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QC100 .use No"'4^5f8‘?9"8?';r9®c‘.rNBS.p Characterization of Long Term

Controlled Release Dynamics and

Identification of Butyltin Species

Released from OMP Impregnated

Wood Pilings

W. R. Blair, G. J. Olson, F. E. Brinckman

U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

Institute for Materials Science and Engineering

Ceramics Division

Ceramics Chemistry and Bioprocesses Group

Gaithersburg, MD 20899

January 1987

i^-QC100

.056

87-3518

1987

c-2

_for

livil Engineering Laboratory

leneme, CA 93043

NBSIR 87-3518

CHARACTERIZATION OF LONG TERM

CONTROLLED RELEASE DYNAMICS AND

IDENTIFICATION OF BUTYLIN SPECIES

RELEASED FROM OMP IMPREGNATED

WOOD PILINGS

MBS

RESEARCH

INFORMATION CENTER

^ C

Q Cf

W. R. Blair, G. J. Olson, F. E. Brinckman

U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

Institute for Materials Science and Engineering

Ceramics Division

Ceramics Chemistry and Bioprocesses Group

Gaithersburg, MD 20899

January 1987

Prepared for Naval Civil Engineering Laboratory

Port Hueneme, CA 93043

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director
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CHARACTERIZATION OF LONG TERM CONTROLLED RELEASE DYNAMICS AND IDENTIFICATION

OF BUTYLTIN SPECIES RELEASED FROM OMP IMPREGNATED WOOD PILINGS.

W. R. Blair, G. J. Olson and F. E. Brinckman

National Bureau of Standards

Ceramics Chemistry and Bioprocesses Group

Gaithersburg, Maryland 20899

Abstract

This report describes a method for determining rates of release of organotin

species leaching from wood pilings impregnated with organotin- containing

copolymers and discusses short and long term results. The analytical method

consists of simultaneous extraction/hydridization of aqueous leachate samples

followed by organotin speciation by gas chromatography coupled with tin

selective flame photometric detection (GC-FPD) . The detection limit for the

butyltin family of organotins is 0.1 to 0.2 ng, depending on the species. The

butyltins (mono- through tetrabutyltin) are speciated within a 15 min

chromatogram, which also provides speciation of any methylbutyltin compounds

that may be present in the sample. Water samples were collected from the

leaching tanks immediately upon immersion of the wood pilings and at interval

thereafter for approximately 1 year. Speciation and release rate data were

obtained on both the early, first order stage of organotin release, and the

latter, zeroth order phase of controlled release. Instrument calibrations

were performed using a specially prepared aqueous butyltin research material.

Key Words; butyltin compounds; chemical speciation; element selective

detection; extraction; gas chromatography; hybridization
1.0 Introduction

Production of organotin compounds has increased significantly during the past

30 years, to a current worldwide level of more than 35,000 tons annually (1).

Numerous applications as catalysts, polymer stabilizers, and tailored biocides

have resulted from the highly varied chemical and biological properties

provided by different classes of organotin(IV) compounds (2-7). With

increasing use of organotins , international concern for the fate and effect of

these compounds in the environment has also increased. These concerns are

reflected in environmental assessments and pollution evaluations compiled by

industry (8) and national environmental agencies of several countries (9-11).

Analytical methods capable of detection and speciation of butyltin compounds

at concentrations in the /xg to ng/L range must be employed to evaluate the

environmental risks associated with organotin usage. For example, aquated

tributyltin ion is toxic to some sensitive aquatic organisms at /xg/L levels

(12), but the dibutyltin ion is comparatively nontoxic (13). It is essential

that monitoring methods provide chemical speciation data for all the

organotins present in an environmental sample in order to provide a rational,

equitable and effective basis for regulation.

Within the past several years many new measurement methods have been described

which provide the required ultratrace sensitivity and speciation information

for organotin compounds (14-24). In general, most of these methods rely on

solvent extraction of the organotins from the environmental sample,

concentration and often derivitization by sodium borohydride or Grignard

reagents, and subsequent chromatographic or boiling point separation with tin

2
determination by a tin-selective (flame photometric) or tin-specific (atomic

absorption) detector.

