2020 PFOA for REACH regulation - Waters Corporation · –1. Shall not be manufactured, or placed...

© 2020 Nihon Waters K.K 1

PFOA for REACH regulation

Waters

© 2020 Waters Corporation


REACH regulation and PFOA characteristics



Entry 68

– Perfluorooctanoic acid (PFOA)

o CAS No 335-67-1, EC No 206-397-9

– And its salts

– Any related substance (including its salts and polymers) having a linear or branched

perfluoroheptyl group with the formula C7F15- directly attached to another carbon atom,

as one of the structural elements.

– Any related substance (including its salt and polymers) having a linear or branched

perfluorooctyl group with the formula C8F17- as one of the structural elements.

– The following substances are excluded from this designation :

o C8F17-X, where X = F, Cl, Br

o C8F17-C(=O)OH, C8F17-C(=O)O-X’ or C8F17-CF2-X’ (where X’ = any group, including

salts).

ANNEX XVII to REACH

O

OHF

F

F

F

F F

F

F

F F

F

F

F

F

F

PFOA C8HF15O2

MW = 413.9737



Entry 68

– Perfluorooctanoic acid (PFOA)

– And its salts

– Any related substance with the

formula C7F15- directly attached to

another carbon atom.

– Any related substance with the

formula C8F17-

– Exclusion

o C8F17-X, where X = F, Cl, Br

o C8F17-C(=O)OH, C8F17-C(=O)O-

X’ or C8F17-CF2-X’ (where X’ =

any group, including salts).

ANNEX XVII to REACH

FF

F

F

F F

F

F

F F

F

F

F

F

F

O

O H (or salt)

FF

F FF

OO H (or salt)

FFF

FF

F

FF

F

F

Branched O

O

F

F

F

F

F

F

F

F

F F

F

F

F

F

F

F

F

H

H

H

H

H n

OH

F

F

F

F

F

F

F

F

F F

F

F

F

F

F

F

F

Telomer alcohol

F

F F

F

F

F F

F

F

F

F

F

F

F

O

O H (or salt)

F

FF

Exclusion

1 8



Conditions of restriction

– 1. Shall not be manufactured, or placed on the market as substances on their own from 4

July 2020.

– 2. Shall not, from 4 July 2020, be used in the production of, or placed on the market in :

o (a) another substance, as a constituent

o (b) a mixture ;

o (c) an article

in a concentration equal to or above 25 ppb of PFOA including its salts or 1000 ppb of

one or a combination of PFOA-related substances

ANNEX XVII to REACH




– 3. Points 1 and 2 shall apply from :

o (a) 4 July 2022 to :

• (i) equipment used to manufacture semi-conductors ;

• (ii) latex printing inks

o (b) 4 July 2023 to :

• (i) textiles for the protection of workers from risks to their health and safety ;

• (ii) membranes intended for use in medical textiles, filtration in water treatment,

production processed and effluent treatment ;

• (iii) plasma nano-coatings

o (c) 4 July 2032 to medical devices other than implantable medical devices within the

scope of Directive 93/42/EEC

ANNEX XVII to REACH




– 4. Points 1 and 2 shall not apply to any of the following :

o (a) perfluorooctane sulfonic acid and its derivatives, which are listed in Part A of Annex I to

Regulation (EC) No 850/2004

o (b) the manufacture of a substance where this occurs as an unavoidable by-product of the

manufacture of fluorochemicals with a carbon chain equal to or shorter than 6 atoms ;

o (c) a substance that is to be used, or is used as a transported isolated intermediate, provided that

the conditions in points (a) to (f) of Article 18(4) of this Regulation are met:

o (d) a substance, constituent of another substance or mixture that is to be used, or is used :

• (i) in the production of implantable medical devixes within the scope of Directive 93/42/ECC

• (ii) in photographic coatings applied to films, papers or printing plates ;

• (iii) in photo-lithography processes for semiconductors or in etching processes for compound

semiconductors ;

o (e) concentrated fire-fighting foam mixtures that were placed on the market before 4 July 2020 and

are to be used, or are used in the production of other fire-fighting foam mixtures :

ANNEX XVII to REACH




– 5. Point 2(b) shall not apply to fire-fighting foam mixtures which were :

o (a) placed on the market before 4 July 2020; or

o (b) produced in accordance with point 4(e), provided that, where they are used for

training purposes, emissions to the environment are minimized and effluents collected

are safely disposed of.

– 6. Point 2(c) shall not apply to :

o (a) articles placed on the market before 4 July 2020 ;

o (b) implantable medical devices produced in accordance with point 4(d)(i) ;

o (c) articles coated with the photographic coatings referred to in point 4(d)(ii) ;

o (d) semiconductors or compound semiconductors referred to in point 4(d)(iii) .

