Figures (6)  Tables (2)
    • Figure 1. 

      Pathway of electrophilic substitution of anisole produces 2,4,6-TCA.

    • Figure 2. 

      Pathway of 2,4, 6-trichlorophenol biosynthesis catalyzed by O-methyltransferase.

    • Figure 3. 

      2,4,6-TCA originates from cork stoppers.

    • Figure 4. 

      2,4,6-TCA originates from water.

    • Figure 5. 

      2,4,6-TCA originates from others.

    • Figure 6. 

      Possible ways in which 2,4,6-TCA can contaminate wine, and recommendations for reducing the risk of 2,4,6-TCA contamination.

    • GenusSpeciesIsolated fromThe rate/ability of converting
      TCP to TCA
      Detection methodsRef.
      FungiAcremoniumStrictumSettled water3.3%−14.24%SPME-GC-MS[27]
      FungiAspergillusRaw one-piece cork stoppersIn MEA medium, 44.5%−54.9%
      On the cork, 19.9%−21.5%
      GC-ECD[20]
      FungiAspergillusNigerCork stoppersOn solid cork medium, 0.16%
      On liquid medium, 0.65%.
      HS-SPME-GC-MS[19]
      FungiAspergillusOryzaeTap water; StoppersOn solid cork medium, 0.21%;
      On liquid medium, 1.17%
      SPME-GC-MS;
      HS-SPME-GC-MS
      [19,27,28]
      FungiAspergillusVersicolorSettled water40.5%SPME-GC-MS[27]
      FungiBjerkanderaAdustaFinished water2.0 × 10−5%−0.18%SPME-GC-MS[27]
      FungiBotrytisCinereaGrapesIn MEA medium, 34.1%;
      On wood plugs, 28.4%
      GC-ECD[20]
      FungiChrysoniliaSitophilaRaw one-piece cork stoppersIn MEA medium, 64.6%;
      On wood plugs, 4.3%
      GC-ECD[20]
      FungiCladosporiumCladosporioidesFinished water7.0 × 10−2%SPME-GC-MS[27]
      FungiCladosporiumOxysporumCork stoppers14.31%HPLC[21]
      FungiCyclotellaHebeianaLakeInitially 0.2 mg/L 2,4,6-TCP; eventually 4.08 ng/L 2,4,6-TCA can be producedSPME-GC-MS[13]
      FungiFusariumAsiaticumFinished water0.28%SPME-GC-MS[27]
      FungiFusicollaMatuoiFinished water2.6%SPME-GC-MS[27]
      FungiFusariumOxysporumCork stoppers28.65%HPLC[21]
      FungiLaccariaAmethystinaRaw water;
      Settled water;
      Post filtration water; Finished water
      2.9 × 10−2%SPME-GC-MS[27]
      FungiMortierellaAlpinaCork stoppers0.11%HPLC[21]
      FungiMucorPlumbeusCork stoppers0.03%HPLC[21]
      FungiMucorRacemosusCork stoppersOn solid cork medium, 5.21%;
      On liquid medium, 5.21%
      HS- SPME-GC-MS[19]
      FungiPaecilomycesVariotiiFibreboard cartons2%−65%HPLC; GC-MS[29]
      FungiPaecilomycesViridisCork stoppers7.88%HPLC[21]
      FungiPaecilomycesCork stoppersOn solid cork medium, 3.65%;
      On liquid medium, 4.45%
      HS- SPME-GC-MS[19]
      FungiPenicilliumRaw one-piece cork stoppersIn MEA medium, 23.2-37%;
      On cork, 1.3%−53.1%
      GC-ECD[20]
      FungiPenicilliumChrysogenumCork stoppers3.29%−7.87%HS- SPME-GC-MS[19]
      FungiPenicilliumCitreonigrumCork stoppers13.28%HPLC[21]
      FungiPenicilliumDecumbensCork stoppers0.11%HPLC[21]
      FungiPenicilliumGlabrumCork stoppers2.18%−20.43%HS- SPME-GC-MS[19]
      FungiPenicilliumPurpurogenumCork stoppers11.02%HPLC[21]
      FungiPhialemoniopsisOcularisPost filtration water0.13%SPME-GC-MS[27]
      FungiPseudomonasLakeSPME-GC-MS[13]
      FungiRhizopusOryzaeBroiler house litter< 1%Gas-Liquid Chromatography[30]
      FungiScopulariopsisBrevicaulisBroiler house litter60%Gas-Liquid Chromatography[30]
      FungiSistotremaBrinkmanniiPost filtration water; Finished water2.3%SPME-GC-MS[27]
      FungiTalaromycesPinophilusFinished water2.7%SPME-GC-MS[27]
      FungiTrichodermaRaw one-piece cork stoppers; LakeIn MEA medium, 64.4%;
      On cork, 13%
      GC-ECD; SPME-GC-MS[13,20]
      FungiTrichodermaLongibrachiatumCork37.56%[31]
      FungiTrichodermaVirideCork stoppers3.37%−4.86%HS- SPME-GC-MS[19]
      FungiVerticilliumPsalliotaeCork stoppers6.9%HPLC[21]
      BacteriaAcinetobacterWater2.4 × 10−10 ug*h (cell/mL)GC-MS[32]
      BacteriaBacillusAustralimarisWaterOMPPC (1.31 × 10−9 ng/CFU)SPME-GC-ECD[33]
      BacteriaBrachybacteriumBrachybacteriumCorkHS-SPME-GC-MS[32]
      BacteriaBrachybacteriumParaconglomeratumCorkHS-SPME-GC-MS[32]
      BacteriaBradyrhizobiumFrederickiiWaterproduce 2,4,6-TCA
      (1.7 × 10−9 ng/CFU)
      SPME-GC-ECD[33]
      BacteriaBrevundimonasWaterSPME-GC-ECD[33]
      BacteriaCaulobacterWaterSPME-GC-ECD[33]
      BacteriaChromobacteriumWaterSPME-GC-ECD[33]
      BacteriaErythrobacterWaterSPME-GC-ECD[33]
      BacteriaEscherichiaColiLakeInitial 0.2 mg/L 2,4,6-TCP;
      generated 4.6 ng/L 2,4,6-TCA
      SPME-GC-MS[13]
      BacteriaFlavobacteriumCorkHS-SPME-GC-MS[32]
      BacteriaMicrobacteriumOxydansCorkHS-SPME-GC-MS[32]
      BacteriaPaenibacillusWaterSPME-GC-ECD[33]
      BacteriaPelomonasWaterSPME-GC-ECD[33]
      BacteriaRalstoniaMannitolilyticaWaterSPME-GC-ECD[33]
      BacteriaRhodoccoccusAcinetobacterLakeSPME-GC-MS[13]
      BacteriaRhodococcusWater5.5 × 10−8 ug*h (cell/mL)GC-MS[34]
      BacteriaXanthobacterWaterSPME-GC-ECD[33]
      CyanobacteriaChlorellaVulgarisLakeInitial 0.2 mg/L 2,4,6-TCP;
      generated 30.5 ng/L 2,4,6-TCA
      SPME-GC-MS[13]
      AlgaeAnabaenaFlos-aquaeLakeInitially 0.2 mg/L 2,4,6-TCP;
      generated 10.2 ng/L 2,4,6-TCA
      SPME-GC-MS[13]

