Total sulfonamides determination in bovine milk using smartphone-based digital images

Abstract

Sulfonamides are low-cost synthetic antimicrobials that are widely used in both veterinary and human medicine to treat diseases and control and prevent infections. Long periods of exposure to sulfonamides may cause adverse effects such as heart problems, allergic reactions, and hepatic and digestive dysfunction in humans. The maximum residue limit established for the total quantity of sulfamethazine, sulfadimethoxine, and sulfathiazole in bovine milk is 100 μg L⁻¹. This study aims to employ dispersive liquid–liquid microextraction (DLLME) as a green chemistry technique for the extraction of total sulfonamides in bovine milk samples. The procedure involves the formation of an imino salt, posterior DLLME with 1-butanol, and measurement using digital images. A linear response was observed between 50 and 1000 µg L⁻¹ for total sulfonamides, described by the equation: Analytical signal = 3.02 + 0.03 C (µg L⁻¹) (R²=0.999). The coefficient of variation (n=11; 250 µg L⁻¹ total sulfonamides) and the detection limit were estimated to be 0.49% and 20 µg L⁻¹, respectively. For 0.50 mL of milk sample, 0.75 mg p-DAC, 17.30 mg SDS, 49.02 mg of trichloroacetic acid, and 0.50 mL 1-butanol were consumed. Recovery tests using the addition-recuperation method were performed, achieving 88 and 100% recovery. The results agreed with those obtained by a HPLC procedure at 95% confidence level.

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L.A. Maroubo et al. Microchemical Journal xxx (xxxx) 106657
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F:MKB<>L 7–8 EMAHN@A E>LL L>GLBMBO> MA:G <AKHF:MH@K:IAB<
M><AGBJN>L =B@BM:E F>:LNK>F>GML :ELH ?>:MNK> AB@A L>GLBMBOBMR :<AB>O
BG@ EHP =>M><MBHG EBFBML :G= AB@A K>IKH=N<B;BEBMR F:DBG@ BM IHLLB;E> MH
F>:LNK> FNEMBIE> L:FIE>L BG : LAHKM MBF>
%G MABL LMN=R P> IKHIHL> MA> :IIEB<:MBHG H? LNK?:<M:GM;:L>= (()!
:L :G :EM>KG:MBO> F>MAH= ?HK MA> >QMK:<MBHG :G= IK><HG<>GMK:MBHG H? MH
M:E LNE?HG:FB=>L BG ;HOBG> FBED L:FIE>L ;:L>= HG MA> =>M>KFBG:MBHG ;R
F>:LNK>F>GML H? =B@BM:E BF:@>L
2. Material and methods
2.1. Chemicals and solutions
0A> LHENMBHGL P>K> IK>I:K>= NLBG@ NEMK:INK> =>BHGBS>= P:M>K
)>K<D )BEEBIHK> :KFLM:=M #>KF:GR FH=>E /RG>K@R^ 3:M>K ,NKBc
<:MBHG /RLM>F :G= :G:ERMB<:E @K:=> K>:@>GML /B@F:E=KB<A /M (HNBL
)+ 1/  LMH<D LHENMBHG H? MHM:E LNE?HG:FB=>L LNE?:F>MA:SBG>/)6
LNE?:=BF>MAHQBG>/ 4 :G= LNE?:MB:SHE>/06 P:L IK>I:K>= ;R =BLLHEO
BG@  F@ H? >:<A LNE?HG:FB=> BG  F( H? NEMK:INK> =>BHGBS>= P:M>K
 a/ <F−  LHENMBHG H?  FHE (−MKB<AEHKH:<>MB< :<B= 0 P:L
IK>I:K>= BG P:M>K
0A> K>:@>GM LHENMBHG P:L IK>I:K>= ;R :==BG@  F@ H? 
=BF>MARE:FBGH<BGG:F:E=>AR=> p   FFHE (− :G=  F( H?
<HG<>GMK:M>= GBMKB< :<B= BG  F( H? =>BHGBS>= P:M>K $*+ FHE
(−
0A> LNK?:<M:GM LMH<D LHENMBHGL P>K> IK>I:K>= ;R FBQBG@ MA> ?HEEHP
BG@ K>:@>GML BG  F( H? =>BHGBS>= P:M>K LH=BNF =H=><RE LNE?:M> / /
 @ A>Q:=><REMKBF>MARE:FFHGBNF ;KHFB=> 0  @ =H=>
<REMKBF>MARE:FFHGBNF ;KHFB=>  0  @ =H=><RE=BF>MARE:F
FHGBNF ;KHFB=>    @ =BH<MRE LNE?HLN<<BG:M> LH=BNF L:EM
+0  @ :G= =><RE=BF>MARE:FFHGBH IKHI:G>LNE?HG:M> BGG>K
L:EM /  @
0A> >QMK:<MBHG LHEO>GML ;NM:GHE H<M:GHE =><:GHE 
NG=><:GHE =H=><:GHE :G= >MARE :<>M:M> P>K> >O:EN:M>= /B@F:
E=KB<A /M (HNBL )+ 1/
0A> >??><ML H? : "> ' )@ )G *: :G= 6G  F@
(− HG MA> =>M>KFBG:MBHG H? LNE?HG:FB=>L P>K> >O:EN:M>= BG INK> FBED
:G= FBED =HI>= PBMA MHM:E LNE?HG:FB=> LHENMBHGL  :G=  a@ (−
)BED L:FIE>L H? LDBFF>= L>FBLDBFF>= PAHE> 1$0 NEMK:AB@A
M>FI>K:MNK> :G= I:LM>NKBS>= FBED ?KHF L>O>K:E F:GN?:<MNK>KL P>K>
INK<A:L>= ?KHF EH<:E LNIIEB>KL BG ,BK:<B<:;: /, K:SBE ?M>K HI>GBG@
MA> L:FIE>L P>K> LMHK>= BG IE:LMB< ;HMME>L :G= ?KHS>G ?HK E:M>K NL>
2.2. Apparatus
0H =>M>KFBG> MA> ;>LM P:R H? =BLI>KLBG@ MA> >QMK:<M:GM MAKHN@AHNM
MA> L:FIE> : OHKM>Q :@BM:MHK 2HKM>Q#>GB>  /<B>GMBc< %G=NLMKB>L %G<
HA>FB: *5 1/ FH=>E /% :G NEMK:LHGB< ;:MA -NBFBL /,
K:SBE FH=>E -  :G= :G HK;BM:E LA:D>K -NBFBL /, K:SBE
FH=>E -) P>K> >O:EN:M>= ,A:L> L>I:K:MBHG P:L :<<>E>K:M>= NLBG@
: <>GMKB?N@> -NBFBL /, K:SBE FH=>E -0)
B@BM:E BF:@>L F>:LNK>F>GML P>K> I>K?HKF>= NLBG@ :G LNL 6>G
"HG> LF:KMIAHG> FH=>E 6'( PBMA :  F>@:IBQ>E <:F>K: PBMA
PAB<A IK>L>GML : K>LHENMBHG H?  g  IBQ>EL 0A> ?K>> :IIEB<:
MBHG HEHK#K:; (HHF:MBQ^ O>KLBHG   P:L NL>= MH <HGO>KM
MA> BF:@>L BGMH .# <A:GG>EL 0ABL LMN=R P:L I>K?HKF>= NMBEBSBG@ MA> #
<A:GG>E ?KHF MA> .# LRLM>F
/MRKH?H:F ;HQ  <F AB@A  <F PB=MA :G=  <F =>>I P:L
:=:IM>= MH BGL>KM MA> !II>G=HK?^ MN;>L :G= : LNIIHKM P:L NL>= MH cQ
MA> LF:KMIAHG>  <F ?KHF MA> F>:LNK>F>GM MN;> ,AHMHF>MKB< F>:
LNK>F>GML P>K> <:KKB>= HNM :M MA> <>GM>K H? MA> MN;> PBMA : K>@BHG H? BG


