Appendix C

Draft Facility Report on Emissions

October 2012 Submission

APFN

NON CBI
2010/15 PFOA Stewardship Program

Draft Facility Report on Emissions

I. CHEMICAL IDENTIFICATION

Identify the chemical for which you are submitting information:

Chemical name:___APFN

CAS number:___77623-77-9__________

II. COMPANY IDENTIFICATION

Identify the company and location of the facility submitting information:

Company name:_SOLVAY SOLEXIS, INC.______________________

Site location:____THOROFARE, NJ__________

Identify a company technical contact who can respond to inquiries about the information

submitted:

Technical contact:______VIRGINIA HUBERT_______

Phone:________________(713)525-6051__________

Address:______10 LEONARD LANE_

_______THOROFARE, NJ ________
III. ON-SITE ACTIVITIES

Calendar year for which you are reporting: Jan 1, 2011 to Dec 31, 2011

Provide the amount of chemical identified above for the reporting year at specific site:

Imported (virgin) [___]__kgs/yr

Imported (externally recycled) _[___]______kgs/yr

Manufactured __[___]________kgs/yr

Estimate the amount of subject chemical distributed off-site:

____[___]______% of manufacture/import

Provide the amount used (including any that was manufactured, imported [virgin or

externally recycled], or internally recycled) of the subject chemical for the reporting year

at specific site:

____[___]______kgs/yr

Narrative Description and Process Flow Schematic:

Provide overall material balance of the chemical being reported, showing releases

and products (kgs/year). Use the following page to provide a narrative description and

process flow schematic of on-site activities, and include information that gives an

understanding of the nature and extent of potential exposures to the subject chemical.

Attach additional pages if desired. The narrative and process flow schematic should cover

major unit operations and chemical conversions for manufacturing and on-site uses, if

applicable. The narrative should provide insight into why and how releases are caused by

the process. The schematic should show the points of release of the subject chemical in

the workplace and to the environment. In the event the subject chemical is used in many

different processes, provide information on each major process instead of each individual

process.
Narrative Description and Process Flow Schematic:

IV. SITE RELEASE AND TRANSFER INFORMATION

(For manufacturing and on-site processing/use if applicable)

In this section, estimate the total media-specific releases after on-site treatment of

the chemical from your facility. You may estimate the releases by using monitoring data

or any other method you believe appropriate. Estimates should be reported in kgs per

year for the reporting period. Enter the values as whole numbers to no more than two

significant figures. For example, if your annual releases are estimated to be 12,360 kgs,

an estimate of 12,000 kgs should be reported.

Estimate the number of days per year the release occurs. Enter a whole number

with a maximum of 2 significant figures.

Insert “NA” for release activities not associated with the chemical or “0” for

releases of less than 0.5 kgs per year.

For all releases, the source of data and/or basis for determination should be

described in detail. Suggested information about the possible sources/basis includes:

1. If the source/basis is an analytical measurement, then

• Describe the method (including analytical standards used, sampling,

sample treatment, analysis).

• Describe the uncertainties and assumptions made.

• Give the Level of Detection (LOD)/Level of Quantification (LOQ).

2. If the source/basis is a mass balance, then

• Show the mass balance calculation.

• Show that the mass balance closes.

• If the mass balance does not close, then report the fraction of total

feedstock that is not accounted for and the assumptions you made to

correct the balance. Describe the uncertainties.

3. If the source/basis is other than measurement or mass balance, then

• Describe the method used. For example, if engineering calculations are

used, give a general description and state your assumptions. Describe the

uncertainties.
Part IV (cont.)

A. ON-SITE AIR RELEASES

Estimate the total fugitive or non-point releases to air and the number of days per

year the releases occur. These releases include equipment leaks from valves, pump seals,

flanges, compressors, sampling connections, and open-ended lines; evaporative losses

from surface impoundments and spills; releases from building ventilation systems; and,

any other fugitive or non-point air emission.

In addition, estimate the total releases that occur through stacks, vents, pipes, or

other confined air streams as stack or point source releases. Include storage tank

emissions and releases from pollution control equipment.

If desired, you can provide estimates of the accuracies of your release estimates.

Estimated Total Estimated % # Days/year

Annual Releases Accuracy Release Occurs

(kgs) (Optional)

Fugitive (non-point) [___]____ _____ _ ____

Stack (point) _[___] _____ __365___

Basis for each release estimate:

(See discussion on source/basis in beginning of Section IV.)

MASS BALANCE – CALCULATED BY DIFFERENCE content in the wash water and

in the solids were measured

Comments:

(This section is available to clarify your responses. Attach additional pages if desired.)
Part IV (cont.)

B. WATER RELEASES FROM SITE N/A

Estimate the total releases of the chemical leaving the fence line of your facility

from all discharge points to all streams or water bodies. Include all discharges from

process outfalls such as pipes, open trenches, releases from on-site wastewater treatment,

and contribution from storm water runoff, if applicable. Do not include discharges to a

POTW or other off-site wastewater treatment facilities. If desired, you can provide an

estimate of the accuracy of your release estimate.

Estimated Total Estimated % # Days/year

Annual Releases Accuracy Release Occurs

(kgs) (Optional)

Water releases: [___]_____ [___]_____ _365____

Enter the names of the streams or water bodies to which the facility directly

discharges the chemical. Also, enter the NPDES permit number for the facility. If more

than one number is assigned to the facility, list each number for the appropriate discharge

quantity and receiving water identified.

Receiving Water Name(s):____________

NPDES number(s):_______________

Basis for each release estimate:

(See discussion on source/basis in beginning of Section IV.)

Comments:

(This section is available to clarify your responses. Attach additional pages if desired.)
Part IV (cont.)

C. ON-SITE LAND RELEASES N/A

Estimate the total releases of the chemical for each category of land disposal, if

applicable. Estimate only on-site releases. Do not estimate leaks from landfills separately.

This should be accounted for in your estimate of total landfill release.

Releases to land treatment/land amendment include all waste containing the

chemical that is applied or incorporated into soil on-site. Do not include waste that is

landfilled.

Surface impoundments are natural topographic depressions, man-made

excavations, or diked areas formed primarily of earthen materials designed to hold an

accumulation of the chemical.

Underground injection is the technology of placing fluids underground, in porous

formations of rocks, through wells or other similar conveyance systems.

Other releases include any amount of the chemical that is released to land other

than those listed. An example is the accidental release of the chemical from an

underground pipeline or storage tank.

Estimated Total Estimated %

Annual Releases Accuracy

(kgs) (Optional)

Landfill [___]_____ _[___]____

Land Treatment/Land Amendment _[___]___ __[___]___

Surface Impoundments _[___]____ __[___]___

Underground Injection _[___]____ _[___]____

Other (specify): _[___]____ _[___]____

Basis for each release estimate:

(See discussion on source/basis in beginning of Section IV.)
Comments:

(This section is available to clarify your responses. Attach additional pages if desired.)

Part IV (cont.)

D. OFF-SITE TRANSFERS

Estimates of off-site transfers should be similar in accuracy and precision to

previous release estimates.

