eyp 2005 - mms conferencing · 2008-06-13 · eyp 2005 “lab on a ship – obtaining high quality...
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EYP 2005EYP 2005
““Lab on a ship – Obtaining high quality analytical data in adynamic environment”
Professor Paul Worsfold
Biogeochemistry & Environmental Analytical Chemistry(BEACh) Group
School of Earth, Ocean and Environmental Sciences
University of Plymouth
Plymouth, England
email [email protected]
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““Challenges in the determination ofChallenges in the determination ofnutrient species in natural watersnutrient species in natural waters””
• Environmental Analytical Chemistry and Biogeochemistry•New measurement technologies and methods; high temporal andspatial resolution data; interaction of chemistry with biology, ecology& ecotoxicology and with land use, hydrology, physicaloceanography, GIS & modelling; emerging legislation; physico-chemical speciation (including colloids), data quality.
• Major nutrients (N and P species) in Freshwater / Terrestrial systems•Flow injection with solid state detection, instrument design, in situdeployment, estuarine transects, eutrophication, catchmentmanagement (Water Framework Directive), colloids (FFF), CRMs.
• Minor nutrients (Iron species) in Marine systems•Flow injection with chemiluminescence detection, picomolardetection limits, selectivity and contamination, Atlantic transects,Southern Ocean (SOIREE) fertilization and iron budget, iron redoxspeciation, size fractionation, siderophore identification,intercomparison exercises.
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Environmental Analytical ChemistryEnvironmental Analytical Chemistry
Understandingenvironmental
processes
High qualityanalytical chemistry
data
LIMITING FACTORHypothesisgenerating
Data archivingand datamining
Other chemical,biological, physical andsocio-economic factors
Hypothesistesting
Legislation
Novel techniquesand methods
High temporaland spatialresolution
Detection limit
Qualityassurance
Speciation
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Environmental monitoring objectivesEnvironmental monitoring objectives•• The aim is to obtain high quality analytical data in orderThe aim is to obtain high quality analytical data in order
to:to:•• Elucidate environmental processes and biogeochemicalElucidate environmental processes and biogeochemical
cyclescycles•• Study chemical fluxes, pathways and fatesStudy chemical fluxes, pathways and fates•• Test and generate environmental hypothesesTest and generate environmental hypotheses•• Monitor compliance with legislation, e.g. WFDMonitor compliance with legislation, e.g. WFD•• Provide archival data and baseline surveys, e.g. EIAProvide archival data and baseline surveys, e.g. EIA•• BUT sampling is expensive and time consumingBUT sampling is expensive and time consuming•• AND sample integrity may be lostAND sample integrity may be lost THEREFORE we need THEREFORE we need in situin situ monitoring monitoring
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River Frome PORiver Frome PO44-P storage-P storage
01234
0 20 40 60 80Day
PO4 -P
(uM
)
0.00.51.01.52.0
0 20 40 60 80Day
PO4 -P
(uM
)
01234
0 20 40 60 80Day
PO4 -P
(uM
)01234
0 20 40 60 80Day
PO4 -P
(uM
)
01234
0 20 40 60 80Day
PO4 -P
(uM
)
01234
0 20 40 60 80Day
PO4 -P
(uM
)
Fridge ControlFridge Control Fridge ChloroformFridge Chloroform Freezer ChloroformFreezer Chloroform
FridgeFridge FreezerFreezer Deep FreezerDeep Freezer
Water Research 35 (2001)3670
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In situ environmental monitoringIn situ environmental monitoring•• The aim is to provide high quality data with excellentThe aim is to provide high quality data with excellent
temporal and spatial resolution for process studies andtemporal and spatial resolution for process studies andmapping. For this we require:mapping. For this we require:
•• Rugged, portable, automated instrumentationRugged, portable, automated instrumentation•• Contamination free environment (includes reagents,Contamination free environment (includes reagents,
containers, sampling apparatus, shipcontainers, sampling apparatus, ship))•• Sensitive and selective detectionSensitive and selective detection•• Removal of matrix interferences e.g. sea saltsRemoval of matrix interferences e.g. sea salts•• System stability (reagents, standards, pumps, detector,)System stability (reagents, standards, pumps, detector,)•• On-board filtration and prevention of On-board filtration and prevention of biofoulingbiofouling•• Remote calibration, validation and maintenanceRemote calibration, validation and maintenance•• FLOW INJECTION and CONTINUOUS FLOW techniquesFLOW INJECTION and CONTINUOUS FLOW techniques
meets these requirements.meets these requirements.
