Abstract

Laser-induced breakdown spectroscopy (LIBS) has been applied to the analysis of toxic metals Pb and Cd in Pb(NO3)2 and Cd(NO3)2.4H2O aqueous solutions, respectively. The plasma is generated by focusing a nanosecond Nd:YAG (λ=1064nm) laser on the surface of liquid in the homemade liquid jet configuration. With an assumption of local thermodynamic equilibrium (LTE), calibration curves of Pb and Cd were obtained at different delay times between 1 to 5μs. The temporal behavior of limit of detections (LOD) was investigated and it is shown that the minimum LODs for Pb and Cd are 4 and 68 parts in 106 (ppm), respectively. In order to demonstrate the correctness of the LTE assumption, plasma parameters including plasma temperature and electron density are evaluated, and it is shown that the LTE condition is satisfied at all delay times.

© 2011 Optical Society of America

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2010 (2)

2008 (5)

Zh. Chen, H. Li, M. Liu, and R. Li, “Fast and sensitive trace metal analysis in aqueous solutions by laser-induced breakdown spectroscopy using wood slice substrates,” Spectrochim. Acta Part B 63, 64–68 (2008).
[CrossRef]

M. Kampa and E. Castanas, “Human health effects of air pollution,” Environ. Pollut. 151, 362–367 (2008).
[CrossRef]

I. Al-Saleh, S. Coskun, A. Mashhour, N. Shinwari, I. El-Doush, G. Billedo, K. Jaroudi, A. Al-Shahrani, M. Al-Kabra, and G. El Din Mohamed, “Exposure to heavy metals (lead, cadmium and mercury) and its effect on the outcome of in-vitro fertilization treatment,” Int. J. Hyg. Environ. Health 211, 560–579 (2008).
[CrossRef]

X. K. Shen and Y. F. Lu, “Detection of uranium in solids by using laser-induced breakdown spectroscopy combined with laser-induced fluorescence,” Appl. Opt. 47, 1810–1815 (2008).
[CrossRef] [PubMed]

E. G. Snyder, C. A. Munson, J. L. Gottfried, F. C. De Lucia, B. Gullett, and A. Miziolek, “Laser-induced breakdown spectroscopy for the classification of unknown powders,” Appl. Opt. 47, G80–G87 (2008).
[CrossRef]

2006 (3)

N. Mirlean and A. Roisenberg, “The effect of emissions of fertilizer production on the environment contamination by cadmium and arsenic in southern Brazil,” Environ. Pollut. 143, 335–340 (2006).
[CrossRef] [PubMed]

D. M. Díaz Pace, C. A. D’Angelo, D. Bertuccelli, and G. Bertuccelli, “Analysis of heavy metals in liquids using laser induced breakdown spectroscopy by liquid-to-solid matrix conversion,” Spectrochim. Acta Part B 61, 929–933 (2006).
[CrossRef]

D. M. Díaz Pace, C. A. D’Angelo, D. Bertuccelli, and G. Bertuccelli, “Analysis of heavy metals in liquids using laser induced breakdown spectroscopy by liquid-to-solid matrix conversion,” Spectrochim. Acta Part B 61, 929–933 (2006).
[CrossRef]

2005 (6)

C. R. Dockey, J. E. Pender, and S. R. Goode, “Speciation of chromium via laser-induced breakdown spectroscopy of ion exchange polymer membranes,” Appl. Spectrosc. 59, 252–257(2005).
[CrossRef]

P. Yaroshchyk, R. J. S. Morrison, D. Body, and B. L. Chadwick, “Quantitative determination of wear metals in engine oil using LIBS: the use of paper substrates and a comparison between single- and double-pulse LIBS,” Spectrochim. Acta Part B 60, 1482–1485 (2005).
[CrossRef]

P. Yaroshchyk, R. J. S. Morrison, D. Body, and B. L. Chadwick, “Quantitative determination of wear metals in engine oil using LIBS: the use of paper substrates and a comparison between single- and double-pulse LIBS,” Spectrochim. Acta Part B 60, 1482–1485 (2005).
[CrossRef]