UNCORRECTED PROOF
L.A. Maroubo et al. Microchemical Journal xxx (xxxx) 106657
M>K>LM  (! ;:L>= E:FI PBMA  AB@A ;KB@AMG>LL (! /)   3
 2 IHP>K>= ;R : EBMABNF ;:MM>KR 'B:G /VH #HGW:EH .& K:SBE P:L
<HNIE>= MH MA> ;HMMHF H? MA> ;HQ MH D>>I MA> BEENFBG:MBHG <HGLM:GM =NK
BG@ MA> IAHMHF>MKB< F>:LNK>F>GML
2.3. Clean-up procedure
/:FIE> <E>:GNI P:L <:KKB>= HNM :<<HK=BG@ MH *:L<BF>GMH >M :E
 78 BG PAB<A  F( H?  FHE (−0 P:L :==>= MH
 F( H? FBED 0ABL P:L LA:D>G PBMA :G HK;BM:E LA:D>K ?HK  FBG :M
 KIF :G= <>GMKB?N@>= ?HK  FBG :M  KIF
2.4. Surfactant-based DLLME procedure
EBJNHML  F( H? MA> LM:G=:K= HK <E>:K LHENMBHG <HGM:BGBG@ MA>
:G:ERM> P>K> FBQ>= PBMA  F( p   FFHE (− BG $*+
 FHE (−  F( H? / /  FHE (− :G=  F( ;NM:GHE
"B@  LM>I  0A> :G:ERM> P:L OHKM>Q>= ?HK  FBG LM>I  :G= <>G
MKB?N@>= MH :<<>E>K:M> IA:L> L>I:K:MBHG ?HK  FBG :M  KIF LM>I
 0A> =B@BM:E F>:LNK>F>GML P>K> MA>G <:KKB>= HNM =BK><MER BG MA> NI
I>K IA:L> LM>I 
2.5. Reference procedure
0A> L:FIE> <E>:GNI P:L LM:KM>= BG MA> L:F> P:R :L BG BM>F  ?HE
EHP>= ;R MA> :==BMBHG H?  F( H?  FO H? 0KBMHG 4 BG
 F( H? MA> LNI>KG:M:GM ?HK <EHN= IHBGM >QMK:<MBHG 78 0A> FBQMNK>
P:L A>:M>= BG : P:M>K ;:MA :M  ] ?HK  FBG MH BG=N<> <EHN= IHBGM
<>GMKB?N@>= ?HK  FBG :M  KIF ?HK IA:L> L>I:K:MBHG :G= MA> I$ P:L
:=CNLM>= MH – BG MA> LNI>KG:M:GM IKBHK MH $,( BGC><MBHG
$B@A ,>K?HKF:G<> (BJNB= AKHF:MH@K:IAR 78 PBMA 12 =>M><MBHG
:M  GF P:L >FIEHR>= ?HK LNE?HG:FB=>L =>M><MBHG #%(!*0 FH=>E
 />KB>L 23 >M><MHK  <HENFG #%(!*0 !<EBIL> 4   <HE
NFG  FF g  FF B= g I:KMB<E> LBS>  aF P:L NL>= ?HK L>I:K:
MBHG 0A> FH;BE> IA:L> <HGLBLM>= H? :G :JN>HNL LHENMBHG H? :<>MHGBMKBE>
LHEO>GM  :G=  ?HKFB< :<B= LHEO>GM  P:L :M : dHP K:M> H?  F(
FBG #K:=B>GM >ENMBHG P:L I>K?HKF>= :L ?HEEHPL BGBMB:E <HG<>GMK:MBHG H?
  EBG>:KER BG<K>:L>= MH  BG  FBG :G= MA>G EBG>:KBMR BG<K>:L>=
MH  BG  FBG A>E= :M  ?HK  FBG K>MNKG>= MH BGBMB:E <HG=BMBHG BG
 FBG
3. Results and discussion
0A> >QMK:<MBHG :G= IK><HG<>GMK:MBHG H? LNE?HG:FB=>L BG FBED P:L
;:L>= HG MA> ?HKF:MBHG H? :G BFBG> L:EM MAKHN@A MA> <HG=>GL:MBHG K>:<
MBHG ;>MP>>G MA> IKHMHG:M>= :FBGH @KHNI H? MA> LNE?HG:FB=>L :G= MA>
<:K;HGRE @KHNI H? MA> <AKHFHIAHK> p  BG :<B= F>=BNF 78
0ABL IKH<>LL P:L :LLBLM>= ;R : LNK?:<M:GM :G= MA> IHLM>KBHK :==BMBHG H? :
=BLI>KL>K>QMK:<MBHG LHEO>GM 0ABL K>:<MBHG IKH=N<>L : IBGD BFBG> L:EM
/<AB??’L ;:L> PBMA F:QBFNF :;LHKIMBHG :M λ  GF B@BM:E F>:
LNK>F>GML P>K> >FIEHR>= NMBEBSBG@ MA> .# LRLM>F LI><B?B<:EER MA> #
<A:GG>E PAB<A K>IK>L>GML : <HFIE>F>GM:KR <HEHK
3.1. Optimization of experimental parameters
0A> <A>FB<:E :G= IARLB<:E >QI>KBF>GM:E I:K:F>M>K HIMBFBS:MBHGL
LN<A :L OHENF> :G= K>:@>GM <HG<>GMK:MBHG OHENF> H? >QMK:<M:GM LHE
O>GM :G= MA> MRI> :G= MBF> H? :@BM:MBHG :G= <>GMKB?N@:MBHG P>K> I>K
?HKF>= LH MA:M MA> AB@A>LM :G:ERMB<:E K>LIHGL>L <HNE= ;> :<AB>O>= FBGB
FBSBG@ MA> >FIEHRF>GM H? HK@:GB< LHEO>GML :G= K>=N<BG@ MA> >QI>KB
F>GM:E IKH<>=NK> LM>IL
3.1.1. Type and acid concentration
0A> IKHIHL>= F>MAH= BL ;:L>= HG MA> K>:<MBHG ;>MP>>G LNE?HG
:FB=>L :G= p  BG MA> IK>L>G<> H? :G :<B= :G= : LNK?:<M:GM PAB<A
IKH=N<>L :G BFBG> L:EM /NE?HG:FB=>L A:O> : ?K>> I:BK H? >E><MKHGL HG
MA> GBMKH@>G :MHF :G= MABL >E><MKHG I:BK <:G K>:<M PBMA :G >E><MKHG :<
<>IMHK LN<A :L p  NG=>K :<B=B< <HG=BMBHGL BG MA> FB<>EE:K F>=BNF
78 0A>K>?HK> BM BL G><>LL:KR MH HIMBFBS> MA> MRI> :G= <HG<>GMK:
MBHG H? :<B= 0ANL =B??>K>GM cG:E <HG<>GMK:MBHGL H? AR=KH<AEHKB< :G= GB
MKB< :<B=L P>K> >O:EN:M>= ?M>K M>LMBG@ <HG<>GMK:MBHGL BG MA> K:G@> H?
 MH  FHE (− MA> ;>LM :G:ERMB<:E K>LIHGL> P:L H;L>KO>= ?HK
GBMKB< :<B= :M : cG:E <HG<>GMK:MBHG H?  FHE (−?HK IKHMHG:MBHG H?
LNE?HG:FB=>L "B@ :
3.1.2. Type and surfactant concentration
GHMA>K BFIHKM:GM I:K:F>M>K MA:M P:L HIMBFBS>= BL MA> BHGB<
LMK>G@MA /:EM :==BMBHG <:G BFIKHO> MA> >QMK:<MBHG ;R =><K>:LBG@ MA> :G
:ERM> LHEN;BEBMR BG MA> :JN>HNL IA:L> :G= BG<K>:LBG@ MA> >QMK:<MBHG K:M>
?HK MA> HK@:GB< IA:L> 78
%G LHF> <:L>L LNK?:<M:GML <:G ;> NL>= :L =BLI>KLBG@ LHEO>GML ;><:NL>
H? MA>BK LHEN;BEBMR BG MA> :JN>HNL :G= HK@:GB< IA:L>L :G= MA>BK :;BEBMR MH
=><K>:L> MA> LNK?:<> M>GLBHG ;>MP>>G MA>F $HP>O>K MA>K> BL : KBLD
MA:M LHF> LNK?:<M:GM <:G ;> >QMK:<M>= ?KHF MA> :JN>HNL L:FIE> :EHG@
PBMA MA> >QMK:<MHK LHEO>GM :G= MABL IKH;E>F EBFBML MA> <AHB<> H? =>M><
MBHG LRLM>F 78 .><>GMER LMN=B>L HG (()! A:O> BGMKH=N<>= LNK?:<
M:GML :L =BLI>KL>K :@>GML %G MABL F>MAH= :G >GOBKHGF>GM:EER ?KB>G=ER
BHGB< LNK?:<M:GM P:L NL>= :L : =BLI>KL>K :@>GM BGLM>:= H? MHQB< HK@:GB<
LHEO>GM 78
%G MABL LMN=R MAK>> <:MBHGB< LNK?:<M:GML 0 0 :G= 
MPH :GBHGB< LNK?:<M:GML / / :G= +0 :G= SPBMM>KBHGB< / P>K>
BGO>LMB@:M>= ?HK MA>BK >??><M HG (()! I>K?HKF:G<> 0A> ;>LM K>LNEML
P>K> H;L>KO>= PBMA MA> :GBHGB< LNK?:<M:GML 0ABL BL ;>EB>O>= MH ;> ;>
<:NL> MA> K>:<MBHG F>=BNF <HGM:BG>= IHLBMBO> <A:K@>L ?KHF MA> IK>OB
HNLER :==>= GBMKB< :<B= FHG@ MA> :GBHGB< LNK?:<M:GML / / ?:OHK>= MA>
?HKF:MBHG H? BFBG> L:EM :G= :??HK=>= MA> AB@A>LM IK><HG<>GMK:MBHG ?:<
Fig. 1. /BFIEBc>= =B:@K:F LAHPBG@ MA> LM>IL BGOHEO>= BG (()! : HMMHFE>LL /MRKH?H:F ;HQ A>B@AM  <F PB=MA  <F =>IMA  <F ; !F>K@>G<R >QBM (!
EB@AM


