Supplementary Information:

Appendix:

Aromatic hydrocarbons in air, water and soil. Sampling, and pre-treatment techniques

Nadeem Razaa1, Beshare Hashemib,c1, Ki-Hyun Kimc*, Sang-Hun Leed, Akash Deepe*

aGovt. Emerson College affiliated with Bahauddin Zakariya University Multan, 60800 Pakistan; bDepartment of Chemistry, Razi University, 67149-67346 Kermanshah, Iran;cDepartment of Civil and

Environmental Engineering, Hanyang University, 222 Wangsimni-Ro, Seoul, 04763 Republic of

Korea;dDepartment of Environmental Science, Keimyung University, 1095 Dalgubeol-Daero, Daegu,

42601, S. Korea; eCentral Scientific Instruments Organization (CSIR-CSIO), Sector 30 C Chandigarh,

160030, India.

1

Table S1. A list of aromatic compounds present in environmental media and their physiochemical

characteristics

Sr. No.

Name Molecular formula

CAS No.

Molar mass (g/mole)

Color/Flash or boiling point

Structure Concerns Estimated daily intake µg/d

A: Volatile organic compounds1 Benzene C6H6 71-

43-278.11 Colorless/

277.59 KMutagenic Air: 90-1300,

Smoking: 1800, Food: 250, Water:

10b

2 Toluene C7H8 108-88-3

92.14 Colorless/277.59 K

Reproductive organ damage

Air: 2-12000, Smoking: 2000,

Food: 64, Water: 433 Ethyl benzene C8H10 100-

41-4106.07 Colorless/

288.15 KCarcinogenici

tyAir: 2-3600,

Smoking: 40a, Food: NA, Water: 20b

4 O-Xylene C8H10 1330-20-7

106.17 Colorless /305.37 K

Respiratory issues

Air: 70-2000, Smoking: 190a,

Food: NA, Water: 24b

B: Semi-volatile aromatic compounds5 Anthracene C14H10 120-

12-7178.22 White-

yellow solid/ 613.15 K

Carcinogenic

6 Pyrene C16H10 129-00-0

202.25 Colorless solid/ 677 K

Respiratory and skin irritation

0.001*

7 Naphthalene C10H8 91-20-3

128.17 White crystalline

solid/ 490.92 K

Carcinogenic 0.001*

8 Chrysene C12H12 218-01-9

228.3 Colorless crystalline

solid/ 720.93 K

Carcinogenic 0.01*

9 Fluorene C13H10 86-73-7

166.21 White leaflets/

568.15 K

Respiratory irritation

0.001*

10 Acenaphthene C12H10 83-32-9

154.2 White needles/ 552 K

Eye damage 0.001*

11 Phenanthrene C14H10 85-01-8

178.22 Colorless monoclinic

crystals/ 612

Toxic when orally ingested

0.001*

2

K12 Benzo[a]pyren

eC20H12 50-

32-8252.3 Yellow

crystals/ 768.15 K

Carcinogenic 1*

C: Polychlorinated biphenyls 13 PCB 8 C12H8Cl2 34883

-43-7223.1 Carcinogenic 20 ng kg-1**

14 PCB 26 C12H7Cl3 38444-81-4

257.5 Organ toxicity

15 PCB 47 C12H4Cl4 2437-79-8

291.98 Organ toxicity

16 PCB 52 C12H6Cl4 35693-99-3

291.98 Organ toxicity

17 PCB 77 C12H6Cl4 32598-13-3

291.98 Organ toxicity

18 PCB 95 C12H5Cl5 38379-99-6

326.4

19 PCB 118 C12H5Cl5 31508-00-6

326.4 Organ toxicity

20 PCB 126 C12H5Cl5 57465-28-8

326.4 Organ toxicity

21 PCB 136 C12H4Cl6 38411-22-2

360.86 Organ toxicity

D: Phenols22 Phenol C6H6O 108-

95-294.1 colorless

crystals/ 352.6 K

Skin and eye irritation

100

23 Octylphenol C14H22O 2719-28-8

206.33 448 K Skin and eye irritation

24 Nonylphenol C15H24O 25154-52-3

220.35 Pale yellow liquid/ 422 K

Eye irritant 31.4

25 O-cresol C7H8O 95-48-7

108.14 Yellow liquid/

365.92 K

Burn to skin

26 2,6-Dimethyl phenol

C8H10O 1300-71-6

122.17 White crystals/ 347 K

Acute toxicity

Notes: Unless otherwise indicated, all data in this table are from [1-12]. a Assuming 5 cigarettes/d; b Assuming 2 L/d. NA: Not applicable * Toxic equivalent factor, ** Tolerable daily intake for all PCBs

3

Table S2. Comparative assessment of different methods employed for the sampling and

subsequent analysis of aromatic hydrocarbon compounds in air.