Recent research in our laboratory has been directed to the development of

sensitive methods for the chromatographic speciation of butyltins in natural

waters (25) and the generation of stable, aqueous solutions of tributyltin for

use as standards in organotin measurement method intercomparisons (26) and for

instrument calibrations. The importance of the above methods development and

standards work is reflected in this report. The determination of butyltin

release rates from tributyltin copolymer impregnated wood pilings was

accomplished by application of the NBS developed butyltin speciation

measurement method. Instrument calibrations and verification of the identity

of tributyltin were based upon measurements of the aqueous butyltin research

material distributed for an international comparison of organotin measurment

methods. Protocols for the preparation and distribution of the dilute (ca.

1 mg/L) , aqueous solution of tributyltin used in this methods intercomparison

have been described thoroughly in an NBS interagency report (26).

The NBS butlytin speciation method relies on a simultaneous

hydridization/extraction step to remove and concentrate butyltin compounds

from water samples. Identification and quantitation of butyltin species is

accomplished by injecting small aliquots of the organic extract into a gas

chromatograph equipped with a flame photometric detector (GC/FPD) . Butyltins

(Bu^SnX^.j,, n = 1 to 4) and mixed methylbutyltin species are detected at /zg

per liter concentrations. Variations in salinity (fresh water to seawater)

and pH (6.3 to 9.4) have no effect on butyltin detection with this method.

3
The reproducibility of the method is approximately 10% and extraction

efficiency for tributyltin is close to 100%.

Organotin compounds, specifically tributyltin species, are being used as the

biocidal components in marine antifouling coatings. Advanced coating

formulations contain tributyltin bound to carboxyl groups in a high molecular

weight copolymer of tributyltin methacrylate and methyl methacrylate. Applied

to ships hulls, the butyltin copolymer coatings have demonstrated years of

fouling free performance (27). The longevity of the coating is attributed to

the controlled release, at near zeroth order, of tributyltin toxicant from the

copolymer matrix. Tributyltin copolymers are also being investigated for use

as preservatives for the protection of wood pilings. Pilings are impregnated

with a solution containing the respective monomers, which undergo reactions

including polymerization in situ (28)

.

The primary goal of the piling release rate experiment was to determine the

identity of the butyltin species released from tributyltin copolymer treated

pilings and the rates of their release into artificial seawater. The

experiment was designed to continue for approximately 1 year, during which

time the release rate was expected to drop from a relatively high initial rate

to a low, near zeroth order rate.

2.0 Experimental

2.1 OMP Impregnated Wood Pilings

Two types of wood pilings, both made from debarked southern yellow pine but

impregnated with different tributyltin copolymer formulations, were provided

by the Naval Civil Engineering Laboratory, Port Hueneme , CA 93043. The

4
copolymers were formed in situ from reaction of tributyltin methacrylate

(TBTM) and either methyl methacrylate (MMA) or glycidyl methacrylate (GMA)

The pilings, 11 to 12 cm in diameter, were cut with a hand saw into small

sections (22 to 24 cm long) for use as test specimens. The ends of the test

specimens were sealed with epoxy glue so that the cylindrical surface area of

the piling would be the only site of butyltin release. The amount of

copolymer retained by the piling test specimens and the surface areas that

were exposed to artificial seawater in this experiment are listed in Table 1.

2.2 Vessels and Artificial Seawater

Pyrex glass jars were used as containers for artificial seawater and piling

specimens. Prior to use, the jars were cleaned, first by washing with a warm

water and soap solution, then by leaching for two to three days with dilute

(10%) aqueous nitric acid at ca. 20 °C. Following acid leaching, the jars

were rinsed 4 to 5 times with deionized water. The jars were then filled with

32 liters of artificial seawater, prepared by adding salts in the following

amounts (grams per liter) to deionized water; NaCl, 23.9 g; MgCl2’6H20,

10.8 g; Na2 S 04 , 4.0 g; CaCl2 , 1.15 g; KCl, 0.7 g. This formula was a

modification of the sea salts mixture reported by Kester et al. (29). All

salts used in preparation of the artificial seawater were of reagent grade.