ANNEX XVII to REACH



PFOA in market

Use

– PFOS and its salt

o Processing agent for fluoroelastomer and fluoropolymer such as

PTFE(polytetrafluoroethylene)

– PFOA related compound

o Surfactant, Surface treatment agent for textile, paint, fire fighting foam

o Intermediates for manufacturing polymers having fluorinated side chains



Fluoropolymer & Fluororesin

Characteristics & Features

– High Heat-resistance Automotive device

– High Chemical resistance Semiconductor manufacturing equipment

– Low friction Lubricant

– Non-Tackiness Mold-releasing agent

– High Insulation Liquid crystal, Piezoelectric material

– High Weather resistance Paint, Construction materials

– Low Surface tension Surfactant

– High Water/Oil repellency Water/Oil repellency

– Low Refractive index Optical related materials



PFOA

CAS No 335-67-1

Formula C8HF15O2

Monoisotopic MW 413.9737

Melting point 55-56 C

Boiling point 189-192 C

Log P

pKa ~ 1

Solubility 3.4 g/L water

Well soluble in alcohol


O

OHF

F

F

F

F F

F

F

F F

F

F

F

F

F

High background

contaminants in environment

– From mobile phase (water)

– From PTFE(Teflon) in LC

– From air


PFOA analysis not affected by contaminants



Challenges for PFOA analysis

Positive error

– Background contaminants from sample preparation products

and LCo Contaminants source is Teflon material in equipment

– Background contaminants from aqueous mobile phase and

environmento As contaminant from water accumulates on the column during equilibration at

gradient analysis, ghost peak is always detected.

Negative error

– Adsorption to wall surface of container, vial due to reduced

solubilityo Poorly soluble in water, easily soluble in Methanol

o When methanol ratio in solution reduces, PFOA becomes insoluble and adsorb

to wall surface, especially longer carbon chain PFAs


Less Methanol

Water

Teflon

At equilibration

in column

Air LC system


Isocratic? or gradient? for high sensitivity


Isocratic (B=40%)

Blank

STD

No ghost peak but higher baseline

(contaminant elutes all the time)

Not including ghost but broad peak

Blank

STD

Low baseline but ghost peak detects

Sharp peak but including ghost peak

Gradient (B=10→90%)

Not meeting regulation limit

Not easy to

control ghost

peak in every

batch

Peak intensity depends on

how much contaminants

accumulate during

equilibration

Not need to

control ghost

peak

Sharp peak and not including ghost peak

Ideal LC condition

Low baseline and no ghost peak

Blank

STD


How to remove ghost peak at gradient


Mobile phase

SPE

(C18+Active Carbon+C18)

Pump

Injector

Analytical Column

MS/MS

Mobile phase

Pump

Isolation column

Injector

Analytical column

MS/MS

C18

C18

Active carbon


SPE before the Pump


C18

C18

Active carbon

Mobile phase

SPE

(C18+Active Carbon+C18)

Pump

Injector

Analytical Column

MS/MS

1) SPE can not be placed between

Pump and Injector due to back

pressure and leakage concerns

First injection after

attaching SPE

After several

injections

Time0.20 0.40 0.60 0.80 1.00 1.20

%

8

0.20 0.40 0.60 0.80 1.00 1.20%

20

0.20 0.40 0.60 0.80 1.00 1.20

%

21

20070824_05 1: MRM of 6 Channels ES- 313 > 268.9

117

0.230.01

0.10

0.700.620.27

0.470.30 0.94

0.880.771.201.09 1.28


122

1.020.10

0.51

0.16

0.29 0.36

0.920.710.65

0.580.81

1.10

1.19

1.28


444

0.52

0.010.32

0.180.44

0.54

0.990.830.601.06

1.22

1.26

Time0.20 0.40 0.60 0.80 1.00 1.20

%

4

0.20 0.40 0.60 0.80 1.00 1.20

%

2

0.20 0.40 0.60 0.80 1.00 1.20

%

7


273

0.99

0.590.13 0.19 0.31 0.42 0.760.710.83

1.001.28

1.171.12


1.12e3

0.83

0.020.17 0.420.23 0.760.58

0.891.09 1.17


2.42e3

0.72

0.13 0.440.380.22

0.690.49 1.060.821.17 1.28

2) Will break through after several injections(can not be rejuvenated)