Method ID

Analytes LODs Sampling and analysis

approach

Advantages Disadvantages Ref.

TO-1 VOCs (80-200 oC)

0.01-100 ppbv

Tenax, GC/MS or GC/FID

Moisture is not an issueLarge volumes of air can be sampledLow LODsStandard procedures are available

Highly volatile compounds are not collected Contamination from adsorbent No possibility of multiple analysisLow breakthrough volumes of some compounds

[13]

TO-2 Highly volatile VOCs (-15 to +120 oC)

0.1-200 ppbv

CMS, GC/MS or GC/FID

Efficient collection of polar compoundsWide range of applicationsEasy to use in the field

Trace levels of some species are difficult to recoverWater is collected and can deactivate sorbentinterferences Structural isomers are common

[14]

TO-3 VOCs non-polar (-10 to +200 oC)

0.1-200 ppbv

Cryogenic trap, GC/FID/ECD

Consistent recoveriesLarge databaseSOPs are availableCollects a wide variety of VOCs

Moisture can cause freezing problems in cryogenic trapExpensive and difficult to use in the fieldIntegrated sampling is difficult

[15]

TO-13A PAHs 0.5-500 ngm-3

PUF or XAD-2 cartridge, GC/MS

Low cost Repeated analyses are possibleLarge sampling volumes are possible

Contamination from solvents can occurHeat, oxides of nitrogen, and ozone can decompose samples

[16]

TO-14A VOCs non polar

0.2-25 ppbv

Special canisters, GC/FID/ECD or GC/MS

Best method for broad spectrum analysisLarge database Proven field and analytical technology

Only non-polar compounds can be analyzed due to use of a permeation type drierExpensive detection techniquesHigh levels of moisture cause problem

[17]

TO-15 VOCs polar and non-polar

0.2-25 ppbv

Special canisters, GC/MS

Water management through multiple adsorbentsEstablished methodsEnhanced provision for QC

Significant expertise requiredExpensive detection techniques

[18]

TO-16 VOCs polar and non-polar

25-500 ppbv

Open path FTIR spectrometer

Maintains sample integrity, multi-gas analysis is possible, monitoring in remote areas is possible, possibility of real-time analysis of VOCs

Significant expertise requiredSpectral interpretation is required, Relatively high LODs, Significant interference from moisture and CO2

[19]

TO-17 VOCs polar and non-polar

0.2-25 ppbv

Multi-bed adsorbent tubes, GC/MS

Low cost, Good water management compared to TO-14A, Possibility of selection of sorbent according to analyte nature

Rigorous cleanup is requiredMultiple analysis is not possibleContamination from adsorbents can occur

[20]

325A VOCs polar and non-polar

0.5-500 µgm-3

Sorbent tubes, Passive sampling GC/FID, GC/MS

Integrated analysis is possibleLow cost Active and passive sampling can be used

Requires metrological dataComplex topography can interfere

[21]

325B VOCs 0.05-0.1 Passive Multi-detector GC techniques CO2, O3, and S can interfere [22]

4

polar and non-polar

ppbv sampling GC/MS, GC/FID

can be applicableWater management system is good

Highly volatile compounds cannot be analyzed

5

Table S3. Comparative assessment of different methods employed for the sampling and

subsequent analysis of aromatic hydrocarbon compounds in water

Method ID

Analytes LODs Sampling and analysis

approach

Advantages Limitations

502.2 VOCs MDL: 0.01-3 µg/LCalibration range: 0.02-200 µg/L

Purge and trap, TD, Capillary GC/PID/ELCD

Good applicability to a number of VOCsStandard procedures are available

Low concentrations are not measured accurately Moisture management is frequently problematic Interference from structural isomers is common

[23]

505 Organohalide pesticides and PCBs

MDL: 0.002-15 µg/LConcentration calibration range: 0.03-180 µg/L

Grab sampling, Micro-extraction, GC/ECD

Multiple analysis is possibleHigh sensitivity for some compounds (hexachlorobenzene)

Experienced analysts are requiredExpensive solvents are requiredCleanup of sample extracts is requiredSpecial precaution is needed for Endrin analysis

[24]

525.2 Highly volatile VOCs (-15 to +120 oC)

MDL: 0.03-3 µg/LCalibration range: 0.2-10 µg/L

C18 in a disk or cartridge, LSE, Capillary GC/MS

Multiple analysis is possibleWide range of applications (especially for non-polar analytes)

Contamination from reagents and LSE devices.

