A new procedure combining GC-MS with accelerated solvent extraction for the analysis of phthalic acid esters in contaminated soils

Abstract

An optimized procedure based on gas chromatography-mass spectrometry (GC-MS) combined with accelerated solvent extraction (ASE) is developed for the analysis of six phthalic acid esters (PAEs), which are priority soil pollutants nominated by United States Environmental Protection Agency (USEPA). Quantification of PAEs in soil employs ultrasonic extraction (UE) (USEPA 3550) and ASE (USEPA 3545), followed by clean up procedures involving three different chromatography columns and two combined elution methods. GC-MS conditions under selected ion monitoring (SIM) mode are described and quality assurance and quality control (QA/QC) criteria with high accuracy and sensitivity for target analytes were achieved. Method reliability is assured with the use of an isotopically labeled PAE, di-n-butyl phthalate-d4 (DnBP-D4), as a surrogate, and benzyl benzoate (BB) as an internal standard, and with the analysis of certified reference materials (CRM). QA/QC for the developed procedure was tested in four PAE-spiked soils and one PAE-contaminated soil. The four spiked soils were originated from typical Chinese agricultural fields and the contaminated soil was obtained from an electronic waste dismantling area. Instrument detection limits (IDLs) for the six PAEs ranged 0.10–0.31 µg·L^-1 and method detection limits (MDLs) of the four spiked soils varied from a range of 20–70 µg·kg^-1 to a range of 90– 290 µg·kg^-1. Linearity of response between 20 µg·L^-1 and 2 mg·L^-1 was also established and the correlation coefficients (R) were all>0.998. Spiked soil matrix showed relative recovery rates between 75 and 120% for the six target compounds and about 93% for the surrogate substance. The developed procedure is anticipated to be highly applicable for field surveys of soil PAE pollution in China.

Keywords

phthalic acid esters / quality assurance and quality control / soil type / accelerated solvent extraction / certified reference materials

References

[1] Guo B Y, Wen B, Shan X Q, Zhang S Z, Lin J M. Separation and determination of phthalates by micellar electrokinetic chromatography. Journal of Chromatography A, 2005, 1095(1-2): 189-192

[2] Hu X Y, Wen B, Shan X Q. Survey of phthalate pollution in arable soils in China. Journal of Environmental Monitoring, 2003, 5(4): 649-653

[3] Jin X C. Organic Compound Pollution and Chemistry — Toxic Organic Compound Pollution and Chemistry. Beijing: Tsinghua University Press, 1990 (in Chinese)

[4] Liu H, Liang H C, Liang Y, Zhang D, Wang C, Cai H S, Shvartsev S L. Distribution of phthalate esters in alluvial sediment: a case study at JiangHan Plain, Central China. Chemosphere, 2010, 78(4): 382-388

[5] Wang F, Xia X H, Sha Y J. Distribution of phthalic acid esters in Wuhan section of the Yangtze River, China. Journal of Hazardous Materials, 2008, 154(1-3): 317-324

[6] Wang P, Wang S L, Fan C Q. Atmospheric distribution of particulate- and gas-phase phthalic esters (PAEs) in a Metropolitan City, Nanjing, East China. Chemosphere, 2008, 72(10): 1567-1572

[7] Xu G, Li F H, Wang Q H. Occurrence and degradation characteristics of dibutyl phthalate (DBP) and di-(2-ethylhexyl) phthalate (DEHP) in typical agricultural soils of China. The Science of the Total Environment, 2008, 393(2-3): 333-340

[8] Zeng F, Lin Y J, Cui K Y, Wen J X, Ma Y Q, Chen H L, Zhu F, Ma Z L, Zeng Z X. Atmospheric deposition of phthalate esters in a subtropical city. Atmospheric Environment, 2010, 44(6): 834-840

[9] Zhang D, Liu H, Liang Y, Wang C, Liang H C, Cai H S. Distribution of phthalate esters in the groundwater of Jianghan plain, Hubei, China. Frontiers of Earth Science in China, 2009, 3(1): 73-79in Chinese)

[10] Chee K K, Wong M K, Lee H K. Optimization of microwave-assisted solvent extraction of polycyclic aromatic hydrocarbons in marine sediments using a microwave extraction system with high-performance liquid chromatography-fluorescence detection and gas chromatography-mass spectrometry. Journal of Chromatography. A, 1996, 723(2): 259-271

[11] Chen Y S. Analytical methods modification, pollution characteristics, environmental risks dissipation of phthalate esters and antibiotics in soils and water bodies of a typical basin. Dissertation for the Doctoral Degree. Beijing: Graduate School of the Chinese Academy of Sciences, 2010, 43-45 (in Chinese)