      Table 1. 

      Microorganisms associated with 2,4,6-TCA production.

    • Microextraction methodologiesDetection methodologiesLODLOQAnalysis time per sampleRef.
      InstrumentSample typeAnalytesFiber typeExtraction conditionInstrumentColumn typeGC conditionMS conditionInternal standards
      HS-SPMEWined5-TCAPDMS,
      100 μm
      Incubation
      temperature: 55 °C
      Incubation time: 3 min
      Sample extraction time: 11 min
      Sample desorb time:
      4 min
      QP-2010 Plus GC-MS (Shimadzu, Kyoto, Japan)RTX-5MSGas flow 1.61 mL/min

      Oven program:
      90 °C for 0 min,
      10 °C/min to 205 °C, and then 30 °C/min to 280 °C
      SIMd5-TBA0.4 ng/L1 ng/L32 min[44]
      HS-SPMEWineTCA, TCP, 2,3,4,6-TeCA, TBA, 2,3,4,6-TeCP, 2,3,4,5-TeCA, PeCA, TBP, PeCPDVB/CAR/
      PDMS,
      50/30 µm
      Incubation
      temperature: 60 °C
      Incubation time: 5 min
      Sample extraction time: 45 min
      Sample desorb time:
      5 min
      Agilent 7890A
      GC-7000B triple quadrupole MS
      HP-5Flow rate: 1.18 mL/min

