stefano polesellostefano polesello* *cnr*cnr- … · spm true solution particles and ... analytical...
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Twinning Bulgaria Twinning Bulgaria –– ItaliaItaliaTraining 3.3Training 3.3
Simitli 17Simitli 17--19 February 200919 February 2009
Water analysis for WFD:ypartitioning of organic pollutants
and “whole water” analysisand “whole water” analysis
Stefano POLESELLO*Stefano POLESELLO*Stefano POLESELLOStefano POLESELLO*CNR*CNR--IRSA, Water Research Institute, Brugherio, ItalyIRSA, Water Research Institute, Brugherio, [email protected]@irsa.cnr.it
Partitioning of organic pollutantsPartitioning of organic pollutantsPartitioning of organic pollutants Partitioning of organic pollutants between solid and liquid phases in between solid and liquid phases in
ttwaterwater
⇒ Basis is equilibrium partition⇒ Basis is equilibrium partition theory for sorption of organic pollutants to solids and biota inpollutants to solids and biota in aquatic systems
Chemical aspects• Sedimentation
Biological aspects• Bioavailability
Sedimentation
• Long distance transport
• Colloidal pumping
• Routes of exposure
• Trophic and indirect effects
• Feeding strategies
Environmental aspects-Sediment-water interactions
Modelling aspects -Hydrology and Geology
-Input variability
-Nature and concentration of
Modelling aspects-Contaminant partitioning (e.g., HAM, EqP) Colloids
True solutionSPM
particles and colloids
-Intrinsic pollutant properties
EqP)
-Contaminant bioavailability (e.g.,BLM, QSAR)
Colloids
Technical / analytical aspectsRegulatory
t -Sampling
-Sample preservation
-Sample fractionation
aspects-Sampling matrix
-Sampling frequency
-Technical limitations
-In situ techniques
-Sampling strategy (e.g., filtered vs. raw water)
From Vignati et al., submitted to TRAC
The solidThe solid--water distribution water distribution coefficientcoefficient
C equilibrium “constant” describing
iw
isid C
CK =q g
partitioning between solid and water phases
Cis = mol/kg solid or mg/kg solid
C l/L t /L lidCiw = mol/L water or mg/L solid
Kid = L/kg
This type of equilibrium constant assumes:All sorption sites have equal energyp q gyAn infinite number of sorption sites
The problem with sorption is that these twoThe problem with sorption is that these two assumptions are generally not true!
The complex nature of KThe complex nature of KddThe apparent distribution of a compound between water and solids (Kd) may be a result of many ( d) y ydifferent types of sorption processes.
These processes include:These processes include:exchangeableadsorption of
covalently bonded
d ti fsorption to organic carbon
adsorption to mineral surface
ionized form to charged surface
adsorption of ionized form to mineral surface
surfisurfisurfiocioc ACACACfCK rxn surfrxnex surfexmin ⋅⋅+⋅⋅+⋅+⋅
=σσ
ioniwneutiwid CC
K,, +
=
l i di l d h i fσ refers to conc
total amount in dissolved phase consists of neutral and ionized forms
of suitable sites (mol/m2)
the equilibrium “ ” K i“constant” Kd varies over more than an order of magnitude!order of magnitude!
Kd is strong function of foc
Therefore, define the organic-carbon normalized partition coefficient: K
oc
idioc f
KK =
But: how to obtain KBut: how to obtain KOCOC??
logKoc vs. logKow for PAHs i R it Bin Raritan Bay
Karickhoff (1981) has argued that the slope ofargued that the slope of this plot should be one.
So: K ≈ K ?So: KOC ≈ KOW?
! Others have observed slopes clearly < 1 !slopes clearly 1 !