UNCORRECTED PROOF
L.A. Maroubo et al. Microchemical Journal xxx (xxxx) 106657
Fig. 2. +IMBFBS:MBHG H? MA> MRI> :G= <HG<>GMK:MBHG H? MA> :<B= :G= LNK?:<M:GM : (BG> @K:IA LAHPBG@ MA> :O>K:@> K>d><M:G<> :<AB>O>= ;R =B@BM:E F>:LNK>F>GML
<A:GG>E # ?KHF MA> .# LRLM>F BG =B??>K>GM cG:E <HG<>GMK:MBHGL H? $E ○ :G= $*+● .:G@> >O:EN:M>= – FHE (− !QI>KBF>GM:E <HG=BMBHGL
 F( H?  FHE (−/ /  F( H?  FFHE (−H? p   F( H? ;NM:GHE /:FIE>  F(  a@ (−LNE?HG:FB=>L ; :K @K:IA LAHPBG@ MA> :O
>K:@> K>d><M:G<> :M =B??>K>GM cG:E / / <HG<>GMK:MBHGL .:G@> >O:EN:M>= – FFHE (− !QI>KBF>GM:E <HG=BMBHGL  F( H?  FHE (−$*+  F( H?
 FFHE (−H? p   F( H? ;NM:GHE /:FIE>  F(  a@ (−LNE?HG:FB=>L ,ARLB<:E I:K:F>M>KL ?HK ;HMA >QI>KBF>GML OHKM>Q MBF>  FBG <>GMKB?N
@:MBHG  FBG  KIF OHENF> H? <HEE><M>= >QMK:<M  F( !KKHK ;:KL <HKK>LIHG= MH MA> LM:G=:K= =>OB:MBHG G  
MHK A>G<> BM P:L L>E><M>= :L MA> HIMBF:E =BLI>KL>K :@>GM /N;L>JN>GMER
/ / P:L >O:EN:M>= :M : cG:E <HG<>GMK:MBHG H?  F( "B@ ; 0ANL
MA> / / <HG<>GMK:MBHG P:L >O:EN:M>= BG MA> K:G@> H?  MH  FFHE (−
:G= P:L ?HNG= MH =>FHGLMK:M> : ;>MM>K :G:ERMB<:E K>LIHGL> :M : cG:E
<HG<>GMK:MBHG H?  FFHE (− %M P:L :ELH H;L>KO>= MA:M :M AB@A>K <HG
<>GMK:MBHGL :?M>K >QMK:<MBHG :G= <>GMKB?N@:MBHG MA> ?HKF>= IA:L> ;>
<:F> <EHN=R 0ABL IA>GHF>GHG BL ;>EB>O>= MH ;> <:NL>= ;R :G BG<K>:L>
BG MA> LHEN;BEBMR H? / / BG MA> L:FIE> :G= ;R : =><K>:L> BG MA> LHEN;BEBMR
H? MA> >QMK:<MBG@ LHEO>GM PAB<A BGM>K?>K>= PBMA MA> ?HKF:MBHG H? MA>
BFBG> L:EM MA> FHE:K :;LHKIMBOBMR H? MA> ?HKF>= <HFIHNG= MA> K><HO
>KR H? MA> LNE?HG:FB=>L :G= <HGL>JN>GMER : =><K>:L> BG MA> >GKB<A
F>GM ?:<MHK 78
3.1.3. Extraction solvent
0H ?:<BEBM:M> BG LBMN :G:ERLBL MA> ?HEEHPBG@ EHP=>GLBMR >QMK:<MBG@
LHEO>GML P>K> >O:EN:M>= ;NM:GHE H<M:GHE =><:GHE NG=><:GHE
:G= =H=><:GHE "HK >:<A M>LM  F( H? LHEO>GM P:L NL>= 0A> K>
LNEML =>FHGLMK:M> MA:M :EMAHN@A MA> LHEO>GML M>LM>= :K> E>LL =>GL> MA:G
P:M>K PBMA <EHL> O:EN>L – @ <F−:M  ' MA> LHEO>GML
=B??>K BG MA>BK =>@K>> H? LHEN;BEBMR BG P:M>K :<<HK=BG@ MH MA> LBS> H? MA>BK
<:K;HG <A:BG ;><:NL> MA> E:K@>K MA> LHEO>GM FHE><NE> MA> FHK> GHGIH
E:K :G= BGLHEN;E> BM ;><HF>L BG :G :JN>HNL F>=BNF 3ABE> MA> HMA>K
LHEO>GML A:O> LHEN;BEBMR O:EN>L H? :IIKHQBF:M>ER – @ <F−:M
 ' ;NM:GHE A:L : LHEN;BEBMR H?  @ <F−PAB<A ?:<BEBM:M>L =BL
I>KLBHG BG MA> L:FIE> ;R L>E><MBO>ER >QMK:<MBG@ MA> =>LBK>= LI><B>L "B@

0H BFIKHO> MA> >QMK:<MBHG >?c<B>G<R :G= H;M:BG : AB@A >GKB<AF>GM
?:<MHK : L<K>>GBG@ P:L <:KKB>= HNM MH >O:EN:M> MA> OHENF> H? ;NM:GHE
0A> K:G@> ?KHF  MH  F( P:L LMN=B>= D>>IBG@ MA> cG:E HIMBFBS>=
<HG<>GMK:MBHG H? MA> K>:@>GML /BG<> MA>K> P:L GH LB@GB?B<:GM =B??>K>G<>
BG MA> F>:LNK>F>GML ?HK OHENF>L :;HO>  F( H? ;NM:GHE
3.1.4. Factorial designs
0H HIMBFBS> MA> <A>FB<:E :G= IARLB<:E >QI>KBF>GM:E I:K:F>M>KL
?:<MHKB:E =>LB@GL L<K>>GBG@L P>K> <:KKB>= HNM MH HIMBFBS> MA> FH=>L
:G= LA:DBG@ MBF>L 0ANL NEMK:LHNG= HK;BM:E LA:DBG@ :G= OHKM>Q P>K>
>O:EN:M>= :M  :G=  FBG :M AB@A IHP>K L >QI><M>= OHKM>Q LA:DBG@
IKHOB=>= ;>MM>K >QMK:<MBHG H? LNE?HG:FB=>L ?KHF FBED L:FIE>L LBG<>
MABL FH=> P:L FHK> BGM>GL> %G :==BMBHG MA>K> P>K> GH LB@GB?B<:GM =B?
?>K>G<>L ;>MP>>G  :G=  FBG 0A>K>?HK> PBMA MA> :BF H? =>O>EHIBG@ :
?:LM>K IKH<>=NK> MA> OHKM>Q FH=> P:L L>E><M>= :EHG@ PBMA : LA:DBG@
MBF> H?  FBG
/N;L>JN>GMER MPH ?:<MHKB:E =>LB@GL P>K> IKHIHL>= PBMA MAK>>
<>GMK:E :G= :QB:E IHBGML 0A> IK>L>GM>= =>LB@G BG<EN=>=  >QI>KBF>GML
Fig. 3. +IMBFBS:MBHG H? >QMK:<MBHG LHEO>GM MRI> !QI>KBF>GM:E <HG=BMBHGL LHE
O>GM OHENF>  F(  F( H?  FFHE (−p   F( H?  FHE
(−$*+  F( H?  FHE (−/ / /:FIE>  F(  a@ (−/L
OHKM>Q MBF>  FBG <>GMKB?N@:MBHG  FBG  KIF 2HENF> H? <HEE><M>=
>QMK:<M  F( !KKHK ;:KL <HKK>LIHG= MH MA> LM:G=:K= =>OB:MBHG G  
BG >:<A =>LB@G I>K?HKF>= BG : K:G=HFBS>= HK=>K MH FBGBFBS> :GR >KKHKL
0:;E>  0A> <A>FB<:E <HG=BMBHGL <HGLB=>K>= P>K> L:FIE> OHENF> x1
– F( :G= LHEO>GM x2 – F( MA> IARLB<:E <HG=B
MBHGL <HGLB=>K>= P>K> MBF> x3 – FBG :G= <>GMKB?N@> LI>>= x4
– KIF %G ;HMA <:L>L :G " M>LM P:L :IIEB>= ?HK K>@K>LLBHG
:G= K>LB=N> :G= MH >O:EN:M> MA> E:<D H? cM :G= INK> >KKHK 0A> K>LNEML
=>FHGLMK:M> MA:M MA> K:MBH ;>MP>>G MA> <:E<NE:M>= :G= M:;NE:M>= " O:E
N>L K>F:BG>=  :G= MA> E:<D H? :=CNLMF>GM P:L =>FHGLMK:MBG@
MA:M MA> IKHIHL>= FH=>E BL :<<>IM:;E> 0A> >QI>KBF>GM:E =:M: P>K> <HK
Table 1
?:<MHKB:E =>LB@GL IKHIHL>= PBMA MAK>> <>GMK:E IHBGML :G= :QB:E IHBGML
,:K:F>M>KL 2:KB:;E> (>O>EL
− −   
A>FB<:E /:FIE> F(     
/HEO>GM F(     
,ARLB<:E 0BF> FBG ′′″′″′″′
/I>>= KIF     
/:FIE> =HI>= :M  a@ (−/L