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High qualityanalytical chemistry
data
LIMITING FACTOR
High Quality data forN & P (also Si, C)
LIMITING FACTOR
Macronutrients in natural watersMacronutrients in natural waters
Understandingenvironmental
processes
Hypothesisgenerating
Data archivingand datamining
Other chemical,biological, physical andsocio-economic factors
Hypothesistesting
Legislation
Novel techniquesand methods
High temporaland spatialresolution
Detection limit
Qualityassurance
Speciation
UnderstandingEutrophication
WFD
Excessive nutrientloads causeeutrophication.
FI, Ecotox,ISEs
Diurnal, seasonalcycles. estuarine
transects
uM – nM
CRMs,intercomparisons,
stability
Inorganic/organic
E.A. database.Predictivemodels
pH, DO, chl. a, turbidity,river flow, rainfall, land use,human & animal populations.
Inorganic/organicspeciation & N/P ratioare the critical factors.
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Water Framework DirectiveWater Framework Directive• Defines the need to establish
monitoring programmes todetermine water status.
• Provides management based onriver basins (catchments).
• Nutrients are key chemicalparameters because eutrophicationis a major water quality issue.
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Challenges in monitoring macronutrientsChallenges in monitoring macronutrients• High temporal resolution, e.g. transient events, diurnal
cycles• Long term deployment, e.g. seasonal trends• Good spatial resolution, e.g. catchment management,
estuarine modelling• Acceptable accuracy, precision and detection limit• Speciation capability for N and P• Sediment-water, atmosphere-water and water column
processes• Need to measure other physico-chemical parameters
and hydrographic data
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Flow injection analysisFlow injection analysisPump
Injection valve
Mixing coil Detector
WasteData output
Time (s)
Resp
on
se
Sample
Carrier stream
•On-line physical sample treatment•On-line chemical sample treatment•Speed, flexibility and low cost•Automated & reproducible samplepresentation• Easily automated, rugged and portable•Automatic on-board calibration•Enclosed environment (reducedcontamination)•Compatible with most detection systems
Http://Http://www.fia.unf.eduwww.fia.unf.edu (Stuart Chalk)(Stuart Chalk)Http://Http://www.flowinjection.comwww.flowinjection.com ((EloElo Hansen) Hansen)
Focused LED (6000 mcd)
Photodiode, Peak Response at 560nm
Path length20 x 1.5 mm
Inlet
Outlet
Microscopicallydeburred andpolished toprevent bubbletrapping
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Submersible nitrate manifoldSubmersible nitrate manifold
Ammonium chloride(10 g l-1)
Mixed colourreagent
0.32
0.16
Flow cell
1 m reaction coil
ml min -1Packed reduction column
260 ul sample injected via 5 um filter
20 mm path: LOD 2.8 ug L-1 N
Linear range 5 - 100
10 mm path: LOD 85 ug L-1 N Linear range 100 - 2500
ACA 361 (1998) 63
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CRM for nutrients in seawaterCRM for nutrients in seawaterNitrate z scores
-8
-6
-4
-2
0
2
4
6
2b 2a 23a
3b 5a 7b 3a 29b
14a
5b 14b
15b
29a
21a
10b
26b
25b
21b
25a
11a
16a
19b
26a
9a 11b
18a
6b 1b 7a 12b
19a
1a 9b 16b
31b
18b
6a 12a
30a
30b
32b
4b 31a
32a
4a 27a
27b
15a
FI a
SF
A a
SF
A b
FI b 8b 23
b24
b8a 17
a10
a17
b24
a
Laboratory
z sc
ore
s
NOAA TechnicalMemorandum 143
MOOS-1 nowavailable from NRCin Canada as astable seawater CRMfor nutrients.