Isolation column between Pump & Injector


Mobile phase

Pump

Isolation column

Injector

Analytical column

MS/MS

Mobile phase A

PFOA

background

contaminants

Isolation column

PFOA from

sample

Sample Vial

Injector

Analytical column

Mobile phase B




Mobile phase A

PFOA

background

contaminants

Isolation column

PFOA from

sample

Sample Vial

Injector

Analytical column

Mobile phase B

1ppb Trap100mm add M-Mix

Time1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60

%

0

100

1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60

%

0

100

Test009 MRM of 14 Channels ES- 213 > 168.8 (PFBA01)

1.24e4

2.60

3.293.15

3.52 3.66

Test034 1: MRM of 6 Channels ES- 213 > 168.9 (PFBA01)

8.03e3

3.34

2.81

3.67

3.76

Real time




Mobile phase A

PFOA

background

contaminants

Isolation column

PFOA from

sample

Sample Vial

Injector

Analytical column

Mobile phase B


Time1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60

%

0

100

1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60

%

0

100


1.24e4

2.60

3.293.15

3.52 3.66


8.03e3

3.34

2.81

3.67

3.76

Real time

PFOA from

sample




Mobile phase A

PFOA

background

contaminants

Isolation column

Sample Vial

Injector

Analytical column

Mobile phase B


Time1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60

%

0

100

1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60

%

0

100


1.24e4

2.60

3.293.15

3.52 3.66


8.03e3

3.34

2.81

3.67

3.76

Real timePFOA from

sample

PFOA

background

contaminants




Mobile phase A

PFOA

background

contaminants

Isolation column

Sample Vial

Injector

Analytical column

Mobile phase B


Time1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60

%

0

100

1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60

%

0

100


1.24e4

2.60

3.293.15

3.52 3.66


8.03e3

3.34

2.81

3.67

3.76

Real time

Larger system volume

→Takes longer time for equilibration

→Accumulate more contaminants

→Becomes harder to separate

separate


Isolation column size



Time1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60

%

0

100

1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60

%

0

100


1.24e4

2.60

3.293.15

3.52 3.66


8.03e3

3.34

2.81

3.67

3.76

Isolation column : 2.1mmID x 50mm 1.7um


Time1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60

%

0

100

1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60

%

0

100


1.24e4

2.60

3.293.15

3.52 3.66


8.03e3

3.34

2.81

3.67

3.76

Isolation column : 2.1mmID x 100mm 1.7um

If isolation column does not have

enough capacity to separate PFAs

and its contaminants,

or if the LC system has large system

volume,

separation of them become harder

especially for shorter carbon chain

PFAs


Sample preparation



SPE : Oasis


O

OHF

F

F

F

F F

F

F

F F

F

F

F

F

F

Hydrophobic interaction

+ Anion exchange

pKa ~1


Basic sample preparation protocol


Ultrasonication

with MeOH

Filtration with PE

filter

Concentration

under N2

Add Formic acid and

water

Load to Oasis WAX

Wash with 2%

Formic acid aq

Wash with MeOH

Elute with

NH4/MeOH(1/99)

LC/MS/MS

Oasis WAX

Hydrophobic & Weak Anion Exchange

Remove polar

basic compound

Remove compound

absorbing with

hydrophobic interaction

Sample preparation is not always necessary.

It depends on sample, how much matrix (residual monomer

oligomer etc) is in extracted solution


PFAs analytical



Sample preparation of PTFE sheet


PTFE Sheet (100 mg)Sonication

At least 30 min

Add MeOH(10 mL) Filtration

PP/PE disposable

syringe with PE filter

Concentration

1 mL by N2 gasLC-MS/MS analysis


UPLC condition


ACQUITY UPLC I-Class Xevo TQ-S micro

UPLC

Instrument: ACQUITY UPLC I-Class / 30 cm CH/C

Analytical column: BEH C18 2.1 x 50 mm, 1.7 μm

Isolation column: BEH C18 2.1 x 100 mm, 1.7 μm

Flow rate: 0.35 mL/min.

Column heater: 40 C

Mobile Phese A: 5 mmol/L Ammonium acetate aq.

Mobile Phese B: Acetonitrile

Gradient :

Time(min) %A %B Curve

0.0 99 1 -

0.5 90 10 6

8.0 5 95 6

10.0 99 1 11

Run time: 11 min


MS condition


ACQUITY UPLC I-Class Xevo TQ-S micro

MS

Instrument: Xevo TQ-S micro

Ionization mode: ESI negative

Capillary: 0.75 kV

Source Temp: 120 degree celsius

Desolvation Temp: 550 degree celsius

Cone Gas Flow: 70 L/hr.

Desolvation Gas Flow: 700 L/hr.

