Skip to main content
SpringerLink
Log in

GC/MS analysis of triclosan and its degradation by-products in wastewater and sludge samples from different treatments

  • Research Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

A gas chromatography/mass spectrometry (GC/MS)-based method was developed for simultaneous determination of triclosan (TCS) and its degradation products including 2,4-dichlorophenol (2,4-DCP), 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD), and methyl triclosan (MTCS) in wastewater and sludge samples. The method provides satisfactory detection limit, accuracy, precision and recovery especially for samples with complicated matrix such as sewage sludge. Liquid-liquid extraction and accelerated solvent extraction (ASE) methods were applied for the extraction, and column chromatography was employed for the sample cleanup. Analysis was performed by GC/MS in the selected ion monitoring (SIM) mode. The method was successfully applied to wastewater and sludge samples from three different municipal wastewater treatment plants (WWTPs). Satisfactory mean recoveries were obtained as 91(±4)–106(±7) %, 82(±3)–87(±4) %, 86(±6)–87(±8) %, and 88(±4)–105(±3) % in wastewater and 88(±5)–96(±8) %, 84(±2)–87(±3) %, 84(±7)–89(±4) %, and 88(±3)–97(±5) % in sludge samples for TCS, 2,4-DCP, 2,8-DCDD, and MTCS, respectively. TCS degradation products were detected based on the type of the wastewater and sludge treatment. 2,8-DCDD was detected in the plant utilizing UV disinfection at the mean level of 20.3(±4.8) ng/L. 2,4-DCP was identified in chemically enhanced primary treatment (CEPT) applying chlorine disinfection at the mean level of 16.8(±4.5) ng/L). Besides, methyl triclosan (MTCS) was detected in the wastewater collected after biological treatment (10.7 ± 3.3 ng/L) as well as in sludge samples that have undergone aerobic digestion at the mean level of 129.3(±17.2) ng/g dry weight (dw).

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

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

Similar content being viewed by others

References

  • Aranami K, Readman JW (2007) Photolytic degradation of triclosan in freshwater and seawater. Chemosphere 66:1052–1056

    Article  CAS  Google Scholar 

  • Balmer M, Poiger T, Droz C, Romanin K, Bergqvist P, Müller M, Buser H (2004) Occurrence of methyl triclosan, a transformation product of the bactericide triclosan, in fish from various lakes in Switzerland. Environ Sci Technol 38:390–395

    Article  CAS  Google Scholar 

  • Bester K (2005) Fate of triclosan and triclosan-methyl in sewage treatment plants and surface waters. Arch Environ Contam Toxicol 49:9–17

    Article  CAS  Google Scholar 

  • Buth JM, Grandbois M, Vikesland PJ, Mcneill K, Arnold WA (2009) Aquatic photochemistry of chlorinated triclosan derivatives: potential source of polychlorodibenzo-p-dioxins. Environ Toxicol Chem 28:2555–2563

    Article  CAS  Google Scholar 

  • Buth JM, Steen PO, Sueper CH, Blumentritt D, Vikesland PJ, Arnold WA, Neill KM (2010) Dioxin photoproducts of triclosan and its chlorinated derivatives in sediment cores. Environ Sci Technol 44:4545–4551

    Article  CAS  Google Scholar 

  • Butler E, Whelan MJ, Sakrabani R, van Egmond R (2012) Fate of triclosan in field soils receiving sewage sludge. Environ Pollut 167:101–109

    Article  CAS  Google Scholar 

  • Canosa P, Morales S, Rodríguez I, Rubí E, Cela R, Gómez M (2005) Aquatic degradation of triclosan and formation of toxic chlorophenols in presence of low concentrations of free chlorine. Anal Bioanal Chem 383:1119–1126

    Article  CAS  Google Scholar 

  • Chen X, Jeppe L-N, Furgal K, Liu Y, Lolas I-B, Bester K (2011) Biodegradation of triclosan and formation of methyl-triclosan in activated sludge under aerobic conditions. Chemosphere 84(4):452–456