30 participatingexpert laboratoriesof which Plymouthwas the only non-North Americanrepresentative.
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North Sea Submersed DeploymentNorth Sea Submersed Deployment
0
10
20
30
40
50
Nitr
ate-
N(m
g/L
x10
0). T
urbi
dity
(pp
m)
29.15
29.55
29.95
30.35
30.75
Salin
ity (
1/PS
U x
100
0)
1145 19451345 1545 1745
Time (BST)
Submersible Sensor Turbidity Salinity AutoAnalyzer
High Tide: 1230 Low Tide: 1930
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PTFE tubing0.75mm i.d.Perspex cylinder
PTFE support screenMembrane filterPTFE spacer
PerspexblockPlan view
8 l min-1
Side view
5-10 ml min-1
Tangential filtration unit for turbid watersTangential filtration unit for turbid waters
Dual channel sampling from turbid waters
Analyst 125 (2000) 51
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Portable gas pressurised FI manifold for PPortable gas pressurised FI manifold for P
S, sample inlet; PP, peristaltic pump; TFF, 0.2 µm tangential flow filter; FS, differential flowsplitter; PG, propellant gas and regulator; MC, mixing coil; FC, flow cell; V0, 2-way valve; V1,V2 and V3, miniature solenoid valves; R1, ammonium molybdate reagent; R2, tin(II) chloridereagent; Std, standard; W, waste; 0.5 mm id PTFE tubing for liquid flow and gas delivery
Talanta 58 (2002) 1043
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Manifold for dissolved phosphorus speciationManifold for dissolved phosphorus speciation
Acid Peroxydisulphate
690
Sample(600 ul)1.3
1.0
0.5
0.4
ml min-1
Water
Ammonium Molybdate
Tin(II) Chloride
.
UV photoreactor
Debubblers
Mixing Coils
Talanta 45 (1997) 47
P speciation manifold;Lamp off gives DRP; lamp on gives DRP + DOP (+ condensed P)
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Novel features of gas pressurised manifoldNovel features of gas pressurised manifold
Rapid segmentation of thereagent and sample streams
Multi-reflection photometricflow cell
ACA 499 (2003) 81
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High throughput phosphorus mappingHigh throughput phosphorus mappingTalanta 58 (2002) 1043
•Port Phillip Bay•225 analyses per hour.•542 analyses over 150 km.
0
10
20
30
40
50
60
Time
0
5
10
15
20
25
Yarra river salinity gradient trials
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Organic P release from sedimentOrganic P release from sediment
0
10
20
30
40
50
60
70
70 90 110 130 150 170 190Time elapsed (hr)
P co
ncen
trat
ion
(µg
L
P)
Inorganic P Organic P
5 ‰10 ‰
15 ‰
20 ‰
Water Research 38 (2004)688
Release of filterableorganic phosphorus(FOP) and filterablereactive phosphorus(FRP) from aerobicriver sediment as afunction of increasingsalinity.Elapsed time refers tototal time of theexperiment andincludes equilibrationtime prior to seawateradditions.Mean control concs. forFRP/FOP over 4-dayexperiment were 17.5 ±4.6 and 17.0 ± 4.8 µg L-1
P respectively (±2s,n=16).
Concentration data volume corrected and error bars ± 2s (n = 3).
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Data output
Computer
Data acquisition
Control
Standard
Sample
Gas diffusion cell
BTBWater
635nm
Waste
All 0.7 ml min-1
50 cmreaction
coil
NaOH
Integrating in situ chemistry & ecotoxicologyIntegrating in situ chemistry & ecotoxicologyACA 314 (1995) 33
96 hour exposure tests
Heart rate monitor
PhagocytosisAssay
cell viability and health
Neutral RedAssay
cell viability and health
Stress?