[25]

550 PAHs MDL: 0.002-3.3 µg/L

Grab sampling, LLE, HPLC/UV/FLD

Multiple analysis is possible Contamination from solvents Matrix interference is common for benzo(a) anthracene, benzo(a)pyrene, and benzo(g,h,i)perylene

[26]

610 PAHs MDL: 0.013-2.3 µg/L

Grab sampling, LLE, GC/FID, optional HPLC/UV or FLD

Silica gel column removes many interferences

Four pairs of classes: Anthracene and phenanthrene; chrysene and benzo(a)anthracene; benzo(b) fluoranthene and benzo(k)fluoranthene; and dibenzo(a,h) anthracene and indeno (1,2,3-cd) pyrene are difficult to analyze with GC/MSContamination from solvents and reagents

[27]

8100-2 PAHs Grab sampling, SPE or LLE, packed or capillary GC/FID

Both neat and dilute samples can be analyzedMultiple analysis possible

Four pairs of classes: anthracene and phenanthrene; chrysene and benzo(a)anthracene; benzo(b) fluoranthene and benzo(k) fluoranthene; and dibenzo(a,h)anthracene and indeno(1,2,3-cd)pyrene are difficult to analyze with packed column GC

[28]

8272 PAHs MDL: 0.06-9 µg/L

Grab sampling, centrifugation,

Multiple analysis is possibleOnly 1.5 mL per

Non-target hydrocarbons can interfere

[29]

6

Calibration range: 0.03-180 µg/L

SPME, GC/MS determination is requiredNo solvent extraction waste is generated

Experienced analysts are requiredPAHs with high Mol. Wt. require extra extraction

8310 PAHs MDL: 0.013-2.3 µg/L

Grab sampling, LLE, HPLC/UV-FLD

Sensitivity is usually not dependent on instrumental limitations

Experienced analysts are requiredMatrix artifacts can interfere

[30]

Fig. S1. Potential sources of aromatic hydrocarbon compounds in air, water, and soil.

References

7

[1] ASTDR, Toxicological profile for toluene. US department of health and human services,

Agency for toxic substances and disease registry, USA., DOI (2000).

[2] ASTDR, Draft toxicological profile for ethylbenzene. US department of health and human

services, agency for toxic substances and disease registry, USA, DOI (2007b).

[3] ASTDR, Toxicological profile for xylene. US department of health and human services,

agency for toxic substances and disease registry, USA., DOI (2007c).

[4] ATSDR, Toxicological profile for benzene. US department of health and human services,

agency for toxic substances and disease registry, USA., DOI (2007a).

[5] NTP, Report on carcinogens. Eleventh Ed. US department of health and human services,

public health service, national toxicology program, USA., DOI (2005).

[6] NHMRC, Australian drinking water guidelines. National health and medical research council

and natural resource

management ministerial council, Canberra, Australia., DOI (2004).

[7] WHO, Guidelines for drinking water quality. Third Edition incorporating the first and second

addenda. World Health

Organization, Geneva, Switzerland., DOI (2008).

[8] IPCS, Environmental health criteria 52: toluene. International programme on chemical safety,

World Health Organization, Geneva, Switzerland. , DOI (1985).

[9] IPCS, Environmental health criteria 150: benzene. International programme on chemical

safety, World Health Organization, Geneva, Switzerland. , DOI (1993).

[10] IPCS, Environmental health criteria 186: ethylbenzene. International programme on

chemical safety, World Health Organization, Geneva, Switzerland., DOI (1996).

[11] IPCS, Environmental health criteria 190: xylenes. International programme on chemical

safety, World Health Organization, Geneva, Switzerland., DOI (1997).

[12] N. Raza, K.-H. Kim, Quantification techniques for important environmental contaminants in

milk and dairy products, TrAC Trends in Analytical Chemistry, DOI (2017).

[13] USEPA-TO-1, Method for the determination of volatile organic compounds (VOCs) in

ambient air using Tenax® adsorption and gas chromatography/mass spectrometry (GC/MS).

DOI (1999).

8

[14] USEPA-TO-2, Method for the determination of volatile organic compounds (VOCs) in

ambient air by carbon molecular sieve adsorption and gas chromatography/mass spectrometry

(GC/MS), DOI (1999).

[15] USEPA-TO-3, Method for the determination of volatile organic compounds in ambient air

using cryogenic preconcentration techniques and gas chromatography with flame ionization and

electron capture detection, DOI (1999).

[16] USEPA-TO-13A, Determination of polycyclic aromatic hydrocarbons (PAHs) in ambient

air using gas chromatography/mass

spectrometry (GC/MD), Compendium method TO-13A, 2nd edn (Cincinnati, OH 45268). DOI

(1999).