MRM

PFBA 213 > 169 PFNA 463 > 419

PFPeA 263 > 219 PFDA 513 > 469

PFHxA 313 > 269 PFBS 299 > 80

PFHpA 363 > 319 PFHxS 399 > 80

PFOA 413 > 369 PFOS 499 > 80


SRM chromatogram


STD Mix(100 ppt)

Time3.00 3.20 3.40 3.60 3.80 4.00 4.20 4.40 4.60 4.80 5.00 5.20 5.40 5.60 5.80 6.00 6.20 6.40 6.60 6.80

%

0

100

190626_F6 1: MRM of 1 Channel ES- BPI (PFBA)

9.73e4

PFBA PFBS PFHxS PFOS

PFPeA

PFHxA

PFHpA PFOA PFNAPFDA

Background

PFAS

Contaminant

PFAS in

Sample

Pump A

Background PFAS

Contaminant

Isolation column

Pump B

Injector

Sample

PFAS in Sample

Analytical column

Binary solvent manager

Sample manager


STD calibration


Compound name: PFOA

Correlation coefficient: r = 0.999978, r^2 = 0.999956

Calibration curve: 31.4142 * x + 11.0201

Response type: External Std, Area

Curve type: Linear, Origin: Exclude, Weighting: 1/x, Axis trans: None

Conc-0 1000 2000 3000 4000 5000

Re

sp

on

se

-0

50000

100000

150000

Compound name: PFOS

Correlation coefficient: r = 0.999584, r^2 = 0.999169

Calibration curve: 4.52485 * x + 1.18604

Response type: External Std, Area

Curve type: Linear, Origin: Exclude, Weighting: 1/x, Axis trans: None

Conc-0 1000 2000 3000 4000 5000

Re

sp

on

se

-0

5000

10000

15000

20000

PFOA

0.5 – 5000 ppt

R^2 = 1.000

PFOS

5 – 5000 ppt

R^2 = 0.999


SRM chromatogram (STD 0.5 ppt & sample)


min5.400 5.450 5.500 5.550

%

1

F7:MRM of 1 channel,ES-

412.777 > 368.849

190627_F1

STD Mix(0.5 ppt)

8.113e+002PFOA

5.43

min5.400 5.450 5.500 5.550

%

0

100

F7:MRM of 1 channel,ES-

412.777 > 368.849

190627_F14

Sample(PTFE Sheet thin)

9.784e+002PFOA

5.455.58

PFOA STD 0.5 ppt PTFE sheet sample


STD and spiked sample results


Compounds Range (ppt) R^2Concentration

(ppt, n=5)

Concentration of Spike sample

(Add 10ppt, n=5)

Yield of Spike

sample (%)

Repeatability

(%RSD, n=5)

Repeatability

(%RSD, Three days)

PFBA 5 - 5000 >0.999 ND 9.9 99 1.8 4.1

PFPeA 1 - 5000 >0.999 ND 10.9 109 2.8 1.6

PFHxA 1 - 5000 >0.999 ND 10.9 109 3.3 2.3

PFHpA 1 - 5000 >0.999 ND 10.1 101 2.2 2.5

PFOA 0.5 - 5000 >0.999 0.84 10.8 108 4.9 5.4

PFNA 1 - 5000 >0.999 ND 11.0 110 4.0 4.8

PFDA 1 - 5000 >0.999 ND 10.5 105 3.9 2.0

PFBS 1 - 5000 >0.999 ND 11.6 116 6.8 5.3

PFHxS 1 - 5000 >0.999 ND 10.1 101 4.6 1.3

PFOS 5 - 5000 >0.999 ND 9.9 99 5.3 5.1

Spiked sample : STD spiked after concentration with Nitrogen

Spiked sample concentration : 10 ppt in final solution (10 pg/100mg sample = 0.1 ppb in sample)


Conclusion


Regulatory limit of PFOA has been dramatically reduced to 25 ppb in the material

Need to pay attention for both positive and negative error during whole operation

SPE with hydrophobic interaction and anion exchange is valid for materials sample preparation

Contaminations from aqueous mobile phase, and Teflon materials in system are unavoidable– Gradient is better for sensitivity, however ghost peak always detects

– Ghost peak intensity depends on equilibration time and Teflon in system (system with low system volume and less Teflon in use is appropriate)

– Contaminants can be separated by placing isolation column between pump and injector.

– As a result of separating contaminants, data with high sensitivity and high quantitative accuracy can achieve.

System and PFS kit– ACQUITY UPLC I-Class plus / Xevo TQ-S micro

– PFC kit (PFAS standard, Isolation column, Analytical column, Oasis WAX for sample preparation)

Date post:	18-Aug-2020
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2020 PFOA for REACH regulation - Waters Corporation · –1. Shall not be manufactured, or placed...

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