Tiêu chuẩn iso 18254 1 2016

© ISO 2016 Textiles — Method for the detection and determination of alkylphenol ethoxylates (APEO) — Part 1 Method using HPLC MS Textiles — Méthode de détection et de détermination des alkylphénols ét[.]

Tex tiles — Method for the detection

Part 1:

Te xtile s — Méth de de détec tion et de déte mination de s alkylp é ols

éth x lés (APE )—

Partie 1: Méth de utilisant la CLHP- SM

Fir t edition

2 16-04-1

Refer ence n mb r

ISO 1 2 4-1:2 16(E)

COPYRIGHT PROTECTED DOCUMENT

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F reword i v

Introduction v

1 Sc ope 1

2 Principle 1

3 Re g ents 1

4 A pparatus 2

4.1 A pp r atus an auxi aries for pr ep ring the sample 2

4.2 Chromatog r aphic eq ipment 2

5 Proc ed re .2

5.1 Stan ar d pr ep ration 2

5.2 Sample pr eparation 3

5.3 A nalysis 3

6 Calculation of results 3

6.1 Dete mination of the R v lue for each cong ene of A PEO 3

6.2 Calbration curve 3

6.3 Calculation of conc ntr ation of A PEO r esult 4

7 Test rep rt 4

A nne x A (informative)Examples of chr omatog raphic meth d – L /MS 5

A nne x B (informative)Examples of chromatog raphic meth d – L /MS MS

8 Biblog raphy 10

ISO (he Int ernational Org nization for Stan ardization) is a worldwidefede ation of national s an ards

b dies (ISO membe b dies) The work of pr p ring Int ernational Stan ards is normaly car ied out

through ISO t ech ical committ ees Each membe b dy int er st ed in a subje t for w hich a t ech ical

committ ee has be n es a lshed has the right t o be r pr sent ed on that committ ee Int ernational

org nizations, g ove nmental an non-g ove nmental, in laison with ISO, also take part in the work

ISO cola orat es closely with the Int ernational Ele trot ech ical C mmis ion (IEC) on al matt ers of

ele trot ech ical s an ardization

The proc d r s used t o develo this document an those int en ed for it furthe maint enanc ar

desc ibed in the ISO/IEC Dir ctives, Part 1 In p rticular the dife ent a pro al c it eria ne ded for the

dife ent ty es of ISO document should be not ed This document was draft ed in ac ordanc with the

edit orial rules of the ISO/IEC Dir ctives, Part 2 ( e www.iso.org dir ctives)

A tt ention is drawn t o the p s ibi ity that some of the element of this document ma be the subje t of

p t ent right ISO shal not be held r sp nsible for identifying any or al such p t ent right Detais of

any p t ent right identified d ring the develo ment of the document wi be in the Introd ction an / r

on the ISO ls of p t ent de larations r c ived ( e www.iso.org p t ent )

Any trade name used in this document is information given for the convenienc of use s an does not

cons itut e an en orsement

F or an ex lanation on the meaning of ISO spe ific t erms an ex r s ions r lat ed t o conformity

as es ment, as wel as information a out ISO’ s adhe enc t o the WTO principles in the Te h ical

Bar ie s t o Trade (TBT) se the fol owing URL: F or word - Sup lementary information

ISO 1 2 4-1 was pr par d b the Euro ean Committ ee for Stan ardization (CEN) in col a oration with

ISO Te h ical C mmitt ee ISO/TC 3 , Tex ties , an Te h ical Committ ee CEN /TC 248, Tex ties a d tex tie

produc ts in ac ordanc with the Agr ement on t ech ical co pe ation betwe n ISO and CEN (V ien a

Agr ement)

ISO 1 2 4 consis s of the folowing p rt u de the g ene al title Tex ties — Meth d fr the detec tio a d

dete min tio o alkylp en l eth x lates (APE ):

— Part 1: Meth d us in HPLC-MS

The folowing p rt is un e pr paration:

— Part 2 ; Meth d us in NPLC

Alky lphenol etho y lat es (AP Os) ar high-v lue prod ct commonly used in in us rial an consume

det erg ent an cleane s, some plas ics an many in us rial a plcations Their “down the drain” uses

ma r sult in their pr senc in wast ewat er s r ams an r c iving wat er b dies Human ex osur t o