[12] Li X H, Ma L L, Liu X F, Fu S, Cheng H X, Xu X B. Phthalate ester pollution in urban soil of Beijing, People’s Republic of China. Bulletin of Environmental Contamination and Toxicology, 2006, 77(2): 252-259

[13] Mo C H, Cai Q Y, Tang S R, Zeng Q Y, Wu Q T. Polycyclic aromatic hydrocarbons and phthalic acid esters in vegetables from nine farms of the Pearl River Delta, South China. Archives of Environmental Contamination and Toxicology, 2009, 56(2): 181-189

[14] Zeng F, Cui K Y, Xie Z Y, Wu L N, Liu M, Sun G Q, Lin Y J, Luo D L, Zeng Z X. Occurrence of phthalate esters in water and sediment of urban lakes in a subtropical city, Guangzhou, South China. Environmental Pollution, 2008, 156(2): 425-434

[15] Fisher J A, Scarlett M J, Stott A D. Accelerated solvent extraction: an evaluation for screening of soils for selected U.S. EPA semivolatile organic priority pollutants. Environmental Science & Technology, 1997, 31(4): 1120-1127

[16] Reid A M, Brougham C A, Fogarty A M, Roche J J. Accelerated solvent-based extraction and enrichment of selected plasticisers and 4-nonylphenol, and extraction of tin from organotin sources in sediments, sludges and leachate soils. Analytica Chimica Acta, 2009, 634(2): 197-204in Chinese)

[17] Luo C H, Guo Z S, Sun J. Determination of phthalate esters in sediment by accelerated solvent extraction and gas chromatography-triple quadrupole mass spectrometry. Chinese Journal of Chromatography, 2010, 28(5): 487-490in Chinese)

[18] Cai Q Y, Mo C H, Wu Q T, Zeng Q Y. Polycyclic aromatic hydrocarbons and phthalic acid esters in the soil-radish (Raphanus sativus) system with sewage sludge and compost application. Bioresource Technology, 2008, 99(6): 1830-1836

[19] Vikelsøe J, Thomsen M, Carlsen L. Phthalates and nonylphenols in profiles of differently dressed soils. The Science of the Total Environment, 2002, 296(1-3): 105-116

[20] Peijnenburg W J G M, Struijs J. Rapid communication occurrence of phthalate esters in the environment of the Netherlands. Ecotoxicology and Environmental Safety, 2006, 63(2): 204-215

[21] Zhang Y H, Chen X D, Li Z S, Lei Z H, Liang X M. GC/MS analysis of PAEs in lake sediments. Journal of Instrumental Analysis, 1995, 14(5): 17-21 (in Chinese)

[22] Wang S J, Jian Z H, Luo J. Soil heavy metal pollution character and remove technique in Luqiao District, Taizhou of Zhejiang Province. Earth and Environment, 2006, 34(1): 35-43in Chinese)

[23] Chen D H, Li L P, Bi X H, Zhao J P, Sheng G Y, Fu J M. PBDEs pollution in the atmosphere of a typical e-waste dismantling region. Environmental Science, 2008, 29(8): 2105-2110in Chinese)

[24] Li Y M, Jiang G B, Wang Y W, Wang P, Zhang Q H. Pollution level and phase partition regulation of PCDD/Fs, PCBs and PBDEs in atmosphere of e-waste recycling sites. Chinese Science Bulletin, 2008, 53(4): 165-171 (in Chinese)

[25] Ni J Z, Luo Y M, Wei R, Li X H, Qian W. Reasearch on soil environmental quality and remediation of the Yangtze River delta region V. polycyclic aromatic hydrocarbons (PAHs) contamination status and source apportionment in agricultural soils of typical areas. Acta Pedologica Sinica, 2008, 45 (2): 234-239 (in Chinese)

[26] USEPA. Ultrasonic Extraction, Organic extraction and sample preparation. Method USEPA 3550. Washington, DC: USEPA, 1996

[27] USEPA. Accelerated Solvent Extraction, Test Methods for Evaluating Solid Waste. Method USEPA 3545. Washington, DC: USEPA, 1995

[28] USEPA. Semivolatile Organic Compounds by Gas Chromatography/Mass Spectrometry (GC/MS). Method USEPA 8270C. Washington, DC: USEPA, 1996

[29] USDA. USDA Soil Texture Calculator. Washington, DC: USDA, 2011

[30] Kim S C, Carlson K. Temporal and spatial trends in the occurrence of human and veterinary antibiotics in aqueous and river sediment matrices. Environmental Science & Technology, 2007, 41(1): 50-57

[31] Shao C M, Zhu W P. ASE-GPC purification-GC/MS for PAEs analysis in soil. Arid Environmental Monitoring, 2009, 23(2): 73-76 (in Chinese)