      Oven program:
      50 °C for 1 min,
      10 °C/min to 200 °C, and then 40 °C/min to 280 °C hold for 3 min
      MS/
      MS-MRM
      TCA-d5Haloanisoles:
      3 ng/L

      Halophenols:
      10 ng/L
      Haloanisoles:
      10 ng/L

      Halophenols: 30−100 ng/L
      76 min[46]
      HS-SPMEWineTCA, TeCA, TBA, PCAPDMS,
      100 μm
      Incubation
      temperature: 40 °C
      Incubation time: 5 min
      Sample extraction time: 30 min
      Sample desorb time:
      15 min
      ScionGC system (Bruker Corporation, Freemont, CA, USA) × Scion QqQ-MS/MS instrument (Bruker)VF-5msFlow rate: 1 mL/min

      Oven program:
      90 °C for 5 min,
      30 °C/min to 280 °C hold for 7 min
      SRM4-iodoanisoleTCA: 0.1 ng/L

      TeCA: 0.2 ng/L

      TBA: 0.3 ng/L

      PCA: 0.1 ng/L
      TCA: 0.4 ng/L

      TeCA: 0.6 ng/L

      TBA: 0.9 ng/L

      PCA: 0.3 ng/L
      68.33 min[47]
      HS-SPMECiderTCA, TeCA, TBA, PCAPDMS,
      100 μm
      Incubation
      temperature: 40 °C
      Incubation time: 5 min
      Sample extraction time: 30 min
      Sample desorb time:
      15 min
      ScionGC system (Bruker Corporation, Freemont, CA, USA) × Scion QqQ-MS/MS instrument (Bruker)VF-5msFlow rate: 1 mL/min

      Oven program:
      90 °C for 5 min,
      30 °C/min to 280 °C hold for 7 min
      SRM4-iodoanisoleTCA: 0.2 ng/L

      TeCA: 0.2 ng/L

      TBA: 0.3 ng/L

      PCA: 0.1 ng/L
      TCA: 0.5 ng/L

      TeCA: 0.7 ng/L
      TBA: 1.1 ng/L

      PCA: 0.5 ng/L
      68.33 min[47]
      HS-SPMECavaTCA, TeCA, TBA, PCAPDMS,
      100 μm
      Incubation
      temperature: 40 °C
      Incubation time: 5 min
      Sample extraction time: 30 min
      Sample desorb time:
      15 min
      ScionGC system (Bruker Corporation, Freemont, CA, USA) × Scion QqQ-MS/MS instrument (Bruker)VF-5msFlow rate: 1 mL/min

      Oven program:
      90 °C for 5 min,
      30 °C/min to 280 °C hold for 7 min
      SRM4-iodoanisoleTCA: 0.1 ng/L
      TeCA: 0.2 ng/L

      TBA: 0.4 ng/L

      PCA: 0.2 ng/L
      TCA: 0.4 ng/L
      TeCA: 0.6 ng/L

      TBA: 1.3 ng/L

      PCA: 0.7 ng/L
      68.33 min[47]
      HS-SPMEWaterTCA, TCPPDMS,
      100 μm
      GC-2010/parvum 2, Shimadzu, Kyoto, Japan5MS/SilFlow rate: 42 cm/s

      Oven program:
      40 °C for 3 min,
      10 °C/min to 80 °C, and then 15 °C/min to
      250 °C hold for 3 min
      SIM> 21.3 min[74]
      HS-SPMEWater2-CP, 2-BP, 2,4-DCP, 2,4,6-TCP, 2,4-DBP, 2,4,6-TBP, 2,4,6-TCA, 2,4,6-TBAPDMS/DVB,
      65 μm
      Incubation
      temperature: 60 °C
      Incubation time: 10 min
      Sample extraction time: 30 min
      Sample desorb time:
      3 min
      Agilent 7890 GC × Agilent 5975 MSHP-5MSFlow rate: 1 mL/min

      Oven program:
      40 °C for 3 min,
      15 °C/min to 235 °C hold for 1 min
      SIM4-iodoanisoleHaloanisoles: 0.23−0.29 ng/L
      Halophenols: 0.24−0.91 ng/L
      Haloanisoles: 0.97−0.77 ng/L
      Halophenols: 0.80−3.30 ng/L
      60 min[75]
      HS-SPMEGarlicTCA, TBACWR/PDMS, 120 µmIncubation
      temperature: 80 °C
      Sample extraction
      time: 20 min
      Shimadzu GC-2010 × Shimadzu TQ8050Rxi-5 msFlow rate: 35 cm/s