Sub-lethal Exposures
FI Ammonia gas diffusionmanifold (minimal reagents)
LED sensors to monitorcardiac activity inorganisms, e.g. crayfishand swan mussels
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Integrated chemical / ecotoxicology monitorIntegrated chemical / ecotoxicology monitor
Physical probeslogger
Ammonia
CAPMON Computer
Computer
Computer
Reservoir
PumpOverflow
Holding tank
Test organisms - crayfish (Pacifastacus leniusculus)
Sample
Ecotoxicology 8 (1999) 225
0.1 1.0 5.0 15 30Ammonia (mg l-1)
Heart rate (bpm)
Control40
80
120
160
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Colloids in environmental matricesColloids in environmental matrices
Traditional membrane filtration techniques use filter pore sizes of 0.2 or 0.45 µmto operationally define the ‘dissolved’ and ‘particulate’ fractions, therefore boththe dissolved and particulate fraction will include colloidal material
0.2
0.001 µm 0.01 µm 0.1 µm 1 µm 10 µm 100 µm
COLLOIDS
Colloidal NOM, Humic colloids
Amorphous iron and manganese oxides
Clay minerals
Bacteria
0.45
Algae
Colloidal material (0.001 – 1 µm) in soil leachate and agricultural drainagewaters is an important mechanism for the transport of contaminants
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Flow Field Flow Fractionation (Flow Field Flow Fractionation (FlFFFFlFFF))Crossflow
Frit
SpacerMembrane
FritChannel Flow
Frit
Crossflow
Membrane
Channel floww
Frit
l l
Field-flow fractionation (FFF) is anemerging family of techniques usedto obtain information on particle sizeor relative molecular mass (RMM)distributions in complex matricessuch as environmental andbiological samples.
Flow FFF (FlFFF) is the most widelyused version of the technique and isapplicable to macromolecules,particles and colloids ranging from0.001 µm (approximately 1,000molecular mass) up to at least 50 µmin diameter. w = 50 – 250 um.
Trends in Analytical Chemistry 22 (2003)615
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Soil solutions Soil solutions –– Centrifugation vs. Filtration Centrifugation vs. FiltrationAnalysis by Sedimentation FFFAnalysis by Sedimentation FFF
Time basedcentrifugation to give<0.45 and <0.2 um cut-off(axis in um).
Membrane filtration togive <0.45 and <0.2 umcut-off (axis in time(s)).
Clayey Lilydale soil solution settled to give <1.0 um fraction prior tocentrifugation and filtration. Membrane filtration recovered 79% lessmaterial than centrifugation for the <0.45 µm and 73% less for the <0.2µm fractions
(A)
0
10000
20000
30000
40000
50000
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Diameter (µm)
Rel
ativ
e m
ass
<1 µm<0.45 µm centrifuged
<0.2 µm centrifuged
(B)
0
1
2
3
4
5
6
0 1000 2000 3000
Time (s)
Ab
sorb
ance
(ar
bit
rary
u
nit
s)
<1 µm
<0.45 µm filtered
<0.2 µm filtered
(B)
0
1
2
3
4
5
6
0 1000 2000 3000
Time (s)
Ab
sorb
ance
(ar
bit
rary
u
nit
s)
<1 µm
<0.45 µm filtered
<0.2 µm filtered
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High qualityanalytical chemistry
data
LIMITING FACTOR
High quality data foriron species.
LIMITING FACTOR
Hypothesistesting
Legislation
Micronutrients in natural watersMicronutrients in natural waters
Understandingenvironmental
processes
Hypothesisgenerating
Data archivingand datamining
Other chemical,biological, physical andsocio-economic factors
Novel techniquesand methods
High temporaland spatialresolution
Detection limit
Qualityassurance
Speciation
Understandingiron
fertilization
Hypothesistesting
LegislationUNEP/ICES
Iron is a ratelimiting nutrientin HNLC regions
FI-CL,preconcentration
Surface transectsand depth profiles
nM - pM
CRMs,intercomparisons,
contamination
Redox, colloidal
Fe biogeochemistryClimate modelling
DO, DOC, chl. a, turbidity,salinity, temperature,macronutrients, depth
Fe(II) is an importantspecies in surface
waters
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Iron biogeochemistry & analytical challengesIron biogeochemistry & analytical challenges
• Major component of Earth’s crust (and research vessels!)• Highly reactive trace element• Dissolved Fe in seawater at very low concentrations (sub-nM)• Complex biogeochemistry, e.g. redox speciation, organic
complexation (siderophores, porphyrins), colloids• Speciation studies (e.g. Fe(II)/Fe(III) at even lower concns.