Dl. Transfer to Publicly Owned Treatment Works (POTW)

Number of days/year the release occurs: _365____

Estimate the total quantity of the subject chemical, not the waste stream,

transferred to the POTW. Complete section below for each POTW to which your facility

discharges wastewater containing the chemical. Enter the POTW’s NPDES permit

number, if known.

Annual Transfer (kgs):

Estimated % Accuracy of Transfer Estimate (optional) _____

POTW Name:_GLOUCESTER COUNTY UTILITY AUTHORITY______

Street Address: _ 2 PARADISE ROAD_____________________________

City: __WEST DEPTFORD_____ County: GLOUCESTER______

State: _NJ____ Zip Code: _08066____

NPDES number: __NJ0024686_______

Basis for each release estimate:

(See discussion on source/basis in beginning of Section IV.)

The surfactant content in the wash water was measured per the attached method

PF 89/110 WAS E - Perfluorooctanoate and Higher Homologues in Wastewater

and Surface Water – Concentration on Porapack Q and Esterification

Comments: This is the method that was used in 2009 to obtain the data for the mass

balance .
D2. Transfers to other off-site locations

In this section, estimate the quantity of the subject chemical, not the waste stream,

transferred and the accuracy of the estimate for each category listed. If your facility sends

the subject chemical in waste to an off-site location where some of the chemical will be

recycled and the remainder will be treated, estimate each amount separately (i.e., waste

treatment and recycling activities).

Estimated Annual Estimated %

Transfers (kgs) accuracy

(Optional)

Incineration __[___]___ __[___]___

Wastewater Treatment

(Excluding POTW) __[___]___ [___]_____

Underground Injection _[___]____ _[___]____

Hazardous Waste (RCRA

Subtitle C) Landfill _[___]____ __[___]___

Other Landfill _[___]___ _[___]____

Recycle or Recovery _[___]____ ___[___]__

(Does not include internally recycled)

Internally Recycled _[___]____ [___]_____

Unknown or Other __[___]___ _[___]____

Basis for each release estimate:

The surfactant content in the polymer was measured per the attached method PF

89/110 GC E - Perfluorooctanoate and Higher Homologues in Algoflon Matrices

– Analysis using GC-FID

Comments:
Appendix D

Draft Facility Report on Product Content

APFN

October 2012 Submission

NONCBI
2010/15 PFOA Stewardship Program

Draft Facility Report on Product Content

I. CHEMICAL IDENTIFICATION

Identify the product (e.g fluoropolymer dispersion) for which you are submitting information:

Product name:

_____FLUOROPOLYMER_____________________________________

Product description (including concentrations of perfluoroalkyl chemicals

identified in Section IV below and year of production):

_ APFN CAS number:_77623-779______________

0

II. COMPANY IDENTIFICATION

Identify the company and location of the facility submitting information:

Company name:____SOLVAY SOLEXIS, INC_____________________

Site location:_______THOROFARE, NJ_______

Identify a company technical contact who can respond to inquiries about the information

submitted:

Technical contact:_____VIRGINIA HUBERT_______________

Phone: (713)525-6051____________________________

Address:___10 Leonard Lane, Thorofare, NJ__________________

III. PRODUCTION

Calendar year for which you are reporting: Jan 1, 2011_ to Dec 31, 2011_

Provide the amount of the product for the reporting year at each specific site:

Imported ___[___]_______kgs/yr

Manufactured [___]___kgs/yr
IV. PRODUCT CONTENT

A. CONCENTRATIONS OF RELEVANT PERFLUOROALKYL CHEMICALS

Please provide the concentrations (ppb) of various perfluoroalkyl chemicals in your product. For

chemicals for which you do not have actual data, please provide range estimates.

[ ] CAS # 77623-77-9

The following is a nonexhaustive list of chemicals that should be included:

PFOA and its salts

• Octanoic acid, pentadecafluoro- (CAS 335-67-1)

• Octanoic acid, pentadecafluoro- ammonium salt (CAS 3825-26-1)

PFOA precursors

• Octane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7, 8,8-heptadecafluoro-8-iodo- (CAS 507-63-1)

• 1-Decanol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro- (CAS 678-39-7)

• 1-Decene, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro- (CAS 21652-58-4)

• 2-Propenoic acid, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl ester (CAS

27905-45-9)

• 2-Propenoic acid, 2-methyl-, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl

ester (CAS 1996-88-9)

• 2-Decenoic acid, 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-hexadecafluoro- (CAS 70887-84-2)

• Decanoic acid, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro- (CAS 27854-31-5)

Higher homologues

• Dodecane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-pentacosafluoro-12-iodo-

(CAS 307-60-8)

• Decane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-heneicosafluoro-10-iodo- (CAS 423-62-

1)

• Nonanoic acid, heptadecafluoro- (CAS 375-95-1)

• Decanoic acid, nonadecafluoro- (CAS 335-76-2)

• 1-Decanol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro- (CAS 678-39-7)

• Decane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-10-iodo- (CAS 2043-53-0)

• Dodecane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-heneicosafluoro-12-iodo- (CAS

2043-54-1)

• 2-Propenoic acid, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl ester (CAS

4980-53-4)

• 2-Propenoic acid, 2-methyl-, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-

heneicosafluorododecyl ester (CAS 17741-60-5)
Part IV (cont.)

B. ANALYTICAL METHODS

The surfactant content in the polymer was measured per the attached method PF 89/110

POW E - Perfluorooctanoate and Higher Homologues in Polymer Bulk or Sintered –

Extraction and Esterification.

Comments:
AUSIMONT S.P.A.

Centro Ricerche e Sviluppo

Bollate

Analytical Method

PF 89/110 GC E

Perfluorooctanoate and higher homologues

in Algoflon matrices

Analysis using GC-FID

This document is composed by:

N° pages: 45

N° figures:

N° tables:

N° attachments:

Edition: 4 Date: Oct 2001

Laboratory: GC Author: Oriani

Verification: Morandi Approval: Pace

1 Scope and application

1.1 This method is for the analysis of extracts of perfluorooctanoate (APFO) and related homologues.

1.2 Applicable compounds are: perfluorooctanoate (APFO) [C7F15COO

-

], perfluorononanoate

[C8F17COO

-

], perfluorodecanoate [C9F19COO

-

], perfluoroundecanoate [C10F21COO

-

],

perfluorododecanoate [C11F23COO

-

] and higher homologues.

1.3 Matrices: Algoflon based formulations and environmental samples compatible with esterification

and GC-FID determination.

2 Summary

2.1 Analysis of APFO and homologues extracted matrices is performed by injection in a packed column,

glass, 2m long, 6mm o.d., 3mm i.d., packed with metyl-siloxane rubber SE 30 20% on Chromosorb

W AW DMCS 80-100 mesh, isothermal run at 80°C, flame ionisation (FID) detector.

3 Definitions
3.1 APFO: perfluorooctanoate.

3.2 Gaschromatograph (GC) with flame ionisation detector (FID): model 8000 top from Fisons equipped

with standard packed column injector.