[17] USEPA-TO-14A, Compendium method TO-14A: Determination of volatile organic

compounds (VOCs) in ambient air using specially prepared canisters with subsequent analysis by

gas chromatography. In: Compendium of methods for the determination of toxic organic

compounds in ambient air, 2nd edn. US Environmental Protection Agency, DOI (1999).

[18] USEPA-TO-15, Compendium method TO-15: Determination of volatile organic compounds

(VOCs) in ambient air using specially prepared canisters with subsequent analysis by gas

chromatography. In: Compendium of methods for the determination of toxic organic compounds

in ambient air, 2nd edn. US Environmental Protection Agency DOI (1999).

[19] USEPA-TO-16, Long path open path fourier transform infrared monitoring of atmospheric

gases, DOI (1999).

[20] USEPA-TO-17, Compendium method TO-17: Determination of volatile organic compounds

in ambient air using active sampling onto sorbent tubes. In: Compendium of methods for the

determination of toxic organic compounds in ambient air, 2nd edn. US Environmental Protection

Agency, DOI (1999).

[21] USEPA-Method-325A, Volatile organic compounds from fugitive and area sources:

sampler deployment and VOC sample collection.

40 CFR Part 63, Subpart UUU [EPA-HQ-OAR-2010-0682; FRL-9720-4], RIN 2060-AQ75,

Petroleum Refinery Sector

Risk and Technology Review and New Source Performance Standards. Available at

http://www3.epa.gov/9

ttn/emc/promgate/m-325a.pdf, DOI (2015).

[22] USEPA-Method-325B, Volatile organic compounds from fugitive and area sources: sampler

preparation and analysis. 40 CFR Part 63, Subpart UUU [EPA-HQ-OAR-2010-0682; FRL-9720-

4], RIN 2060- AQ75, Petroleum Refinery Sector Risk and Technology Review and New Source

Performance Standards., DOI (2015).

[23] USEPA-Method-502.2, Volatile organic compounds in water by purge and trap capillary

column gas chromatography with photionization and electrolytic conductivity detectors in series.

National exposure research laboratory office of research and development, Cincinnati, Ohio.,

DOI (1995).

[24] USEPA-Method-505, Analysis of organochloride pesticides and commercial

polychlorinated biphenyl products in water by microextraction and gas chromatography, DOI

(1995).

[25] USEPA-Method-525.2, Determination of organic compounds in drinking water by liquid

solid extraction and capillary column gas chromatography/mass spectrometry. National exposure

research laboratory office of research and development, Cincinnati, Ohio., DOI (1991).

[26] USEPA-Method-550, Determination of polycyclic aromatic hydrocarbons in drinking water

by liquid liquid extraction and HPLC with coupled ultraviolet and flouorescence detection, DOI

(1990).

[27] USEPA-Method-610, Polynuclear aromatic hydrocarbons. National technical information

service, PB82-258799, Springfield, Virginia. , DOI (1984).

[28] USEPA-Method-8100, Determination of polynuclear aromatic hydrocarbons in solid waste

by gas chromatography, (US Government printing office, Washington DC, USA). DOI (1986).

[29] USEPA-Method-8272, Parent and alkyl polycyclic aromatics in sediment pore water by

solid-phase microextraction and gas chromathography/mass spectrometry in selected ion

monitoring mode, ss-846. , DOI (2007).

[30] USEPA-Method-8310, Determination of polynuclear aromatic hydrocarbons in ground

water and wastes by liquid chromatography, (US Government Printing Office, Washington DC,

USA). DOI (1986).

10

References used in Tables of the main text (T-numbered references)

[T1] F. Soxhlet, Die gewichtsaiialytische Bestimmung des Milchfettes; von, DOI (1879).

[T2] G. Eiceman, A. Viau, F. Karasek, Ultrasonic extraction of polychlorinated dibenzo-p-

dioxins and other organic compounds from fly ash from municipal incinerators, Anal. Chem. 52

(1980) 1492-1496.

[T3] K. Ganzler, A. Salgó, K. Valkó, Microwave extraction: A novel sample preparation method

for chromatography, J Chromatogr. A 371 (1986) 299-306.

[T4] G. Audunsson, Aqueous/aqueous extraction by means of a liquid membrane for sample

cleanup and preconcentration of amines in a flow system, Anal. Chem. 58 (1986) 2714-2723.

[T5] F.A. DiGiano, D. Elliot, D. Leith, Application of passive dosimetry to the detection of trace

organic contaminants in water, Environ. Sci. Technol. 22 (1988) 1365-1367.

