Rapid Detection of H2S in Heart Blood by Chemical Method and GC / MS

Pian Xu1, a, *, Daiqin Tao1, a, Wenwen Liu1, a

1Chongqing Engineering Research Center for Criminal Investigation Technology, Institute of

Forensic Science, Chongqing Public Security Bureau, Chongqing 400021, China

a E-mail: taodaiqin@hotmail.com

* Corresponding author: Pian Xu, Ph.D., is now handling of criminal laboratory technical work in

Chongqing Municipal Public Security Bureau of Interpol Corps, and mainly engaged in poisoning,

chemical and ethanol inspection and appraisal work. Tel/Fax: +86-023-637-51602.

Keywords: Hydrogen sulfide; poisoning; effort; chemical method; gas chromatography - mass

spectrometry methods

Abstract. Objective To establish and verify analytical methods of hydrogen sulfide(H2S) detection

in heart blood by Chemical Method and Gas Chromatography - Mass Spectrometry (GC/MS).

Method Take 3-5mL of heart blood, placed in 20mL vial, adding 3-5mL of deionized water, 1mL of

2mol/L hydrochloric acid (HCl), stamped seal, and denatured at 60 ℃ water bath for 30min. Both

Chemical Method and GC/MS were used to assay the headspace inside vial. Results These two

methods are all detected H2S in the heart blood of the poisoning death. Conclusion These two

methods are rapid, simple, reliable, and of high sensitivity, reproducibility, and suitable for rapid

analysis of hydrogen sulfide in forensic and criminal casework.

1 Introduction

On November 3, 2012, in the kimchi pool of a food factory in Yubei District of Chongqing, there

was an unknown toxic gas poisoning occurred in the accident, resulting in three deaths. After the

investigation, the gas was confirmed as hydrogen sulfide (H2S).

2 Experiments

2.1 Sample Pretreatment

Take 3 - 5mL heart blood, placed in the 20mL vial; add 3 - 5mL of deionized water, adding 1mL

of 2mol / L hydrochloric acid (HCl), stamped seal and denatured at 60 ℃ water bath for 30min.

Take 0.5mL headspace waiting for GC-MS testing.

2.2 Preparation of Standard Blood.

Configuring 1mol / L solution of Na2S: Weigh 7.8g Na2S dissolved in 100mL deionized water.

Take 3mL ~ 5mL pure fresh blood; plus 1mL of Na2S solution; add 3 - 5mL of deionized water,

added 1mL of 2mol / L hydrochloric acid (HCl), stamped seal and denatured at 60 ℃ water bath

for 30min. Take 0.5mL headspace waiting for GC-MS testing.

2.3 Chemical Test

Take the treated blood samples in 2.1 and 2.2. Suspend the test strip impregnated with lead

acetate solution inside the vial. Be in airtight after a certain time, if the sample contained H2S, it

would become dark brown in the test strip due to the generation of lead sulfide (PbS); if not, the

color were unchanged and there were no H2S [2].

Applied Mechanics and Materials Vols. 496-500 (2014) pp 528-531Online available since 2014/Jan/16 at www.scientific.net© (2014) Trans Tech Publications, Switzerlanddoi:10.4028/www.scientific.net/AMM.496-500.528

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2.4 GC-MS Test

2.4.1 The instrument conditions

GC/MS Analyzer (Shimadzu 2010, Japan). Column: Rtx-5msSilica capillary column

(30m×0.25mm×0.25µm); Column temperature: 50℃ keeping 3min, rising to 100 ℃ at 60 ℃ / min,

keeping 1min; Inlet temperature: 250℃；Carrier gas: He; Line speed: 37.5 mL/min; Injection: Split.

MS: EI source; Electron energy: 70 ev; Multiplier power supply: 1.25 kv; Transfer line temperature:

220℃; Ion source temperature: 200℃; Scan mode: Selected ion scan; Ion range: 33 amu, 34 amu

and 36 amu.

3 Results

H2S were detected in Yang's, Ma's, Zuo's and standard blood samples. (Figure 1 to 5)

Figure 1 Color charts of lead acetate strips.

2(a)

2(b)

Figure 2 The selected ion flow diagrams (a) and mass spectra (b) of Yang's heart blood.

3(a)

33.00 33.25 33.50 33.75 34.00 34.25 34.50 34.75 35.00 35.25 35.50 35.75 36.000

50

100

%

34

36

1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 0.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00

2.25

(x10,000)

36.00 (100.00)35.00 (1.00)33.00 (22.25) 34.00 (5.33)TIC

1/0/ H2S

1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.50.0

0.5

1.0

1.5

2.0

(x10,000)

36.00 (100.00)35.00 (1.00)33.00 (23.48)34.00 (4.92)TIC

1/0/H2S

Applied Mechanics and Materials Vols. 496-500 529

3(b)

Figure 3 The selected ion flow diagrams (a) and mass spectra (b) of Ma's heart blood.