3.3 Data system: Electronic integrator mod. Chromjett from Fisons or PC based acquisition system mod.

Chromcard from Fisons.

4 Safety precautions

4.1 Use caution with temperatures of GC injector and detector. When running temperatures are of about

250°C.

4.2 When handling samples or solvents wear appropriate protective gloves, eyewear, clothing and any

other protective devices mandatory in your working area.

5 Interferences

5.1 To minimise interferences when analysing samples PTFE vials and tubing should not be used for

sample storage or handling.

6 Equipment

6.1 GC FID mod. 8000 from Fisons

6.2 Electronic recording integrator mod. Chromjett from Fisons or PC running Chromcard software from

Fisons

7 Supplies and materials

7.1 GC grade Nitrogen used as carrier gas

7.2 GC grade Hydrogen used for FID

7.3 GC grade Air used for FID

7.4 Micro-syringes glass 10 μl

7.5 Centrifuge tubes glass 10ml

7.6 Vials 10ml

8 Reagents and standards

8.1 CFC 113 Fluka for IR or equivalent

8.2 Standard

Typically one method and matrix blank and one continuing calibration standard S20ppm are

prepared with each group of samples.
9 Quality control

9.1 Method and matrix blank

Analyse a method and matrix blank prior to each group of samples.

9.2 Matrix spike

Analyse a matrix spike prior to standard calibration curve.

9.3 Continuing calibration check

9.3.1 Analyse S20ppm sample first to assure the accuracy of initial calibration curve.

9.3.2 Analyse S20ppm every tenth samples.

9.3.3 If a significant change (i.e. >25%) in peak area occurs, relative to the initial calibration curve,

subsequent analysis will be invalid.

10 Calibration and standardisation

10.1 Prepare and analyse a standard calibration curve after each maintenance intervention

10.2 The r

2

value for linear regression of data should be 0.98 or greater

10.3 If curve does not meet requirements change analytical column or re-prepare calibration standards.

11 Procedures

11.1 Use a packed column, , glass, 2m long, 6mm o.d., 3mm i.d., packed with metyl-siloxane rubber SE

30 20% on Chromosorb W AW DMCS 80-100 mesh

11.2 Carrier: Nitrogen, flow rate: 40ml/min measured at room temperature connecting flow meter to

detector outlet.

11.3 Injector: standard packed at 250°C

11.4 Detector: FID at 250°C, Hydrogen flow rate: 30ml/min, Air flow rate 500ml/min

11.5 Oven temperature: isothermal at 80°C

11.6 Injection volume: liquid measured 1μl

11.7 APFO retention time: 3 minutes

12 Data analysis and calculations

Calculate actual concentration of APFO, or other applicable compounds, from calibration line using

an external standard method.

13 Method performances

Method detection limit and method quantitation limit are referred to each matrix and reported in

specific methods.
14 Pollution prevention and waste management

Samples in CFC are disposed in dedicated container.

Samples in water / methanol are disposed in dedicated container

Solid polymer residuals are disposed in dedicated container

Disposable glass vials are disposed in broken glass containers located in laboratory.

15 Records
APPROVED –COPY N°________

AUSIMONT S.P.A.

Centro Ricerche e Sviluppo

Bollate

Analytical Method

PF 89/110 POW E

Perfluorooctanoate and higher homologues

in polymer bulk or sintered

Extraction and esterification

This document is composed by:

N° pages: 45

N° figures:

N° tables:

N° attachments:

Edition: 3 Date: June 2001

Laboratory: GC Author: Oriani

Verification: Morandi Approval: Pace

16 Scope and application

16.1 This method is for the extraction of perfluorooctanoate (APFO) and related homologues from

Algoflon (PTFE) polymer bulk or sintered.

16.2 Applicable compounds are: perfluorooctanoate (APFO) [C7F15COO

-

], perfluorononanoate

[C8F17COO

-

], perfluorodecanoate [C9F19COO

-

], perfluoroundecanoate [C10F21COO

-

],

perfluorododecanoate [C11F23COO

-

] and higher homologues.

16.3 Matrices: Algoflon polymer, bulk or sintered, dry (humidity lower than 5% by weight).

17 Summary

17.1 About 500mg (1g if sintered) of Algoflon is weighed in a 10 ml vial. Add 2ml of methanol

containing 1% Sulphuric acid. Close carefully the vial with a PTFE capped septum, then allow

APFO esterification at 70°C over night. At room temperature add 1ml of CFC 113, centrifuge then

transfer 2 ml of clear solution in a 10ml vial. Wash out acidic methanol with 4ml water. Close vial
and allow phases separation at 40°C for 15 minutes. Inject 1μl of lower liquid layer. Analyse using

method PF 89/110 GC E.

18 Definitions

18.1 APFO: perfluorooctanoate.

19 Safety precautions

19.1 When handling samples or solvents and hot vials wear appropriate protective gloves, eyewear,

clothing and any other protective devices mandatory in your working area.

20 Interferences

20.1 To minimise interferences when analysing samples PTFE vials and tubing should not be used for

sample storage or handling.

21 Equipment

21.1 Centrifuge ALC CENTRIFUGETTE 4236

21.2 Shaker IKA-VIBRAX-VXR

21.3 Balance (+/- 1mg)

22 Supplies and materials

22.1 Gloves

22.2 Timer

22.3 Syringes glass 1 cc, 5 cc

22.4 Micro-syringes glass 10 μl, 250 μl,

22.5 Centrifuge tubes glass 10ml

22.6 Vials 10ml

22.7 Glass bottles nominal 100ml

22.8 Glass volumetric flasks 100ml volume

22.9 Athermic gloves

23 Reagents and standards

23.1 Concentrated sulphuric acid R.P.E. Carlo Erba or equivalent

23.2 Methanol R.S. Carlo Erba or equivalent

23.3 CFC 113 Fluka for IR or equivalent

23.4 Ammonia 30% R.P.E. Carlo Erba or equivalent

23.5 Reagent preparation
1% sulphuric acid in methanol: in a bottle of nominal 100ml (true volume 116ml) weigh 49.5g of

methanol then add slowly 0.5 g concentrated sulphuric acid.

23.6 Standard preparation

Sol.A: weigh 100mg of solid ammonium salt of perfluoro-acid, dissolve in 100ml methanol in

volumetric flask.

S200ppm: transfer 100μl of Sol.A in a 10ml vial, add 1.6ml of methanol 1% sulphuric acid and

follow the esterification procedure.

S100ppm: transfer 50μl of Sol.A in a 10ml vial, add 1.8ml of methanol 1% sulphuric acid and follow

the esterification procedure.

S50ppm: transfer 25μl of Sol.A in a 10ml vial, add 1.9ml of methanol 1% sulphuric acid and follow

the esterification procedure.

S20ppm: transfer 10μl of Sol.A in a 10ml vial, add 2ml of methanol 1% sulphuric acid and follow

the esterification procedure.