AP O can oc ur through diverse sour es such as environmental, fo d, or skin contact Conside ing their

t oxicity on several animal spe ies, minimization of ex osur t o AP O is r co niz d as imp rtant t o the

pr se v tion of h man health

Nony lphenol etho y lat es belong t o the non-ionic surfactant cat eg ory an ar of particular conc rn

The biodegradation of nony lphenol etho y lat e r leases the branched nony lphenol, w hich is diff icult t o

biodegrade Nony lphenol is a subs anc ha ing endoc ine disruptive pro e ties that can ha e se ious

efe t on aq atic an many othe org nisms F or this r ason, the r lease of nony lphenol etho y lat e

int o the environment should be a oided

Chemical prod ct containing nony lphenol an / r nony lphenol etho y lat es in conc ntrations eq al t o

or gr at er than 0,1 % ar r s rict ed within the EU for spe ific uses, among othe s, the proc s ing of

leathe an t exti es, in us rial, an ins itutional cleaning

This r s riction is p rt of the entry 46 of Annex XVI of the REACH r gulation EU 1 0 / 0 6, w hich

r pealed the forme Dir ctive 2 0 / 3 EC

The cur ent r s riction is d e t o be widened t o a ply t o t exti e prod ct that can be washed in wat er A

l mit v lue of 0,0 % (1 0p m) is ex e t ed

Tex tiles — Method for the detection and determination of

Part 1:

SAFETY PRECAUTIONS — It is the user’s responsibi ity to use safe an pro er techniques in

handl ng materials in this test method Co sult manufacturer for specific detai s such as

material safety, data she ts, and othe recommendatio s Goo laboratory practice sh uld be

folowed User sho ld comply with an national and local safety re ulatio s

This p rt of ISO 1 2 4 desc ibes analy ses that ar used t o det ect extracta le alky lphenol etho y lat es

(nony lphenol etho y lat es an octy lphenol etho y lat es) in t extie prod ct This document pro ides

a method that uses Liq id Chromat ogra h (L ) with Mas Spe trometry (MS) sy st em t o det ect an

q antify alky lphenol etho y lat es of defined etho y lat e chain length

The t extie sample is cut int o smal pie es, trans e r d t o a vial, an extract ed with methanol using

ultrasoun The extract is filt er d an not subje t ed t o any ad itional cleaning Subseq ently, the

methanol extract is analy sed b Liq id Chromat ogra hy (L )with Mas Spe trometry (MS)

During the analy sis, unles othe wise s at ed, only r ag ent of r co niz d analytical grade shal be used

NOTE OP O an NP O are availa le cur ently as t ech ical grade

3.1 Sol vents, of q alty for HPL analysis

3.2 Octylphenol ethox ylates, (Triton®

1)

X-1 0), (OP Os) CAS no 9 02-9 -1, Sig ma-A ldrich® Part

numbe T9 84 ( e Note in 3.3)

3.3 Nonylp enol ethox ylates, (IGE A L®

2)

CO-6 0), (NPEOs) CAS no 6 41 -54-4, Sig ma-A ldrich®

Part numbe 542 34 ( e Note)

NOTE T e mentioned bran names in 3.2an 3.3 are given t o improve the compara ility of the test results

amongst la orat ories Using another b t ch or another su plier could le d t o diferent results

3.4 Methanol

3.5 Ac etonitr ile (ACN)

1) Triton® is an e ample of a suitable prod ct a vaila le commercialy T is information is g iven for the con venience

of user of this document an do s not constitute an en or ement by ISO of this pr od ct

2) IGE A L® is an example of a suita le pr od ct a vaila le commer cialy T is information is g iven for the

con enience of user of this document an do s not constitute an en or ement by ISO of this pr od ct

3.6 HPL g rade water

3.7 F r mic acid, v lume fraction of 3 %

3.8 A mmo ium ac etate

3.9 10 mM ammonium ac etate, pH 3,6

3.9.1 0,7 1 g of ammonium ac tate is dis olved in 9 0 ml of wate (3.6)