Gigliotti et al. 2002
Algorithms for water monitoring dataAlgorithms for water monitoring dataAlgorithms for water monitoring dataAlgorithms for water monitoring data
log Klog KOCOC = 0.74 log K= 0.74 log KOWOW + 0.15+ 0.15OCOC OWOW
KKdd = C= CSS/C/CWW and Kand KOCOC = K= Kdd/f/fOCOC = C= CSS/(C/(CWW*f*fOCOC))
CCTT = C= CSS + C+ CWW[all expressed in mass per volume (e.g., μg/L)] and also [all expressed in mass per volume (e.g., μg/L)] and also CCWW = f= fWW*C*CTT as well as Cas well as CSS = f= fSS*C*CTT
Cs [μg /L] = CCs [μg /L] = CSPMSPM [μg/kg] * TSM [kg/L][μg/kg] * TSM [kg/L]
ffWW = 1/(1 + TSM*K= 1/(1 + TSM*Kdd) = 1/(1 + TSM*) = 1/(1 + TSM*ffOC*OC*KKOCOC) ) and fand fSS = TSM*f= TSM*fOC*OC*KKOCOC/(1 + TSM*f/(1 + TSM*fOC*OC*KKOCOC); ); SS OCOC OCOC OCOC OCOCof course: fof course: fWW + f+ fSS = 1= 1
Minimum input needs for partitioningMinimum input needs for partitioningMinimum input needs for partitioning Minimum input needs for partitioning estimationestimation
•• KKOWOW or Kor KOCOC of the chemical substanceof the chemical substance•• KKOWOW or Kor KOCOC of the chemical substanceof the chemical substance
•• Total suspended matter (TSM or SPM)Total suspended matter (TSM or SPM)
•• ffOCOC of the suspended matterof the suspended matter
1,0
1,2
102
3
fw = (TSM , foc, K ow )
fw
0 4
0,6
0,8
,103
104
105
106
foc = 0 .05
0,0
0,2
0,4
1,2
106
107
2fw
0 ,6
0,8
1,0102
103
104
105foc = 0 .15
f
0,0
0,2
0,4105
106
107
0,8
1,0
1,2
102
103
104
fw
0 ,2
0,4
0,6104
105
106
107
foc = 0.35
0 5 10 15 20 25 30 35
0,0
TSM , m g/L
10
1 0 2
31 0
1 .21 0 2
fw = (T S M , fo c , K o w )
1 0 3
1 0 4
1 0 5
fw
0 .4
0 .6
0 .8
1 .0 1 0 3
1 0 4
1 0 5fo c = 0 .0 5
1 0
1 0 6
1 0 70 .0
0 .21 0 5
1 0 6
1 0 7
w
0 .6
0 .8
1 .0
1 .2
1 0 2
1 0 3
1 0 4
fo c = 0 1 5fw
0 .0
0 .2
0 .4
1 0 5
1 0 6
1 0 7
fo c = 0 .1 5
1 0 2
1 0 31 0 31 0 3
0 .8
1 .0
1 .21 0 2
1 0 3
fw
0 .0
0 .2
0 .4
0 .6
1 0 4
1 0 5
1 0 6
fo c = 0 .3 5
0 1 0 0 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0
0 .01 0 7
T S M , m g /L
KK and fand fKKOCOC and fand fwwSubstanceSubstance Log Log
KKOCOC
ffWW forforTSM TSM =1mg/L=1mg/L
ffWW forforTSM TSM =10mg/L=10mg/L
ffWW forforTSM TSM =100mg/L=100mg/L=1mg/L,=1mg/L,
ffOCOC = 0.05= 0.05=10mg/L, =10mg/L, ffOCOC = 0.1= 0.1
=100mg/L, =100mg/L, ffOCOC = 0.2= 0.2
PentabromodiPentabromodi 4 494 49 99 8%99 8% 97%97% 14%14%PentabromodiPentabromodiphenyletherphenylether
4.494.49 99.8%99.8% 97%97% 14%14%
B (b)flB (b)fl 5 345 34 99%99% 82%82% 2 2%2 2%Benzo(b)fluorBenzo(b)fluorantheneanthene
5.345.34 99%99% 82%82% 2.2%2.2%
Benzo(g,h,i)pBenzo(g,h,i)peryleneerylene
6.436.43 88%88% 27%27% 1.8%1.8%
KKOCOC valuesvaluesSubstanceSubstance Log KLog KOCOC
AnthraceneAnthracene 4 314 31AnthraceneAnthracene 4.314.31PentabromodiphenyletherPentabromodiphenylether 4.494.49FluorantheneFluoranthene 4.974.97NonylphenolNonylphenol 4.784.78y py pOctylphenolOctylphenol 4.524.52Benzo(a)pyreneBenzo(a)pyrene 5 825 82Benzo(a)pyreneBenzo(a)pyrene 5.825.82Benzo(b)fluorantheneBenzo(b)fluoranthene 5.345.34Benzo(k)fluorantheneBenzo(k)fluoranthene 6.246.24Benzo(g,h,i)peryleneBenzo(g,h,i)perylene 6.436.43(g, , )p y(g, , )p yIndeno(1,2,3Indeno(1,2,3--cd)pyrenecd)pyrene 6.026.02
Nonlinear KNonlinear KNonlinear KNonlinear Kococ
Adsorption to black carbon can beAdsorption to black carbon can be important for PAHs and other compounds.