S10ppm: transfer 5μl of Sol.A in a 10ml vial, add 2ml of methanol 1% sulphuric acid and follow the

esterification procedure.

24 Quality control

24.1 Method and matrix blank

In a 10ml vial weigh 500mg of Hyflon

® MFA powder, follow esterification procedure.

Note: Hyflon polymers are free from APFO and Surflon surfactants

With each batch of samples prepare and analyse a blank as first sample.

24.2 Matrix spike

In a 10ml vial weigh 500mg of Hyflon

® MFA powder, add 5 μl of Sol.A then follow esterification

procedure.

Note: Hyflon polymers are free from APFO and Surflon surfactants.

With each complete calibration prepare a matrix spike and a blank.

As last samples after calibration inject in triplicate blank and matrix spike.

24.3 Continuing calibration check

24.3.1 With each batch of samples prepare S20ppm calibration solution.

24.3.2 Analyse S20ppm sample first to assure the accuracy of initial calibration curve.

24.3.3 Analyse S20ppm sample per group of 10 samples, followed by a blank (9.1).

24.3.4 Analyse S20ppm sample last to assure the accuracy of data.

25 Calibration and standardisation

25.1 Prepare calibration standards
25.2 Inject 1μl each at least in triplicate

25.3 Calculate concentration of APFO in dispersion from APFO concentration in solution assuming that

Sol.A contains about 1μg APFO/μl solution and Algoflon weight is 500mg. Correct concentration

only if weighed APFO differs from nominal 100mg more that + / - 10% (namely less than 90mg or

more than 110mg).

26 Procedures

26.1 Weigh about 500mg (1g if sintered) Algoflon in a 10ml vial

26.2 Record weight and label vial with sample ID

26.3 Prepare S20ppm solution and label accordingly

26.4 At room temperature, add 2ml of methanol containing 1% Sulphuric acid.

26.5 Close carefully the vial with a PTFE capped septum.

26.6 Allow APFO esterification at 70°C over night.

26.7 At room temperature add 1ml of CFC 113, centrifuge then transfer 2 ml of clear solution in a 10ml

vial.

26.8 Wash out acidic methanol with 4ml water. Close vial and allow phases separation at 40°C for 15

minutes.

26.9 Using a syringe take out the aqueous layer. Wash a second time with 4ml water. Close vial and allow

phases separation at 40°C for 15 minutes.

26.10 At room temperature, inject 1μl of lower liquid layer. Analyse using method PF 89/110 GC E.

27 Data analysis and calculations

Calculate actual concentration of APFO, or other applicable compounds, from calibration line using

an external standard method. Correct data calculated from calibration line only if the amount of

polymer used differ from 500mg by a quote higher than +/- 5% using the formula:

Conppm = Calppm * (Trueamt/500)

Where:

Conppm = Concentration in ppm of surfactant corrected for polymer weight

Calppm = Concentration in ppm of surfactant from calibration line

Trueamt = Weight in mg of polymer used

28 Method performances

Method detection limit is 4ppm APFO in Algoflon. Method quantitation limit is 10ppm.

For sintered Algoflon method detection limit is 2ppm APFO. Method quantitation limit is 6ppm.

Precision and accuracy are calculated from data of calibration line; precision is percent standard

deviation at each point, accuracy is percent ratio of average calculated amount to nominal

concentration at each point.

Recovery is percent ratio of average area of matrix spike to average area of S10ppm calibration

point.
29 Pollution prevention and waste management

Samples in CFC are disposed in dedicated container.

Samples in water / methanol are disposed in dedicated container

Solid polymer residuals are disposed in dedicated container

Disposable glass vials are disposed in broken glass containers located in laboratory.

30 Records

None
APPROVED –COPY N°________

AUSIMONT S.P.A.

Centro Ricerche e Sviluppo

Bollate

Analytical Method

PF 89/110 WAS E

Perfluorooctanoate and higher homologues

in wastewater and surface water

Concentration on Porapack Q

and esterification

This document is composed by:

N° pages: 45

N° figures:

N° tables:

N° attachments:

Edition: 3 Date: June 2001

Laboratory: GC Author: Oriani

Verification: Morandi Approval: Pace

31 Scope and application

31.1 This method is for the extraction of perfluorooctanoate (APFO) and related homologues from

wastewater and surface water.

31.2 Applicable compounds are: perfluorooctanoate (APFO) [C7F15COO

-

], perfluorononanoate

[C8F17COO

-

], perfluorodecanoate [C9F19COO

-

], perfluoroundecanoate [C10F21COO

-

],

perfluorododecanoate [C11F23COO

-

] and higher homologues.

31.3 Matrices: waste water and aqueous matrixes with APFO concentration lower than 5ppm.

32 Summary

32.1 Transfer about 70ml of acidic water in a 100ml dreschel bottle. Connect to gas dispersion side tube a

cartridge packed with about 700mg of Porapack Q 60-80 mesh. Connect the second line of dreschel

bottle to a Nitrogen supply and pressurise at about 20-50 kPa allowing a liquid flow rate through the

cartridge of about 1 ml/min. Collect effluent water in a cylinder and stop flow after collection of
about 50ml. Connect the cartridge directly to Nitrogen supply for 5 minutes to remove the most part

of water. Elutes with 6ml of ethanol in a 10ml vial. Add 0.4ml NaOH 0.1% in ethanol and allow

drying at room temperature under Nitrogen flow. Add 2ml of methanol containing 1% Sulphuric

acid. Close carefully the vial with a PTFE capped septum, then allow PFOA esterification at 70°C

over night. At room temperature add 0.5ml of CFC 113. Wash out acidic methanol with 6ml water.

Remove water layer then wash again with 3ml water. Allow phases separation at room temperature

for 15 minutes. Inject 1μl of lower liquid layer. Analyse using method PF 89/110 GC E.

33 Definitions

33.1 APFO: perfluorooctanoate.

34 Safety precautions

34.1 When handling samples or solvents and hot vials wear appropriate protective gloves, eyewear,

clothing and any other protective devices mandatory in your working area.

35 Interferences

35.1 To minimise interferences when analysing samples PTFE vials and tubing should not be used for

sample storage or handling.

36 Equipment

36.1 Balance (+/- 1mg)

37 Supplies and materials

37.1 Gloves

37.2 Timer

37.3 Syringes glass 1 cc, 5 cc

37.4 Micro-syringes glass 10 μl, 250 μl

37.5 Pasteur pipette 8x6mm diameter

37.6 Centrifuge tubes glass 10ml

37.7 Vials 10ml

37.8 Glass bottles nominal 100ml

37.9 Volumetric flasks 100ml, 500ml volume

37.10 Athermic gloves

37.11 Dreschel bottle 100ml and 500ml

37.12 Glass graduated cylinder 100ml and 500ml

38 Reagents and standards

38.1 Concentrated sulphuric acid R.P.E. Carlo Erba or equivalent

38.2 Methanol R.S. Carlo Erba or equivalent
38.3 Ethanol anhydrous R.S. Carlo Erba or equivalent

38.4 Acetone R.S. Carlo Erba or equivalent

38.5 CH2Cl2 R.S. Carlo Erba or equivalent

38.6 CFC 113 Fluka for IR or equivalent

38.7 Ammonia 30% R.P.E. Carlo Erba or equivalent

38.8 NaOH R.P.E. Carlo Erba or equivalent

38.9 Nitrogen GC grade

38.10 Porapack Q 60-80 mesh

38.11 Reagent preparation

1% sulphuric acid in methanol: in a bottle of nominal 100ml (true volume 116ml) weigh 49.5g of

methanol then add slowly 0.5 g concentrated sulphuric acid.

