Chalmers University of Technology

Usingthepassivesamplersystem
fornitrateandphosphate
monitoring
calibration,factorvariationanalysis
andfieldtrial
KatarinaSvensson,GregMorrisonandJesperKnutsson
ChalmersUniversityofTechnology

Chalmers University of Technology

PropertiesoftheEmporeanionSR
extractionDisk
Properties Empore Anion-SR disk
Average pore size
Average particle size
Surface area
Capacity per disk

80
12 m
2
350 m /g
> 0.20 meq

Poly (styrene-divinylbenzene)
copolymer
R1

CH2

CH

CH2

CH

Quatenary Ammonium
functional group

CH2

CH

R1

H
R1

CH

CH

CH2
CH2

CH2

CH

R1

H
+

R1

Chalmers University of Technology

Splitviewofthepassivesampler
1.
2.
3.
4.
5.
6.

Protectivemesh
Diffusionlimitingmembrane
(0.45mCA)
Receivingdisk(Empore
AnionSR)
Disksupport
Samplerhousing
Samplerhousing
(Bjrklund,2002)

Chalmers University of Technology

Diffusionalpathofapassivesampler
Diffusion limiting membrane
Aqueous diffusion layer

NO3HPO42-

concentration

NO3-

Acceptor phase

csi
cs

cmo
cmi
cwi

Diffusional path

cw

NO3-

Chalmers University of Technology

Calibration
Thesamplingrate(Rs)issubstance
specificandisexpressedasthe
volumeofclearedsamplepertime:

Rs

B
cw

WhereBistheslopeoftheuptake
curve,andcwistheaverage
concentrationofthesubstance
duringthecalibrationperiod.

Thetimeaveragedconcentrationin
thewaterphasecanthenbe
calculated:

Ms M0
cw
Rs t

Chalmers University of Technology

Calibrationresults
Nitrate calibration curve

Phosphate calibration curve

3500

1600
1400

y = 5.7621x + 684.43
R2 = 0.6286

Accumulation factor (mL)

Accumulation factor (mL)

3000
2500
2000
1500
1000
500

1200

y = 3.1406x - 0.8663
R2 = 0.9369

1000
800
600
400
200

0
0

50

100

150

200

250

300

350

400

450

t (h)

50

100

150

200

250

300

350

time (h)

Rs=75.7mLday1

Rs=138.5mLday1
Calibration
parameters
Temperature

14C

pH

7.0

400

450

Chalmers University of Technology

Factorvariationtest
Factoralexprimentdesignto
examinetheinfluenceofpH,
temperatureandturbulence

6.0
Nitrate
Phosphate

5.0

ANOVAanalysisofresults
3factorsand3levelsofvariation

Amount (mg)

4.0

3.0

2.0

pH5,7and9

1.0

temperature7,14and21C

0.0

turbulence50,200and400
rpm

5
Trial set

Chalmers University of Technology

Factorvariationtest
Temperature influence

amount (mg)

5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0

phosphate
nitrate

pH

disk amount (mg)

amount (mg)

pH influence

5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0

turbulence influence

5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0

phosphate
Nitrate

14
tempearature (C)

phosphate
nitrate

50

200
rpm

400

21

Chalmers University of Technology

Factorvariationtest
Temperatureisamajorfactor
influencingtheuptakerate,
whichcouldindicatethatthe
diffusionrateiscontrolled
mainlybytheboundrylayer

Influence of factors
100%

80%

60%
Other
Turbulence
Temperature
pH

40%

20%

Phosphateisalsosignificantly
dependantonpH.Seebelow.
Turbulenceisnotsignificant
atthevariationlevelschosen.

0%
Nitrate

Phosphate

-20%

H 3 PO4 pK a 2.1 H 2 PO4 pK a 7.2 HPO4 pK a 12 .4 PO4

Chalmers University of Technology

Ryawatertreatmentplanttrial
1.6

0.16
nitrate

1.4

phosphate

0.12

0.1

0.8

0.08

0.6

0.06

0.4

0.04

0.2

0.02

0
18-25 Aug

9-16 sept

16-23 sept

mg (phosphate)

mg (nitrate)

1.2

0.14

Chalmers University of Technology

Watertreatmentplantresults
Calculation of results

Calculation of results
0.25

4.5
4

0.2

3.5
3
c (mg/L)

c (mg/L)

0.15
2.5
2

Sampler Cw (mg/L)

Sampler Cw (mg/L)

WTP data c (mg/L)

WTP data c (mg/L)