No butyltin contaminates were detected in the artificial seawater. The pH of

the artificial seawater in the leaching tanks, measured periodically during

the course of the experiment, ranged from pH 6.9 to pH 7.9, with the majority

of the measurements indicating a pH of 7.3 to 7.6. Temperature of the

artificial seawater reflected the stable air temperature in the laboratory,

22.0 ± 0.4 °C for the duration of the experiment.

5
2.3 Piling Release Rate Determination

To prevent the concentration of butyltins in the jars from reaching levels

that might inhibit further release from the piling specimens, water was pumped

continuously from the jars and passed through traps containing activated

charcoal. (Activated Charcoal, type OL, Calgon Carbon Corp., Bridgewater,

N.J.). Monitoring of butyltin concentration in the water returning to the

tanks from the activated charcoal traps showed that the traps were removing

all butyltins and returning butyltin- free water to the jars. A peristaltic

pump with adjustable flow rate was used to pump just enough water through the

charcoal traps to keep the butyltin concentration in the jars at a low but

measurable concentration, typically 5 to 15 ng per liter. The water in the

jars was circulated and mixed constantly by the action of the peristaltic pump

and Teflon-covered stirring bars rotating at approximately 650 rpm at the

bottoms of the jars.

The piling specimens were completely submerged in the artificial seawater to

initiate the release rate determination experiment. Water samples of

approximately 100 mL volume were taken from the jars containing the piling

test specimens and from the water returning to the jars from the charcoal

traps. For approximately the first 48 hours of the experiment, the charcoal

adsorption system for organotin removal was not operated so that the initial

release of butyltins could be determined. Samples that could not be analyzed

immediately after collection were stored on crushed ice at 0 °C until they

were analyzed.

6
3.0 Chemical Speciation of Butyltin Compounds Released from the Pilings

3.1 Speciation Methodology

The following procedure was followed for 100 mL artificial seawater samples

with a butyltin concentration in the low /ig per liter range (25). The sample

was put into a 125 mL glass separatory funnel equipped with a Teflon stopcock

and Teflon- lined screw cap. A spike from an aqueous solution of di-n-propyltin

dichloride was added to all samples as an internal standard at a concentration

of 5 or 10 ng per liter. Following addition of 2.8 mL of dichlorome thane and

2.0 mL of aqueous (4% w/v) sodium borohydride, the funnel was capped and

manually shaken for 1 minute. The funnel was then vented and placed on a

wrist action shaker for 10 minutes. After shaking, five minutes were allowed

for phase separation. The organic layer at the bottom of the funnel was then

removed and placed in a 1.5 mL polypropylene centrifuge tube, and a gentle

stream of compressed air was directed over the tube. An additional 1.4 mL of

dichloromethane was added to the funnel and the extraction repeated. The

organic layers were combined and evaporation continued until 1 mL of solution

remained. Five microliters of this concentrated extract was then injected

into the GC/FPD for identification and quantitation of the butyltin species

present in the sample. Appropriate artificial seawater blanks were carried

through the entire procedure

3.2 Gas Chromatograph/Flame Photometric Detector System

A packed-column gas chromatograph equipped with a flame photometric detector

was used for sample extract analysis (Hewlett-Packard Model 5730, Avondale,

PA). Separations were performed on a 2mm i.d. by 6 foot glass column packed

with 1.5% OV-101 on Chromosorb G HP (100-200 mesh) (Varian, Sunnyvale, CA)

7
A hydrogen-rich flame was used in the FPD, with the following gas flow rates:

H2 at 140 to 150 mL/min, air at 50 mL/min and O2 at 5 to 10 mL/min. The

addition of a small amount of O2 to the flame greatly enhanced flame stability

without decreasing sensitivity. For tin selective detection, the FPD was

equipped with a 600-nm cut-on interference filter (Ditric Optics, Inc,,

Hudson, MA) with a band pass of 600 to 2000 nm to monitor SnH molecular

emission (16,30). A strip chart recorder and a plotting integrator recorded

the signal from the FPD. The GC oven temperature program started at 25 °C,

which was maintained for 2 min following sample injection, then increased at a

heating rate of 32 °C/min to 170 °C, which was maintained until the

chromatogram ended 12 to 15 min from the time of sample injection. . Injection

port temperature was maintained at 150 °C and the FPD temperature at 200 ®C.