1% NaOH in ethanol: in a 500ml volumetric flask weigh 0.5g of NaOH then add 500ml ethanol.

38.12 Standard preparation

Sol.A: weigh 100mg of solid ammonium salt of perfluoro-acid, dissolve in 100ml methanol in

volumetric flask.

S200ppm: transfer 100μl of Sol.A in a 10ml vial, add 1.9ml of methanol 1% sulphuric acid and

follow the esterification procedure.

S100ppm: transfer 50μl of Sol.A in a 10ml vial, add 2ml of methanol 1% sulphuric acid and follow

the esterification procedure.

S50ppm: transfer 25μl of Sol.A in a 10ml vial, add 2ml of methanol 1% sulphuric acid and follow

the esterification procedure.

S20ppm: transfer 10μl of Sol.A in a 10ml vial, add 2ml of methanol 1% sulphuric acid and follow

the esterification procedure.

S10ppm: transfer 5μl of Sol.A in a 10ml vial, add 2ml of methanol 1% sulphuric acid and follow the

esterification procedure.

38.13 Cartridge preparation

Weigh about 700mg Porapack Q. Introduce a small plug of glass wool in a Pasteur pipette down to

diameter restriction. Transfer to the pipette the Porapack Q then insert a second small plug of glass

wool to keep polymer bed in place.

Wash with 15ml Acetone, 15ml Ethanol and 15ml CH2Cl2. Keep cartridge under Ethanol until use.

Before use let ethanol flowing out then wash with 10ml distilled water. Connect moist cartridge to

the sampling line.

38.14 Sample preparation

Transfer 70ml of water sample, measured in a graduated cylinder, into dreschel bottle. Add, slowly

0.3ml sulphuric acid.

38.15 Water spike preparation
Sp500- In a volumetric flask measure 100ml drinking water. Add 50μl Sol.A, shake for few minutes

then follow 8.14 Sample preparation.

Sp250- In a volumetric flask measure 100ml drinking water. Add 25μl Sol.A, shake for few minutes

then follow 8.14 Sample preparation.

Sp100- In a volumetric flask measure 100ml drinking water. Add 10μl Sol.A, shake for few minutes

then follow 8.14 Sample preparation.

Sp50- In a volumetric flask measure 100ml drinking water. Add 5μl Sol.A, shake for few minutes

then follow 8.14 Sample preparation.

39 Quality control

39.1 Method and matrix blank

Use drinking water and apply sample preparation, as in 8.14, recovery and esterification procedure.

39.2 Matrix spike

Prepare spiked samples as in 8.15 and apply recovery and esterification procedure.

39.3 Continuing calibration check

39.3.1 With each batch of samples prepare S20ppm calibration solution.

39.3.2 Analyse S20ppm sample first to assure the accuracy of initial calibration curve.

39.3.3 Analyse S20ppm sample per group of 10 samples.

39.3.4 Analyse S20ppm sample last to assure the accuracy of data.

40 Calibration and standardisation

40.1 APFO response line

40.1.1 Prepare calibration standards

40.1.2 Inject 1μl each at least in duplicate

40.1.3 Calculate concentration of APFO in solution assuming that Sol.A contains 1μg APFO/μl solution.

Correct concentration only if weighed APFO differs from nominal 100mg more that + / - 10%

(namely less than 90mg or more than 110mg).

40.2 Calibration line

40.2.1 Prepare spiked samples as in 8.15

40.2.2 Apply each the recovery procedure

40.2.3 Inject 1μl each at least in triplicate
40.2.4 Calculate concentration of APFO in water from APFO concentration in spiked samples assuming

that Sol.A contains 1μg APFO/μl solution. Correct concentration only if weighed APFO differs

from nominal 100mg more that + / - 10% (namely less than 90mg or more than 110mg).

41 Procedures

41.1 Prepare samples as in 8.14 or 8.15 for spiked samples and label flasks with sample ID.

41.2 Connect to gas dispersion side tube the cartridge prepared as in 8.13.

41.3 Connect the second line of dreschel bottle to a Nitrogen supply and pressurise at about 20-50 kPa

allowing a liquid flow rate through the cartridge of about 1 ml/min.

41.4 Collect effluent water in a cylinder and stop flow after collection of about 50ml.

41.5 Connect the cartridge directly to Nitrogen supply for 5 minutes to remove the most part of water.

41.6 Elutes with 6ml of ethanol in a 10ml vial. Add 0.4ml NaOH 1% in ethanol and allow drying at room

temperature under Nitrogen flow.

41.7 Add 2ml of methanol containing 1% Sulphuric acid. Close carefully the vial with a PTFE capped

septum, then allow PFOA esterification at 70°C over night.

41.8 At room temperature add 0.5ml of CFC 113. Wash out acidic methanol with 6ml water. Remove

water layer then wash again with 3ml water.

41.9 Allow phases separation at room temperature for 15 minutes.

41.10 At room temperature, inject 1μl of lower liquid layer. Analyse using method PF 89/110 GC E.

42 Data analysis and calculations

Calculate actual concentration of APFO, or other applicable compounds, from calibration line (10.2)

using an external standard method.

43 Method performances

Method detection limit is 50ppb APFO in water. Method quantitation limit is 100ppb in water.

Precision and accuracy are calculated from data of calibration line; precision is percent standard

deviation at each point, accuracy is percent ratio of average calculated amount to nominal

concentration at each point.

Recovery at each point is percent ratio of average area of calibration line to average area of APFO

response line calculated at same nominal concentration.

44 Pollution prevention and waste management

Samples in CFC are disposed in dedicated container.

Samples in water / methanol are disposed in dedicated container

Solvents are disposed in dedicated container

Disposable glass vials are disposed in broken glass containers located in laboratory.

45 Records
None
AUSIMONT S.P.A.

Centro Ricerche e Sviluppo

Bollate

Analytical Method

PF 89/110 GC E

Perfluorooctanoate and higher homologues

in Algoflon matrices

Analysis using GC-FID

This document is composed by:

N° pages: 45

N° figures:

N° tables:

N° attachments:

Edition: 4 Date: Oct 2001

Laboratory: GC Author: Oriani

Verification: Morandi Approval: Pace

46 Scope and application

46.1 This method is for the analysis of extracts of perfluorooctanoate (APFO) and related homologues.

46.2 Applicable compounds are: perfluorooctanoate (APFO) [C7F15COO

-

], perfluorononanoate

[C8F17COO

-

], perfluorodecanoate [C9F19COO

-

], perfluoroundecanoate [C10F21COO

-

],

perfluorododecanoate [C11F23COO

-

] and higher homologues.

