Quantifying Biocide Release from A/F Coatings

Alistair Finnie

ASTM Technical Seminar

Antifouling Paint Highlights:
Regulatory, Technology and Performance Testing
June 23rd 2009
Quantifying Biocide Release from A/F Coatings

• What do we mean by biocide release rate?

(aka leaching rate, LR)

• Common methods
• Standard (ASTM & ISO) and non-standard
methods
• Laboratory, calculation & field methods

• How do the methods relate to each other and to

‘reality’?

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 What do we mean by biocide release rate?

• Release rate is the flux of biocide from an immersed A/F paint

• expressed as µg cm-2 d-1
• Biocide release is governed by physical and chemical
processes driving dissolution and diffusion
• strongly influenced by temperature, salinity, pH, water flow,
paint age, etc
• Instantaneous biocide release
rate will:
• depend on local conditions
• depend on paint history
• change with time
• True for laboratory testing and
‘real life’

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 What do we mean by biocide release rate?

• Historically used as product

development & evaluation tool
• Assumption is that release rate
characteristics are linked to in-service
performance
Wood’s Hole, 1952

Anderson & Milne, 1984

• Focus on trend analysis

• change in release rate with time
• Many proprietary and literature
methods used

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 What do we mean by biocide release rate?

• Release rate is a critical input parameter in environmental

risk and exposure assessments for antifouling products
Chemical fate processes of antifouling products in the marine
environment

van Hattum et al, 2002

• Generally requires a representative value of the
release rate under the relevant exposure scenario

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 Regulatory framework

• Release rate data often required by regulatory

authorities as part product approval process
• eg FIFRA (USA) and BPD (Europe)
• National A/F product approval schemes
increasingly underpinned by environmental risk
and exposure assessments
• Reliability of risk assessment depends upon
reliability of the inputs to the model
• LR values used must accurately reflect
release from ship/boat hull in normal use
• Currently no practical method for routine release
rate measurement directly from a hull
• Most common indirect methods are:
• ASTM & ISO ‘rotating cylinder’ method
• ISO (CEPE) mass-balance calculation

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 ‘Real-life’ methods – US Navy Dome

• Most reliable measurements of environmental

release rates from in-service vessels probably
from US Navy/SPAWAR Dome
• Direct sampling from vessel hulls at pier-side in
natural waters
• Can be used at any point in lifetime of paint
• Published data for copper and organotin release
rates from a range of paint systems on pier-side
US Navy vessels (all from San Diego Bay) Photocredit: Earley/SPAWAR

• Labour intensive method usually requiring divers

and pilot boat
• not suitable for routine use but further
method-development is ongoing (SPAWAR)
30 cm

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 ISO/ASTM rotating cylinder method

LR

time

Known surface area Periodic rotation in fixed Chemical analysis Biocide conc., volume,
immersed in artificial volume of seawater, of leachate area, and rotation time
seawater for ≥ 45 days ≤ 1 hr, 1-2x per week Æ LR, µg cm-2 d-1

• ISO/ASTM ‘rotating cylinder’ method is the only internationally recognised

laboratory method for quantifying biocide release rates
• Painted test cylinders immersed in standard artificial seawater under
closely controlled pH, salinity and T for 45 day test-period (minimum)
• Principal outputs are:
• Mean release rate from day 21-end (often 45 days)
• Mean ‘pseudosteady state’ release rate (if there is one!)
• 14 day cumulative release

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
Release rate measuring container
- capacity: 1,8 litres to 2,2 litres;
- diameter (A) 120 mm to 150 mm;
- height (B): 170 mm to 210 mm;
- baffles (C) : three circular cross section rods
of 4 mm to 8 mm diameter
Test cylinder
- diameter (D): 60 mm to 70 mm
- paint-free zone (E): 10 mm to 20 mm
ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 ASTM/ISO published standards (rotating cylinder)

Method Description Status

ISO 15181 – Part 1 Generation of leachate First published 2000, revised
(generic rotating cylinder method) 2007 to fully harmonise with
ASTM D6442
– Part 2 Analysis for copper in leachate
– Part 3 Analysis for zineb in leachate Published 2007
– Part 4 Analysis of pyridine triphenylborane Published 2008
– Part 5 Analysis of dichlofluanid and tolylfluanid Published 2008
– Part 6 Analysis of tralopyril in leachate NWIP – CD – DIS – FDIS –
approval (end 2010?)
ASTM D5108-90 Organotin release rate Published 1990
ASTM D6442-06 Copper release rate First published 1999, revised
2006 to harmonise with
ISO15181-1,2
ASTM D6903-07 DCOIT )
Zinc pyrithione ) release rates Published 2007
Copper pyrithione )
CDMTD/Cybutryn )

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
ISO/ASTM rotating cylinder method

• Not designed to produce ‘real-life’ release rate data

• Widely recognised that results do not generally
reflect release rates under environmentally relevant
conditions
• Typically ~x10 higher
• Reproducibility is relatively poor
• Interlab. variation of 24-81%, depending on
coating
• Expensive and time consuming to perform

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 ASTM/ISO rotating cylinder – illustrative results

biocide release rate (rotating cylinder method)

7 5 .0 0

release rate (µg cm -2 d-1)

6 2 .5 0

5 0 .0 0

3 7 .5 0
Cu
Cobiocide

2 5 .0 0

1 2 .5 0
Finnie, 2008

00
. 0

0 5 10 15 20 25 30 35 40 45
time (days)