H. Wake, “Oil refineries: a review of their ecological impacts on the aquatic environment,” Estuar. Coast. Shelf S. 62, 131–140 (2005).
[CrossRef]

D. Il’yasova and G. G. Schwartz, “Cadmium and renal cancer,” Toxicol. Appl. Pharmacol. 207, 179–186 (2005).
[CrossRef] [PubMed]

C. R. Dockey, J. E. Pender, and S. R. Goode, “Speciation of chromium via laser-induced breakdown spectroscopy of ion exchange polymer membranes,” Appl. Spectrosc. 59, 252–257(2005).
[CrossRef]

2004 (1)

L. St.-Onge, E. Kwong, M. Sabsabi, and E. B. Vadas, “Rapid analysis of liquid formulations containing sodium chloride using laser-induced breakdown spectroscopy,” J. Pharm. Biomed. Anal. 36, 277–284 (2004).
[CrossRef] [PubMed]

2003 (3)

2002 (4)

H. Palacios, I. Iribarren, M. J. Olalla, and V. Cala, “Lead poisoning of horses in the vicinity of a battery recycling plant,” Sci. Total Environ. 290, 81–89 (2002).
[CrossRef] [PubMed]

J. Y. Cabon, “Determination of Cd and Pb in seawater by graphite furnace atomic absorption spectrometry with the use of hydrofluoric acid as a chemical modifier,” Spectrochim. Acta Part B 57, 513–524 (2002).
[CrossRef]

B. Charfi and M. A. Harith, “Panoramic laser-induced breakdown spectrometry of water,” Spectrochim. Acta Part B 57, 1141–1153 (2002).
[CrossRef]

N. E. Schmidt and S. R. Goode, “Analysis of aqueous solutions by laser-induced breakdown spectroscopy of ion exchange membranes,” Appl. Spectrosc. 56, 370–374 (2002).
[CrossRef]

2001 (4)

J. O. Cáceres, J. Tornero López, H. H. Telle, and A. González Ureña, “Quantitative analysis of trace metal ions in ice using laser-induced breakdown spectroscopy,” Spectrochim. Acta Part B 56, 831–838 (2001).
[CrossRef]

J. Chen and K. C. Teo, “Determination of cobalt and nickel in water samples by flame atomic absorption spectrometry after cloud point extraction,” Anal. Chim. Acta 434, 325–330 (2001).
[CrossRef]

R. M. Tripathi, R. Raghunath, S. Mahapatra, and S. Sadasivan, “Blood lead and its effect on Cd, Cu, Zn, Fe and hemoglobin levels of children,” Sci. Total Environ. 277, 161–168 (2001).
[CrossRef] [PubMed]

J. O. Cáceres, J. Tornero López, H. H. Telle, and A. González Ureña, “Quantitative analysis of trace metal ions in ice using laser-induced breakdown spectroscopy,” Spectrochim. Acta Part B 56, 831–838 (2001).
[CrossRef]

2000 (3)

O. Samek, D. C. S. Beddows, J. Kaiser, S. V. Kukhlevsky, M. Liska, H. H. Telle, and J. Young, “Application of laser-induced breakdown spectroscopy to in-situ analysis of liquid samples,” Opt. Eng. 39, 2248–2262 (2000).
[CrossRef]

M. T. Antonio and M. L. Leret, “Study of the neurochemical alterations produced in discrete brain areas by perinatal low-level lead exposure,” Life Sci. 67, 635–642 (2000).
[CrossRef]

S. Tong, Y. E. R. von Schirnding, and T. Prapamontol, “Environmental lead exposure: a public health problem of global dimensions,” Bull. W.H.O. 78, 1068–1077 (2000).
[PubMed]

1999 (2)

1998 (2)

U. Panne, C. Haisch, M. Clara, and R. Niessner, “Analysis of glass melts during the verification process of fly and bottom ashes by laser-induced plasma spectroscopy. Part I: normalization and plasma diagnostics,” Spectrochim. Acta Part B 53, 1957–1968 (1998).
[CrossRef]