A i d i th (li l F dli h) iA mixed isotherm (linear plus Freundlich) is then appropriate:
70CfCfC 7.0iwibcbciwiococis CKfCKfC ⋅⋅+⋅⋅=
for black carbon (bc), an exponent of 0.7 seems to work
To estimate Kbc for planar sorbates and some others via:To estimate Kbc for planar sorbates and some others via:
4.1log6.1log −≅ iowibc KK gg iowibc
Other factors influencing KOther factors influencing K ::Other factors influencing KOther factors influencing KDD::
SALINITY i h i l i ffSALINITY i h i l i ffSALINITY in the estuaries: salting out effectsSALINITY in the estuaries: salting out effects
PARTICLE CONCENTRATION EFFECTPARTICLE CONCENTRATION EFFECTPARTICLE CONCENTRATION EFFECTPARTICLE CONCENTRATION EFFECTincrease in particle concentration leads to an in increase in fw
KD = a SPM-b
Thi ff t ld b d b i i t ti f di l dThi ff t ld b d b i i t ti f di l dThis effect could be caused by increasing concentrations of dissolved This effect could be caused by increasing concentrations of dissolved organic carbon (DOC) in dependence of the SPM content. This organic carbon (DOC) in dependence of the SPM content. This increased DOC (humic substances) effects enhanced the solubility of increased DOC (humic substances) effects enhanced the solubility of the compounds in form of colloids, which leads to decreased the compounds in form of colloids, which leads to decreased enrichment rates in the particulate phase.enrichment rates in the particulate phase.
Typical SPM concentrationTypical SPM concentration
COASTAL ZONE: in the low mg/L range, towards open sea < 1 mg/Lopen sea < 1 mg/L.
LAKES: around 5 mg/L
Large European RIVERS:
20-40 mg/L in normal conditions.g
up to 1000 mg/L during flood events
Multiannual averages are 40 mg/L
ESTUARIES: 150-1500 mg/L.
Experimental partition:Experimental partition:
Partitioning of different classes of organic pollutants between SPM anes
and aqueous phase in water samples of the River Elbe
(Hamburg, November 1995)
n-al
ka
( g, )
SPM range= 20-43 mg/L
H
n-alkanes (top), PAHs (middle), and
CHs (bottom)
PAH
CHs (bottom)
ed
ons
lorin
ate
roca
rbo
From Heemken et al. , Arch. Environ. Contam. Toxicol. 38, 11–31 (2000)
Ch
hydr
HYDROLOGICAL effect on KHYDROLOGICAL effect on KDD::Nonylphenol Monitoring of Lambro riverNonylphenol Monitoring of Lambro river –– 20042004Nonylphenol Monitoring of Lambro river Nonylphenol Monitoring of Lambro river 20042004
MAY 2004: FLOOD EVENTMAY 2004: FLOOD EVENT JULY 2004: LOW DISCHARGEJULY 2004: LOW DISCHARGENPpNPw
75%
100%
75%
100%NPw
25%
50%
25%
50%
0% 0%
WHOLE WATER NP (μg/L)
1,50
2,00
1,50
2,00WHOLE WATER NP (μg/L)
0,50
1,00
0,50
1,00
0,00
0,50
Monza Brugherio Melegnano S.Angelo Orio L.