3.9.2 10 ml of ACN (3.5) is ad ed an mixed wel

3.9.3 The pH isadjus ed to 3,6 with v lume fraction of 3 % formic acid an made up to the mar k with

wate (3.6) in a 1 l v lumetric flask

3.9.4 The bufer ed solution should be fitered before use

4 A pparatus

4.1 A pparatus and aux il aries for pr eparing the sample

4.1.1 Standar d laboratory eq ipment

4.1.2 A nal ytical balanc e, r esolution at 0,01 g , for tes spe imen pr ep r ation

4.1.3 A nal ytical balanc e, r esolution at 0,00 g , for standar d pr ep ration

4.1.4 Glas c ontainer w ith s rew to , 40 ml has be n fou d suita le

4.1.5 Ultrasonic water bath, to be set upat 70 °C ± 5 °C

4.1.6 Membrane fiter , with 0,45 μ m p r e siz

4.1.7 Glas vial, with septum ca (HPL vial)

4.1.8 pH meter , resolution of 0,1 pH

4.2 Chromatog raphic equipment

4.2.1 High-per formanc e Liquid C romatog raphy (L )w ith Mas Spectrometr y (MS) and Electro

Spray Ionizatio (ESI

4.2.2 Rever se phase c olumn w ith g uar d c olumn

5.1 Standard preparation

St ock solutions of a) OP O and b) NPEO ar pr par d in methanol containing 1 00 mg l OP O (3.2)

an NP O (3.3)

5.2 S mple pr eparation

Cut the t extie sample int o pie es of a pro imat ely 5 mm × 5 mm an mix them homog eneously

Pr p r a pro imat ely 1 g of the cut t extie, weigh it t o the near s 1 mg, an then plac it int o the

glas containe (extraction ves el)

Pipett e 2 ml of methanol int o the glas containe (extraction ves el)

Plac the glas containe (extraction ves el)int o an ultrasonic b th at 7 °C for (6 ± 5) min

Aft erwards, let he extract co l down t o ro m t empe atur

Fit er a out 1 ml of the extraction solution int o a HPL vial using a disp sa le syring e eq ip ed with a

membrane f ilt er

5.3 A nal ysis

The det ection an q antif ication of def ined alky lphenol etho y lat es is con uct ed using L /MS with

gradient elution an ESI mas spe tromet er

Cong ene s with 2 t o 1 etho y lat e groups shal be used for q antification

Guidel nes for suita le chromat ogra hic con itions ar given in An ex A for L /MS an in Annex B for

L /MS /MS

6 Calculation of results

6.1 Determination of the R value for e ch c ong ener ofA PEO

Calbrat e the mas fraction ( R) for each AP O cong ene an calculat e the conc ntration of each AP O

isome as folow s

A mas fraction in each APEO (n ), R (%)

A O

AOT

1 0

w he e

AO is the ar a r sp nse of each AP O cong ene ;

AOT is the t otal sum of AP O ar a r sp nses (from AP O 2 t o AP O 1 )

Ex ct conc ntration in each AP O (n ), Ex ct conc ntration (mg /l)

1 0

sd

=

×

R C

w he e

C

s d

is theconc ntration of AP O s an ard mix solution of each working solution

6.2 Cal bration curve

Calbration curves with s an ardsof a) OP O an b) NP O at 0,5 mg l, 2 mg l, an 5 mg l ar pr p r d

with at leas thr e calbration point

NOTE Concentration rang s for the calibration stan ards are subject t o chang u on the ne d of e ch

la oratory an eq ipment used

F or q antification, the calbration curve shal ha e a cor elation coeff icient gr at er than 0, 99 ( R

2

gr at er than 0, 99 )

6.3 Calculation of conc entration of A PEO result

The AP O level in the t extie sample is calculat ed ac ording t o F ormula (3)

NP Os in sample, NP Os (mg /kg)=

×













×

∑

C V

M

w he e

C

is thet otal sum of conc ntration of each NP O isome (mg l), with:

i i

∑

NP O ;

i r pr sent the etho y lat e chain length;

R

i

is the pe c ntag e of “i in a s an ard solution;

V is the extraction v lume ac ording t o 5.1;

M is the mas of the t extie spe imen, in grams;

DF is the di ution fact or

OP Os in sample, OPEOs (mg kg)=

×













×

∑

C V

M

w he e

C

is thet otal sum of conc ntration of each OP O isome (mg l), with: C R

i i

∑

i r pr sent the etho y lat e chain length;

R

i

is the pe c ntag e of “i in a s an ard solution;