L. P. Eksperiandova, Y. N. Makarovska, and A. B. Blank, “Determination of small quantities of heavy metals in water-soluble salts and natural water by X-ray fluorescence,” Anal. Chim. Acta 371, 105–108 (1998).
[CrossRef]

1997 (2)

1995 (3)

M. Sabsabi and P. Cielo, “Quantitative analysis of aluminum alloys by laser induced breakdown spectroscopy and plasma characterization,” Appl. Spectrosc. 49, 499–507(1995).
[CrossRef]

M. C. Yebra-Biurrun, A. Bermejo-Barrera, M. P. Bermejo-Barrera, and M. C. Barciela-Alonso, “Determination of trace metals in natural waters by flame atomic absorption spectrometry following on-line ion-exchange preconcentration,” Anal. Chim. Acta 303, 341–345 (1995).
[CrossRef]

S. Dudka, M. Piotrowska, A. Chlopeckaand, and T. Witek, “Trace metal contamination of soils and crop plants by the mining and smelting industry in Upper Silesia, South Poland,” J. Geochem. Explor. 52, 237–250 (1995).
[CrossRef]

1994 (2)

H. Horiguchi, H. Teranishi, K. Niiya, K. Aoshima, T. Katoch, N. Sakuragawa, and M. Kasuya, “Hypoproduction of erythropoietin contributes to anemia in chronic cadmium intoxication: clinical study on Itai-itai disease in Japan,” Arch. Toxicol. 68, 632–636 (1994).
[PubMed]

L. J. Radziemski, “Review of selected analytical applications of laser plasmas and laser ablation,” Microchem. J. 50, 218–234 (1994).
[CrossRef]

1989 (1)

G. D. Nuyts, M. M. Elseviers, and M. E. De Broe, “Health impact of renal disease due to nephrotoxicity,” Toxicol. Lett. 46, 31–44 (1989).
[CrossRef] [PubMed]

1985 (1)

E. Guinat, “Spectrometric oil analysis: atomic emission spectrometric analysis of wear metals in lube oils by RDE method,” Tribol. Int. 18, 246 (1985).
[CrossRef]

1984 (1)

1983 (1)

D. A. Cremers and L. J. Radziemski, “Detection of chlorine and fluorine in air by laser induced breakdown spectrometry,” Anal. Chem. 55, 1252–1256 (1983).
[CrossRef]

1981 (1)

J. A. C. Broekaert, F. Leis, and K. Laqua, “The application of an argon/nitrogen inductively-coupled plasma to the analysis of organic solutions,” Talanta 28, 745–752 (1981).
[CrossRef] [PubMed]

1968 (1)

A. W. Morris, “The simultaneous determination of vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc in sea water by x-ray fluorescence spectrometry,” Anal. Chim. Acta 42, 397–406 (1968).
[CrossRef]

Al-Kabra, M.

I. Al-Saleh, S. Coskun, A. Mashhour, N. Shinwari, I. El-Doush, G. Billedo, K. Jaroudi, A. Al-Shahrani, M. Al-Kabra, and G. El Din Mohamed, “Exposure to heavy metals (lead, cadmium and mercury) and its effect on the outcome of in-vitro fertilization treatment,” Int. J. Hyg. Environ. Health 211, 560–579 (2008).
[CrossRef]

Al-Saleh, I.

I. Al-Saleh, S. Coskun, A. Mashhour, N. Shinwari, I. El-Doush, G. Billedo, K. Jaroudi, A. Al-Shahrani, M. Al-Kabra, and G. El Din Mohamed, “Exposure to heavy metals (lead, cadmium and mercury) and its effect on the outcome of in-vitro fertilization treatment,” Int. J. Hyg. Environ. Health 211, 560–579 (2008).
[CrossRef]

Al-Shahrani, A.