0.1

1.5
1

0.05

0.5
0

0
WTP 1

WTP 2

WTP 3

WTP 1

trial

WTP 2
trial

Calibration

Field

Temperature

14C

19.619.0C

pH

7.0

6.96.6

WTP 3

Chalmers University of Technology

Furtherworkanddevelopment
Redothenitratecalibrationcurve
Findanddevelopaninternalorexternalstandard
Performfurtherfieldtrials
Performfurtherfactorvariationanalysis

Chalmers University of Technology

Calibrationofpassivesamplers
forselectedtargetmetals
(Cu,Cd,PbandZn)
KatarinaSvensson,GregMorrisonandJesperKnutsson
ChalmersUniversityofTechnology

Chalmers University of Technology

Calibration Database
for metallic Pollutants

Metals: Cu, Cd, Pb, Zn and Ni

Concentration range: 1, 10 and 50 g/l
Temperature range: 4, 11 and 18C
Convection : none, 40 and 70 rpm
pH 7
Buffer 0.01M PO43Diffusion Membrane: Cellulose Acetate 0.45m
Receiving Phase: 3M Empore Chelating extraction disk

Chalmers University of Technology

Flow-through system for Constant

Concentrations
constantbulkconcentrationsetup(flowrate
>>Rsxn)
termostatecontrolledbulktemperature
rotatingturntableforhomogenous
convection

Chalmers University of Technology

Loaded Turntable

Chalmers University of Technology

PropertiesoftheEmporeChelating
extractionDisk
Properties of the Empore Chelating disk
Sorbent
Average particle size
pH stability
Functional group

AtpH=2,thecarboxylategroupsareionizedandexist
asneutralspecies;however,thenitrogenwillhaveanet
positivechargeandthemoleculebehavesasaweakanion
exchanger.

Poly (styrene-divinylbenzene)
copolymer
R1

CH2

CH

CH2

CH

R1

CH

CH

CH2

CH

R1

CH2
CH2

IncreasingthepH>5ionizesthecarboxylategroupsand
botharenegativelycharged.

CH2

CH

Poly(styrenedivinylbenzene)
10 m
0-14
Sodium salt of iminodiacetic acid

R1

AsthepHapproachesneutral,themoleculefunctionsasa
cationexchangerormetalcationchelator

Chalmers University of Technology

Conditioningandelution

Chalmers University of Technology

Conditioningandelution
Conditioning the chelating disk

Elution

Twoelutionswith10mLof3.0Mnitric
aicd
Note:somemetalsmightbedifficulttoelute
(e.g.Chromium)

Wetthediskwith20mLof
reagentwaterundervacuum.
Washthediskwith20mLof
3.0Mnitricacidor3.0M
hydrochloricacidfollowedbytwo
50mLwaterwashes.Letthedisk
godrybetweeneachwash.
Toputthediskintheammonium
form(itsmostactiveform),wash
with50mLof0.1Mammonium
acetatebufferatpH5.3followed
byseveralreagentwaterwashes.

Analysis
PerkinElmerELAN6000ICPMS
instrumentandcommercialcalibration
standards.
Instrumentisoptimizedtomeet
manufacturerspecifications

Chalmers University of Technology

Samplingrates
1200

1000

1000
y = 2.48x + 69.77
R2 = 0.96

800
600

Zn 64

400
200

accumulation factor (mL)

accumulation factor (mL)

Rs=59.5mLday1

1200

0
0

100

200

300

Rs=78.8mLday1
y = 3.2774x - 44.463
R2 = 0.9833

800
600

Pb

400
200
0

400

100

time (h)

y = 3.6945x + 0.2613
R2 = 0.9784

400

Rs=52.6mLday1

1000

800
600

Cd

400
200
0

accumulation factor (mL)

1000
accumulation factor (mL)

300

1200

1200

Rs=89mLday1

200
time (h)

y = 2.1895x + 37.086
R2 = 0.9699

800
600

Cu 63

400
200
0

100

200
time (h)

300

400

100

200
time (h)

300

400

Chalmers University of Technology

Considerationsforfielduse

Possiblecontaminationofsamplerduringtransport/handlinguseaproceduralblank
sampler
Samplermountingdependantonthesamplingsituation
Physicalinterferacefromhumanactivityifpossiblechoosesamplingspotinrestricted
accessareas
Otherphysicalinterference(debrislikebranches,leafsetc)
Biofoulingbioinhibitors,internal/externalstandardcorrection

Chalmers University of Technology

Internalstandardforchelating
disks?

PreloadingthediskusingforexampleCu
Saturatingthediskvs.limitedamount
Triggeredreleaseapplyingsmallamountofacidtothediskbeforedeployment