46.3 Matrices: Algoflon based formulations and environmental samples compatible with esterification

and GC-FID determination.

47 Summary

47.1 Analysis of APFO and homologues extracted matrices is performed by injection in a packed column,

glass, 2m long, 6mm o.d., 3mm i.d., packed with metyl-siloxane rubber SE 30 20% on Chromosorb

W AW DMCS 80-100 mesh, isothermal run at 80°C, flame ionisation (FID) detector.

48 Definitions
48.1 APFO: perfluorooctanoate.

48.2 Gaschromatograph (GC) with flame ionisation detector (FID): model 8000 top from Fisons equipped

with standard packed column injector.

48.3 Data system: Electronic integrator mod. Chromjett from Fisons or PC based acquisition system mod.

Chromcard from Fisons.

49 Safety precautions

49.1 Use caution with temperatures of GC injector and detector. When running temperatures are of about

250°C.

49.2 When handling samples or solvents wear appropriate protective gloves, eyewear, clothing and any

other protective devices mandatory in your working area.

50 Interferences

50.1 To minimise interferences when analysing samples PTFE vials and tubing should not be used for

sample storage or handling.

51 Equipment

51.1 GC FID mod. 8000 from Fisons

51.2 Electronic recording integrator mod. Chromjett from Fisons or PC running Chromcard software from

Fisons

52 Supplies and materials

52.1 GC grade Nitrogen used as carrier gas

52.2 GC grade Hydrogen used for FID

52.3 GC grade Air used for FID

52.4 Micro-syringes glass 10 μl

52.5 Centrifuge tubes glass 10ml

52.6 Vials 10ml

53 Reagents and standards

53.1 CFC 113 Fluka for IR or equivalent

53.2 Standard

Typically one method and matrix blank and one continuing calibration standard S20ppm are

prepared with each group of samples.
54 Quality control

54.1 Method and matrix blank

Analyse a method and matrix blank prior to each group of samples.

54.2 Matrix spike

Analyse a matrix spike prior to standard calibration curve.

54.3 Continuing calibration check

54.3.1 Analyse S20ppm sample first to assure the accuracy of initial calibration curve.

54.3.2 Analyse S20ppm every tenth samples.

54.3.3 If a significant change (i.e. >25%) in peak area occurs, relative to the initial calibration curve,

subsequent analysis will be invalid.

55 Calibration and standardisation

55.1 Prepare and analyse a standard calibration curve after each maintenance intervention

55.2 The r

2

value for linear regression of data should be 0.98 or greater

55.3 If curve does not meet requirements change analytical column or re-prepare calibration standards.

56 Procedures

56.1 Use a packed column, , glass, 2m long, 6mm o.d., 3mm i.d., packed with metyl-siloxane rubber SE

30 20% on Chromosorb W AW DMCS 80-100 mesh

56.2 Carrier: Nitrogen, flow rate: 40ml/min measured at room temperature connecting flow meter to

detector outlet.

56.3 Injector: standard packed at 250°C

56.4 Detector: FID at 250°C, Hydrogen flow rate: 30ml/min, Air flow rate 500ml/min

56.5 Oven temperature: isothermal at 80°C

56.6 Injection volume: liquid measured 1μl

56.7 APFO retention time: 3 minutes

57 Data analysis and calculations

Calculate actual concentration of APFO, or other applicable compounds, from calibration line using

an external standard method.

58 Method performances

Method detection limit and method quantitation limit are referred to each matrix and reported in

specific methods.
59 Pollution prevention and waste management

Samples in CFC are disposed in dedicated container.

Samples in water / methanol are disposed in dedicated container

Solid polymer residuals are disposed in dedicated container

Disposable glass vials are disposed in broken glass containers located in laboratory.

60 Records
APPROVED –COPY N°________

AUSIMONT S.P.A.

Centro Ricerche e Sviluppo

Bollate

Analytical Method

PF 89/110 POW E

Perfluorooctanoate and higher homologues

in polymer bulk or sintered

Extraction and esterification

This document is composed by:

N° pages: 45

N° figures:

N° tables:

N° attachments:

Edition: 3 Date: June 2001

Laboratory: GC Author: Oriani

Verification: Morandi Approval: Pace

61 Scope and application

61.1 This method is for the extraction of perfluorooctanoate (APFO) and related homologues from

Algoflon (PTFE) polymer bulk or sintered.

61.2 Applicable compounds are: perfluorooctanoate (APFO) [C7F15COO

-

], perfluorononanoate

[C8F17COO

-

], perfluorodecanoate [C9F19COO

-

], perfluoroundecanoate [C10F21COO

-

],

perfluorododecanoate [C11F23COO

-

] and higher homologues.

61.3 Matrices: Algoflon polymer, bulk or sintered, dry (humidity lower than 5% by weight).

62 Summary

62.1 About 500mg (1g if sintered) of Algoflon is weighed in a 10 ml vial. Add 2ml of methanol

containing 1% Sulphuric acid. Close carefully the vial with a PTFE capped septum, then allow

APFO esterification at 70°C over night. At room temperature add 1ml of CFC 113, centrifuge then

transfer 2 ml of clear solution in a 10ml vial. Wash out acidic methanol with 4ml water. Close vial
and allow phases separation at 40°C for 15 minutes. Inject 1μl of lower liquid layer. Analyse using

method PF 89/110 GC E.

63 Definitions

63.1 APFO: perfluorooctanoate.

64 Safety precautions

64.1 When handling samples or solvents and hot vials wear appropriate protective gloves, eyewear,

clothing and any other protective devices mandatory in your working area.

65 Interferences

65.1 To minimise interferences when analysing samples PTFE vials and tubing should not be used for

sample storage or handling.

66 Equipment

66.1 Centrifuge ALC CENTRIFUGETTE 4236

66.2 Shaker IKA-VIBRAX-VXR

66.3 Balance (+/- 1mg)

67 Supplies and materials

67.1 Gloves

67.2 Timer

67.3 Syringes glass 1 cc, 5 cc

67.4 Micro-syringes glass 10 μl, 250 μl,

67.5 Centrifuge tubes glass 10ml

67.6 Vials 10ml

67.7 Glass bottles nominal 100ml

67.8 Glass volumetric flasks 100ml volume

67.9 Athermic gloves

68 Reagents and standards

68.1 Concentrated sulphuric acid R.P.E. Carlo Erba or equivalent

68.2 Methanol R.S. Carlo Erba or equivalent

68.3 CFC 113 Fluka for IR or equivalent

68.4 Ammonia 30% R.P.E. Carlo Erba or equivalent

68.5 Reagent preparation
1% sulphuric acid in methanol: in a bottle of nominal 100ml (true volume 116ml) weigh 49.5g of

methanol then add slowly 0.5 g concentrated sulphuric acid.

68.6 Standard preparation

Sol.A: weigh 100mg of solid ammonium salt of perfluoro-acid, dissolve in 100ml methanol in

volumetric flask.