I. Al-Saleh, S. Coskun, A. Mashhour, N. Shinwari, I. El-Doush, G. Billedo, K. Jaroudi, A. Al-Shahrani, M. Al-Kabra, and G. El Din Mohamed, “Exposure to heavy metals (lead, cadmium and mercury) and its effect on the outcome of in-vitro fertilization treatment,” Int. J. Hyg. Environ. Health 211, 560–579 (2008).
[CrossRef]

Antonio, M. T.

M. T. Antonio and M. L. Leret, “Study of the neurochemical alterations produced in discrete brain areas by perinatal low-level lead exposure,” Life Sci. 67, 635–642 (2000).
[CrossRef]

Aoshima, K.

H. Horiguchi, H. Teranishi, K. Niiya, K. Aoshima, T. Katoch, N. Sakuragawa, and M. Kasuya, “Hypoproduction of erythropoietin contributes to anemia in chronic cadmium intoxication: clinical study on Itai-itai disease in Japan,” Arch. Toxicol. 68, 632–636 (1994).
[PubMed]

Arca, G.

Barciela-Alonso, M. C.

M. C. Yebra-Biurrun, A. Bermejo-Barrera, M. P. Bermejo-Barrera, and M. C. Barciela-Alonso, “Determination of trace metals in natural waters by flame atomic absorption spectrometry following on-line ion-exchange preconcentration,” Anal. Chim. Acta 303, 341–345 (1995).
[CrossRef]

Beddows, D. C. S.

O. Samek, D. C. S. Beddows, J. Kaiser, S. V. Kukhlevsky, M. Liska, H. H. Telle, and J. Young, “Application of laser-induced breakdown spectroscopy to in-situ analysis of liquid samples,” Opt. Eng. 39, 2248–2262 (2000).
[CrossRef]

Bermejo-Barrera, A.

M. C. Yebra-Biurrun, A. Bermejo-Barrera, M. P. Bermejo-Barrera, and M. C. Barciela-Alonso, “Determination of trace metals in natural waters by flame atomic absorption spectrometry following on-line ion-exchange preconcentration,” Anal. Chim. Acta 303, 341–345 (1995).
[CrossRef]

Bermejo-Barrera, M. P.

M. C. Yebra-Biurrun, A. Bermejo-Barrera, M. P. Bermejo-Barrera, and M. C. Barciela-Alonso, “Determination of trace metals in natural waters by flame atomic absorption spectrometry following on-line ion-exchange preconcentration,” Anal. Chim. Acta 303, 341–345 (1995).
[CrossRef]

Bertuccelli, D.

D. M. Díaz Pace, C. A. D’Angelo, D. Bertuccelli, and G. Bertuccelli, “Analysis of heavy metals in liquids using laser induced breakdown spectroscopy by liquid-to-solid matrix conversion,” Spectrochim. Acta Part B 61, 929–933 (2006).
[CrossRef]

D. M. Díaz Pace, C. A. D’Angelo, D. Bertuccelli, and G. Bertuccelli, “Analysis of heavy metals in liquids using laser induced breakdown spectroscopy by liquid-to-solid matrix conversion,” Spectrochim. Acta Part B 61, 929–933 (2006).
[CrossRef]

Bertuccelli, G.

D. M. Díaz Pace, C. A. D’Angelo, D. Bertuccelli, and G. Bertuccelli, “Analysis of heavy metals in liquids using laser induced breakdown spectroscopy by liquid-to-solid matrix conversion,” Spectrochim. Acta Part B 61, 929–933 (2006).
[CrossRef]

D. M. Díaz Pace, C. A. D’Angelo, D. Bertuccelli, and G. Bertuccelli, “Analysis of heavy metals in liquids using laser induced breakdown spectroscopy by liquid-to-solid matrix conversion,” Spectrochim. Acta Part B 61, 929–933 (2006).
[CrossRef]

Billedo, G.