      Oven program:
      70 °C for 1 min,
      10 °C/min to 300 °C hold for 3 min.
      MS/MS-MRMTCA-d5TCA:
      0.02 μg/kg

      TBA:
      0.03 μg/kg
      47 min[76]
      SPMEWater2,4,6-TCA, 2,3,6-TCA, 2,3,4-TCA, 2,4,6-TBAPDMS/DVB/
      CAB,
      50/30 µm
      Incubation temperature: 70 °C
      Incubation time: 10 min
      Sample extraction time: 30 min
      Sample desorb time:
      10 min
      GC-MSHP-17MSOven program:
      45 °C for 4 min,
      10 °C/min to 240 °C hold for 1 min,
      30 °C/min to 280 °C
      hold for 4 min
      SIM2,4,6-TCA:
      0.098 ng/L
      2,3,6-TCA:
      0.127 ng/L
      2,3,4-TCA:
      0.109 ng/L
      2,4,6-TBA:
      0.086 ng/L
      79.8 min[77]
      Vacuum-assisted HSSPMEWineTCA, TeCA, PCA, TBAPDMS/DVB,
      65 μm
      Incubation
      temperature: 25 °C
      Incubation time: 10 min
      Sample extraction time: 30 min
      Sample desorb time:
      15 min
      Shimadzu GC-17 A, GC-ECDDB-5MSFlow rate: 1 mL/min

      Oven program:
      90 °C for 5 min,
      20 °C/min to 280 °C hold for 5 min
      TCA 0.16 ng/L

      TeCA 0.18 ng/L

      PCA 0.19 ng/L

      TBA 0.13 ng/L
      74.5 min[78]
      LLEWineTCA, TeCA, PCA, TBA, TCP, TeCP, PCP, TBPAgilent HP 5980 GC × ECD (Agilent Technologies, USA)CP-Sil 5CBOven program:
      40 °C for 0 min,
      3 °C/min to 160 °C, and then 5 °C/min to
      220 °C hold for 10 min
      >
      38 min
      [79]
      Pressurized liquid extractionCorkMDMP, IPMP, IBMP, TCA, TCP, TeCA, TeCP, TBA, TBP, PCAAgilent 6890 N GC × Agilent 5973 N MSDB-5Flow rate: 1 mL/min

      Oven program:
      40 °C for 10 min,
      2 °C/min to 155 °C, and then 20 °C/min to
      260 °C hold for 9 min
      SIM2,3,6-trichloroanisole0.10 ng/g> 81.75 min[80]
      DLLMEWine2-CA, 4-CA, 2-BA, 2,6-DCA, 2-CP, 4-BA, 4-CP, 2-BP, 2,4-DCA, 4-BP, 2,6-DCP, 2,4,6-TCA, 3M4CP, 2,4-DCP, 2,4,6-TCP, 2,4-DBA, 2,3,4,6-TeCA, 2,4-DBP, 2,4,6-TBA, 2,3,4,6-TeCP, 2,3,4,5-TeCA, PCA, 2,4,6-TBP, PCPAgilent 6890 N GC × Agilent 5973 MSHP-5MSFlow rate: 1 mL/min

      Oven program:
      40 °C for 5 min,
      5 °C/min to 105 °C hold for 3.5 min,
      5 °C/min to 120 °C hold for 3 min,
      10 °C/min to 145 °C,
      and then
      5 °C/min to 185 °C,
      10 °C/min to 200 °C
      hold for 0.5 min
      SIM0.006–0.05 ng/mL40 min[81]
      CorkTCA, TeCA, TBA, PCAAgilent 6890N GC × Agilent 5973 MSHP-5MSFlow rate: 1 mL/min

      Oven program:
      80 °C for 0.6 min,
      25 °C/min to 180 °C hold for 0.6 min
      25 °C/min to 210 °C
      hold for 0.8 min,
      50 °C/min to 300 °C
      hold for 1.4 min
      SIM5-Bromo-2-chloroanisoleTCA: 1.6 ng/g

      TeCA: 2.6 ng/g

      TBA: 1.7 ng/g

      PCA: 2.5 ng/g
      TCA: 5.4 ng/g

      TeCA: 8.8 ng/g

      TBA: 5.7 ng/g

      PCA: 8.5 ng/g
      > 9.6 min[82]

      Table 2. 

      Analysis methodology regarding 2,4,6-TCA.