[T6] J. Huckins, M. Tubergen, J. Lebo, R. Gale, T. Schwartz, Polymeric film dialysis in organic

solvent media for cleanup of organic contaminants, J. Assoc. Off. Anal. Chem. 73 (1990) 290-

293.

[T7] J.K. Kingston, R. Greenwood, G.A. Mills, G.M. Morrison, L.B. Persson, Development of a

novel passive sampling system for the time-averaged measurement of a range of organic

pollutants in aquatic environments, J. Environ. Monit. 2 (2000) 487-495.

[T8] J.A. Koziel, M. Odziemkowski, J. Pawliszyn, Sampling and analysis of airborne particulate

matter and aerosols using in-needle trap and SPME fiber devices, Anal. Chem. 73 (2001) 47-54.

[T9] S.J. Lehotay, A.d. Kok, M. Hiemstra, P.v. Bodegraven, Validation of a fast and easy

method for the determination of residues from 229 pesticides in fruits and vegetables using gas

and liquid chromatography and mass spectrometric detection, J. AOAC. Int. 88 (2005) 595-614.

[T10] M. Rezaee, Y. Assadi, M.-R.M. Hosseini, E. Aghaee, F. Ahmadi, S. Berijani,

Determination of organic compounds in water using dispersive liquid–liquid microextraction, J.

Chromatogr. A 1116 (2006) 1-9.

[T11] S.G. Attari, A. Bahrami, F.G. Shahna, M. Heidari, Solid-phase microextraction fiber

development for sampling and analysis of volatile organohalogen compounds in air, J. Environ.

Health Sci. Eng. 12 (2014) 123-130.

11

[T12] F. Bianchi, A. Bedini, N. Riboni, R. Pinalli, A. Gregori, L. Sidisky, E. Dalcanale, M.

Careri, Cavitand-based solid-phase microextraction coating for the selective detection of

nitroaromatic explosives in air and soil, Anal. Chem. 86 (2014) 10646-10652.

[T13] X. Wang, Y. Wang, Y. Qin, L. Ding, Y. Chen, F. Xie, Sensitive and selective

determination of polycyclic aromatic hydrocarbons in mainstream cigarette smoke using a

graphene-coated solid-phase microextraction fiber prior to GC/MS, Talanta 140 (2015) 102-108.

[T14] H.C. Menezes, B.P. Paulo, N.T. Costa, Z.L. Cardeal, New method to determination of

naphthalene in ambient air using cold fiber-solid phase microextraction and gas

chromatography–mass spectrometry, Microchem. J. 109 (2013) 93-97.

[T15] H. Mokbel, E.J. Al Dine, A. Elmoll, C. Liaud, M. Millet, Simultaneous analysis of

organochlorine pesticides and polychlorinated biphenyls in air samples by using accelerated

solvent extraction (ASE) and solid-phase micro-extraction (SPME) coupled to gas

chromatography dual electron capture detection, Environ. Sci. Pollut. Res. 23 (2016) 8053-8063.

[T16] X.Y. Cui, Z.Y. Gu, D.Q. Jiang, Y. Li, H.F. Wang, X.P. Yan, In situ hydrothermal growth

of metal− organic framework 199 films on stainless steel fibers for solid-phase microextraction

of gaseous benzene homologues, Anal. Chem. 81 (2009) 9771-9777.

[T17] Z. G. Shi, H.K. Lee, Dispersive liquid− liquid microextraction coupled with dispersive μ-

solid-phase extraction for the fast determination of polycyclic aromatic hydrocarbons in

environmental water samples, Anal. Chem. 82 (2010) 1540-1545.

[T18] D. Ge, H.K. Lee, Water stability of zeolite imidazolate framework 8 and application to

porous membrane-protected micro-solid-phase extraction of polycyclic aromatic hydrocarbons

from environmental water samples, J. Chromatogr. A 1218 (2011) 8490-8495.

[T19] J. Ma, R. Xiao, J. Li, J. Yu, Y. Zhang, L. Chen, Determination of 16 polycyclic aromatic

hydrocarbons in environmental water samples by solid-phase extraction using multi-walled

carbon nanotubes as adsorbent coupled with gas chromatography–mass spectrometry, J.

Chromatogr. A 1217 (2010) 5462-5469.

[T20] J. López Darias, V. Pino, Y. Meng, J.L. Anderson, A.M. Afonso, Utilization of a benzyl

functionalized polymeric ionic liquid for the sensitive determination of polycyclic aromatic

hydrocarbons; parabens and alkylphenols in waters using solid-phase microextraction coupled to

gas chromatography–flame ionization detection, J. Chromatogr. A 1217 (2010) 7189-7197.