S200ppm: transfer 100μl of Sol.A in a 10ml vial, add 1.6ml of methanol 1% sulphuric acid and

follow the esterification procedure.

S100ppm: transfer 50μl of Sol.A in a 10ml vial, add 1.8ml of methanol 1% sulphuric acid and follow

the esterification procedure.

S50ppm: transfer 25μl of Sol.A in a 10ml vial, add 1.9ml of methanol 1% sulphuric acid and follow

the esterification procedure.

S20ppm: transfer 10μl of Sol.A in a 10ml vial, add 2ml of methanol 1% sulphuric acid and follow

the esterification procedure.

S10ppm: transfer 5μl of Sol.A in a 10ml vial, add 2ml of methanol 1% sulphuric acid and follow the

esterification procedure.

69 Quality control

69.1 Method and matrix blank

In a 10ml vial weigh 500mg of Hyflon

® MFA powder, follow esterification procedure.

Note: Hyflon polymers are free from APFO and Surflon surfactants

With each batch of samples prepare and analyse a blank as first sample.

69.2 Matrix spike

In a 10ml vial weigh 500mg of Hyflon

® MFA powder, add 5 μl of Sol.A then follow esterification

procedure.

Note: Hyflon polymers are free from APFO and Surflon surfactants.

With each complete calibration prepare a matrix spike and a blank.

As last samples after calibration inject in triplicate blank and matrix spike.

69.3 Continuing calibration check

69.3.1 With each batch of samples prepare S20ppm calibration solution.

69.3.2 Analyse S20ppm sample first to assure the accuracy of initial calibration curve.

69.3.3 Analyse S20ppm sample per group of 10 samples, followed by a blank (9.1).

69.3.4 Analyse S20ppm sample last to assure the accuracy of data.

70 Calibration and standardisation

70.1 Prepare calibration standards
70.2 Inject 1μl each at least in triplicate

70.3 Calculate concentration of APFO in dispersion from APFO concentration in solution assuming that

Sol.A contains about 1μg APFO/μl solution and Algoflon weight is 500mg. Correct concentration

only if weighed APFO differs from nominal 100mg more that + / - 10% (namely less than 90mg or

more than 110mg).

71 Procedures

71.1 Weigh about 500mg (1g if sintered) Algoflon in a 10ml vial

71.2 Record weight and label vial with sample ID

71.3 Prepare S20ppm solution and label accordingly

71.4 At room temperature, add 2ml of methanol containing 1% Sulphuric acid.

71.5 Close carefully the vial with a PTFE capped septum.

71.6 Allow APFO esterification at 70°C over night.

71.7 At room temperature add 1ml of CFC 113, centrifuge then transfer 2 ml of clear solution in a 10ml

vial.

71.8 Wash out acidic methanol with 4ml water. Close vial and allow phases separation at 40°C for 15

minutes.

71.9 Using a syringe take out the aqueous layer. Wash a second time with 4ml water. Close vial and allow

phases separation at 40°C for 15 minutes.

71.10 At room temperature, inject 1μl of lower liquid layer. Analyse using method PF 89/110 GC E.

72 Data analysis and calculations

Calculate actual concentration of APFO, or other applicable compounds, from calibration line using

an external standard method. Correct data calculated from calibration line only if the amount of

polymer used differ from 500mg by a quote higher than +/- 5% using the formula:

Conppm = Calppm * (Trueamt/500)

Where:

Conppm = Concentration in ppm of surfactant corrected for polymer weight

Calppm = Concentration in ppm of surfactant from calibration line

Trueamt = Weight in mg of polymer used

73 Method performances

Method detection limit is 4ppm APFO in Algoflon. Method quantitation limit is 10ppm.

For sintered Algoflon method detection limit is 2ppm APFO. Method quantitation limit is 6ppm.

Precision and accuracy are calculated from data of calibration line; precision is percent standard

deviation at each point, accuracy is percent ratio of average calculated amount to nominal

concentration at each point.

Recovery is percent ratio of average area of matrix spike to average area of S10ppm calibration

point.
74 Pollution prevention and waste management

Samples in CFC are disposed in dedicated container.

Samples in water / methanol are disposed in dedicated container

Solid polymer residuals are disposed in dedicated container

Disposable glass vials are disposed in broken glass containers located in laboratory.

75 Records

None
APPROVED –COPY N°________

AUSIMONT S.P.A.

Centro Ricerche e Sviluppo

Bollate

Analytical Method

PF 89/110 WAS E

Perfluorooctanoate and higher homologues

in wastewater and surface water

Concentration on Porapack Q

and esterification

This document is composed by:

N° pages: 45

N° figures:

N° tables:

N° attachments:

Edition: 3 Date: June 2001

Laboratory: GC Author: Oriani

Verification: Morandi Approval: Pace

76 Scope and application

76.1 This method is for the extraction of perfluorooctanoate (APFO) and related homologues from

wastewater and surface water.

76.2 Applicable compounds are: perfluorooctanoate (APFO) [C7F15COO

-

], perfluorononanoate

[C8F17COO

-

], perfluorodecanoate [C9F19COO

-

], perfluoroundecanoate [C10F21COO

-

],

perfluorododecanoate [C11F23COO

-

] and higher homologues.

76.3 Matrices: waste water and aqueous matrixes with APFO concentration lower than 5ppm.

77 Summary

77.1 Transfer about 70ml of acidic water in a 100ml dreschel bottle. Connect to gas dispersion side tube a

cartridge packed with about 700mg of Porapack Q 60-80 mesh. Connect the second line of dreschel

bottle to a Nitrogen supply and pressurise at about 20-50 kPa allowing a liquid flow rate through the

cartridge of about 1 ml/min. Collect effluent water in a cylinder and stop flow after collection of
about 50ml. Connect the cartridge directly to Nitrogen supply for 5 minutes to remove the most part

of water. Elutes with 6ml of ethanol in a 10ml vial. Add 0.4ml NaOH 0.1% in ethanol and allow

drying at room temperature under Nitrogen flow. Add 2ml of methanol containing 1% Sulphuric

acid. Close carefully the vial with a PTFE capped septum, then allow PFOA esterification at 70°C

over night. At room temperature add 0.5ml of CFC 113. Wash out acidic methanol with 6ml water.

Remove water layer then wash again with 3ml water. Allow phases separation at room temperature

for 15 minutes. Inject 1μl of lower liquid layer. Analyse using method PF 89/110 GC E.

78 Definitions

78.1 APFO: perfluorooctanoate.

79 Safety precautions

79.1 When handling samples or solvents and hot vials wear appropriate protective gloves, eyewear,

clothing and any other protective devices mandatory in your working area.

80 Interferences

80.1 To minimise interferences when analysing samples PTFE vials and tubing should not be used for

sample storage or handling.