[32] Petrovicè M, Eljarrat E, López de Alda M J, Barceló D. Analysis and environmental levels of endocrine disrupting compounds in freshwater sediments. TrAC Trends in Analytical Chemistry, 2001, 20(11): 637-648

[33] Lou J. Determination of phthalate esters in plastic tablecloth by accelerated solvent extraction and gas chromatography-mass spectrometry. Chemical Research, 2011, 2(18): 65-67 (in Chinese)

[34] Li B P, Lin Q B, Song H, Li L L. Determination of DEHP and DNOP in PVC Film by ASE-RP-HPLC. Chinese Journal of Applied Chemistry, 2008, 25(01): 63-66 (in Chinese)

[35] Huang P C, Tien C J, Sun Y M, Hsieh C Y, Lee C C. Occurrence of phthalates in sediment and biota: relationship to aquatic factors and the biota-sediment accumulation factor. Chemosphere, 2008, 73(4): 539-544

[36] Wang M L, Kou L J, Zhang Y Q, Shi Y X. Matrix solid-phase dispersion and gas chromatography/mass spectrometry for the determination of phthalic acid esters in vegetables. Chinese Journal of Chromatography, 2007, 25(4): 577-580in Chinese)

[37] Zeng F, Chen L X, Cui K Y, Zhang Q. PAEs analysis in sediments by silicon gel-alumina-GC. FENXIHUAXUE Chinese Journal of Analytical Chemistry, 2005, 33(8): 1063-1067 (in Chinese)

[38] Jiang Y X, Ye L, Tang M R. Simultaneously residual analysis of seven organophosphorus pesticides in tea. Chinese Journal of Analysis Laboratory, 2007, 26(1): 97-101 (in Chinese)

[39] Tienpont B, DavidF, DewulfE, SandraP. Pitfalls and solutions for the trace determination of phthalates in water samples. Chromatographia, 2005, 61(7-8): 365-370

[40] Giam C S, Chan H S, Neff G S. Sensitive method for determination of phthalate ester plasticizers in open-ocean biota samples. Analytical Chemistry, 1975, 47(13): 2225-2229

[41] Cai Q Y, Mo C H, Li Y H, Zeng Q Y, Wang B G, Xiao K E, Li H Q, Xu G S. The study of PAEs in soils from typical vegetable fields in areas of Guangzhou and Shenzhen, South China. Acta Ecologica Sinica, 2005, 25(2): 283-288 (in Chinese)

[42] MacMillan D K, Dalton S R, Bednar A J, Waisner S A, Arora P N. Influence of soil type and extraction conditions on perchlorate analysis by ion chromatography. Chemosphere, 2007, 67(2): 344-350

[43] Zhang Z H, Jin S W, Duan J M, Li M, Huang Y. Phthalates levels in soil samples from the e-waste disassembly sites. Journal of Wuhan Institute of Chemical Technology, 2010, 32(7): 28-32 (in Chinese)

[44] Liu W L, Shen C F, Zhang Z, Zhang C B. Distribution of phthalate esters in soil of e-waste recycling sites from Taizhou City in China. Bulletin of Environmental Contamination and Toxicology, 2009, 82(6): 665-667

[45] Tu C, Teng Y, Luo Y M, Pan C, Sun X H, Li Z G. Phytoremediation of polychlorinated biphenyls contaminated soil by leguminosae-gramineae intercropping: a field trial. Environmental Science, 2010, 31(12): 3062-3066in Chinese)

[46] Cai Q Y, Mo C H, Zhu X Z, Wu Q T, Wang B G, Jiang C A, Li H Q. Effect of municipal sludge and chemical fertilizers on phthalic acid esters (PAEs) contents in Ipomoea aquatica grown on paddy soils. Chinese Journal of Applied Ecology, 2003, 14(11): 2001-2005in Chinese)

[47] Cong H F, Wang L X, Shao L. Determination of phthalates in vegetables by liquid chromatography-electrospray ionization mass spectrometry. Food Science and Technology, 2008, (8): 222-224 (in Chinese)

Acknowledgements

This research was supported by the China National Environmental Protection Special Funds for Scientific Research on Public Causes “Studies on the regulation of agricultural soil environmental quality, environmental risk and key control techniques” (No. 201109018) and the Program of Innovative Engineering of the Chinese Academy of Sciences (No. KZCX2-YW-Q02-06-02). We thank Dr. Shiping Deng in the Department of Plant and Soil Sciences at Oklahoma State University in the USA for language revision of this manuscript. We are grateful to the State Key Laboratory of Soil and Sustainable Agriculture at the Institute of Soil Science, Chinese Academy of Sciences, for the supply of Dionex ASE200.

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