12

[T21] M. C. Wei, J. F. Jen, Determination of polycyclic aromatic hydrocarbons in aqueous

samples by microwave assisted headspace solid-phase microextraction and gas

chromatography/flame ionization detection, Talanta 72 (2007) 1269-1274.

[T22] C. Basheer, A.A. Alnedhary, B.M. Rao, R. Balasubramanian, H.K. Lee, Ionic liquid

supported three-phase liquid–liquid–liquid microextraction as a sample preparation technique for

aliphatic and aromatic hydrocarbons prior to gas chromatography-mass spectrometry, J.

Chromatogr. A 1210 (2008) 19-24.

[T23] W.C. Tseng, P.S. Chen, S.D. Huang, Optimization of two different dispersive liquid–

liquid microextraction methods followed by gas chromatography–mass spectrometry

determination for polycyclic aromatic hydrocarbons (PAHs) analysis in water, Talanta 120

(2014) 425-432.

[T24] A. Mehdinia, E. Khojasteh, T.B. Kayyal, A. Jabbari, Magnetic solid phase extraction using

gold immobilized magnetic mesoporous silica nanoparticles coupled with dispersive liquid–

liquid microextraction for determination of polycyclic aromatic hydrocarbons, J. Chromatogr. A

1364 (2014) 20-27.

[T25] N.P. Petridis, V.A. Sakkas, T.A. Albanis, Chemometric optimization of dispersive

suspended microextraction followed by gas chromatography–mass spectrometry for the

determination of polycyclic aromatic hydrocarbons in natural waters, J. Chromatogr. A 1355

(2014) 46-52.

[T26] E. Rianawati, R. Balasubramanian, Optimization and validation of solid phase micro-

extraction (SPME) method for analysis of polycyclic aromatic hydrocarbons in rainwater and

stormwater, Phys. Chem. Earth Parts A/B/C, 34 (2009) 857-865.

[T27] P. Popp, C. Bauer, B. Hauser, P. Keil, L. Wennrich, Extraction of polycyclic aromatic

hydrocarbons and organochlorine compounds from water: A comparison between solid‐phase

microextraction and stir bar sorptive extraction, J. Sep. Sci. 26 (2003) 961-967.

[T28] L. Guo, S. Tan, X. Li, H.K. Lee, Fast automated dual-syringe based dispersive liquid–

liquid microextraction coupled with gas chromatography–mass spectrometry for the

determination of polycyclic aromatic hydrocarbons in environmental water samples, J.

Chromatogr. A 1438 (2016) 1-9.

13

[T29] L.O. Santos, J.P. dos Anjos, S.L. Ferreira, J.B. de Andrade, Simultaneous determination of

PAHS, nitro-PAHS and quinones in surface and groundwater samples using SDME/GC-MS,

Microchem. J. 133 (2017) 431-440.

[T30] A. Amiri, M. Baghayeri, M. Kashmari, Magnetic nanoparticles modified with polyfuran

for the extraction of polycyclic aromatic hydrocarbons prior to their determination by gas

chromatography, Microchim. Acta 183 (2016) 149-156.

[T31] Z. Wang, Q. Han, J. Xia, L. Xia, M. Ding, J. Tang, Graphene‐based solid‐phase extraction

disk for fast separation and preconcentration of trace polycyclic aromatic hydrocarbons from

environmental water samples, J. Sep. Sci. 36 (2013) 1834-1842.

[T32] X.F. Chen, H. Zang, X. Wang, J.G. Cheng, R.S. Zhao, C.G. Cheng, X.Q. Lu, Metal–

organic framework MIL-53 (Al) as a solid-phase microextraction adsorbent for the determination

of 16 polycyclic aromatic hydrocarbons in water samples by gas chromatography–tandem mass

spectrometry, Analyst 137 (2012) 5411-5419.

[T33] S. Zhang, W. Yao, J. Ying, H. Zhao, Polydopamine-reinforced magnetization of zeolitic

imidazolate framework ZIF-7 for magnetic solid-phase extraction of polycyclic aromatic

hydrocarbons from the air-water environment, J.Chromatogr. A 1452 (2016) 18-26.

[T34] M.S. Shahriman, M.R. Ramachandran, N.N.M. Zain, S. Mohamad, N.S.A. Manan, S.M.

Yaman, Polyaniline-dicationic ionic liquid coated with magnetic nanoparticles composite for

magnetic solid phase extraction of polycyclic aromatic hydrocarbons in environmental samples,

Talanta 178 (2018) 211-221.