UNCORRECTED PROOF
L.A. Maroubo et al. Microchemical Journal xxx (xxxx) 106657
Fig. 4. +IMBFBS:MBHG H? >QI>KBF>GM:E I:K:F>M>KL : A>FB<:E L:FIE> OHENF> :G= >QMK:<MBHG LHEO>GM ; ,ARLB<:E <>GMKB?N@> LI>>= :G= MBF> !QI>KBF>GM:E <HG=B
MBHGL  F( H?  FFHE (−p   F( H?  FHE (−$*+  F( H?  FHE (−/ /
K>E:M>= :G= :G >FIBKB<:E K>E:MBHGLABI ;>MP>>G MA> K>LIHGL> :G= MA>
O:KB:;E>L P:L >QIK>LL>= ;R MA> ?HEEHPBG@ cMMBG@ L><HG=HK=>K IHERGH
FB:EL !J  :G=  "KHF MA> K>LNEML PBMA MA> FHLM LB@GB?B<:GM <H>?c
<B>GML BM P:L IHLLB;E> MH H;M:BG : K>LIHGL> LNK?:<> :G= MA> JN:=K:MB< K>
@K>LLBHG FH=>E ?HK MA> =:M: H;M:BG>= <:G ;> >QIK>LL>= :L


L =>FHGLMK:M>= MA> JN:=K:MB< M>KFL A:O> MA> @K>:M>LM BGdN>G<> HG
MA> >QMK:<MBHG >?c<B>G<R 0ABL BL <HGLBLM>GM PBMA K>IHKML BG MA> EBM>K:MNK>
78
"KHF MA> IK>>LM:;EBLA>= K>:<MBHG <HG=BMBHGL  F( H?
 FFHE (−p   F( H?  FHE (−$*+ :G=  F( H?
 FHE (−/ / :G= MAKHN@A LHEOBG@ MA> !JN:MBHGL  :G=  MA>
HIMBFNF >QI>KBF>GM:E <HG=BMBHGL P>K> ?HNG= MH ;>  F( H? ;HMA
L:FIE> :G= ;NM:GHE "B@ :  FBG H? OHKM>QBG@ :M AB@A LI>>= :G=
 FBG H? <>GMKB?N@:MBHG :M  KIF "B@ ;
0H ?NKMA>K K>=N<> MA> OHENF> H? MA> >QMK:<MBHG LHEO>GM MA> IKH<>
=NK> P:L I>K?HKF>= :L =>L<KB;>= BG BM>FL  :G=  :G= <HFI:K>= MH
MA> IK>OBHNLER HIMBFBS>= IKH<>=NK> :EB;K:MBHG <NKO>L P>K> H;M:BG>=
?HK >QMK:<MBHG PBMA  :G=  F( H? ;NM:GHE 0A> ;>LM EBG>:K K>
LIHGL> H;L>KO>= BG MA> K:G@> H?  :G=  a@ (−P:L IKH=N<>= PBMA
 F( H? ;NM:GHE 0A>L> K>LNEML >QAB;BM>= : L>GLBMBOBMR ?HE= AB@A>K
MA:G PBMA  F( ;NM:GHE %M BL CNLMBc>= MA:M : EHP>K OHENF> H? LHE
O>GM BG<K>:L>L MA> IK><HG<>GMK:MBHG ?:<MHK
3.2. Analytical features
 EBG>:K K>LIHGL> P:L H;L>KO>= ;>MP>>G  :G=  a@ (− :L >Q
IK>LL>= ;R MA> >JN:MBHG G:ERMB<:E LB@G:E     a@ (−
.  0A> <H>?c<B>GM H? O:KB:MBHG G    a@ (−MHM:E
LNE?HG:FB=>L :G= MA> =>M><MBHG EBFBM P>K> >LMBF:M>= MH ;>  :G=
 a@ (− K>LI><MBO>ER "HK  F( H? L:FIE>  F@ I 
 F@ / /  F@ H? 0 :G=  F( ;NM:GHE P>K> <HG
LNF>= :G= MABL K>LNEM>= BG MA> @>G>K:MBHG H?  F( H? P:LM>
3.3. Effect of concomitant species
0A> >??><M H? IHM>GMB:E BGM>K?>KBG@ LI><B>L : "> ' )@
)G *: :G= 6G HG LNE?HG:FB=> =>M>KFBG:MBHG P:L >O:EN:M>=
/HENMBHGL H?  a@ (−LNE?HG:FB=> BG FBED <HGM:BGBG@  F@ (−H?
>:<A LI><B>L P:L >FIEHR>= 0A> K>LNEML P>K> <HFI:K>= MH MAHL> H;
M:BG>= BG MA> :;L>G<> H? <HG<HFBM:GM =KN@L 0A>L> ?HK>B@G BHGL =B= GHM
<:NL> BGM>K?>K>G<> LB@G:E O:KB:MBHG   BG MA> IKHIHL>= IKH<>=NK>
3.4. Applications and validation
"HNK L:FIE>L H? ;HOBG> FBED P>K> :G:ERS>= NLBG@ MA> :==B<MBHG
K><HO>KR F>MAH= 0A> IKHIHL>= IKH<>=NK> P:L :IIEB>= MH =>M>KFBG>
MA> MHM:E LNE?HG:FB=>L BG ;HOBG> FBED :?M>K MA> L:FIE>L P>K> >GKB<A>=
PBMA  :G=  a@ (−:G= =HG> BG MKBIEB<:M>L 0A> K>LNEML :K> LAHPG BG
0:;E>  K><HO>KR O:EN>L H?  :G=  P>K> H;M:BG>= BG=B<:MBG@
MA> :;L>G<> H? F:MKBQ >??><ML :G= =>FHGLMK:MBG@ MA> :<<NK:<R H? MA> =>
O>EHI>= IKH<>=NK> 0A> IKHIHL>= IKH<>=NK> P:L MA>G :IIEB>= MH LNE?HG
:FB=>L =>M>KFBG:MBHG BG FBED :?M>K L:FIE> LIBDBG@ :G= MA> K>LNEML
0:;E>  :@K>>= PBMA MA> K>?>K>G<> IKH<>=NK> ;:L>= HG $,( 78 PBMA
:  <HGc=>G<> E>O>E
%G <HFI:KBLHG PBMA HMA>K (()! F>MAH=L ?HK MA> :G:ERLBL H? LNE?HG
:FB=>L BG FBED 0:;E>  MA> :G:ERMB<:E <A:K:<M>KBLMB<L H;M:BG>= PBMA
MA> IKHIHL>= IKH<>=NK> P>K> L:MBL?:<MHKR K>:<ABG@ K><HO>KR O:EN>L
PBMABG MA> >QI><M>= K:G@> 0A> =>M><MBHG EBFBM  a@ (−MHM:E LNE?HG
:FB=>L BL ;>EHP MA> F:QBFNF =>M><MBHG EBFBM >LM:;EBLA>= ;R MA> K>@N
E:MHKR :@>G<B>L H?  a@ (−MHM:E LNE?HG:FB=>L BG ;HOBG> FBED
Table 2
==B<MBHGK><HO>KR >QI>KBF>GM H? LNE?HG:FB=>L BG ;HOBG> FBED L:FIE>L
)BED L:FIE> /NE?HG:FB=>L a@ (−
/IBD>= "HNG= .><HO>KR  /IBD>= "HNG= .><HO>KR 
3AHE> 1$0    `     ` 
3AHE> 1$0    `     ` 
3AHE> 1$0    `     ` 
/DBFF>= 1$0    `     ` 
!QI>KBF>GM:E <HG=BMBHGL  μ( PA>R IK>OBHNLER >QMK:<M>= PBMA  F( H?
 FHE (−0  F( H?  FFHE (−p  BG  FHE (−$*+
 μ( H?  FHE (−/ /  F( H? ;NM:GHE OHKM>Q MBF>  FBG <>G
MKB?N@:MBHG  FBG  KIF /M:G=:K= =>OB:MBHG <HKK>LIHG=L MH :G:ERLBL
BG MKBIEB<:M> G  
Table 3
)>:G O:EN>L :G= >LMBF:M>L G   ?HK LNE?HG:FB=>L =>M>KFBG:MBHG BG FBED
:?M>K :==BMBHG H?  HK  a@ (−LNE?HG:FB=>L
/:FIE> /NE?HG:FB=>L a@ (−
,KHIHL>= IKH<>=NK> .>?>K>G<> IKH<>=NK> 78
  `   ` 
  `   ` 
  `   ` 
  `   ` 
  `   ` 
  `   ` 