    Article  CAS  Google Scholar 

  • Chow AYK, Hirsch GH, Buttar HS (1977) Nephrotoxic and hepatotoxic effects of triclosan and chlorhexidine in rats. Toxicol Appl Pharmacol 42:1

    Article  CAS  Google Scholar 

  • Colby BN, Rosecrance AE, Colby ME (1981) Measurement parameter selection for quantitative isotope dilution gas chromatography/mass spectrometry. Anal Chem 53:1907–1911

    Article  CAS  Google Scholar 

  • Dai X, Zhao Y, Li M, Fang X, Li X, Li H, Xu B (2012) Determination of urea in milk by liquid chromatography isotope dilution mass spectrometry. Anal Lett 45:1557–1565

    Article  CAS  Google Scholar 

  • Diemer J, Heumann KG (2000) Development of an ICP-IDMS method for accurate routine analyses of toxic heavy metals in polyolefins and comparison with results by TI-IDMS. Fresen J Anal Chem 368:103–108

    Article  CAS  Google Scholar 

  • Federle T, Kaiser S, Nuck B (2002) Fate and effects of triclosan in activated sludge. Environ Toxicol Chem 21:1330–1337

    Article  CAS  Google Scholar 

  • Ferrer I, Mezcua M, Gomez MJ, Thurman EM, Aguera A, Hernando MD, Fernandez-Alba AR (2004) Liquid chormatography/time-of-flight mass spectrometric analysis for the elucidation of the photodegradation products of triclosan in wastewater samples. Rapid Commun Mass Spectrom 18:443–450

    Article  CAS  Google Scholar 

  • Gatidou G, Thomaidis NS, Stasinakis AS, Lekkas TD (2007) Simultaneous determination of the endocrine disrupting compounds nonylphenol, nonylphenol ethoxylates, triclosan and bisphenol A in wastewater and sewage sludge by gas chromatography-mass spectrometry. J Chromatogr A 1138:32–41

    Article  CAS  Google Scholar 

  • Glaze WH, Henderson JE (1975) Formation of organochlorine compounds from the chlorination of a municipal secondary effluent. J Water Pollut Control Fed 47(10):2511–2515

    CAS  Google Scholar 

  • Greyshock AE, Vikesland PJ (2006) Triclosan reactivity in chloraminated waters. Environ Sci Technol 40:2615–2622

    Article  CAS  Google Scholar 

  • International Agency for Research on Cancer, World Health Organization (1999) Hydrazine and hydrogen peroxide summary of data reported and evaluation, re-evaluation of some organic chemicals

  • Itoh N, Fushimi A, Yarita T, Aoyagi Y, Numata M (2011) Accurate quantification of polycyclic aromatic hydrocarbons in dust samples using microwave-assisted solvent extraction combined with isotope-dilution mass spectrometry. Anal Chim Acta 699:49–56

    Article  CAS  Google Scholar 

  • Jones RD, Jampani HB, Newman JL, Lee AS (2000) Triclosan: a review of effectiveness and safety in health care settings. Am J Infect Control 28:184–196

    Article  CAS  Google Scholar 

  • Kanetoshi A, Ogawa H, Katsura E, Kaneshima H (1987) Chlorination of Irgasan DP3000 and formation of dioxins from its chlorinated derivatives. J Chromatogr A 389:139–153

    Article  CAS  Google Scholar 

  • Kanetoshi A, Ogawa H, Katsura E, Kaneshima H (1988) Formation of polychlorinated dibenzo-p-dioxin from 2,4,4′-trichloro-2′-hydroxydiphenyl ether (Irgasan DP3000) and its chlorinated derivatives by exposure to sunlight. J Chromatogr A 454:145–155

    Article  CAS  Google Scholar 

  • Kazama M, Mizuishi K, Nakamura Y, Harada H, Totani T (1974) Studies on analytical method of specific materials in cosmetics IX analysis of hexachlorophene by thin-layer and gas chromatography. Eisei Kagaku 20:248