[T35] J.L. Benedé, J.L. Anderson, A. Chisvert, Trace determination of volatile polycyclic

aromatic hydrocarbons in natural waters by magnetic ionic liquid-based stir bar dispersive liquid

microextraction, Talanta 176 (2018) 253-261.

[T36] N. Fattahi, S. Samadi, Y. Assadi, M.R.M. Hosseini, Solid-phase extraction combined with

dispersive liquid–liquid microextraction-ultra preconcentration of chlorophenols in aqueous

samples, J. Chromatogr. A 1169 (2007) 63-69.

[T37] W. Chen, J. Zeng, J. Chen, X. Huang, Y. Jiang, Y. Wang, X. Chen, High extraction

efficiency for polar aromatic compounds in natural water samples using multiwalled carbon

nanotubes/Nafion solid-phase microextraction coating, J. Chromatogr. A 1216 (2009) 9143-

9148.

14

[T38] G. Zhang, Z. Li, X. Zang, C. Wang, Z. Wang, Solid‐phase microextraction with a

graphene‐composite‐coated fiber coupled with GC for the determination of some halogenated

aromatic hydrocarbons in water samples, J. Sep. Sci. 37 (2014) 440-446.

[T39] J. Ji, C. Deng, W. Shen, X. Zhang, Field analysis of benzene, toluene, ethylbenzene and

xylene in water by portable gas chromatography–microflame ionization detector combined with

headspace solid-phase microextraction, Talanta 69 (2006) 894-899.

[T40] M. R. Lee, C. M. Chang, J. Dou, Determination of benzene, toluene, ethylbenzene,

xylenes in water at sub-ngl−1 levels by solid-phase microextraction coupled to cryo-trap gas

chromatography–mass spectrometry, Chemosphere 69 (2007) 1381-1387.

[T41] A. Sarafraz Yazdi, G. Rounaghi, I. Razavipanah, H. Vatani, A. Amiri, New polypyrrole–

carbon nanotubes–silicon dioxide solid‐phase microextraction fiber for the preconcentration and

determination of benzene, toluene, ethylbenzene, and o‐xylene using gas liquid chromatography,

J. Sep. Sci. 37 (2014) 2605-2612.

[T42] H. Faraji, A. Feizbakhsh, M. Helalizadeh, Modified dispersive liquid-liquid

microextraction for pre-concentration of benzene, toluene, ethylbenzene and xylenes prior to

their determination by GC, Microchim. Acta 180 (2013) 1141-1148.

[T43] K. Farhadi, R. Tahmasebi, R. Maleki, Preparation and application of the titania sol–gel

coated anodized aluminum fibers for headspace solid phase microextraction of aromatic

hydrocarbons from water samples, Talanta 77 (2009) 1285-1289.

[T44] H. Tabani, K. Khodaei, S.K. Movahed, A.Z. Moghaddam, F.D. Zare, S. Mirzaei,

Evaluation of three dimensional high nitrogen doped graphene as an efficient sorbent for the

preconcentration of BTEX compounds in environmental samples, RSC Adv. 6 (2016) 7198-

7211.

[T45] F. Zhou, X. Li, Z. Zeng, Determination of phenolic compounds in wastewater samples

using a novel fiber by solid-phase microextraction coupled to gas chromatography, Anal. Chim.

Acta 538 (2005) 63-70.

[T46] G.H. Wang, Y.Q. Lei, H.C. Song, Evaluation of Fe3O4@SiO2–MOF-177 as an

advantageous adsorbent for magnetic solid-phase extraction of phenols in environmental water

samples, Anal. Methods 6 (2014) 7842-7847.

15

[T47] H.B. Shang, C.X. Yang, X.P. Yan, Metal–organic framework UiO-66 coated stainless

steel fiber for solid-phase microextraction of phenols in water samples, J. Chromatogr. A 1357

(2014) 165-171.

[T48] L. Guo, H.K. Lee, Electro membrane extraction followed by low-density solvent based

ultrasound-assisted emulsification microextraction combined with derivatization for determining

chlorophenols and analysis by gas chromatography–mass spectrometry, J. Chromatogr. A 1243

(2012) 14-22.

[T49] S. Piramoon, P. Aberoomand Azar, M. Saber Tehrani, S. Mohammadiazar, A. Tavassoli,

Solid‐phase nanoextraction of polychlorinated biphenyls in water and their determination by gas

chromatography with electron capture detector, J. Sep. Sci. 40 (2017) 449-457.

[T50] S. Zhou, J. Qiu, Y. Liang, Y. Ma, W. Wang, Q. Zhou, X. Chen, P. Shi, A. Li,

Development of a magnetic solid‐phase extraction coupled with gas chromatography and mass

spectrometry method for the analysis of semivolatile organic compounds, J. Sep. Sci. 38 (2015)

3295-3303.