UNCORRECTED PROOF
Table 4
G:ERMB<:E ?>:MNK>L H? LHF> FB<KH>QMK:<MBHG F>MAH=L ?HK MA> =>M>KFBG:MBHG H? LNE?HG:FB=>L BG FBED L:FIE>L
!QMK:<MBHG
0RI>
E>:GNI K>:@>GML !QMK:<MBHG=BLI>KLBO> LHEO>GM G:ERLBL K>:@>GML >M>KFBG:MBHG
F>MAH=
,KH<>=NK>
MBF> FBG
>M>KFBG:MBHG
MBF> FBG
(BG>:K K:G@>
μ@ (−
(+
a@ (−
.>?>K>G<>
(()! 0 AEHKH?HKF  F(*
 F(
"ENHK>L<:FBG> .,$,("(   – –

78
-N!A!./ )@/+*:ELH=BNF
<BMK:M>$*:+,/
 :<>MB< :<B= BG
*dNHK>L<:FBG>0KBL ;Ne>K
.,$,("(   – –

78
1%(%(
(()!
+KMAHIAHLIAHKB< :<B=*$,"7)%)87,"8
 a( 7)%)87"8 a(
*  ?HKFB< :<B= .,$,(,    – – 78
%() (()! 0 LH=BNF :<>M:M> ;Ne>K 7)%)87,"8
 a(*:EF>MA:GHE
 F(
*dNHK>L<:FBG> $,("(   – –

78
)%( (()! 0FFHGBNFAR=KHQB=> )%( IHP=>K*="> F:@G>MB< ;:K ',":JN>HNL LHENMBHG $,(12   – –

78
/NK?:<M:GM
;:L>=
(()!
0 ;NM:GHE F( p  B@BM:E
BF:@>LF>:LNK>F>GML
  –  0ABL PHKD
* :<>MHGBMKBE> (()! BLI>KLBO> (BJNB=(BJNB= )B<KH>QMK:<MBHG $,("( AB@A I>K?HKF:G<> EBJNB= <AKHF:MH@K:IAR PBMA =>M><MBHG ;R dNHK>L<>G<> %() (()! %HGB< EBJNB=;:L>= FB<KHP:O>:LLBLM>= =BL
I>KLBO> EBJNB=–EBJNB= FB<KH>QMK:<MBHG )%( (()! F:@G>MB< BHGB< EBJNB= =BLI>KLBO> EBJNB=–EBJNB= FB<KH>QMK:<MBHG p  =BF>MARE:FBGH<BGG:F:E=>AR=> ,/ IKBF:KR :G= L><HG=:KR :FBG> -N!A!./
-NB<D !:LR A>:I !??><MBO> .N@@>= /:?> .,$,("( K>O>KL>= IA:L> AB@A I>K?HKF:G<> EBJNB= <AKHF:MH@K:IAR NLBG@ : dNHK>L<>G<> =>M><MHK .,$,(,  K>O>KL>= IA:L> AB@A I>K?HKF:G<> EBJNB= <AKHF:MH@
K:IAR PBMA =>M><MBHG ;R IAHMH=BH=> :KK:R 0 MKB<AEHKH:<>MB< :<B= 1%(%( (()! 1EMK:LHNG=:LLBLM>= BHGB< EBJNB=;:L>= =BLI>KLBO> EBJNB=–EBJNB= FB<KH>QMK:<MBHG

UNCORRECTED PROOF
L.A. Maroubo et al. Microchemical Journal xxx (xxxx) 106657
0A> L:FIE> IK>I:K:MBHG LM>I H? MA> IKHIHL>= IKH<>=NK> =B??>KL ?KHF
MA> -N!A!./ F>MAH=HEH@R ;R HGER HG> LM>I MA> :==BMBHG H? : 0 LH
ENMBHG 78 0A> -N!A!./ F>MAH=HEH@R >FIEHRL L>O>K:E LM>IL LN<A :L
>QMK:<MBHG PBMA LHEO>GM :G= L:EMBG@ HNM L>I:K:MBHG E>:GNI PBMA ,/ BL
MA> FHLM E:;HKBHNL I:KM H? MA> IKH<>=NK> :G= BM BG<K>:L>L MA> <A:G<> H?
>KKHK ;>MP>>G MA> :G:ERL>L 0A> L:F> H<<NKL PBMA MA> NL> H? IKH<>=NK>L
BGOHEOBG@ BHGB< EBJNB=L PAB<A BG :==BMBHG MH L>O>K:E L:FIE> IK>I:K:
MBHG LM>IL K>JNBK> : =BENMBHG LM>I PBMA :<>MHGBMKBE> ?HK $,( :G:ERLBL
78
0A> F:BG :=O:GM:@> H? MA> IKHIHL>= IKH<>=NK> BL MA> IHLLB;BEBMR H?
>QIEHBMBG@ =B@BM:E F>:LNK>F>GML ?HK LNE?HG:FB=> JN:GMBc<:MBHG BG FBED
PBMA :<<>LLB;E> :G= EHP<HLM >JNBIF>GM LN<A :L : LF:KMIAHG> %G :==B
MBHG MH MA> LAHKM MBF> K>JNBK>= MH I>K?HKF MA> IKHIHL>= IKH<>=NK> :I
IKHQBF:M>ER  FBG <HFI:K>= MH MA> EBM>K:MNK> 78
GHMA>K :=O:GM:@> H? MA> IKHIHL>= IKH<>=NK> BL MA> <HGLB=>K:;ER
EHP K>:@>GM <HGLNFIMBHG MANL <:NLBG@ MA> P:LM> @>G>K:MBHG :G= MA>
NL> H? MHQB< HK@:GB< LHEO>GML LN<A :L * <AEHKH?HKF 78
F>MA:GHE 78 HKMAHIAHLIAHKB< :<B= :FFHGBNF A>Q:dNHKHIAHLIA:M>
:G= ?HKFB< :<B= 78 %G MABL LMN=R I>K =>M>KFBG:MBHG ?>P OHENF>L H?
K>:@>GML  F( p  BG $*+F>=BNF :G=  F( H? / / :G= >G
OBKHGF>GM:EER ?KB>G=ER HK@:GB< LHEO>GM  F( H? ;NM:GHE :K> NL>=
@>G>K:MBG@ ?>P FB<KHEBM>KL H? EHP MHQB<BMR K>LB=N> 3BMA MA> IKHIHL>=
F>MAH= <HGLNFIMBHG BL K>=N<>= ;R :IIKHQBF:M>ER  <HFI:K>= MH :
MRIB<:E -N!A!./ F>MAH= PBMA $,("( =>M><MBHG :G= BL ?HE= EHP>K
MA:G MA:M H? (()! PBMA =>KBO:MBS:MBHG ;R dNHK>L<:FBG> 78 0ANL
MA> IKHIHL>= IKH<>=NK> P:L LB@GB?B<:GMER @K>>G>K MA:G MAHL> IK>OBHNLER
K>IHKM>= :G= F:R A:O> : AB@AER ;>G>c<B:E >??><M MAKHN@A MA> K>=N<MBHG
H? ;HMA <HLM :G= P:LM> @>G>K:MBHG
4. Conclusions
0A> EBJNB=–EBJNB= =BLI>KLBO> FB<KH>QMK:<MBHG F>MAH= PBMA =B@BM:E
BF:@> =>M>KFBG:MBHG BL ?:LM >:LR >?c<B>GM L>E><MBO> :G= L>GLBMBO> ?HK
MA> =>M><MBHG H? MHM:E LNE?HG:FB=>L PBMAHNM BGM>K?>K>G<> ?KHF ?HK>B@G
BHGL :M <HG<>GMK:MBHGL :;HO> MAHL> ?HNG= BG ;HOBG> FBED L:FIE>L
%G :==BMBHG BM P:L =>FHGLMK:M>= MH ;> <A>:I>K L:?>K :G= FHK> >G
OBKHGF>GM:EER ?KB>G=ER ;><:NL> H? MA> EHP>K <HGLNFIMBHG H? MHQB<
K>:@>GML <HFI:K>= MH HMA>K F>MAH=L K>IHKM>= BG MA> EBM>K:MNK> 0A>
F>MAH= IKHO>= MH ;> LN?c<B>GMER IK><BL> :G= :<<NK:M> IKHOB=BG@ :G :M
MK:<MBO> :EM>KG:MBO> ?HK MA> =>M><MBHG H? LNE?HG:FB=> :GMB;BHMB<L BG
;HOBG> FBED
Uncited reference
78
Declaration of Competing Interest
3:G>LL: . )>E<A>KM K>IHKML cG:G<B:E LNIIHKM P:L IKHOB=>= ;R
/M:M> H? /:H ,:NEH .>L>:K<A "HNG=:MBHG
Acknowledgements
0A> :NMAHKL :<DGHPE>=@> MA> cG:G<B:E LNIIHKM ?KHF MA> K:SBEB:G
#HO>KGF>GM @>G<B>L BG<EN=BG@ MA> HHK=BG:MBHG ?HK MA> %FIKHO>F>GM
H? $B@A>K !=N<:MBHG ,>KLHGG>E  K:SBE ,!/  
 :G= /VH ,:NEH .>L>:K<A "HNG=:MBHG ",!/,  @K:GM 