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 ASTM/ISO rotating cylinder – illustrative results
biocide release rate (rotating cylinder method)
7 5 .0 0
release rate (µg cm-2 d-1)

6 2 .5 0

5 0 .0 0

3 7 .5 0
Cu
Cobiocide biocide release rate (rotating cylinder method)
2 5 .0 0

0 0 .0 0
1

1 2 .5 0

0 .0 0

0 5 10 15 20 25 30 35 40 45
normalised rel. release rate
time (days)

8 0 .0 0
R45 >> R360 for Cu and
cobiocide
6 0 .0 0

Cu
Cobiocide
4 0 .0 0

2 0 .0 0
Finnie, 2008

0 0
. 0

0 50 100 150 200 250 300 350

time (days)

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 ASTM/ISO standard methods (rotating cylinder)

Standards clearly state that they should not be used

directly for environmental risk assessment purposes

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 ISO mass-balance calculation method

Original European Paint Makers Association (CEPE) mass-balance calculation

method is being developed as an ISO standard
– ISO/DIS 10890 (final publication expected 2010)
• Basic principle – amount of biocide released over a
CEPE model
paint’s lifetime cannot exceed amount in the paint film

Release rate
assumptions
at application
• Core input – mass of biocide present in the paint film X
Y

• Core output – maximum mean release rate over the

14 days t
paint’s lifetime time

• Unlike CEPE model, ISO mass-balance calculation

does not assume any particular behaviour (eg 14-day ISO model
biocide burst then steady-state) assumptions

Release rate
• Maths are independent of release rate change over
Mean RR
lifetime and calculation of average release rate
over lifetime
designed to be valid for all biocides and all paints
t
• Designed to provide more-representative values for time

use in ERA than rotating cylinder method

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 ISO mass-balance calculation method

Max amount of biocide released a mass fraction of biocide in the biocidal ingredient
Wa % mass content of biocide in the paint
L a × a × W a × ρ × DFT VS % volume solids of the paint
M rel = ρ wet paint density (kg dm-3 or g cm-3)
VS DFT dry film thickness (µm) applied for the specified
lifetime
La % biocide released from the paint over the
specified lifetime [default = 90%]

Mean release rate over paint lifetime

M rel M
R= = 0.0329 × rel t specified lifetime for the paint (months)
⎛ 365× t ⎞ t
⎜ ⎟
⎝ 12 ⎠
Optional calculation of 14-day cumulative release

R0,14 = R × f f factor to reflect change in release rate over first

14 days [default f =30 for ‘typical’ behaviour]

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 ISO mass-balance calculation method

• Principal output is average release rate over entire

specified product lifetime
• Conservative worst case average release rate as
default assumption is 90% release of biocide over
lifetime
• Approach is valid for all paint types and all biocides
• Simple and transparent calculation
• Release rate generally higher when vessel is moving so
calculation will tend to particularly over-estimate
release for stationary vessels in harbour and marina
scenarios

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 Method-dependency of release rates

TM
Method-dependent copper release rate: Interspeed 640 Data from Finnie, 2006
70

n=8 • ASTM/ISO typically overestimates in situ pier side/

60 harbour copper and tin release rate about x10
• Typically about x4 for mass-balance calculation
copper release rate (µg cm-2 d-1)

50 • Proposed that default conservative correction factors

based on 95% CI approach should be applied if data
used for environmental risk assessment
40
• 5.4 (ASTM/ISO) & 2.9 (mass-balance)
• Correction factor approach accepted in principle by
30 European regulatory authorities

20
estimated range

10 n=5

0
ASTM/ISO Mass-balance Calculation Dome Dome
calculation (polishing rate) (ships) (panels)
adapted from Finnie, 2006
ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 Other recent method development work

Seligman et al., 2003

• Ongoing development of Dome method by
SPAWAR for use on ships and panels
• Substantial work also done by SPAWAR on
alternative panel methods

Kojima et al., 2007

• Interesting recent work in Japan (NMRI) on
alternative methods
• Flumes and ‘on-site sampler’ for direct
measurements from ship hulls

Honma et al., 2008

• Problem of practical method for routine
direct measurement from ship/boat hulls
has still to be solved

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
 Comparison of methods

ASTM/ISO ISO mass- Dome & other

rotating balance field methods
cylinder calculation
International standard methods 9 (9) 8
Accepted by regulatory authorities 99 9 ?
Available for all biocides & all paints 8 9 8
Data quality/reproducibility 8 99 (9?)
Suitable for direct use in ERA 88 8/9 99
Known correlation with env. release rates 9 9 99
Low cost 88 99 88
No specialist equipment 8 99 8
No specialist skills 8 99 8
Transparency of results 8 99 8

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings
Conclusion

• No suitable method for routine direct measurement of

release rate from ship/boat hulls
• Most common indirect methods are ASTM/ISO rotating
cylinder method and ISO mass balance calculation
• ASTM/ISO rotating cylinder results are grossly
unrepresentative of release to environment
• Not suitable for ERA unless corrected
• ISO mass-balance calculation provides worst-case
average release rate over lifetime of the paint
• Better reflection of reality than ASTM/ISO but
correction factors recommended for improved
accuracy and reliability of ERAs
• At present, the most accurate and cost-effective route to
representative release rate data for ERA is mass-balance
calculation in conjunction with suitable correction factors

ASTM Technical Seminar – Antifouling Paint Highlights, June 2009 Marine & Protective Coatings