0,00Monza Brugherio Melegnano S.Angelo Orio L.
The evidence that SPM fraction can not be overriden in water monitoring The evidence that SPM fraction can not be overriden in water monitoring has been acknowledged in the EQS Directive:has been acknowledged in the EQS Directive:has been acknowledged in the EQS Directive:has been acknowledged in the EQS Directive:
DIRECTIVE OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL on environmental quality standards in the field of water
policy and amending Directives 82/176/EEC, 83/513/EEC, 84/156/EEC, 84/491/EEC, 86/280/EEC and 2000/60/EC84/156/EEC, 84/491/EEC, 86/280/EEC and 2000/60/EC
Which states in Annex I Part C: Compliance with EQS
Organic pollutantsOrganic pollutants: : total concentration in the whole total concentration in the whole water samplewater sample (dissolved and particulate fractions)(dissolved and particulate fractions)pp ( p )( p )
Metals (Cd, Pb, Hg, Ni)Metals (Cd, Pb, Hg, Ni): dissolved fraction (obtained by : dissolved fraction (obtained by ( g )( g ) ( y( yfiltration through a 0.45 µm filter or filtration through a 0.45 µm filter or any equivalent preany equivalent pre--treatment)treatment)
Method Requirements from EQS Daughter Directive and QA/QC Directive
Matrix Matrix –– “Whole water”“Whole water”, sediment, biota, sediment, biota
key point 1
Limit of quantification (LOQ)Limit of quantification (LOQ) key point 2Limit of quantification (LOQ)Limit of quantification (LOQ)–– … … LOQ (quantification limit) ≤ 1/3 EQS
key point 2
Relative Target UncertaintyRelative Target Uncertainty key point 3Relative Target UncertaintyRelative Target Uncertainty–– … … a a U % (relative uncertainty, k=2) ≤ 50%
at EQS levelat EQS level
SPM and standard analytical methodsSPM and standard analytical methods
No or not clear statements on the suitability of the methods No or not clear statements on the suitability of the methods for “for “whole water sampleswhole water samples” ” –– No methods for water with remarkable SPM content No methods for water with remarkable SPM content
(>20 mg/L)(>20 mg/L)–– none or only inadequate information (e.g.” none or only inadequate information (e.g.” filtration of filtration of
the sample where appropriatethe sample where appropriate”) on how to deal with ”) on how to deal with the sample where appropriatethe sample where appropriate”) on how to deal with ”) on how to deal with SPMSPM
Lack of Lack of representativenessrepresentativeness of the of the Validation trialsValidation trials in the in the Lack of Lack of representativenessrepresentativeness of the of the Validation trialsValidation trials in the in the existing standards respect to relevant domains of existing standards respect to relevant domains of applications for WFD (e.g. Coastal waters, high SPM applications for WFD (e.g. Coastal waters, high SPM waters)waters)waters)waters)
One main issue is to find an agreement between the One main issue is to find an agreement between the concept of ‘‘water compartment’’ addressed by the WFD concept of ‘‘water compartment’’ addressed by the WFD co cept o ate co pa t e t add essed by t eco cept o ate co pa t e t add essed by t eand the scope of CEN standards, which typically include all and the scope of CEN standards, which typically include all water types (up to 20 mg/L for SPM level) without complete water types (up to 20 mg/L for SPM level) without complete validation for complex matrices.validation for complex matrices.
