BallastBallast Water Exchange Verification Water Exchange Verification Using the Optical Characteristics of Using the Optical Characteristics of

Dissolved Organic MatterDissolved Organic Matter

Jennifer R. Boehme and Mark Wells

University of MaineDarling Marine Center

• 10,000s of organisms daily transported in ballast tanks

• 21 billion gallons of ballast discharged in North America annually

• Treatment measures up to 10 years away

Species Transport via Ballast WaterSpecies Transport via Ballast Water

Ballast water exchange locations (SERC)

Goal Goal -- Reduce invasive species transport Reduce invasive species transport

BWE currently the only accepted means of controlling spread of eBWE currently the only accepted means of controlling spread of exotic xotic species Murphy et al., 2004species Murphy et al., 2004

U.S. moving quickly towards mandatory exchange for all U.S. moving quickly towards mandatory exchange for all vesselsvessels

Ballast Water Exchange Ballast Water Exchange -- VerificationVerification

450

350

250

Exci

tatio

n (n

m)

A

C/M

300 400 500Emission (nm)

Monitoring challengeMonitoring challenge

Salinity methods not always definitive

Optical characteristics of seawater Optical characteristics of seawater -- chromophoricchromophoricdissolved organic matter (CDOM)dissolved organic matter (CDOM)

Absorbance

Fluorescence via Excitation Emission Matrix Spectroscopy

Fluo

resc

ence

(QSE

)

300 400 500Emission (nm)

BATS seasonal CDOM absorption (Nelson and Siegel, 2002)

World Oceans World Oceans -- CDOM Variability CDOM Variability Seasonality and PhotochemistrySeasonality and Photochemistry

Summer

Winter

http://seawifs.gsfc.nasa.gov/SEAWIFS/IMAGES/IMAGES.html

World Oceans World Oceans -- CDOM Variability CDOM Variability Biological ProductivityBiological Productivity

World Oceans World Oceans -- CDOM Variability CDOM Variability Terrestrial RunoffTerrestrial Runoff

August 2000

Boehme et al., 2004

World Oceans World Oceans -- CDOM Variability CDOM Variability What We KnowWhat We Know

Observed Seasonal Changes

Biological production

PhotochemistryTerrestrial runoff Species Composition?

In addition, potential for CDOM variability In addition, potential for CDOM variability based on differences in regional ecologybased on differences in regional ecology

WWorld Oceans orld Oceans -- Biogeochemical ProvincesBiogeochemical Provinces

Pauly et al., ICES 2000 Annual Science Conference

DOM Variability DOM Variability -- StatisticsStatistics

???

Statistics are useful in discriminating changes Statistics are useful in discriminating changes in DOM fluorescence via EEMSin DOM fluorescence via EEMS

Mahlinobis distance (Murphy et al, 2004); 12 wavelength pairsPARAFAC (Stedmon et al., 2003); 3d

Principal Component Analysis Principal Component Analysis –– PCA PCA ((BoehmeBoehme et al., et al., 2004); 3d2004); 3d

DOM Variability DOM Variability -- PCAPCA

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PC1

• Clusters: similar EEM, water masses

DOM Variability DOM Variability -- PCAPCA

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26

28

30

32

• Over 600 samples• Water masses identified• Basis for global

database

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-11 -9 -7 -5 -3 -1 1 3 5

Oligotrophic

Marine Transitional

Atchafalaya

Mississippi

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DOM Variability DOM Variability –– PCA and Ballast Water PCA and Ballast Water ExchangeExchange

• PCA of fluorescence data set from Murphy, et al. 2004

Fos Sur Mer (France), June 2001 S: 37.2-37.6

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Principal Component 1

Prin

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l Com

pone

nt 2

Side Exchange Control

Exchange 1

Exchange 2

Exchange 4

Exchange 3

San Francisco, November 2000 S: 20.6-22.5

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30

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Prin

cipa

l Com

pone

nt 2

ER Exchange FT Exchange Control

Exchange 1Exchange 2

Future work Future work –– instrument development instrument development

UN Atlas of the Oceans

AB

Two routes, one issue…

Future work Future work –– instrument development instrument development

UN Atlas of the Oceans

Case I: Verified exchange

A

Future work Future work –– instrument development instrument development

UN Atlas of the Oceans

Case II: more testing

B

SummarySummary

Ballast water exchange requirementsBallast water exchange requirements

USCG currently looking for verification testUSCG currently looking for verification test

DOM fluorescence a promising method, DOM fluorescence a promising method, independent of port salinityindependent of port salinity

Utility of statistical tests with EEMS Utility of statistical tests with EEMS provides a method of ballast water provides a method of ballast water exchange verificationexchange verification

• End

Ballast Water Exchange Ballast Water Exchange -- VerificationVerification••Fluorescence diagnostic propertiesFluorescence diagnostic properties

Changes of Wavelength, Spectral bandwidth,

Fluorescence Intensity

••Effectiveness based on our understanding of DOM Effectiveness based on our understanding of DOM variability in the global oceansvariability in the global oceans

Quantify seasonal and spatial differences

Murphy et al., Final Report to USCG R&D Center, 2001

Results : fluorescence of Results : fluorescence of CDOM has the greater CDOM has the greater potential for determining potential for determining ballast water exchangeballast water exchange

• Significant for removal of terrestrial CDOM in coastal waters

• Alters bioavailability of CDOM

• Alters measured fluorescence and absorption characteristics

World Oceans World Oceans -- CDOM Variability CDOM Variability PhotochemistryPhotochemistry

Siegel et al., 2002

DOM Variability DOM Variability -- PCAPCA

???

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PC1

Scores: Scores: differences differences between between samplessamples

• 3d EEMS based on CCD technology

• Fiber optic probes• Software development

– incorporate statistical comparisons

Future work Future work –– instrument development instrument development

Where can we go from here?Where can we go from here?

Spex 3D, JY Horiba