(pM)• Essential trace micro-nutrient for phytoplankton• Bio-limiting in HNLC (High nutrient, low chlorophyll) regions,
implications for global carbon cycles
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Fe biogeochemical cycleFe biogeochemical cycle
Fedesorption
volcanic Fe
aeolian
dry deposition wet deposition
continentalshelf anaerobic
sediments
deep ocean
upwelling
sinking
hydrothermalvents
aggregation
assimilation
grazing trophicrecycling
riverineFe2+
Fe3+
FeLx
FeLy
O 2
sedimentation
light
L = iron bindingligands such ashydroxamate andcatacholatesiderophoreswith high stabilityconstants
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Historical open ocean Fe concentrationsHistorical open ocean Fe concentrationsYYYeeeaaarrr Concentration (nM)
100 - 800
0.2 - 2.0
25,000 1924500 - 1400 1931
193560 1954
19890.6 1996
Profile of Fe in North Pacific (fromJ.H. Martin et al., Deep Sea Research,1989, 36: 649)
-4000
-3000
-2000
-1000
0
0.0 0.2 0.4 0.6 0.8 1.0
Fe (nmol kg-1)
Dep
th (
m)
2003 0.3Decreases in reportedconcentrations due to improvementsin analytical protocols rather thanenvironmental change.
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In general laboratory:1. Immerse 50 1 L LDPE bottles in 5% detergent bath (e.g. Decon, Merck) for a week.2. Rinse 3x with DI water thoroughly until there is no trace of detergent.3. Rinse 3x with UHP (ultra-high purity; e.g. Milli-Q) water.4. Immerse in 6 M analytical grade HCl bath (2 weeks, e.g. Aristar, Merck BDH).5. Rinse 3x with UHP water.6. Immerse in 3 M analytical grade HNO3 bath (2 weeks, e.g. Aristar, Merck BDH).7. Rinse 3x with UHP water.
In clean air (class-100) laboratory:8. Fill with UHP water and acidify to pH 2 with 1 ml ultra-pure Q-HCl (9 M)
per 1 l UHP sample (ultra-pure Q-acids are sub-boiling quartz distilled reagents).9. Double bag, seal and store inside large plastic bag within plastic box until use.
10. Sample collection: empty acidified UHP water, rinse 3x with UHP,rinse 3x with seawater sample, fill and acidify sample (if necessary). Double bag, seal and store for analysis.