REFERENCE: Coquery, M.; Morin, A.; Bécue, A.; Lepot, B. (2005) Trends in REFERENCE: Coquery, M.; Morin, A.; Bécue, A.; Lepot, B. (2005) Trends in Analytical Chemistry 24(2), 117Analytical Chemistry 24(2), 117--127127
What is “whole water”?
Water
Operational Definition ?
Dissolved Suspended
p
(Colloid) Particulate
M tteMatter
SedimentSediment
Particle Size SpectrumParticle Size Spectrum
Continuous size distribution from truely dissolved to particles
(crossing colloidal range 1 nm - 1 µm )
In a sample collected with centrifugation:In a sample collected with centrifugation:
50 % of the particles have a size below 9 µm.
10 % of the particles have a size below 2 µm
< 63 µm
< 20 µm
T i l t ff l f di t t diTypical cut-off values from sediment studies
How to define and separate SPM fraction?SPM fraction is operationally defined
through applied separation method ! e.g.
p
g pp p g
0 45 µm membrane filter0.45 µm membrane filter
Whatman GF/C depth filter
Whatman GF/F depth filterWhatman GF/F depth filter
Continuous Flow Centrifuge
Conventionally, an operational but widely accepted definition that reflects current practice in Conventionally, an operational but widely accepted definition that reflects current practice in environmental monitoring of metals is to pass the sample through a filter membrane of nominal environmental monitoring of metals is to pass the sample through a filter membrane of nominal pore size 0.45 pore size 0.45 μμm which is the smallest pore size that is suitable for routine filtration of the m which is the smallest pore size that is suitable for routine filtration of the sample volumes.sample volumes.
However, it should be noted that the choice of 0.45 However, it should be noted that the choice of 0.45 μμm as the particle size that separates m as the particle size that separates suspended matter from the “dissolved” phase is arbitrary because particles (eg bacteria, viruses, suspended matter from the “dissolved” phase is arbitrary because particles (eg bacteria, viruses, colloidal clay and organic material) of smaller particle size are thereby categorised as dissolved.colloidal clay and organic material) of smaller particle size are thereby categorised as dissolved.
Filtration
Variables in filtration of surface water:Variables in filtration of surface water:
• Filter material
• Filter size
• Filter poresize/retention
Filt it• Filter capacity
• Filtered volume
• Adsorption of dissolved material on filter
Filtrationt at oPRO:
– Simplicity– Simplicity– Possibility for on-line filtration in situ
CONS: – Variabilities in materials and pore sizes among different
manufacturers– Filter clogging– Adsorption – Systematic or random contamination y
When clogging occurs, the filtration rate decreases and the effective pore diameter of the filter decreases: on the consequence species in thepore diameter of the filter decreases: on the consequence species in the filtrate are no longer accurately defined according to pore size.This problem is reduced to some extent by using depth filters instead of screen membrane filtersscreen membrane filters.
Glasfiber filter
Membrane filter
Alternative to filtration:Alternative to filtration:SPM trapSPM trap
Sample device for collecting SPM. Pipe I 5 overflow for passing water, pipe II 5 outlet for supernatant waterpipe II 5 outlet for supernatant water,pipe III 5 outlet for collected SPM
F h li tiFor research applications
From Heemken et al. , Arch. Environ. Contam. Toxicol. 38, 11–31 (2000)
Alternative to filtration:Alternative to filtration:Centrifugation
Parameters to be optimised:
• Centrifugal force
• Residence time in centrifuge
Sample inlet/pumping system• Sample inlet/pumping system
20-25 sec at 17670 g20 25 sec at 17670 g
C ti flContinuous flow CentrifugeCentrifuge
Centrifugation
PRO:• Good SPM recovery efficiency• Large volume in situ processing
CONS:Lack of comparability with filtration in low ionic strengthLack of comparability with filtration in low ionic strength
waters with low levels of SPMChanges in the particle size distribution during the
centrifugation by a possible particle fragmentation effect.Difficulties in the recovery of a representative sample f th di l d f tiof the dissolved fraction
Alternative approach: Wh l t l i ith t tiWhole water analysis without separation
A t ti th d (li id li id SPE SPEEDISK) it bl fAre extraction methods (liquid-liquid, SPE, SPEEDISK) suitable for analysing “whole water” without SPM separation? At what SPM concentration?