81 Equipment

81.1 Balance (+/- 1mg)

82 Supplies and materials

82.1 Gloves

82.2 Timer

82.3 Syringes glass 1 cc, 5 cc

82.4 Micro-syringes glass 10 μl, 250 μl

82.5 Pasteur pipette 8x6mm diameter

82.6 Centrifuge tubes glass 10ml

82.7 Vials 10ml

82.8 Glass bottles nominal 100ml

82.9 Volumetric flasks 100ml, 500ml volume

82.10 Athermic gloves

82.11 Dreschel bottle 100ml and 500ml

82.12 Glass graduated cylinder 100ml and 500ml

83 Reagents and standards

83.1 Concentrated sulphuric acid R.P.E. Carlo Erba or equivalent

83.2 Methanol R.S. Carlo Erba or equivalent
83.3 Ethanol anhydrous R.S. Carlo Erba or equivalent

83.4 Acetone R.S. Carlo Erba or equivalent

83.5 CH2Cl2 R.S. Carlo Erba or equivalent

83.6 CFC 113 Fluka for IR or equivalent

83.7 Ammonia 30% R.P.E. Carlo Erba or equivalent

83.8 NaOH R.P.E. Carlo Erba or equivalent

83.9 Nitrogen GC grade

83.10 Porapack Q 60-80 mesh

83.11 Reagent preparation

1% sulphuric acid in methanol: in a bottle of nominal 100ml (true volume 116ml) weigh 49.5g of

methanol then add slowly 0.5 g concentrated sulphuric acid.

1% NaOH in ethanol: in a 500ml volumetric flask weigh 0.5g of NaOH then add 500ml ethanol.

83.12 Standard preparation

Sol.A: weigh 100mg of solid ammonium salt of perfluoro-acid, dissolve in 100ml methanol in

volumetric flask.

S200ppm: transfer 100μl of Sol.A in a 10ml vial, add 1.9ml of methanol 1% sulphuric acid and

follow the esterification procedure.

S100ppm: transfer 50μl of Sol.A in a 10ml vial, add 2ml of methanol 1% sulphuric acid and follow

the esterification procedure.

S50ppm: transfer 25μl of Sol.A in a 10ml vial, add 2ml of methanol 1% sulphuric acid and follow

the esterification procedure.

S20ppm: transfer 10μl of Sol.A in a 10ml vial, add 2ml of methanol 1% sulphuric acid and follow

the esterification procedure.

S10ppm: transfer 5μl of Sol.A in a 10ml vial, add 2ml of methanol 1% sulphuric acid and follow the

esterification procedure.

83.13 Cartridge preparation

Weigh about 700mg Porapack Q. Introduce a small plug of glass wool in a Pasteur pipette down to

diameter restriction. Transfer to the pipette the Porapack Q then insert a second small plug of glass

wool to keep polymer bed in place.

Wash with 15ml Acetone, 15ml Ethanol and 15ml CH2Cl2. Keep cartridge under Ethanol until use.

Before use let ethanol flowing out then wash with 10ml distilled water. Connect moist cartridge to

the sampling line.

83.14 Sample preparation

Transfer 70ml of water sample, measured in a graduated cylinder, into dreschel bottle. Add, slowly

0.3ml sulphuric acid.

83.15 Water spike preparation
Sp500- In a volumetric flask measure 100ml drinking water. Add 50μl Sol.A, shake for few minutes

then follow 8.14 Sample preparation.

Sp250- In a volumetric flask measure 100ml drinking water. Add 25μl Sol.A, shake for few minutes

then follow 8.14 Sample preparation.

Sp100- In a volumetric flask measure 100ml drinking water. Add 10μl Sol.A, shake for few minutes

then follow 8.14 Sample preparation.

Sp50- In a volumetric flask measure 100ml drinking water. Add 5μl Sol.A, shake for few minutes

then follow 8.14 Sample preparation.

84 Quality control

84.1 Method and matrix blank

Use drinking water and apply sample preparation, as in 8.14, recovery and esterification procedure.

84.2 Matrix spike

Prepare spiked samples as in 8.15 and apply recovery and esterification procedure.

84.3 Continuing calibration check

84.3.1 With each batch of samples prepare S20ppm calibration solution.

84.3.2 Analyse S20ppm sample first to assure the accuracy of initial calibration curve.

84.3.3 Analyse S20ppm sample per group of 10 samples.

84.3.4 Analyse S20ppm sample last to assure the accuracy of data.

85 Calibration and standardisation

85.1 APFO response line

85.1.1 Prepare calibration standards

85.1.2 Inject 1μl each at least in duplicate

85.1.3 Calculate concentration of APFO in solution assuming that Sol.A contains 1μg APFO/μl solution.

Correct concentration only if weighed APFO differs from nominal 100mg more that + / - 10%

(namely less than 90mg or more than 110mg).

85.2 Calibration line

85.2.1 Prepare spiked samples as in 8.15

85.2.2 Apply each the recovery procedure

85.2.3 Inject 1μl each at least in triplicate
85.2.4 Calculate concentration of APFO in water from APFO concentration in spiked samples assuming

that Sol.A contains 1μg APFO/μl solution. Correct concentration only if weighed APFO differs

from nominal 100mg more that + / - 10% (namely less than 90mg or more than 110mg).

86 Procedures

86.1 Prepare samples as in 8.14 or 8.15 for spiked samples and label flasks with sample ID.

86.2 Connect to gas dispersion side tube the cartridge prepared as in 8.13.

86.3 Connect the second line of dreschel bottle to a Nitrogen supply and pressurise at about 20-50 kPa

allowing a liquid flow rate through the cartridge of about 1 ml/min.

86.4 Collect effluent water in a cylinder and stop flow after collection of about 50ml.

86.5 Connect the cartridge directly to Nitrogen supply for 5 minutes to remove the most part of water.

86.6 Elutes with 6ml of ethanol in a 10ml vial. Add 0.4ml NaOH 1% in ethanol and allow drying at room

temperature under Nitrogen flow.

86.7 Add 2ml of methanol containing 1% Sulphuric acid. Close carefully the vial with a PTFE capped

septum, then allow PFOA esterification at 70°C over night.

86.8 At room temperature add 0.5ml of CFC 113. Wash out acidic methanol with 6ml water. Remove

water layer then wash again with 3ml water.

86.9 Allow phases separation at room temperature for 15 minutes.

86.10 At room temperature, inject 1μl of lower liquid layer. Analyse using method PF 89/110 GC E.

87 Data analysis and calculations

Calculate actual concentration of APFO, or other applicable compounds, from calibration line (10.2)

using an external standard method.

88 Method performances

Method detection limit is 50ppb APFO in water. Method quantitation limit is 100ppb in water.

Precision and accuracy are calculated from data of calibration line; precision is percent standard

deviation at each point, accuracy is percent ratio of average calculated amount to nominal

concentration at each point.

Recovery at each point is percent ratio of average area of calibration line to average area of APFO

response line calculated at same nominal concentration.

89 Pollution prevention and waste management

Samples in CFC are disposed in dedicated container.

Samples in water / methanol are disposed in dedicated container

Solvents are disposed in dedicated container

Disposable glass vials are disposed in broken glass containers located in laboratory.

90 Records
None