Protocols for washing sample bottlesProtocols for washing sample bottlesACA 442 (2001) 1
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Shipboard FI-CLShipboard FI-CL•• Flow injection with chemiluminescence detection (FI-CL)Flow injection with chemiluminescence detection (FI-CL)•• Wide dynamic range and sub-Wide dynamic range and sub-nanomolarnanomolar detection limits detection limits•• Robust, low power, low cost, automated instrumentationRobust, low power, low cost, automated instrumentation•• Selectivity and preconcentration via solid phase chelatingSelectivity and preconcentration via solid phase chelating
micro-columnsmicro-columns•• Sample treatment on-line, e.g. digestion, reduction,Sample treatment on-line, e.g. digestion, reduction,
chelationchelation•• Low blanks due to closed environment & in-line reagentLow blanks due to closed environment & in-line reagent
clean-upclean-up•• Excellent temporal and spatial resolutionExcellent temporal and spatial resolution•• Immediate results and potential for in situ measurementsImmediate results and potential for in situ measurements
Analytical Chemistry 66 (1994)916A
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Luminol reactionLuminol reaction
+ h
-hydroxy hydroperoxide intermediateαluminol
O
2NH
NH2
NH2
2NH
NH
NH
O
O
N
NO- OOH
CO
O-
-O
OC
O
OC
O
OC
H
H
3-aminophthalateexcited state 3-aminophthalate dianion
υ
Base (pH 10.5)
O2 + Fe(II)
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FI-CL manifold for ironFI-CL manifold for iron
Waste
Chartrecorder
Spiralflow cell PMT
Light-tighthousing
Injectionvalve
8-HQ column
'T'-piece
Mixingloop
Reagents pump
ml / min
Sample pump
Wash pump
Autosampler
HCleluent
UHP water
Acid wash
Buffer
Luminolreagent
REAGENT &SAMPLE BOX
‘Y’
1.6
1.6
1.6
1.6
0.2
C
8-HQ
V
V
V
HVsupply
Amp
PC controlunit
Fe(II+III) analysisafter S(IV) reduction
ACA 361 (1998) 189
LOD 40 pM; Range 0.04 – 10 nM; Analytical cycle 3 min;NASS-4 2..01 +/- 0.12 nM cf. certificate of 1.88 +/- 0.29 nM
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Matrix elimination / preconcentrationMatrix elimination / preconcentration
Quartz wool
10mm8-HQ
2.4mm i.d.PTFE 0.75mm i.d.
PTFE
0.089mm i.d.Tygon
8-hydroxyquinoline immobilisedon Toyopearl gel (TSK-8HQ)
Interferences• sea-salt matrix (alkaline-earth metals, halide ions)• selectively preconcentrate Fe ions from seawater– 8-HQ chelating resin microcolumn• highly selective for transition metal cations• redox selectivity using pH buffering control• use in-line before detection mechanism• active groups immobilised on solid support beads
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Underway sampling for trace metalsUnderway sampling for trace metals
Container Lab
RRS James Clark RossRRS James Clark Ross
Kevlar cable
Torpedo fish
FI-CLOn-line
filter
Go-Flo bottles (5-30 L)Vertical profilingSuspended on Kevlar wire
Towed torpedo fishUnderway surface seawaterOn-line uncontaminatedsupply for filtration andanalysis
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AMT-3 latitudinal surface transectAMT-3 latitudinal surface transect
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
-60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60
Latitude (S-N)
Sh
ip T
D-F
e (n
M)
Celticshelf
Saharandusts
Equatorialregion
Frontalsystem
Falkland’sshelf
Averageerror
.
FIC SWApp
NEAOGSAOG NEq/SUp
Eq NWAUpAtlantic Province:Atlantic Province:
Deep Sea Research 1, 49 (2002) 605
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Cruise TrackCruise Track
64oS
40oS
48oS
56oS
140oE
170oE
SouthernOcean
SSouthern outhern OOcean cean IIron ron REREleaselease EExperimentxperiment
Aim: To raise the background level of iron ina coherent patch of seawater and interpretany iron-mediated effects by conducting asuite of biological, chemical and physicalexperiments INside and OUTside thefertilised patch
Release site: 61oS, 141oE HNLC region (ca. 0.25 µg Chl-a l-1) ca. 10 tonnes FeSO4 added over 13 d Inert tracer SF6 used to map patch
First Southern Ocean unenclosed ironenrichment experiment
RV Tangaroa, NIWA (NZ) Previous Equatorial Pacific
experiments
http://tracer.env.uea.ac.uk/soiree
Nature 407 (2000)695
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Southern OceanSouthern Ocean
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Redox speciation (Redox speciation (Fe(IIFe(II) stable in seawater!)) stable in seawater!)[F
e] (n
M)
012345678
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Days since beginning of experiment
D-Fe (nM)D-Fe (nM)Fe(II) (nM)Fe(II) (nM)InfusionInfusion
61.061.0oo SS
60.560.5oo SS
141141oo EE 143143oo EE142142oo EE140140oo EE
Distance (km)
0 20 40 60 80 100
61.061.0oo SS
60.560.5oo SS
141141oo EE 143143oo EE
Distance (km)
0 20 40 60 80 1000 20 40 60 80
SeaWiFSsatellite imageof bloom
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Iron speciation in the Southern OceanIron speciation in the Southern Ocean
0
10
20
30
40
50
21:00 22:00 23:00 00:00 01:00 02:00 03:00 04:00 05:00
8HQ
reac
tive
-Fe(
II) (
pm
ol l
-1),
% F
e(II)
/ F
e(II+
III)
0
50
100
150
200
250
300
Dis
solv
ed F
e(II+
III)
(pm
ol l
-1)
Fe(II) (±1s)
% Fe(II) / dissolved Fe(II+III)
Dissolved Fe(II+III)
Environmental Science & Technology 36 (2002)4600
Approx. 5 - 10% of the dissolved iron is present as Fe(II).Hypothesis: bacterial and/or photochemical reduction.