4.0 Results and Discussion

4.1 Initial Release Rate Measurements

The concentration and distribution of butyltin species present in the water

surrounding the wood pilings and in the water returning to the piling

tanks from the charcoal traps was periodically determined by the simultaneous

extraction/hydridization method described above. Water samples were taken

frequently at the beginning of the experiment (10 samples in the first 48

hours) , with the sampling interval decreasing as the experiment continued.

Graphs showing the release rates of mono-, di- , and tributyltin during

approximately the first 36 hours of piling exposure to artificial seawater are

shown in Figure 1 for the TBTM/MMA copolymer and in Figure 2 for the TBTM/GMA

copolymer. The release rate of tributyltin shows the largest increase for

both copolymers, with lesser amounts of di- and monobutyltin being released.

8
The release rates for ail butyltin species reached a maximum approximately 18

hours after the pilings were placed into the artificial seawater and then

declined. Total butyltin concentrations reached 400 to 600 /ig/L in the

leaching tanks before the activated charcoal adsorption system that controlled

the maximum butyltin concentration was put into operation. Inhibition of

butyltin release from the pilings probably occurred, as concentrations that

exceed 50 /ig/L are considered high enough to inhibit butyltin release from

test panels painted with organotin containing antifoulant paint (31). In a

flow-through leaching tank or one of significantly larger volume, the maximum

release rates and the time needed to attain them may have been significantly

different

For approximately the first month that the pilings were exposed to the

artificial seawater, mono-, di-, and tributyltin species were detected in the

water surrounding the pilings. Both di- and tributyltin species were detected

throughout the course of the experiment. Although the measurement method was

capable of speciating tetrabutyltin, none was ever detected during the

course of this experiment. No butyltins were ever detected in the water

returning to the piling tanks from the activated charcoal adsorption traps

indicating that the traps were 100% efficient in removing butyltins from the

artificial seawater. The data obtained on the concentration of butyltins in

the artificial seawater surrounding the pilings was converted to release rate

data by use of the following equation.

9
Release rate = (Tc - Ec) x (F) x (1440) / A

Tc = Concentration of butyltin species in tank

(4g/L)

•

Ec = Concentration of butyltin species in water

returning to tank from charcoal traps (yug/L)

.

F = Flow rate of water through charcoal traps

(L/min)

.

1440 = Conversion factor for calculating volume of

water passing through charcoal traps per day.

A = Square centimeter area of piling releasing

organotins

.

Graphs showing the release rates of tributyltin for both the TBTM/MMA and

TBTM/GMA copolymer treated pilings from approximately day 9 through day 400 of

exposure to artificial seawater are shown in Figures 3 and 4 respectively.

After an exposure period of 30 to 50 days, the tributyltin release rates for

both copolymers had decreased to relatively stable rates of less than 0.5

/ig/cm^/day. Release rates for mono-, di , and tributyltin species, determined

at various times during the course of the experiment, are listed for both

copolymer formulations in Tables 2 and 3.

Due to the time scale of the graphs presented in Figures 3 and 4, and the

relatively small changes in the tributyltin release rates during the latter

part of the experiment, the graphs show a relatively straight line

10
representing a stable release rate for approximately the final 300 days of the

experiment. An examination of the numerical data plotted in the figures

revealed that release rates were not yet constant but were still declining

slightly. The data in Table 4 indicate a significant decrease in average

tributyltin release rates calculated for two different time periods, the last

175 days versus the last 320 days of the experiment. The tributyltin release

rate for the TBTM/MMA copolymer dropped 55.3% and for the TBTM/GMA formulation

26.7% when the release rates for the 175 day time period are compared to the

release rates for the 320 day time period.