    Article  CAS  Google Scholar 

  • Krasner SW, Weinberg HS, Richardson SD, Pastor SJ, Chinn R, Sclimenti MJ, Onstad GD, Thruston AD Jr (2006) Occurrence of a new generation of disinfection by-products. Environ Sci Techmol 40(23):7175–7185

    Article  CAS  Google Scholar 

  • Latch DE, Packer JL, Arnold WA, McNeill K (2003) Photochemical conversion of triclosan to 2,8-dichlorodibenzop-dioxin in aqueous solution. J Photochem Photobiol A Chem 158:63–66

    Article  CAS  Google Scholar 

  • Latch DE, Packer JL, Stender B, Vanoverbeke J, Arnold WA, McNeill K (2005) Aqueous photochemistry of triclosan, formation of 2,4-dichlorophenol, 2,8-dichlorodibenzo-p-dioxin and oligomerization products. Environ Toxicol Chem 24:517–525

    Article  CAS  Google Scholar 

  • Leikera TJ, Abneya SR, Goodbred SL, Rosenc MR (2009) Identification of methyl triclosan and halogenated analogues in male common carp (Cyprinus carpio) from Las Vegas Bay and semipermeable membrane devices from Las Vegas Wash, Nevada. Sci Total Enviorn 407:2102–2114

    Article  Google Scholar 

  • Li J (2001) Prediction of internal standards in reversed-phase liquid chromatography 1. Initial study on predicting internal standards for use with neutral samples based on linear solvation energy relationships. J Chromatogr A 927:19–30

    Article  CAS  Google Scholar 

  • Lindstorm A, Buerge IJ, Spoiger T, Bergqvist P-A, Muller MD, Rudolfbuser H (2002) Occurrence and environmental behavior of the bactericide triclosan and its methyl derivative in surface waters and in wastewater. Environ Sci Technol 36:2322–2329

    Article  Google Scholar 

  • Lores M, Llompart M, Sanchez-Prado L, Garcia-Jares C, Cela R (2005) Confirmation of the formation of dichlorodibenzo-p-dioxin in the photodegradation of triclosan by photo-SMPE. Anal Bioanal Chem 381:1294–1298

    Article  CAS  Google Scholar 

  • McAvoy DC, Schatowitz B, Jacob M, Hauk A, Eckhoff WS (2002) Measurement of triclosan in wastewater treatment systems. Environ Toxicol Chem 21:1323–1329

    Article  CAS  Google Scholar 

  • Mechlińska A, Wolska L, Czarzbon I, Namieśnik J (2012) Comparison of different extraction techniques of PCBs from sediment samples using the isotope dilution mass spectrometry technique. Crit Rev Anal Chem 42:184–191

    Article  Google Scholar 

  • Mezcua M, Gómez MJ, Ferrer I, Aguera A, Hernando MD, Fernández-Alba AR (2004) Evidence of 2,7/2,8-dibenzodichloro-p-dioxin as a photodegradation product of triclosan in water and wastewater samples. Anal Chim Acta 524:241–247

    Article  CAS  Google Scholar 

  • Milton JTM, Wang J (2002) High accuracy method for isotope dilution mass spectrometry with application to the measurement of carbon dioxide. Int J Mass Spectrom 218:63–73

    Article  CAS  Google Scholar 

  • Miyazaki T, Yamagishi T, Matsumoto M (1984) Residues of 4-chloro-1-(2,4-dichlorophenoxy)-2-methoxybenzene(triclosan methyl) in aquatic biota. Bull Environ Contam Toxicol 32:227–232

    Article  CAS  Google Scholar 

  • O’Neil M (2001) The Merck index—an encyclopedia of chemicals, drugs, and biologicals. 13th ed. Whitehouse Station (NJ): Merck and Co., Inc. p. 1447. [cited in HSDB 2007]

