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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

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Front Envir Sci Eng    2013, Vol. 7 Issue (1) : 31-42    https://doi.org/10.1007/s11783-012-0463-2
RESEARCH ARTICLE
A new procedure combining GC-MS with accelerated solvent extraction for the analysis of phthalic acid esters in contaminated soils
Tingting MA1,2, Ying TENG1,2, Peter CHRISTIE3, Yongming LUO1,2(), Yongshan CHEN4, Mao YE2,5, Yujuan HUANG1
1. Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008, China; 2. Graduate University of the Chinese Academy of Sciences, Beijing 100049, China; 3. Agri-Environment Branch, Agri-Food and Biosciences Institute, Newforge Lane, Belfast BT9 5PX, United Kingdom; 4. State Key Laboratory of Environment Simulation and Pollution Control (Joint), Tsinghua University, Beijing 100084, China; 5. State Key Laboratory of Soil and Sustainable Agriculture, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008, China
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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     
Corresponding Author(s): LUO Yongming,Email:ymluo@yic.ac.cn   
Issue Date: 01 February 2013
 Cite this article:   
Ying TENG,Peter CHRISTIE,Yongming LUO, et al. A new procedure combining GC-MS with accelerated solvent extraction for the analysis of phthalic acid esters in contaminated soils[J]. Front Envir Sci Eng, 2013, 7(1): 31-42.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-012-0463-2
https://academic.hep.com.cn/fese/EN/Y2013/V7/I1/31
Fig.1  Chromatogram of the six PAEs and the internal standard at 1 mg·L
Fig.1  Chromatogram of the six PAEs and the internal standard at 1 mg·L
methodpacking materials (from bottom to top)elution solutions
one2 g Na2SO4 + 5 g florisil15 mL hexane for pre-washing+ sample loading+ 40 mL hexane
two2 g Na2SO4 + 5 g florisil+ 0.5 g activated carbon+ 1 g Na2SO415 mL hexane+ 15 mL acetone:hexane (1∶4 v/v) for pre-washing+ sample loading+ 40 mL acetone:hexane (1∶4 v/v)
three2 g Na2SO4 + 6 g neutral Al2O3 + 12 g neutral silica gel15 mL hexane for pre-washing+ sample loading+ 40 mL hexane
four2 g Na2SO4 + 5 g florisil15 mL hexane+ 15 mL acetone:hexane (1∶4 v/v) for pre-washing+ sample loading+ 40 mL acetone:hexane (1∶4 v/v)
five2 g Na2SO4 + 5 g florisil+ 0.5 g activated carbon+ 1 g Na2SO415 mL hexane for pre-washing+ sample loading+ 40 mL hexane
six2 g Na2SO4 + 6 g neutral Al2O3 + 12 g neutral silica gel15 mL hexane+ 15 mL acetone:hexane (1∶4 v/v) for pre-washing+ sample loading+ 40 mL acetone:hexane (1∶4 v/v)
Tab.1  Clean-up methods using columns and elution solutions specified
compoundlinear equationm/z of characteristic ionscorrelation coefficient (R)RRF (RSD, n = 7)
DMPy = 127.9x + 87.52163.0, 77.0, 194.00.99870.02713
DEPy = 402.9x + 139.3149.0, 77.0, 222.00.99940.01820
DnBPy = -527.5x + 128.6149.0, 223.0, 278.00.99810.07516
BBPy = -2319x + 88.91149.0, 91.0, 206.00.99840.07543
DEHPy = -2372x + 59.75149.0, 167.0, 249.10.99970.08395
DnOPy = -309.5x + 58.04149.0, 167.0, 279.10.99930.1154
Tab.2  Average relative response factors (RRF) and linearity for the six target compounds based on internal standard