5.0 CONCLUSIONS

The method described here has proven to be sensitive for molecular speciation

of butyltin compounds in aqueous solution at low ^ig/'L concentrations. The

sodium borohydride derivitization step is mild enough that it induces no

molecular rearrangements or redistribution of the butyltins present in the

samples and works equally well with fresh or saline water containing butyltins

at environmental concentration levels of /ig/L.

The tributyltin copolymers used to impregnate the wood pilings both

demonstrated controlled release behavior, with relatively low levels of

butyltins being released once the pilings had been in artificial seawater for

30 to 50 days. A possible advantage of the TBTM/GMA formulation over the

TBTM/MMA formulation is that the former copolymer releases less butyltin

overall than the latter and reaches a low level release state somewhat sooner

than the latter, imposing a smaller butyltin impact on the environment.

11
6 . 0 ACKNOWLEDGMENTS

This work was supported in part by the Naval Civil Engineering Laboratory,

Port Hueneme , CA.

,

to whom we extend our thanks for patiently awaiting

development of the new butyltin measurement method employed in this

investigation. We wish to thank Ms. Joyce D. Friedenberg for her assistance

with the reduction and plotting of release rate data and Mr. Paul Schatzberg

of the David Taylor Naval Ship Research and Development Center for valued

discussion and advice.

Certain commercial products or equipment are mentioned in order to adequately

describe experimental procedures. In no case does such identification imply

endorsement by the National Bureau of Standards, nor does it imply that the

material is necessarily the best available for the purpose. Contributions

from the National Bureau of Standards are not subject to copyright

12
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,

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,

(1984) 1-68.

13
9. Thompson, J. A. J., Sheffer, M. G., Pierce, R.C., Chau, Y. K.

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Cooney, J. J., Cullen, W. R. , and Maguire, R. J. Organotin compounds in

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Sci. Technol. 16, (1982) 110-119.

14
17. Soderquist, C. J. and Crosby, D. G. Determination of triphenyltin

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spectrophotometry. Anal. Chem. 54, (1982) 246.

19. Maquire, R. J. and Huneault, H. Determination of butyltin species in

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15
25. Matthias, C. L. , Bellama, J. M. , Olson, G. J., and Brinckman, F. E,

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16
FIGURE CAPTIONS

Figure 1. Graph showing the release rates of mono-, di- , and tributyltin

during approximately the first 36 hours of piling exposure to artificial

seawater for copolymer TBTM/MMA. The maximum release for tributyltin occurred

18 hours into the experiment, with a rate of 29,7 /ig/cm2 /day.

Figure 2. Graph showing the release rates of mono-, di-, and tributyltin

during approximately the first 36 hours of piling exposure to artificial

seawater for copolymer TBTM/GMA. The maximum release for tributyltin occurred

18 hours into the experiment, with a rate of 24,4 /ng/cm^ /day

,

Figure 3. Graph of the release rates for tributyltin from the piling treated

with copolymer TBTM/MMA, Data are plotted for day 9 through day 400 of piling

immersion in artificial seawater. The average tributyltin release rate during

the final 175 days of piling exposure to artificial seawater was 0,17 ± 0,12

Hg/cm^ /day

,

Figure 4, Graph of the release rates for tributyltin from the piling treated

with copolymer TBTM/GMA. Data are plotted for day 9 through day 400 of piling

immersion in artificial seawater. The average tributyltin release rate during

the final 175 days of piling exposure to artificial seawater was 0,11 ± 0.03

/ig/cm^ /day

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TABLE 1

Piline Tvoe Surface Area Polymer content. Ib/ft

TBTM/MMA 795 cm^ 2.4

TBTM/GMA 784 cm^ 3.2

TABLE 2

Release rates of butyltins from TBTM/MMA

copolymer treated piling

Release Rates (/zg/cm^/day)

Immersion Time BuSn+++ Buo Sn~*~ ^3 Sn

'*'