References
78  )HGM:G:KH /NE?HG:FB=> EE>K@R %FFNGHE EE>K@R EBG *HKMA F  
 – AMMIL=HBHK@/
78 ) >GH;BE> ! => / *:L<BF>GMH )>MAH= O:EB=:MBHG ?HK MA> =>M>KFBG:MBHG H? MA>
:GMB;BHMB<L K>LB=N>L HQRM>MK:<R<EBG> M>MK:<R<EBG> <AEHKM>MK:<R<EBG> :G= =HQR<R<EBG>
BG FBED ;R AB@A I>K?HKF:G<> EBJNB= <AKHF:MH@K:IAR .>O K:L B>G<B:L ":KF 
 –
78 ) /MNFI? 0 0>KG>L .  3BED>G /2 .H=KB@N>L 3 :NF:GG ,HE:K =KN@
K>LB=N>L BG L>P:@> :G= G:MNK:E P:M>KL BG MA> LM:M> H? .BH => &:G>BKH K:SBE /<B 0HM:E
!GOBKHG   – AMMIL=HBHK@/
78 $, .:G@ &) .BMM>K .& "EHP>K # $>G=>KLHG ":KF:<HEH@B: MA >= !EL>OB>K
.BH => &:G>BKH 
78 !NKHI>:G HFFBLLBHG !NKHI>:G HFFNGBMR HFFBLLBHG .>@NE:MBHG !! *H
 !! E:RBG@ =HPG : HFFNGBMR IKH<>=NK> ?HK MA> >LM:;EBLAF>GM H?
F:QBFNF K>LB=N> EBFBML H? O>M>KBG:KR F>=B<BG:E IKH=N<ML BG ?HH=LMN??L H? :GBF:E
HKB@BG +?? & !NK HFFNG  – AMMIL><>NKHI:>NA>:EMALBM>L
=>?:NEMcE>LcE>L>N=K:E>QOHEK>@99K>@999>GI=? :<<>LL>=
):R  
78 *2%/ @YG<B: *:<BHG:E => 2B@BEUG<B: /:GBMTKB: .>LHENWVH . *2%/ GH 
=>  => L>M>F;KH =>  ,KH@K:F: => GTEBL> => .>LZ=NHL => )>=B<:F>GMHL
2>M>KBGTKBHL >F EBF>GMHL => +KB@>F GBF:E ,)2>M  AMMIPPPL@<
@HB:L@HO;KNIEH:=:KJNBOHLI:FO>MI=? :<<>LL>= ):R  
78 ), )BGBLMXKBH =: @KB<NEMNK: ,><NTKB: > ;:LM><BF>GMH %GLMKNWVH *HKF:MBO:
/  GH  =>  => =>S>F;KH =>  EM>K: H ,E:GH *:<BHG:E => HGMKHE> =>
.>LZ=NHL > HGM:FBG:GM>L >F ,KH=NMHL => +KB@>F GBF:E  ,*.GBF:E BTKBH
+? : 1GBVH   
78 ./%( )BGBLMXKBH =: @KB<NEMNK: ,><NTKB: > ;:LM><BF>GMH %GLMKNWVH *HKF:MBO:
GH  =>  => =>S>F;KH =>  (>BM> MBIH  E>BM> <KN K>?KB@>K:=H E>BM>
I:LM>NKBS:=H <HE>M: => E>BM> <KN K>?KB@>K:=H > MK:GLIHKM> : @K:G>E BTKBH +? :
1GBVH  
78 %/ %;:KK: &) )BK:G=: & .H=KB@N>S  *>;HM  >I>=: ):@G>MB< LHEB= IA:L>
>QMK:<MBHG ?HEEHP>= ;R AB@AI>K?HKF:G<> EBJNB= <AKHF:MH@K:IAR ?HK MA>
=>M>KFBG:MBHG H? LNEIAHG:FB=>L BG FBED L:FIE>L "HH= A>F   –
AMMIL=HBHK@C?HH=<A>F
78 ! ':K:@>HK@HN * ):GHNLB 2 /:F:GB=HN  ':;BK '# "NKMHG ":;KB< IA:L>
LHKIMBO> >QMK:<MBHG ?HK MA> ?:LM BLHE:MBHG H? LNE?HG:FB=>L K>LB=N>L ?KHF K:P FBED
?HEEHP>= ;R AB@A I>K?HKF:G<> EBJNB= <AKHF:MH@K:IAR PBMA NEMK:OBHE>M =>M><MBHG
"HH= A>F   – AMMIL=HBHK@C?HH=<A>F

78 / /N ) 6A:G@  (B $ 6A:G@ 4 HG@ $,( =>M>KFBG:MBHG H? LNE?:F>MA:SBG> BG
FBED NLBG@ LNK?:<>BFIKBGM>= LBEB<: LRGMA>LBS>= PBMA BGB?>KM>K M><AGBJN> 0:E:GM: 
  – AMMIL=HBHK@CM:E:GM:
78 3 4N / /N , &B:G@ $ 3:G@ 4 HG@ ) 6A:G@ >M>KFBG:MBHG H? LNE?HG:FB=>L
BG ;HOBG> FBED PBMA <HENFGLPBM<ABG@ AB@A I>K?HKF:G<> EBJNB= <AKHF:MH@K:IAR
NLBG@ LNK?:<> BFIKBGM>= LBEB<: PBMA AR=KHIABEB< >QM>KG:E E:R>K :L K>LMKB<M>= :<<>LL
:G= L>E><MBO> >QMK:<MBHG F:M>KB:E & AKHF:MH@K     –
AMMIL=HBHK@C<AKHF:
78 $ 5:G * /NG / (BN '$ .HP 5 /HG@ )BGB:MNKBS>= @K:IA>G>;:L>= IBI>MM> MBI
>QMK:<MBHG <HNIE>= PBMA EBJNB= <AKHF:MH@K:IAR ?HK MA> =>M>KFBG:MBHG H?
LNE?HG:FB=> K>LB=N>L BG ;HOBG> FBED "HH= A>F   – AMMIL=HB
HK@C?HH=<A>F
78  5N  $N <H:M>= LMBK ;:K LHKIMBO> >QMK:<MBHG <HF;BG>= PBMA AB@A
I>K?HKF:G<> EBJNB= <AKHF:MH@K:IAR–>E><MKHLIK:R M:G=>F F:LL LI><MKHF>MKR ?HK
MA> :G:ERLBL H? LNE?HG:FB=>L BG FBED :G= FBED IHP=>K 0:E:GM:   –
AMMIL=HBHK@CM:E:GM:
78 5 (B 4 3N 6 (B / 6AHG@ 3 3:G@  3:G@ & A>G ":;KB<:MBHG H?
H">+–@K:IA>G> G:GH<HFIHLBM> :G= BML :IIEB<:MBHG BG MA> F:@G>MB< LHEB= IA:L>
>QMK:<MBHG H? LNE?HG:FB=>L ?KHF FBED L:FIE>L 0:E:GM:   –
AMMIL=HBHK@CM:E:GM:
78 * KKHRH):GS:G:K>L ( #TFBS#K:<B: ) #:K<Z::FI:[: EM>KG:MBO> L:FIE>
MK>:MF>GML ?HK MA> =>M>KFBG:MBHG H? LNE?HG:FB=>L BG FBED ;R $,( PBMA dNHK>L<>G<>
=>M><MBHG "HH= A>F   – AMMIL=HBHK@C?HH=<A>F

78 / #:H 4 5:G@ 3 5N 6 (BN $ 6A:G@ 1EMK:LHNG=:LLBLM>= BHGB< EBJNB=BHGB<
EBJNB==BLI>KLBO> EBJNB=–EBJNB= FB<KH>QMK:<MBHG ?HK MA> =>M>KFBG:MBHG H?
LNE?HG:FB=>L BG BG?:GM ?HKFNE: FBED IHP=>K NLBG@ AB@AI>K?HKF:G<> EBJNB=
<AKHF:MH@K:IAR 0:E:GM:   – AMMIL=HBHK@CM:E:GM:

78 4 #NH  5BG & ,>G@ 4 $N %HGB< EBJNB=;:L>= LBG@E>=KHI EBJNB=IA:L>
FB<KH>QMK:<MBHG <HF;BG>= PBMA AB@AI>K?HKF:G<> EBJNB= <AKHF:MH@K:IAR ?HK MA>
=>M>KFBG:MBHG H? LNE?HG:FB=>L BG >GOBKHGF>GM:E P:M>K & />I /<B   
– AMMIL=HBHK@CLL<OCLL<
78 ) '><A:@B: 2 /:F:GB=H 0K>G=L BG FB<KH>QMK:<MBHG;:L>= F>MAH=L ?HK MA>
=>M>KFBG:MBHG H? LNE?HG:FB=>L BG FBED />I:K:MBHGL    AMMIL=HBHK@
L>I:K:MBHGL
78 3$ 0L:B 0 $N:G@ $$ A>G 53 3N && $N:G@ $5 AN:G@
>M>KFBG:MBHG H? LNE?HG:FB=>L BG LPBG> FNL<E> :?M>K L:EMBG@HNM :LLBLM>= EBJNB=
>QMK:<MBHG PBMA :<>MHGBMKBE> <HNIE>= PBMA ;:<D>QMK:<MBHG ;R : P:M>K:<>MHGBMKBE>
=B<AEHKHF>MA:G> M>KG:KR <HFIHG>GM LRLM>F IKBHK MH AB@AI>K?HKF:G<> EBJNB=
<AKHF:MH@K:IAR & AKHF:MH@K     – AMMIL=HBHK@
C<AKHF:
78 5 3>G & (B 3 6A:G@ ( A>G BLI>KLBO> EBJNB=EBJNB= FB<KH>QMK:<MBHG <HNIE>=
PBMA <:IBEE:KR >E><MKHIAHK>LBL ?HK LBFNEM:G>HNL =>M>KFBG:MBHG H? LNE?HG:FB=>L PBMA
MA> :B= H? >QI>KBF>GM:E =>LB@G !E><MKHIAHK>LBL    – AMMIL
=HBHK@>EILO>EIL
78 4 4N . /N 4 6A:H 6 (BN 5 6A:G@  (B 4 (B $ 6A:G@ 6 3:G@ %HGB< EBJNB=
;:L>= FB<KHP:O>:LLBLM>= =BLI>KLBO> EBJNB=–EBJNB= FB<KH>QMK:<MBHG :G=
=>KBO:MBS:MBHG H? LNE?HG:FB=>L BG KBO>K P:M>K AHG>R FBED :G= :GBF:E IE:LF: G:E
ABF <M:  –  – AMMIL=HBHK@C:<:
78  -NB@E>R 3 NFFBGL  HGGHEER BLI>KLBO> (BJNB=(BJNB= )B<KH>QMK:<MBHG BG
MA> G:ERLBL H? )BED :G= :BKR ,KH=N<ML  .>OB>P & A>F   –
AMMIL=HBHK@
78 ) .>S:>> 5 5:FBGB ) ":K:CB !OHENMBHG H? =BLI>KLBO> EBJNB=–EBJNB=


UNCORRECTED PROOF
L.A. Maroubo et al. Microchemical Journal xxx (xxxx) 106657
FB<KH>QMK:<MBHG F>MAH= & AKHF:MH@K     – AMMIL
=HBHK@C<AKHF:
78 2 G=KN<A %/ :EH@A ( 'H<\KHOT & f:G=K>CHOT "BO> R>:KL H? =BLI>KLBO> EBJNB=
EBJNB= FB<KH>QMK:<MBHG IIE /I><MKHL< .>O    – AMMIL=HB
HK@
78 ( 'H<\KHOT %/ :EH@A & f:G=K>CHOT 2 G=KN<A .><>GM :=O:G<>L BG =BLI>KLBO>
EBJNB=–EBJNB= FB<KH>QMK:<MBHG NLBG@ HK@:GB< LHEO>GML EB@AM>K MA:G P:M>K  K>OB>P
)B<KH<A>F &   – AMMIL=HBHK@CFB<KH<
78 6 /AB $ &B:G@ & $N 6 (B $ 6A:G@ BLI>KLBO> EBJNB=EBJNB= FB<KH>QMK:<MBHG :G=
AB@AI>K?HKF:G<> EBJNB= <AKHF:MH@K:IAB< =>M>KFBG:MBHG H? :GMAK:JNBGHG>
=>KBO:MBO>L BG ANF:G NKBG> :?M>K HK:E :=FBGBLMK:MBHG H? L:GAN:G@ M:;E>ML & (BJ
AKHF:MH@K .>E:M 0><AGHE    – AMMIL=HBHK@

78 2 'B:KHLM:FB ). .HNBGB . )HA:FF:=B:G $ (:O:L:GB ) #A:S:@AB BG:KR
/HEO>GML BLI>KLBO> (BJNB=(BJNB= )B<KH>QMK:<MBHG / (()! )>MAH= ?HK
>M>KFBG:MBHG H? 0K:F:=HE BG 1KBG> 1LBG@ $B@A,>K?HKF:G<> (BJNB=
AKHF:MH@K:IAR .1 & ,A:KF /<B    AMMIL=HBHK@

78 ( KMANK & ,:PEBLSRG /HEB= IA:L> FB<KH>QMK:<MBHG PBMA MA>KF:E =>LHKIMBHG
NLBG@ ?NL>= LBEB<: HIMB<:E c;>KL G:E A>F    – AMMIL
=HBHK@:<:
78 # +15*# & ,3(%/65* .><>GM =>O>EHIF>GML BG /,)! ?HK HGLBM> :G:ERLBL :G=
FHGBMHKBG@ 0K 0K>G=L G:E A>F    – AMMIL=HBHK@
CMK:<
78 ) .>S:>> 5 LL:=B ). )BE:GB $HLL>BGB ! @A:>> " AF:=B / >KBC:GB
>M>KFBG:MBHG H? HK@:GB< <HFIHNG=L BG P:M>K NLBG@ =BLI>KLBO> EBJNB=–EBJNB=
FB<KH>QMK:<MBHG & AKHF:MH@K   –  – AMMIL=HBHK@
C<AKHF:
78 ) /:K:CB )' HKHNC>GB .><>GM =>O>EHIF>GML BG =BLI>KLBO> EBJNB=–EBJNB=
FB<KH>QMK:<MBHG G:E BH:G:E A>F    – AMMIL=HBHK@
LS
78 ) L>GLBH.:FHL () .:O>EH,XK>S )b #HGSTE>SNK;>EH & $>KGTG=>S
HK@>L (BJNB= IA:L> FB<KH>QMK:<MBHG :IIEB<:MBHGL BG ?HH= :G:ERLBL & AKHF:MH@K
    – AMMIL=HBHK@C<AKHF:
78 2 $>KK>K:$>KK>K: ) L>GLBH.:FHL & $>KGTG=>SHK@>L )b .H=KZ@N>S
>E@:=H BLI>KLBO> EBJNB=EBJNB= FB<KH>QMK:<MBHG ?HK =>M>KFBG:MBHG H? HK@:GB<
:G:ERM>L 0K 0K>G=L G:E A>F    – AMMIL=HBHK@
CMK:<
78  *NAN  :LA>>K  /::= (BJNB=IA:L> :G= =BLI>KLBO> EBJNB=–EBJNB=
FB<KH>QMK:<MBHG M><AGBJN>L PBMA =>KBO:MBS:MBHG .><>GM :IIEB<:MBHGL BG ;BH:G:ERLBL
& AKHF:MH@K   –  – AMMIL=HBHK@C
C<AKHF;
78  /:K:?K:S5:S=B  FBKB (BJNB=IA:L> FB<KH>QMK:<MBHG 0K 0K>G=L G:E
A>F    – AMMIL=HBHK@CMK:<
78 ) KNS2>K: . (N<>G: / TK=>G:L ) 2:E<TK<>E +G>LM>I BGLRKBG@> BHGB< EBJNB=
;:L>= =BLI>KLBO> EBJNB=–EBJNB= FB<KH>QMK:<MBHG & AKHF:MH@K    
– AMMIL=HBHK@C<AKHF:
78  ':;BK ) (H<:M>EEB $ 1ENLHR .><>GM MK>G=L BG FB<KH>QMK:<MBHG M><AGBJN>L
>FIEHR>= BG :G:ERMB<:E :G= ;BH:G:ERMB<:E L:FIE> IK>I:K:MBHG />I:K:MBHGL  
  AMMIL=HBHK@L>I:K:MBHGL
78 & /H:K>L =: /BEO: NK:MH  2:K@:L )>=BG: ( 0HeHEB ! 2:L<HG<>EHL /H:K>L
):<B>E " ):NKH (:GW:L .><>GM :=O:G<>L :G= MK>G=L BG FBGB:MNKBS>= L:FIE>
IK>I:K:MBHG M><AGBJN>L & />I /<B    – AMMIL=HBHK@
CLL<
78 4$ 6:G@ -$ 3N )5 6A:G@ #$ 4B 6 3:G@ >O>EHIF>GML H? =BLI>KLBO>
EBJNB=EBJNB= FB<KH>QMK:<MBHG M><AGBJN> ABG>L> & G:E A>F   
– AMMIL=HBHK@/
78 4 $NH - (B 4 (BG 4 A>G ' B IIEB<:MBHG H? BLI>KLBO> (BJNB=(BJNB=
)B<KH>QMK:<MBHG ?HK MA> G:ERLBL H? /BQ "NG@B<B=>L BG "KNBM /:FIE>L ;R #–! 
AKHF:MH@K:IAB:  –  – AMMIL=HBHK@L

