Quantitative analysis of gallstones using laser-induced breakdown spectroscopy

Vivek K. Singh; Vinita Singh; Awadhesh K. Rai; Surya N. Thakur; Pradeep K. Rai; Jagdish P. Singh

doi:10.1364/AO.47.000G38

Applied Optics
Vol. 47,
Issue 31,
pp. G38-G47
(2008)
•https://doi.org/10.1364/AO.47.000G38

Quantitative analysis of gallstones using laser-induced breakdown spectroscopy

Vivek K. Singh, Vinita Singh, Awadhesh K. Rai, Surya N. Thakur, Pradeep K. Rai, and Jagdish P. Singh

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Vivek K. Singh, Vinita Singh, Awadhesh K. Rai, Surya N. Thakur, Pradeep K. Rai, and Jagdish P. Singh, "Quantitative analysis of gallstones using laser-induced breakdown spectroscopy," Appl. Opt. 47, G38-G47 (2008)

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Abstract

The utility of laser-induced breakdown spectroscopy (LIBS) for categorizing different types of gallbladder stone has been demonstrated by analyzing their major and minor constituents. LIBS spectra of three types of gallstone have been recorded in the $200 - 900 nm$ spectral region. Calcium is found to be the major element in all types of gallbladder stone. The spectrophotometric method has been used to classify the stones. A calibration-free LIBS method has been used for the quantitative analysis of metal elements, and the results have been compared with those obtained from inductively coupled plasma atomic emission spectroscopy (ICP-AES) measurements. The single-shot LIBS spectra from different points on the cross section (in steps of $0.5 mm$ from one end to the other) of gallstones have also been recorded to study the variation of constituents from the center to the surface. The presence of different metal elements and their possible role in gallstone formation is discussed.

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Type	Colors	Patient Age (years), Sex	No. of gallstones
Cholesterol	Creamy yellow	56, Male	2
Mixed	Dark brown, bottle green	35, Male	$4 + 1$
Pigment	Black	40, Male	3

Type	Cholesterol (%)	Bilirubin (%)
Cholesterol	72–79	12–17
Dark brown	30–42	22–29
Bottle green	42	31
Pigment	21–23	52–57

Elements	Wavelengths (nm)
C	247.8, 229.6
Ca	211.2, 239.8, 315.8, 317.9, 336.02, 364.4, 370.6, 373.6, 393.3, 396.8, 422.7, 428.3, 430.3, 442.5, 443.5, 445.5, 458.5
Mg	277.9, 279.5, 280.2, 285.2
Mn	257.6, 259.3, 260.5, 263.08, 362.3
Cu	199.9, 203.5, 204.3, 212.2, 224.2, 324.7, 327.3
Fe	212.5, 218.9, 219.1, 222.9, 229.9, 234.3, 238.2, 239.5, 240.4, 258.5, 259.9, 273.9, 274.8, 275.5, 383.1, 383.7
Zn	202.5, 206.5
Sr	460.7, 407.7
P	213.5, 214.8

	Intensity Ratio ( $\pm %$ RSD)
Analyte Line (nm)	Black Pigment Stone	Bottle Green Stone
$C (247.83 nm) / Ca (396.86 nm)$	$0.24 (\pm 11 %)$	$0.87 (\pm 11.7 %)$
$Cu (324.71 nm) / Ca (396.86 nm)$	$0.062 (\pm 8 %)$	Cu absent
$Fe (238.20 nm) / Ca (396.86 nm)$	$0.018 (\pm 19 %)$	Fe absent
$Mg (280.20 nm) / Ca (396.86 nm)$	$0.191 (\pm 19.4 %)$	$0.11 (\pm 15 %)$
$Mn (257.61 nm) / Ca (396.86 nm)$	$0.007 (\pm 11.4 %)$	$0.022 (\pm 8.2 %)$
$P (214.87 nm) / Ca (396.86 nm)$	$0.0037 (\pm 6.7 %)$	$0.008 (\pm 13.6 %)$
$Sr (460.75 nm) / Ca (396.86 nm)$	$0.0108 (\pm 14.7 %)$	$0.0103 (\pm 2.1 %)$
$Zn (202.55 nm) / Ca (396.86 nm)$	$0.0025 (\pm 14 %)$	Zn absent
$Na (818.26 nm) / Ca (854.17 nm)$	$0.23 (\pm 9.05 %)$	$0.57 (\pm 1.01 %)$
$K (766.44 nm) / Ca (854.17 nm)$	$1.88 (\pm 4.26 %)$	$1.04 (\pm 9.08 %)$
$N (868.39 nm) / Ca (854.17 nm)$	$0.61 (\pm 3.27 %)$	$1.34 (\pm 10.84 %)$
$O (844.67 nm) / Ca (854.17 nm)$	$0.86 (\pm 6.15 %)$	$1.68 (\pm 15.82 %)$

	Concentration $(μg / g)$
Sample	Al	Ca	Cu	Fe	Mg	Mn	Sr	Zn
GS1	144	1950	23.8	0	0	13.1	0	0
GS2	4.47	467	3.14	0	0	1.89	0	0
GS3	44.7	506	3.97	0	0	2.84	0	0
GS4	92.4	2380	229	0	0	27.4	0	0
GS5	67	562	37.3	0	0	1.9	0	0
GS6	163	234	13	0	0	2.69	0	0
GS7	123	26900	21600	3260	940	192	9.98	178
GS8	10.3	12100	743	254	55.5	54.5	0.037	7.30
GS9	114	10700	412	133	22.4	49.7	0	8.54

	Concentration
	$μg / g$								%
Sample	Al	Ca	Cu	Fe	Mg	Mn	Sr	Zn	C	H	N	O	Na	K
GS1	160	59789	37.3	393	58.75	19.67	0	0	35.8	29.3	0.03	0.99	13.5	12.26
GS2	9.45	35359	5.66	163	49.55	6.83	0	0	36.9	30.9	0.02	0.04	11.1	10.7
GS3	47.5	19921	5.47	0	42.47	3.92	0	0	40.3	25.4	0.16	0.018	8.9	9.91
GS4	0	45704	256	168	121	0	0	0	45.6	22.1	0.05	0.024	11.5	10.2
GS5	0	37961	45.2	102	104	0	0	0	40.6	15.9	0.04	0.049	14.1	19.7
GS6	0	14177	0	0	16	0	0	0	35.2	35.8	0.014	7.51	7.2	3.9
GS7	135	78041	23649	3886	1136	231	14	196	35.9	30.5	0.052	0.043	10.9	11
GS8	20.8	55064	767	366	88.9	63.9	11.31	7.97	32.1	28.6	0.12	0.05	12.4	14
GS9	143	14347	541	217	35.8	67.45	5.8	16.3	30.8	32.2	0.015	0.09	14.9	13.6

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Applied Optics