4(a)

4(b)

Figure 4 The selected ion flow diagrams (a) and mass spectra (b) of Zuo's heart blood.

5(a)

5(b)

Figure 5 The selected ion flow diagrams (a) and mass spectra (b) of standard blood sample.

33.00 33.25 33.50 33.75 34.00 34.25 34.50 34.75 35.00 35.25 35.50 35.75 36.000.0

25.0

50.0

75.0

100.0

%

34

36

33.00 33.25 33.50 33.75 34.00 34.25 34.50 34.75 35.00 35.25 35.50 35.75 36.000.0

25.0

50.0

75.0

100.0

%

34

36

33.00 33.25 33.50 33.75 34.00 34.25 34.50 34.75 35.00 35.25 35.50 35.75 36.000

50

100

%

34

36

1. 1. 2. 2. 3. 3. 4. 4.

0.0

0.2

0.5

0.7

1.0

1.2

1.5

1.7

2.0

(x10,000)

36.00 (46.86) 33.00 (4.78)34.00 (2.00)TI

1/0/ H2S

1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5

0.0

0.5

1.0

1.5

2.0

(x10,000)

36.00 (100.00)33.00 (21.60)34.00 (5.38)TIC

1/0/ H2S

530 Frontiers of Manufacturing and Design Science IV

4 Discussion

Hydrogen sulfide (H2S) is a kind of suffocating and irritating colorless gas, with special smell of

rotten egg; Formula is H2S, relative molecular mass of 34.08, boiling point -61.8 ℃, specific

gravity 1.191 (air ratio); is soluble in water, soluble in water is a weak acid; is soluble in alcohol,

glycerol and other organic solvents [2]; has a strong reduction, easy to form colored insoluble salts

with heavy metal ions.

Workers have the opportunity to contact H2S in excavation and remediation marshes, ditches,

wells, sewers, hidden culvert, tunnel and clearing trash, dirt, feces and other operations, as well as

analytical chemistry laboratory; Natural gas, mineral water, fumaroles and minerals under water,

are also often accompanied by the presence of H2S. Human poisonings are more caused due to an

accident, improper protection workers [3, 4].

H2S is a nerve agent. When people inhale large amounts. it will cause hydrogen sulfide

poisoning. Hydrogen sulfide poisoning is mainly through the respiratory tract (the skin can absorb a

small part of) with a relatively large amount of hydrogen sulfide gas inhalation, causing suffocation

cells; it can directly stimulate nerve endings of the olfactory and in the respiratory mucosa, carotid

sinus and aortic body chemoreceptors, causing respiratory center depression and respiratory

paralysis. Clinical manifestations of mild and moderate poisoning are tearing, stinging, blurred

vision, etc., respiratory symptoms such as cough, chest tightness, shortness of breath, and so on, as

well as headache, dizziness, confusion, fatigue and other nervous system symptoms and malignant,

and vomiting. Severe poisoning appears blurred consciousness, coma, heart palpitations, cramps,

incontinence and result of respiratory paralysis and rapid death as if by an electric shock [1].

Hydrogen sulfide test samples is best for heart blood and the lungs. Hydrogen sulfide is mainly

in the sodium form in the body, therefore, the samples test should be firstly make the hydrogen

sulfide overflow by adding an appropriate amount of hydrochloric acid. Then were used Chemical

Method and GC-MS to assay overflowed gas which can quickly get results. After verification, the

two approaches are fast, simple, reliable, and of high sensitivity and good reproducibility, which

can be used for rapid analysis of hydrogen sulfide in forensic and criminal cases.

5 Conclusion

Both Chemical Method and GC / MS were used to assay the headspace inside vial. These two

methods are rapid, simple, reliable, and of high sensitivity, reproducibility, and suitable for rapid

analysis of hydrogen sulfide in forensic and criminal cases.

References

[1] Liang Liu. Forensic Toxicology [M]. Beijing: People's Health Publishing House (2009). (In

Chinese)

[2] Huimin Lu. Toxicology Analysis [M]. Police Education Press (1995). (In Chinese)

[3] LUO Caihui, LI Jianbo, YU Tianxia. et al. Determination of sulfide in the hydrogen sulfide

poisoned blood using gas chromatograpy - mass spectrometry [J]. Journal of Chongqing

Medical University Vol 37, no.12 (2012), p.1025-1028. (In Chinese)

[4] QIAO Jing，YANG Shi-yun. Determination of hydrogen sulfide in blood by GC/MS [J].

Forensic Science and Technology no. 3 (2012), p.22-23. (In Chinese)

Applied Mechanics and Materials Vols. 496-500 531

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