Methylcyclopentadienyl manganese tricarbonyl (MMT) is an organic derivative of manganese (Mn) and is used as an antiknock agent and octane enhancer in gasoline. In this article, we tested the oxidative stress and heat stress protein (Hsp) 70 levels of gasoline station attendants to explore potential plasma biomarkers. Furthermore, the dose–response relationship was also identified.
Methods:
A total of 144 workers, including 96 petrol fillers and 48 cashiers, participated in the study. Ambient concentrations of benzene, toluene, ethylbenzene, and xylene (BTEX) and Mn were monitored at nine filling stations. During the measuring process, the individual cumulative exposure index was calculated. Plasma oxidative stress and Hsp70 levels were also analysed using enzyme-linked immunosorbent assay.
Results:
The BTEX time-weighted average in office areas was significantly lower than in refuelling areas (p < 0.05). In refuelling areas, the content of Mn ranged from 6.44 μg/m3 to 127.34 μg/m3, which was much higher than that in office areas (3.16–7.22 μg/m3; p < 0.05). Exposed workers had significantly different plasma oxidative stress indicators compared with the control group, respectively: superoxide dismutase (SOD), 39.18 ± 6.05 U/mL versus 52.84 ± 3.87 U/mL; glutathione peroxidase (GSH-Px), 186.07 ± 15.63 U versus 194.38 ± 10.42 U; and malondialdehyde (MDA), 1.68 ± 0.52 nmol/L versus 1.43 ± 0.64 nmol/L (in all comparisons, p < 0.05). Plasma Hsp70 level in the exposed group (2.77 ± 0.64 ng/mL) was significantly higher than in the control group (2.32 ± 0.87 ng/mL; p < 0.05). Furthermore, Hsp70 levels were inversely correlated with the activities of SOD (r = −0.305) and GSH-Px (r = −0.302) in the exposed group (p < 0.05). Moreover, a positive correlation (r = 0.653) was found between plasma Hsp70 levels and plasma MDA levels (p < 0.05).
Conclusion:
Exposure to MMT-containing gasoline may result in increasing reactive oxygen stress among filling station attendants. Plasma Hsp70 levels could be used as a sensitive responsive biomarker for exposed workers.
AbeMManolaJBOhWK. (2004) Plasma levels of heat shock protein 70 in patients with prostate cancer: a potential biomarker for prostate cancer. Clinical Prostate Cancer3: 49–53.
2.
BassoAEliaGPetrozziMT. (2004) Oxidative stress in station service workers. Giornale Italiano di Medicina del lavoro ed Ergonomia26: 197–201.
3.
BeaupreLASalehiFZayedJ. (2004) Physical and chemical characterization of Mn phosphate/sulfate mixture used in an inhalation toxicology study. Inhalation Toxicology16: 231–244.
4.
BeckerJCraigEA (1994) Heat-shock proteins as molecular chaperones. European Journal of Biochemistry/ FEBS219: 11–23.
5.
BeerappaRVenugopalDSenS. (2013) Assessment of 8-oxo-7,8-dihydro-2′-deoxyguanosine as a marker of oxidative DNA damage in gasoline filling station attendants. International Journal of Occupational Medicine and Environmental Health26: 780–789.
6.
ButcherDJZybinABolshovMA. (1999) Speciation of methylcyclopentadienyl manganese tricarbonyl by high-performance liquid chromatography-diode laser atomic absorption spectrometry. Analytical Chemistry71: 5379–5385.
7.
ChangCDemokritouPShaferM. (2013) Physicochemical and toxicological characteristics of welding fume derived particles generated from real time welding processes. Environmental Science. Processes & Impacts15: 214–224.
8.
DengYJiaoCMiC. (2015) Melatonin inhibits manganese-induced motor dysfunction and neuronal loss in mice: involvement of oxidative stress and dopaminergic neurodegeneration. Molecular Neurobiology51: 68–88.
9.