1 hr 0.6 1 15 2 02

12 hr 0.8 4 77 13 00

1 .:} days 1.2 13 86 51 18

9

II ND 1 21 3 56

20 II 0.05 0 27 0 60

43 It ND 0 44 0 38

86 II ND 0 34 0 45

100 II ND 0 17 0 47

233 II ND 0 07 0 14

400 II ND 0 08 0 23

ND = not detected
TABLE 3

Release rates of butyltins from TBTM/GMA

copolymer treated piling

Release Rates (/Lig/cm^ /day)

Immersion Time BuSn'^’^'" BU3 Sn~*

1 hr 1.00 1.57 1.81

12 hr 2.64 9.41 16.86

1 3 days 4.70 32.00 76.72

9

tl 0.11 0.36 2.83

20 It 0.17 0.17 0.44

43 tl ND 0.33 0.44

86 It ND 0.32 0.26

100 II ND 0.09 0.16

233 II ND 0.06 0.16

400 II ND 0.05 0.11

ND = not detected

TABLE 4

Release Rate (/xg/cm^/day)

Copolymer Formulation 320 Day Interval 175 Day Interval

TBTM/MMA 0,38 ± 0.37 0.17 ± 0.12

TBTM/GMA 0.15 ± 0.06 0.11 ± 0.03
(4ep/zUi3/6r1) aseaiay
(Aep/zUio/6rf) eseaiay

Time

(hours)
TBTM/MMA

(Aep/gUio/Bri)

9se9|ahi

Time

(days)
(Aep/giuo/Bri)

eseeiey

Time

(days)
U.s Off'T OF c BIBLIOGRAPHIC DATA

SHEET (See instroClions)

1. PUBLICATION OR

REPORT NO.

2. Pfrlofminj 0«f«n. RepoM NoJ 3. Publication Date

4. TITLE AND SUBTITLE

Characterization of Long Term Controlled Release Dynamics and Identification of

Butyltin Species Released from OMP Impregnated wood Pilings

i. AUTHOR(S)

W. R. Blair, G. J. Olson and F. E. Brlnckman

6. PERFORMING ORGANIZATION (If Joint or other than NBS. tee tn structlon t)

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, O.C. 20234

7. Contract/Gtant No. N68305 82MP20019

I. Type of Report & Period Covered

Final

9. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street. City. State, ZIP)

Naval Civil Engineering Laboratory

Port Hueneme, CA 93043

10. SUPPLEMENTARY NOTES

I I Document describes a computer program: SF-185, FIPS Software Summary, is attached.

111.

ABSTRACT (A 200-word or less factual summary of most significant information. If document Includes a significant

bibliography or literature survey, mention it here)

This report describes a method for determining rates of release of organotin

species leaching from wood pilings impregnated with organotin-containing

copolymers and discusses short and long term results. The analytical method

consists of simultaneous extraction/hydridization of aqueous leachate samples,

followed by organotin speciation by gas chromatography coupled with tin

selective flame photometric detection (GC-FPD). The detection limit for the

butyltin family of organotins is 0.1 to 0.2 ng, depending on the species. The

butyltins (mono- through tetrabutyltin) are speciated within a 15 min

chromatogram, which also provides speciation of any methy Ibutyltin compounds

that may be present in the sample. Water samples were collected from the

leaching tanks immediately upon immersion of the wood pilings and at intervals

thereafter for approximately 1 year. Speciation and release rate data were obtained on both the early, first order stage of organotin release, and the

latter, zeroth order phase of controlled release. Instrument calibrations

were performed using a specially prepared aqueous butyltin research material.

1

12.

KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key words by semicolons)

butyltin compounds; chemical speciation j element selective detection; extraction;

gas chromatography; hydrldlzatlon

1 1

13.

AVAILABILITY

[^'Unlimited

I I Fo^Officlal Distribution. Do Not Release to NTIS

r I Order From Superintendent of Documents, U.S. Government Printinj Office. Waihintton, D.C.

20402.

I I Order From National Technical Information Service (NTIS), Sprinxfield, VA. 22161

14, NO. OF

PRINTED PAGES

15. Price

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