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?
SOIREE Iron BudgetSOIREE Iron Budget
19 pM
Dissolved FeParticulate Fe(inorganic & detrital)
SOIREE Feenriched patch(141oE, 61oS)
OUTpatch IN
patch
Upper mixedlayer 65 m
Atmospheric flux
Sinking biogenic Fe(from sediment
trap data,mostly diatom aggregates)
Patch area 56 to 200 km2
Upwelling
0.004 pM d-1 185 pM d-1
?
Sinking non-
biogenic Fe
72 pM d-1
Biogenic Fe
Diffusive flux(pre-infusion)
Eddy diffusion(post-infusion)
Four Fe infusions over 13 d (ferrous sulphate solution)
Horizontaldispersion
180 pM d-1
1073 pM 1110 pM
negligible0.1 pM d-1 0.85 pM d-1 0.72 pM d-1
58 pM
11.9 7.3
11.9 3.3
Producers Micro-zooplankton
Meso-zooplankton
?
Sinking mesozooplankton biogenic Fe
(predicted from biogenic budget)
0.79 pM d-1
6.5
25.2 pM
Deep Sea Res. II 48 (2001)2703
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SPE-LCMS for SPE-LCMS for detndetn. of . of siderophoressiderophores in seawater in seawater
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30Time (min)
0
20
40
60
80
100
20
40
60
80
100
Rel
ativ
e A
bund
ance
NL: 6.31E7
NL: 1.38E6
a
b
FeRA
FeFO
FeFC
a) Total ion chromatogramfor a seawater sample after1400 × preconcentration onan ENV+ SPE cartridge.b) Extracted masschromatograms for thethree spiked iron(III)hydroxamate siderophores rhodotoluate (FeRA),ferrioxamine (FeFO) andferrichrome (FeFC).
LODs (nM):FeRA 26, FeFO 0.23, FeFC 0.40.
Stationary phase: 100 × 2.1 mm 3 µm polystyrene divinyl benzene. Mobile phase: (A) 95 H2O: 5 MeOH: 0.1 formic acid, (B) 100 MeOH: 0.1 formic acid.Gradient elution 100% A – 100 % B; 20 min, then 100 % B; 10 min.