soil typeorganic matter/(g·kg-1)available potassium/(mg·kg-1)available nitrogen/(mg·kg-1)Available phosphorus/(mg·kg-1)clay content/(% v·v-1)pH
red soil9.1114.864.317.951.44.7
brown yellow soil14.6102.896.814.416.77.4
brown soil17.6125.7132.318.410.48.6
black soil48.7123.1239.717.634.97.2
paddy soil (from Taizhou)36.5118.6177.515.138.85.8
Tab.3  Some physico-chemical properties of the five experimental soils
compoundS/Na)IDL /(μg·L-1)
DMP195.270.31
DEP260.730.23
DnBP315.070.19
BBP283.090.21
DEHP226.490.26
DnOP630.740.10
Tab.4  Noise-to- signal ratios and IDLs
Fig.2  Comparison between ASE and UE for extraction of the six PAEs. Each point is the mean value of quadruplicates; error bars denote SEM values
Fig.2  Comparison between ASE and UE for extraction of the six PAEs. Each point is the mean value of quadruplicates; error bars denote SEM values
Fig.3  Comparisons among six combined column chromatography clean-up methods
Fig.3  Comparisons among six combined column chromatography clean-up methods
Fig.4  Average recovery of the six target compounds in method six. Each point is the mean value of quadruplicates, error bars are SEM values
Fig.4  Average recovery of the six target compounds in method six. Each point is the mean value of quadruplicates, error bars are SEM values
soil typeDMPDEPDnBPBBPDEHPDnOP
red soil0.040.060.070.030.030.02
yellow brown soil0.060.050.080.070.100.11
brown soil0.120.050.080.090.120.10
black soil0.090.110.120.130.290.19
Tab.5  MDLs of the six PAEs in the four soils/(mg·kg)
Fig.5  Quantity of the six PAEs in the whole procedure blanks. Each point is the mean value of septuplicates, error bars are SEM values
Fig.5  Quantity of the six PAEs in the whole procedure blanks. Each point is the mean value of septuplicates, error bars are SEM values
compoundred soilbrown yellow soilbrown soilblack soil
Ca) /(μg·kg-1)SEMC /(μg·kg-1)SEMC /(μg·kg-1)SEMC /(μg·kg-1)SEM
DMP39.43.232.10.650.02.727.53.3
DEP3.90.217.30.34.90.111.80.3
DnBP104.41.6142.62.1126.82.049.21.7
BBP-b)-------
DEHP152.32.2194.50.6182.57.2427.07.5
DnOP10.01.610.81.09.62.47.61.9
Tab.6  Soil matrix blanks of six PAEs
compoundallowable concentration/(mg·kg-1)cleanup objective value/(mg·kg-1)
DMP0.022.00
DEP0.077.10
DnBP0.088.10
BBP1.2250.00
DEHP4.3550.00
DnOP1.2050.00
Tab.7  Soil allowable concentrations and cleanup objectives of six PAE compounds in the United States
soil typeDMPDEPDnBPBBPDEHPDnOP
Ra)/%RSD/%R/ %RSD/%R/%RSD/%R/%RSD/%R/%RSD/%R/%RSD/%
red80.33.981.53.390.45.3101.92.8111.52.7119.22.8
brown yellow75.01.876.52.280.91.994.91.1104.30.9112.70.9
brown80.33.784.92.699.11.898.61.2109.32.6108.21.0
black81.114.179.814.889.016.698.014.2105.519.9109.513.2
EPA-8270a)93.295.890.891.294.289.9
Tab.8  QA/QC report of matrix samples spiked with PAEs/(0.1 mg·kg)
compoundgiven confidence interval/(mg·kg-1)determined value/(mg·kg-1)a)
119-100136-100119-100136-100
DMP8.29-11.172.85-3.428.64±0.082.93±0.06
DEP4.21-5.261.29-1.644.55±0.091.49±0.09
DnBPNeb)0.64-0.80NDc)0.73±0.08
BBP12.06-16.346.61-8.3213.75±0.106.84±0.07
DEHP7.65-9.940.82-0.969.38±0.170.92±0.11
DnOP4.93-6.544.78-5.716.31±0.145.47±0.12
Tab.9  Comparison between CRM assigned values and determined values
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