I. Al-Saleh, S. Coskun, A. Mashhour, N. Shinwari, I. El-Doush, G. Billedo, K. Jaroudi, A. Al-Shahrani, M. Al-Kabra, and G. El Din Mohamed, “Exposure to heavy metals (lead, cadmium and mercury) and its effect on the outcome of in-vitro fertilization treatment,” Int. J. Hyg. Environ. Health 211, 560–579 (2008).
[CrossRef]

Blank, A. B.

L. P. Eksperiandova, Y. N. Makarovska, and A. B. Blank, “Determination of small quantities of heavy metals in water-soluble salts and natural water by X-ray fluorescence,” Anal. Chim. Acta 371, 105–108 (1998).
[CrossRef]

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J. O. Cáceres, J. Tornero López, H. H. Telle, and A. González Ureña, “Quantitative analysis of trace metal ions in ice using laser-induced breakdown spectroscopy,” Spectrochim. Acta Part B 56, 831–838 (2001).
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Zh. Chen, H. Li, M. Liu, and R. Li, “Fast and sensitive trace metal analysis in aqueous solutions by laser-induced breakdown spectroscopy using wood slice substrates,” Spectrochim. Acta Part B 63, 64–68 (2008).
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L. P. Eksperiandova, Y. N. Makarovska, and A. B. Blank, “Determination of small quantities of heavy metals in water-soluble salts and natural water by X-ray fluorescence,” Anal. Chim. Acta 371, 105–108 (1998).
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I. Al-Saleh, S. Coskun, A. Mashhour, N. Shinwari, I. El-Doush, G. Billedo, K. Jaroudi, A. Al-Shahrani, M. Al-Kabra, and G. El Din Mohamed, “Exposure to heavy metals (lead, cadmium and mercury) and its effect on the outcome of in-vitro fertilization treatment,” Int. J. Hyg. Environ. Health 211, 560–579 (2008).
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P. Yaroshchyk, R. J. S. Morrison, D. Body, and B. L. Chadwick, “Quantitative determination of wear metals in engine oil using LIBS: the use of paper substrates and a comparison between single- and double-pulse LIBS,” Spectrochim. Acta Part B 60, 1482–1485 (2005).
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U. Panne, C. Haisch, M. Clara, and R. Niessner, “Analysis of glass melts during the verification process of fly and bottom ashes by laser-induced plasma spectroscopy. Part I: normalization and plasma diagnostics,” Spectrochim. Acta Part B 53, 1957–1968 (1998).
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H. Horiguchi, H. Teranishi, K. Niiya, K. Aoshima, T. Katoch, N. Sakuragawa, and M. Kasuya, “Hypoproduction of erythropoietin contributes to anemia in chronic cadmium intoxication: clinical study on Itai-itai disease in Japan,” Arch. Toxicol. 68, 632–636 (1994).
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H. Palacios, I. Iribarren, M. J. Olalla, and V. Cala, “Lead poisoning of horses in the vicinity of a battery recycling plant,” Sci. Total Environ. 290, 81–89 (2002).
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D. M. Díaz Pace, C. A. D’Angelo, D. Bertuccelli, and G. Bertuccelli, “Analysis of heavy metals in liquids using laser induced breakdown spectroscopy by liquid-to-solid matrix conversion,” Spectrochim. Acta Part B 61, 929–933 (2006).
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H. Palacios, I. Iribarren, M. J. Olalla, and V. Cala, “Lead poisoning of horses in the vicinity of a battery recycling plant,” Sci. Total Environ. 290, 81–89 (2002).
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S. Dudka, M. Piotrowska, A. Chlopeckaand, and T. Witek, “Trace metal contamination of soils and crop plants by the mining and smelting industry in Upper Silesia, South Poland,” J. Geochem. Explor. 52, 237–250 (1995).
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D. A. Cremers and L. J. Radziemski, “Detection of chlorine and fluorine in air by laser induced breakdown spectrometry,” Anal. Chem. 55, 1252–1256 (1983).
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R. M. Tripathi, R. Raghunath, S. Mahapatra, and S. Sadasivan, “Blood lead and its effect on Cd, Cu, Zn, Fe and hemoglobin levels of children,” Sci. Total Environ. 277, 161–168 (2001).
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L. St.-Onge, E. Kwong, M. Sabsabi, and E. B. Vadas, “Rapid analysis of liquid formulations containing sodium chloride using laser-induced breakdown spectroscopy,” J. Pharm. Biomed. Anal. 36, 277–284 (2004).
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I. Al-Saleh, S. Coskun, A. Mashhour, N. Shinwari, I. El-Doush, G. Billedo, K. Jaroudi, A. Al-Shahrani, M. Al-Kabra, and G. El Din Mohamed, “Exposure to heavy metals (lead, cadmium and mercury) and its effect on the outcome of in-vitro fertilization treatment,” Int. J. Hyg. Environ. Health 211, 560–579 (2008).
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L. St.-Onge, E. Kwong, M. Sabsabi, and E. B. Vadas, “Rapid analysis of liquid formulations containing sodium chloride using laser-induced breakdown spectroscopy,” J. Pharm. Biomed. Anal. 36, 277–284 (2004).
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J. O. Cáceres, J. Tornero López, H. H. Telle, and A. González Ureña, “Quantitative analysis of trace metal ions in ice using laser-induced breakdown spectroscopy,” Spectrochim. Acta Part B 56, 831–838 (2001).
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H. Horiguchi, H. Teranishi, K. Niiya, K. Aoshima, T. Katoch, N. Sakuragawa, and M. Kasuya, “Hypoproduction of erythropoietin contributes to anemia in chronic cadmium intoxication: clinical study on Itai-itai disease in Japan,” Arch. Toxicol. 68, 632–636 (1994).
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J. O. Cáceres, J. Tornero López, H. H. Telle, and A. González Ureña, “Quantitative analysis of trace metal ions in ice using laser-induced breakdown spectroscopy,” Spectrochim. Acta Part B 56, 831–838 (2001).
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R. M. Tripathi, R. Raghunath, S. Mahapatra, and S. Sadasivan, “Blood lead and its effect on Cd, Cu, Zn, Fe and hemoglobin levels of children,” Sci. Total Environ. 277, 161–168 (2001).
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Figures (6)