DundarzMRTurkbayTAkayC. (2003) Antioxidant enzymes and lipid peroxidation in adolescents with inhalant abuse. The Turkish Journal of Pediatrics45: 43–45.
10.
El-Sayed elSMAbo-SalemOMAbd-EllahMF. (2008) Hesperidin, an antioxidant flavonoid, prevents acrylonitrile-induced oxidative stress in rat brain. Journal of Biochemical and Molecular Toxicology22: 268–273.
11.
GehrmannMSpechtHMBayerC. (2014) Hsp70 – a biomarker for tumor detection and monitoring of outcome of radiation therapy in patients with squamous cell carcinoma of the head and neck. Radiation Oncology9: 131.
HomaJOlchawaESturzenbaumSR. (2005) Early-phase immunodetection of metallothionein and heat shock proteins in extruded earthworm coelomocytes after dermal exposure to metal ions. Environmental Pollution135: 275–280.
14.
HuaLDuo-wenW (2014) Current situation of occupational health in petrol stations. Occupation and Health30: 987–989.
15.
HuangJSZhongXJWuX. (2005) Effects of acrylonitrile on the activities of antioxidant enzymes and levels of lipid peroxidation in rat testes. Zhonghua Lao Dong Wei Sheng Zhi Ye Bing Za Zhi23: 136–138.
16.
IrwinRJ (1997) Environmental Contaminants Encyclopedia Entry for BTEX and BTEX Compounds. Colorado: National Park Service.
17.
JinGBNakayamaHShmyhloM. (2003) High positive frequency of antibodies to metallothionein and heat shock protein 70 in sera of patients with metal allergy. Clinical and Experimental Immunology131: 275–279.
18.
JunhuZChenguangYHaoL (2014) Detection and evaluation of occupational disease harmful factors on the tunneling and mining face of Cuncaota no. 2 coal mine. Journal of North China Institute of Science and Technology11: 90–94.
19.
KangHJMoonHSChungHW (2014) The expression of FAS-associated factor 1 and heat shock protein 70 in ovarian cancer. Obstetrics & Gynecology Science57: 281–290.
20.
KaragözlerAAMehmetNBatciogluK (2002) Effects of long-term solvent exposure on blood cytokine levels and antioxidant enzyme activities in house painters. Journal of Toxicology and Environmental Health. Part A65: 1237–1246.
21.
KumCSekkinSKiralF. (2007) Effects of xylene and formaldehyde inhalations on renal oxidative stress and some serum biochemical parameters in rats. Toxicology and Industrial Health23: 115–120.
22.
LauCSScottNShawJW. (1991) Increased activity of oxygen free radicals during reperfusion in patients with peripheral arterial disease undergoing percutaneous peripheral artery balloon angioplasty. International Angiology: A Journal of the International Union of Angiology10: 244–246.
23.
LehnertKMullerSWeirupL. (2014) Molecular biomarkers in grey seals (Halichoerus grypus) to evaluate pollutant exposure, health and immune status. Marine Pollution Bulletin88: 311–318.
24.
LevyBSNassettaWJ (2003) Neurologic effects of manganese in humans: a review. International Journal of Occupational and Environmental Health9: 153–163.
25.
LiGJZhangLLLuL. (2004) Occupational exposure to welding fume among welders: alterations of manganese, iron, zinc, copper, and lead in body fluids and the oxidative stress status. Journal of Occupational and Environmental Medicine / American College of Occupational and Environmental Medicine46: 241–248.
26.
LudwigDStahlMIbrahimET. (1999) Enhanced intestinal expression of heat shock protein 70 in patients with inflammatory bowel diseases. Digestive Diseases and Sciences44: 1440–1447.
27.
LuoJCHsuKHShenWS (2009) Inflammatory responses and oxidative stress from metal fume exposure in automobile welders. Journal of Occupational and Environmental Medicine/American College of Occupational and Environmental Medicine51: 95–103.
28.
MorimotoRIKlineMPBimstonDN. (1997) The heat-shock response: regulation and function of heat-shock proteins and molecular chaperones. Essays in Biochemistry32: 17–29.