[T51] H. Zang, J. P. Yuan, X. F. Chen, C. A. Liu, C. G. Cheng, R. S. Zhao, Hollow fiber-

protected metal–organic framework materials as micro-solid-phase extraction adsorbents for the

determination of polychlorinated biphenyls in water samples by gas chromatography-tandem

mass spectrometry, Anal. Methods 5 (2013) 4875-4882.

[T52] S. Ozcan, Analyses of polychlorinated biphenyls in waters and wastewaters using vortex‐

assisted liquid–liquid microextraction and gas chromatography‐mass spectrometry, J. Sep. Sci.

34 (2011) 574-584.

[T53] S. Luo, L. Fang, X. Wang, H. Liu, G. Ouyang, C. Lan, T. Luan, Determination of

octylphenol and nonylphenol in aqueous sample using simultaneous derivatization and dispersive

liquid–liquid microextraction followed by gas chromatography–mass spectrometry, J.

Chromatogr. A 1217 (2010) 6762-6768.

[T54] B. Hashemi, M. Shamsipur, A. Barati, Dispersive Liquid-Liquid Microextraction Based on

Solidification of Floating Organic Drop with Central Composite Design for the Determination of

Nitrophenols Using High-Performance Liquid Chromatography, J. Braz. Chem. Soc. 26 (2015)

2046-2053.

16

[T55] M.T. Pena, M.C. Casais, M.C. Mejuto, R. Cela, Development of an ionic liquid based

dispersive liquid–liquid microextraction method for the analysis of polycyclic aromatic

hydrocarbons in water samples, J. Chromatogr. A1216 (2009) 6356-6364.

[T56] Y. Huang, Q. Zhou, G. Xie, Development of micro-solid phase extraction with titanate

nanotube array modified by cetyltrimethylammonium bromide for sensitive determination of

polycyclic aromatic hydrocarbons from environmental water samples, J. Hazard. Mater. 193

(2011) 82-89.

[T57] P. Popp, C. Bauer, L. Wennrich, Application of stir bar sorptive extraction in combination

with column liquid chromatography for the determination of polycyclic aromatic hydrocarbons

in water samples, Anal. Chim. Acta 436 (2001) 1-9.

[T58] S.H. Huo, X.P. Yan, Facile magnetization of metal–organic framework MIL-101 for

magnetic solid-phase extraction of polycyclic aromatic hydrocarbons in environmental water

samples, Analyst 137 (2012) 3445-3451.

[T59] Y. Wang, J. Zhang, Y. Ding, J. Zhou, L. Ni, C. Sun, Quantitative determination of 16

polycyclic aromatic hydrocarbons in soil samples using solid‐phase microextraction, J. Sep. Sci.

32 (2009) 3951-3957.

[T60] L. Guo, H.K. Lee, Microwave assisted extraction combined with solvent bar

microextraction for one-step solvent-minimized extraction, cleanup and preconcentration of

polycyclic aromatic hydrocarbons in soil samples, J. Chromatogr. A 1286 (2013) 9-15.

[T61] Y. Han, L. Ren, K. Xu, F. Yang, Y. Li, T. Cheng, X. Kang, C. Xu, Q. Shi, Supercritical

fluid extraction with carbon nanotubes as a solid collection trap for the analysis of polycyclic

aromatic hydrocarbons and their derivatives, J. Chromatogr. A 1395 (2015) 1-6.

[T62] M. Khajeh, A.A. Moosavi‐Movahedi, M. Shakeri, F. Musavi Zadeh, A. Khajeh, M.

Bohlooli, Dispersive solid phase extraction combined with dispersive liquid–liquid extraction for

the determination of BTEX in soil samples: ant colony optimization–artificial neural network, J.

Chemom. 29 (2015) 245-252.

[T63] D. Tan, J. Jin, F. Li, X. Sun, Y. Ni, J. Chen, Phenyltrichlorosilane-functionalized

magnesium oxide microspheres: preparation, characterization and application for the selective

extraction of dioxin-like polycyclic aromatic hydrocarbons in soils with matrix solid-phase

dispersion, Anal. Chim. Acta DOI (2017).

17

[T64] R.J. Krupadam, B. Bhagat, S.R. Wate, G.L. Bodhe, B. Sellergren, Y. Anjaneyulu,

Fluorescence spectrophotometer analysis of polycyclic aromatic hydrocarbons in environmental

samples based on solid phase extraction using molecularly imprinted polymer, Environ. Sci.

Technol. 43 (2009) 2871-2877.

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