Analytical Chemistry 75 (2003) 2647
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Siderophore extractions from incubated seawaterSiderophore extractions from incubated seawater
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30Time (min)
0
20
40
60
80
1000
20
40
60
80
100
Rel
ativ
e A
bund
ance
NL: 5.88E7
NL: 2.29E6
600 610 620 630 640 650 660 670 680 690 700m/z
13
0246810
Rel
ativ
e A
bund
ance
627.4
629.4NL:2.59E5
m/z600 610 620 630 640 650 660 670 680 690 700
100
020406080
685.4
687.4
NL:2.04E6
a
b
c d
A
B
•Ferrioxamines areexcreted by species ofActinomycetes, a group ofbacteria foundubiquitously in seawaterand marine sediments.• A = FeFO, B = unknownsiderophore•Siderophores identifiedby substitution of Fe withgallium (Mr = 69 and 71,ratio 3:2) and monitoringshift in mass/charge ofparent ion
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Dust storm on 25Dust storm on 25thth Sept 2000 off Western Sept 2000 off WesternAfrica observed by SeaWiFS satelliteAfrica observed by SeaWiFS satellite
AnreiseAnreise dFe intercomparison, dFe intercomparison, Sep 29 Sep 29thth––Oct 23Oct 23rdrd 2000 2000
IRONAGES standard: collectionIRONAGES standard: collection
-10o
-20o
-30o
-40o
50o
40o
30o
20o
10o
0o
0o-20o 20o-40o-60o
Start
Finish
AtlanticAtlanticOceanOcean
<0.25 0.26- 0.50 0.51- 0.75 0.76- 1.00 >1.00
Dissolved Fe (nM)(UoP data)
Longitude (Longitude (ooEE))
Lat
itu
de
(L
atit
ud
e (oo
NN))
“IRONAGES”standard
collected here
(Provided by the SeaWiFSproject NASA/Goddard Space
Flight Center, and ORBIMAGE)
Towards a certified referencematerial for low level iron inseawater
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IRONAGES standard: samplingIRONAGES standard: samplingR.V. R.V. PolarsternPolarstern
HDPE tankHDPE tank
Towed fishTowed fish
• 1000 l HDPE cubic tank• Filled to 700 l over 8 h• South Atlantic Ocean, 6.0oS 5.6oW• Acidified to ~pH 2 using 700 ml Q-HCl• Homogenised by gentle shaking of
tank• Transfer from tank to clean laboratory
using Teflon FEP line and peristalticpump
• 200 x 1 l LDPE bottles filled
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Summary of intercomparison dataSummary of intercomparison data
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
SE-GFAAS
ID-ICPMS
FI-DPD
FI-CL Fe(II)
Overall average
Fe c
once
ntra
tion
(nM
)
FI-CL Fe(III)
CSV DHN
SPE-ICPMS
Method
averages
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ConclusionsConclusions• Determination of nutrient species in natural waters is a
key aspect of understanding environmental processes.• Analytical techniques and methods with appropriate
selectivity and detection limits are often the limitingfactor.
• In situ methods are required to provide the necessarytemporal and spatial resolution.
• Emerging legislation is also a driver for new analyticaltechnologies.
• Flow injection and continuous flow techniques canprovide suitable solutions to the above challenges.
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AcknowledgementsAcknowledgementsBEAChBEACh group group:: Malcolm Nimmo, Miranda Keith-Roach, Charly Braungardt,Richard Sandford, Alan Tappin.ResearchersResearchers:: Simon Ussher, Laura Gimbert, Utra Mankasingh, MohammedOrif, Nduka Omaka, Angie Milne, Cathryn Money, Ed Mawji, Marie Seguret,Rebecca Nimmo Smith, Stephanie Handley, Andy Cartwright.CollaboratorsCollaborators:: Eric Achterberg and Martha Gledhill (SOC), Tamara Galloway,Mike Depledge (EA), Phil Haygarth (IGER), Ian McKelvie and Ron Beckett(Monash, Australia), Grady Hanrahan (CSU-LA), Andy Bowie (UTas, Australia),John Wood, Tony David (Daviron Instruments Ltd), Christophe Quetel (IRMM,Geel, Belgium), Chiang Mai University, Thailand, MBA and PML, CEH Dorset,CEH Wallingford.Erasmus linksErasmus links: : Oviedo, Vienna, Bologna, Valencia.Recent VisitorsRecent Visitors:: German Guttierrez, Orawan Tue-Ngeun, Dezhong Dan, DavidStiles, Mohammad Yaqoob, Yolanda Moliner-Martinez, Alexandra Exenberger.Recent SponsorsRecent Sponsors:: NERC, EU (MAST & SOCRATES), RSC/EPSRC, CEH, Defra,British Council, MBA, Saudi, Thai, Nigerian and Pakistan Govt. Agencies,HiPACT, EA.
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