V is the extraction v lume ac ording t o 5.1;

M is the mas of the t extie spe imen, in grams;

DF is the di ution fact or

If a r sult isbelow 5 mg kg, then r p rt it as“les than 5 mg kg”

7 Test repor t

The t es r p rt shal inclu e the fol owing particulars:

a) a r fe enc t o this p rt of ISO 1 2 4, i.e ISO 1 2 4-1:2 1 ;

b) thekin , origin, an designation of the spe imen (p rtial spe imen, if a plca le);

c) thedet ection method an q antif ication method, inclu ing the n mbe (e.g EO

2

t o EO

16 ) an name

(e.g NPEO an OP O) of al the targ et analyt es det ermined an of al the s andards used;

d) the r sult as sum of NP Os an sum of OP Os in mg kg;

e) any deviation from the given proc d r

A nne x A

A 1 Identification with the L C/MS method

A 1.1 Chromatog raphic c onditions for the LC/MS method

— Mo ie P ase: Ammonium ac tat e 1 mMpH3,6 / ac t onitrie (ACN)

— Gradient:

— 0 min t o 1 min 40% t o 6 % ACN

— 1 min t o 5 min 6 % t o 9 % ACN

— 5 min t o 1 min 9 % ACN

— Flow: 3 0 μl/min

— Inje tion: 5 μl

— Tempe atur column o en:40°C

— R un inje tion:Each b t ch consis s of an initial thr e-point calbration, an then a blan che k an a

Qualty C ntrol (Q C) che k for eve y 2 samples or les

A 1.2 Devic e parameter for the LC/MS method

Ex mple: Suita le p ramet ers for q adrupole mas -spe tromet er

— Polarity: Positive API-ES

— Mode: SCANmode

— Mas rang e: 1 0 amu t o 1 1 0 amu

— Fra ment or:80 V

— EMV an Thr shold: 1 0

— Dry g s t empe atur : 3 0 °C

— Nebulz r pr s ur : 2,4 b r (3 psi)

— Gas flow: 1 l/min

— Ca i lary v ltag e 30 0 V

Table A.1 — C aracteristic mas es for quantification

NPEO

cong ene s

Target mas ,

m/ z

[M + NH4 ]

OPEO

cong ene s

Targ et mas ,

m/ z

[M + NH4 ]

A 2 Rel abi ity ofthe detection method

The folowing data ha e be n o tained b cor elation s u y from De embe (2 1 ) t o Jan ary (2 1 )

pe formed b 1 la orat ories, r lat ed t o alky lphenol etho y lat es (AP O)in a blue denim fa ric, car ying

out the extraction at 40 °C

Al la orat ories g ve consist ent r sult No outle was o se ved in this ex er ise

Table A.2 — APEO co tent in a blue denim fabric

R eprod cibi ty

stan ard deviation

R limit

94

262

Based on the alg orithm A, as desc ibed in ISO 1 5 8:2 0

3)

, the r sult ar :

3) ISO 1 5 8:2 0 has b en revised by ISO 1 5 8:2 1

A nne x B

B.1 Chromatog raphic c onditions for the LC/MS/MS method

Table B.1 — C romatographic conditions

Eluent 1: Ammonium acetate 1 mMpH3,6

Eluent 2: Acetonitrile (ACN)

C lumn: Hy er il Gold (2,1× 1 0 mm)or eq ivalent ones of other man facturer

Gradient

Time pro ram

— 0 min t o 1 min 70 % ACN

— 1 min t o 5 min 9 % ACN

— 5 min t o 7 min 70 % ACN

C lumn t empe atur 40°C

Inje tion v lume: 5 µl

Det ection:

Four tan em ty e pile pole or ion trap mas detect or

SRM ( Selected R eaction Monitoring) method

Prod ct ion mas spectrum

Ionizing: ESI electro spray ionizing method an positive /ne ative ion detection

C pi lary volta e: 3 0 0V

Tempe atur of spra : 1 0 °C

Table B.2 — Characteristic mas es for q antificatio

NPEO

cong ene s

Q1

(m/ )

Q 3

(m/ )

C l ision

ene g

(e V)

OPEO

cong ene s

Q1

(m/ z)

Q 3

(m/ z)

C l ision

ene g

(e V)