29.
MukhopadhyayINazirASaxenaDK. (2003) Heat shock response: hsp70 in environmental monitoring. Journal of Biochemical and Molecular Toxicology17: 249–254.
30.
NadeauDCorneauSPlanteI. (2001) Evaluation for Hsp70 as a biomarker of effect of pollutants on the earthworm Lumbricus terrestris. Cell Stress & Chaperones6: 153–163.
31.
NavasumritPChanvaivitSIntarasunanontP. (2005) Environmental and occupational exposure to benzene in Thailand. Chemico-Biological Interactions153-154: 75–83.
32.
PekariKVainiotaloSHeikkilaP. (1992) Biological monitoring of occupational exposure to low levels of benzene. Scandinavian Journal of Work, Environment & Health18: 317–322.
33.
RajeshkumarSMiniJMunuswamyN (2013) Effects of heavy metals on antioxidants and expression of HSP70 in different tissues of Milk fish (Chanos chanos) of Kaattuppalli Island, Chennai, India. Ecotoxicology and Environmental Safety98: 8–18.
34.
ScieglinskaDKrawczykZ (2015) Expression, function, and regulation of the testis-enriched heat shock HSPA2 gene in rodents and humans. Cell Stress & Chaperones20: 221–235.
35.
SekkalSHaddamNScheersH. (2012) Occupational exposure to petroleum products and respiratory health: a cross-sectional study from Algeria. Journal of Occupational and Environmental Medicine/American College of Occupational and Environmental Medicine54: 1382–1388.
36.
SingarajuMSingarajuSParwaniR. (2012) Cytogenetic biomonitoring in petrol station attendants: a micronucleus study. Journal of Cytology/Indian Academy of Cytologists29: 1–5.
37.
SinghMPRamKRMishraM. (2010) Effects of co-exposure of benzene, toluene and xylene to Drosophila melanogaster: alteration in hsp70, hsp60, hsp83, hsp26, ROS generation and oxidative stress markers. Chemosphere79: 577–587.
38.
SinghMPReddyMMMathurN. (2009) Induction of hsp70, hsp60, hsp83 and hsp26 and oxidative stress markers in benzene, toluene and xylene exposed Drosophila melanogaster: role of ROS generation. Toxicology and Applied Pharmacology235: 226–243.
39.
TianqiWYuehongLRuG. (2014) The determination method of domestic metals and their compounds in the air of workplace. Chinese Journal of Health Laboratory Technology24: 1823–1824.
40.
TukajS (2014) Immunoregulatory properties of Hsp70. Postȩpy Higieny i Medycyny Doświadczalnej (Online)68: 722–727.
41.
UzmaNKumarBSHazariMA (2010) Exposure to benzene induces oxidative stress, alters the immune response and expression of p53 in gasoline filling workers. American Journal of Industrial Medicine53: 1264–1270.
42.
ValavanidisAVlachogianniTFiotakisK. (2013) Pulmonary oxidative stress, inflammation and cancer: respirable particulate matter, fibrous dusts and ozone as major causes of lung carcinogenesis through reactive oxygen species mechanisms. International Journal of Environmental Research and Public Health10: 3886–3907.
43.
VedalSCampenMJMcDonaldJD. (2013) National Particle Component Toxicity (NPACT) initiative report on cardiovascular effects. Res Rep Health Eff Inst178: 5–8.
44.
WeiYHanIKHuM. (2010) Personal exposure to particulate PAHs and anthraquinone and oxidative DNA damages in humans. Chemosphere81: 1280–1285.
45.
YangXZhengJBaiY. (2007) Using lymphocyte and plasma Hsp70 as biomarkers for assessing coke oven exposure among steel workers. Environmental Health Perspectives115: 1573–1577.
46.
ZayedJ (2001) Use of MMT in Canadian gasoline: health and environment issues. American Journal of Industrial Medicine39: 426–433.