78 " .>S:>B  B=:KB , BKC:G=B ). )BE:GB $HLL>BGB 5 LL:=B >O>EHIF>GM H? :
=BLI>KLBO> EBJNB=–EBJNB= FB<KH>QMK:<MBHG F>MAH= ?HK MA> =>M>KFBG:MBHG H?
IHER<AEHKBG:M>= ;BIA>GREL BG P:M>K & $:S:K= ):M>K  –  –
AMMIL=HBHK@CCA:SF:M
78 / >KBC:GB 5 LL:=B ) G;B: ). )BE:GB $HLL>BGB ! @A:>> BLI>KLBO>
EBJNB=–EBJNB= FB<KH>QMK:<MBHG <HF;BG>= PBMA @:L <AKHF:MH@K:IARd:F>
IAHMHF>MKB< =>M><MBHG & AKHF:MH@K     – AMMIL=HBHK@
C<AKHF:
78 ) '><A:@B: 2 /:F:GB=HN  ':;BK '# "NKMHG $,( F>MAH= =>O>EHIF>GM :G=
O:EB=:MBHG ?HK MA> =>M>KFBG:MBHG H? LNE?HG:FB=>L K>LB=N>L BG FBED L:FIE>L BG K=
%)!'+"++ / HG? )>MKHE ,KHFHM $:KFHG /M:G= "HH= *NMK 
78  BM:L  ':;BK ) (H<:M>EEB 2 /:F:GB=HN "HH= L:FIE> IK>I:K:MBHG ?HK MA>
=>M>KFBG:MBHG H? LNE?HG:FB=>L ;R AB@AI>K?HKF:G<> EBJNB= <AKHF:MH@K:IAR /M:M>
H?MA>KM />I:K:MBHGL     AMMIL=HBHK@
L>I:K:MBHGL
78 ., (HI>L 2 N@NLMB " /:GMHL ! 2:K@:L . N@NLMB >O>EHIF>GM :G=
O:EB=:MBHG H? :G >?c<B>GM :G= BGGHO:MBO> F>MAH= ?HK MA> JN:GMBc<:MBHG H? FNEMB<E:LL
O>M>KBG:KR =KN@L BG FBED ;R NLBG@ (–)/)/ :G:ERLBL G:E )>MAH=L   
 AMMIL=HBHK@<:R;
78 + 'PHG 0 ,:KD IIEB<:MBHGL H? /F:KMIAHG> :F>K:L BG @KB<NEMNK>
!GOBKHGF>GM :G= "HH=  K>OB>P & BHLRLM !G@  AMMIL=HBHK@
&!
78 5 ":G & (B 5 #NH ( 4B> # 6A:G@ B@BM:E BF:@> <HEHKBF>MKR HG LF:KMIAHG> ?HK
<A>FB<:E :G:ERLBL  K>OB>P )>:LNK>F>GM    AMMIL=HBHK@
CF>:LNK>F>GM
78 # .:M>GB , :KBH " :O:EEH /F:KMIAHG>:L>= "HH= B:@GHLMB< 0><AGHEH@B>L 
.>OB>P />GLHKL    AMMIL=HBHK@L
78 )& (BF: " *:L<BF>GMH "., .H<A: ">:LB;E> IAHMHF>MKB< F>:LNK>F>GML BG
EBJNB=–EBJNB= >QMK:<MBHG ;R >QIEHBMBG@ LF:KMIAHG>;:L>= =B@BM:E BF:@>L G:E
)>MAH=L    – AMMIL=HBHK@5
78 "/ /BEO: "., .H<A:  GHO>E :IIKH:<A MH =>M><M FBED :=NEM>K:MBHG ;:L>= HG MA>
=>M>KFBG:MBHG H? IKHM>BG <HGM>GM ;R LF:KMIAHG>;:L>= =B@BM:E BF:@> <HEHKBF>MKR
"HH= HGMKHE    AMMIL=HBHK@C?HH=<HGM

78 "/ /BEO: % #HGW:EO>L "., .H<A: /F:KMIAHG>;:L>= =B@BM:E BF:@>L :L :
GHO>E :IIKH:<A MH =>M>KFBG> ?HKF:E=>AR=> :L : FBED :=NEM>K:GM "HH= HGMKHE 
  AMMIL=HBHK@C?HH=<HGM
78 )& (BF: )' /:L:DB +. ):KBGAH 0 "K>BM:L . ":KB: " .>BL ".,
.H<A: /IHM M>LM ?HK ?:LM =>M>KFBG:MBHG H? AR=KH@>G I>KHQB=> :L : FBED :=NEM>K:GM ;R
LF:KMIAHG>;:L>= =B@BM:E BF:@> <HEHKBF>MKR )B<KH<A>F &   
AMMIL=HBHK@CFB<KH<
78 )/)/" <>O>=H )& (BF: " *:L<BF>GMH "., .H<A:  @K>>G :G= <HLM
>??><MBO> IKH<>=NK> ?HK =>M>KFBG:MBHG H? :GBHGB< LNK?:<M:GML BG FBED PBMA EBJNB=
EBJNB= FB<KH>QMK:<MBHG :G= LF:KMIAHG>;:L>= IAHMHF>MKB< =>M><MBHG )B<KH<A>F &
  – AMMIL=HBHK@CFB<KH<
78 " *:L<BF>GMH ( .H<A: "., .H<A:  ?:LM :G= >GOBKHGF>GM:E ?KB>G=ER
:G:ERMB<:E IKH<>=NK> ?HK =>M>KFBG:MBHG H? F>E:FBG> BG FBED >QIEHBMBG@ dNHK>L<>G<>
JN>G<ABG@ "HH= A>F   – AMMIL=HBHK@C?HH=<A>F

78  /:>>= / $:JN> /6 -NK>LAB .>LBG ;>:= =>M><MBHG :G= LI><MKHIAHMHF>MKB<
=>M>KFBG:MBHG H? HQRIA>G;NM:SHG> PBMA I=BF>MARE:FBGH<BGG:F:E=>AR=>
IIEB<:MBHG MH ;NED =KN@ :G= =HL:@> ?HKFL 0:E:GM:    –
AMMIL=HBHK@
78 " ">KG:G=>L / /BEO: &( .NcGH $. ,>SS: ( ,>SS: /<K>>GBG@ :G=
=>M>KFBG:MBHG H? LNEIAHG:FB=> K>LB=N>L BG ;HOBG> FBED L:FIE>L NLBG@ : dHP
BGC><MBHG LRLM>F "HH= A>F   – AMMIL=HBHK@C
?HH=<A>F
78 )% (>HG@ ). "NA /  $N:G@ >RHG= =BLI>KLBO> EBJNB=–EBJNB=
FB<KH>QMK:<MBHG & AKHF:MH@K    – AMMIL=HBHK@C
<AKHF:
78 ) )HK:=B 5 5:FBGB  !LK:cEB / />B=B IIEB<:MBHG H? LNK?:<M:GM :LLBLM>=
=BLI>KLBO> EBJNB=–EBJNB= FB<KH>QMK:<MBHG ?HK L:FIE> IK>I:K:MBHG H? <AEHKHIA>GHEL BG
P:M>K L:FIE>L 0:E:GM:    – AMMIL=HBHK@C
M:E:GM:
78 ) /:K:CB $ B=@HEB BLI>KLBO> EBJNB=–EBJNB= FB<KH>QMK:<MBHG NLBG@ :
LNK?:<M:GM :L =BLI>KL>K :@>GM G:E BH:G:E A>F    –
AMMIL=HBHK@L
78 ) >A;:A:GB " *:C:c / :@A>KB )' HC=B ) /:E:KB:G  :@A>KB IIEB<:MBHG
H? LNK?:<M:GM :LLBLM>= =BLI>KLBO> EBJNB=–EBJNB= FB<KH>QMK:<MBHG :L :G >?c<B>GM L:FIE>
MK>:MF>GM M><AGBJN> ?HK IK><HG<>GMK:MBHG :G= MK:<> =>M><MBHG H? SHGBL:FB=> :G=
<:K;:F:S>IBG> BG NKBG> :G= IE:LF: L:FIE>L & AKHF:MH@K    –
AMMIL=HBHK@C<AKHF:
78 , ">KGTG=>S  #HGSTE>S )0 ,>G: ) :KKH . (HK>GSH  K:IB= NEMK:LHNG=
:LLBLM>= =BLI>KLBO> EBJNB=–EBJNB= FB<KH>QMK:<MBHG ?HEEHP>= ;R NEMK:I>K?HKF:G<>
EBJNB= <AKHF:MH@K:IAR ?HK MA> LBFNEM:G>HNL =>M>KFBG:MBHG H? L>O>G
;>GSH=B:S>IBG>L BG ANF:G IE:LF: L:FIE>L G:E ABF <M:   –
AMMIL=HBHK@C:<:
78 0 5:H ' N /BFNEM:G>HNL =>M>KFBG:MBHG H? LNE?HG:FB=>L BG FBED %GLBMN F:@G>MB<
BHGB< EBJNB= =BLI>KLBO> EBJNB=EBJNB= FB<KH>QMK:<MBHG <HNIE>= PBMA $,( "HH=
A>F    AMMIL=HBHK@C?HH=<A>F
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