  • Okumura T, Nishikawa Y (1996) Gas chromatography-mass spectrometry determination of triclosan in water, sediment and fish samples via methylation with diazomethane. Anal Chim Acta 325:175–184

    Article  CAS  Google Scholar 

  • Puthiya Veetil PG, Vijaya Nadaraja A, Bhasi A, Khan S, Bhaskaran K (2012) Degradation of triclosan under aerobic, anoxic and anaerobic conditions. Appl Biochem Biotechnol 167:1603–1612

    Article  Google Scholar 

  • Samara F, Gullett B, Harrison R, Chu A, Clark G (2009) Determination of relative assay response factors for toxic chlorinated and brominated dioxins/furans using an enzyme immunoassay (EIA) and a chemically-activated luciferase gene expression cell bioassay (CALUX). Environ Int 35:588–593

    Article  CAS  Google Scholar 

  • Samaras VG, Thomaidis NS, Stasinakis AS, Lekkas TD (2011) An analytical method for the simultaneous trace determination of acidic pharmaceuticals and phenolic endocrine disrupting chemicals in wastewater and sewage sludge by gas chromatography-mass spectrometry. Anal Bioanal Chem 399:2549–2561

    Article  CAS  Google Scholar 

  • Singer H, Muller S, Tixier C, Pillonel L (2002) Triclosan: occurrence and fate of a widely used biocide in the aquatic environment: field measurements in wastewater treatment, plants, surface waters, and lake sediments. Environ Sci Technol 36:4998–5004

    Article  CAS  Google Scholar 

  • Son H-S, Choi S-B, Zoh K-D, Khan E (2007) Effects of ultraviolet intensity and wavelength on the photolysis of triclosan. Water Sci Technol 55:209–216

    Article  CAS  Google Scholar 

  • Tan LJ, Nielsen N, Young DC, Trizna Z (2002) Use of antimicrobial agents in consumer products. Arch Dermatol 138:1082–1086

    Article  Google Scholar 

  • US Environmental Protection Agency (1994) Emergency Planning and Community Right to Know Act. http://www.epa.gov/agriculture/lcra.html.

  • Vogl J, Pritzkow W (2010) Isotope dilution mass spectrometry—a primary method of measurement and its role for RM certification. MAPAN- J Metrol Soc I 25:135–164

    Google Scholar 

  • Wang Z, Lau BP-Y, Tague B, Sparling M, Forsyth D (2011) Determination of perchlorate in infant formula by isotope dilution ion chromatography/tandem mass spectrometry. Food Addit Contam: Part A 28:799–806

    Article  CAS  Google Scholar 

  • Waria M, O’Connor GA, Toor GS (2011) Biodegradation of triclosan in biosolids-amended soils. Environ Toxicol Chem 30:2488–2496

    Article  CAS  Google Scholar 

  • Ying G, Kookana RS (2007) Triclosan in wastewaters and biosolids from Australian wastewater treatmetn plants. Environ Int 33:199–205

    Article  CAS  Google Scholar 

Download references

Funding

This study was supported by the National Natural Science Foundation of China (21175025) and Faculty Research Grant from Hong Kong Baptist University (FRG2/12-13/032).

Conflict of interest

The authors declare that they have no conflict of interest.

Author information

Authors and Affiliations

  1. State Key Laboratory of Environmental and Biological Analysis, Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR, China

    Fatemeh Tohidi & Zongwei Cai

Authors
  1. Fatemeh Tohidi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zongwei Cai
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Zongwei Cai.

Additional information

Responsible editor: Leif Kronberg

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(DOCX 34 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Tohidi, F., Cai, Z. GC/MS analysis of triclosan and its degradation by-products in wastewater and sludge samples from different treatments. Environ Sci Pollut Res 22, 11387–11400 (2015). https://doi.org/10.1007/s11356-015-4289-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-015-4289-x

Keywords

Search

Navigation