Fig. 1
Fig. 1

Experimental setup.

Fig. 2
Fig. 2

Typical LIBS spectrum of the liquid samples. (a)  Pb ( NO 3 ) , ( t d = 2 μs ), (b)  Cd ( NO 3 ) 2 . 4 H 2 O , ( t d = 1 μs ).

Fig. 3
Fig. 3

Calibration curves for (a) Pb, (b) Cd at 1 μs delay time.

Fig. 4
Fig. 4

Time evolution of the limit of detection with delay time. (a)  Pb ( NO 3 ) 2 , (b)  Cd ( NO 3 ) 2 . 4 H 2 O .

Fig. 5
Fig. 5

Temporal behavior of plasma temperature in aqueous solution 1250 ppm . (a)  Pb ( NO 3 ) 2 , (b)  Cd ( NO 3 ) 2 . 4 H 2 O .

Fig. 6
Fig. 6

Temporal behavior of electron density (a)  Pb ( NO 3 ) 2 , (b)  Cd ( NO 3 ) 2 . 4 H 2 O .

Tables (2)

Tables Icon

Table 1 Comparison of the Limit of Detections in the Liquid Jet for Pb I and Cd II

Tables Icon

Table 2 Spectral Emission Lines Used for Determination of Plasma Temperature a

Equations (8)

Equations on this page are rendered with MathJax. Learn more.

I j i s = A j i s N j s ,
N j s = N s g j Q ( T ) exp ( E j k T ) .
I j i D s = f E I j i s .
I j i D s = F ( C s ) ,
LOD = 3 σ S ,
T = E α E β k ( L n ( I β I α g α A α g β A β ) ) ,
N e = C ( N e , T ) · ( Δ λ FWHM ) 3 / 2 ,
n e 1.6 × 10 12 T 1 / 2 ( Δ E ) 3 ( cm 3 ) ,

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