectrometry, Multi-element analysis, Sewage, Heavy metal solution

CLC Number:

O657

Lei WU, Ling-Yun LI, Yong-Zhen PENG. Determination of Trace Heavy Metal Elements in Sewage by Total Reflection X-Ray Fluorescence Spectrometry[J]. Chinese Journal of Applied Chemistry, 2023, 40(3): 404-412.

Figures/Tables 6

References 24

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Elements	40 mg/L			4 mg/L			0.4 mg/L			40 μg/L			4 μg/L
Elements	RR/%	SD	RSD/%	RR/%	SD	RSD/%	RR/%	SD	RSD/%	RR/%	SD	RSD/%	RR/%	SD	RSD/%
Mn	99.43	0.38	0.95	101.42	0.06	1.45	100.91	0.01	3.18	＞130	0.02	32.91	＞130	-	＞25
Fe	105.66	5.75	13.62	117.63	0.17	3.69	＞130	0.07	12.20	＞130	0.27	56.99		0.04
Co	99.05	5.89	14.86	101.69	0.19	4.67	95.16	0.06	14.85	126.56	0.01	20.79		-
Ni	108.89	0.95	2.18	107.72	0.11	2.47	106.06	0.02	4.00	128.44	0.03	61.77	93.75	-
Cu	99.98	0.59	1.46	102.17	0.08	2.02	104.19	0.02	4.76	＞130	0.01	11.23	＞130	-
Zn	101.32	1.05	2.58	106.30	0.13	3.12	120.91	0.03	6.43	＞130	0.02	18.71		0.01
As	124.93	0.71	1.42	119.07	0.13	2.77	118.28	0.03	5.78	＞130	0.01	11.67		0.02
Cd	96.23	4.85	12.59	113.74	0.94	20.56	＞130	0.43	39.22	＞130	0.26	56.05		0.16
Pb	101.11	1.35	3.34	99.79	0.34	8.54	93.03	0.01	2.83	96.88	0.00	11.52	96.88	-

Elements	40 mg/L			4 mg/L			0.4 mg/L			40 μg/L			4 μg/L
Elements	RR/%	SD	RSD/%	RR/%	SD	RSD/%	RR/%	SD	RSD/%	RR/%	SD	RSD/%	RR/%	SD	RSD/%
Mn	99.43	0.38	0.95	101.42	0.06	1.45	100.91	0.01	3.18	＞130	0.02	32.91	＞130	-	＞25
Fe	105.66	5.75	13.62	117.63	0.17	3.69	＞130	0.07	12.20	＞130	0.27	56.99		0.04
Co	99.05	5.89	14.86	101.69	0.19	4.67	95.16	0.06	14.85	126.56	0.01	20.79		-
Ni	108.89	0.95	2.18	107.72	0.11	2.47	106.06	0.02	4.00	128.44	0.03	61.77	93.75	-
Cu	99.98	0.59	1.46	102.17	0.08	2.02	104.19	0.02	4.76	＞130	0.01	11.23	＞130	-
Zn	101.32	1.05	2.58	106.30	0.13	3.12	120.91	0.03	6.43	＞130	0.02	18.71		0.01
As	124.93	0.71	1.42	119.07	0.13	2.77	118.28	0.03	5.78	＞130	0.01	11.67		0.02
Cd	96.23	4.85	12.59	113.74	0.94	20.56	＞130	0.43	39.22	＞130	0.26	56.05		0.16
Pb	101.11	1.35	3.34	99.79	0.34	8.54	93.03	0.01	2.83	96.88	0.00	11.52	96.88	-

Element	R²	Slope	Intercept
Mn	0.934 1	1 970.61	269.77
Fe	0.900 5	2 473.18	1 787.11
Co	0.890 0	3 041.53	324.42
Ni	0.932 3	3 522.39	595.48
Cu	0.935 7	4 138.75	581.89
Zn	0.942 7	4 779.82	1 323.28
As	0.939 8	5 461.11	946.55
Pb	0.945 8	3 822.09	329.83

Element	R²	Slope	Intercept
Mn	0.934 1	1 970.61	269.77
Fe	0.900 5	2 473.18	1 787.11
Co	0.890 0	3 041.53	324.42
Ni	0.932 3	3 522.39	595.48
Cu	0.935 7	4 138.75	581.89
Zn	0.942 7	4 779.82	1 323.28
As	0.939 8	5 461.11	946.55
Pb	0.945 8	3 822.09	329.83

Element	W1			W2			W3			W4			W5
Element	Average value/（μg·L^-1）	RSD/%	RR/%	Average value/（μg·L^-1）	RSD/%	RR/%	Average value/（μg·L^-1）	RSD/%	RR/%	Average value/（μg·L^-1）	RSD/%	RR/%	Average value/（μg·L^-1）	RSD/%	RR/%
Mn	50.5	2.8	95.9	37.1	3.6	95.4	32.3	1.8	95.8	33.8	1.3	96.7	57.3	1.1	98.1
Fe	49.6	2.9	98.5	307.5	2.2	100.1	161.1	3.6	101.3	35.6	3.9	102.4	78.6	3.6	100.1
Co	36.6	4.4	99.6	20.6	4.9	98.2	21.3	4.5	98.3	17.3	5.1	95.5	35.5	3.2	97.7
Ni	89.1	2.7	102.1	74.8	5.1	100.1	74.6	2.4	102.2	68.5	1.8	102.6	77.1	0.4	104.3
Cu	44.3	1.5	97.7	38.3	2.8	97	42.6	1.8	96.8	11.8	1.8	97.4	38.2	1.5	99.5
Zn	152.6	3.6	107.8	120	4.9	101.9	158.3	2.0	102.5	23.5	2.9	102.1	28.6	2.0	104.4
As	11.8	3.9	95.9	11.1	4.1	180.5	11.2	5.4	102.8	33.3	3.3	123.1	31.6	1.9	125.7
Pb	64.2	31.1	105.4	43.5	19.1	90.8	24.1	19.8	100.2	38.5	16.8	93.2	66.5	26.4	98.1

Determination of Trace Heavy Metal Elements in Sewage by Total Reflection X-Ray Fluorescence Spectrometry

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References 24

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No.	Elements	X-ray line used	Energy/keV
1	Mn	Kα	5.849
1	Mn	Kβ	6.421
2	Fe	Kα	6.355
2	Fe	Kβ	7.015
3	Co	Kα	6.882
3	Co	Kβ	7.61
4	Ni	Kα	7.435
4	Ni	Kβ	8.222
5	Cu	Kα	8.011
5	Cu	Kβ	8.871
6	Zn	Kα	8.603
6	Zn	Kβ	9.541
7	As	Kα	10.502
8	Pb	Lα	10.531
9	Cd	Lα	3.076
10	Sn	Lα	3.38
11	Sb	Lα	3.591