Traditional LLE methods have been used in order to deal with “dirty” or not filterable samples but – recovery is questionable (it is good when the sample is spiked)– It produces large amount of waste solvent (often chlorinated one)
Literature (e.g. Lacorte et al., J. Chrom. 1999) suggests that SPEEDISKs are a reliable approach for high TOC waters to analyse samples without a prior filtration stepsamples without a prior filtration step
SPEEDISK embodies a filtration membrane on top of the SPE sorbent– High flow rates
Th di k ill b t t d l i th t CEN th d li it lThese disks will be tested also in the next CEN methods esplicitely developed for WFD
Nonylphenol: Comparison between SPEEDISK and whole water determination by filtration and SPE
SPM
whole water determination by filtration and SPE
1,2
1,4 SPM
12.7 mg/L
SPM
38.4 mg/L
0,8
1
SPM (FILTER)SPM
2 6 mg/Lg/L
0,6
0,8 SPM (FILTER)DISS (SPE)
SPEEDISK
2.6 mg/L
NP μg
0,2
0,4 SPEEDISK
0SEVESO RIVER SEVESO RIVER OLONA RIVER
30/07/08 11/07/08 09/07/08
Source: our unpublished work
30/07/08 11/07/08 09/07/08
First CMA On-Site Technical Workshop10th and 11th of October 200610th and 11th of October 2006
River Po – Pontelagoscuro, Italy
AIM: Compare different methods pof whole water determination
Methods employed by JRC IES during Methods employed by JRC IES during CMA on siteCMA on site 11CMA on siteCMA on site--11
2 L liquid/liquid extraction2 L liquid/liquid extractionThi th d d f h it t t It d t ll ti fThi th d d f h it t t It d t ll ti fThis method was used for homogeneity tests. It does not allow separation of This method was used for homogeneity tests. It does not allow separation of
particulate and dissolved contaminant fraction.particulate and dissolved contaminant fraction.
20 L GF/F filtration + liquid/liquid extraction20 L GF/F filtration + liquid/liquid extraction20 L GF/F filtration + liquid/liquid extraction20 L GF/F filtration + liquid/liquid extractionThis large volume version of a classical liquid/liquid extraction approach allowed the reduction This large volume version of a classical liquid/liquid extraction approach allowed the reduction
of blank values in relation to sample volume. of blank values in relation to sample volume.
226 L GFC filtration + 2x 250 g XAD226 L GFC filtration + 2x 250 g XAD226 L GFC filtration + 2x 250 g XAD226 L GFC filtration + 2x 250 g XADThe large volume filtration/adsorption approach using a 2” glass fibre cartridge and The large volume filtration/adsorption approach using a 2” glass fibre cartridge and
subsequently 2 large, 250 g XAD cartridges has been used in analysis of dioxins in water and in subsequently 2 large, 250 g XAD cartridges has been used in analysis of dioxins in water and in ultra trace applications in marine chemistry. ultra trace applications in marine chemistry.
45 L GF/F filtration + 2 x 50 g XAD45 L GF/F filtration + 2 x 50 g XADFiltration in combination with adsorptive extraction of a medium size sample was used. With Filtration in combination with adsorptive extraction of a medium size sample was used. With
the XAD column containing 50 g adsorbent these columns are suitable for extraction of up to ca. the XAD column containing 50 g adsorbent these columns are suitable for extraction of up to ca. 300 L water in inland surface water bodies300 L water in inland surface water bodies300 L water in inland surface water bodies.300 L water in inland surface water bodies.
2.3 L GF/F filtration + C18 extraction Empore Disk2.3 L GF/F filtration + C18 extraction Empore DiskA glass fibre filter on top of the extraction disk allowed the separate determination of A glass fibre filter on top of the extraction disk allowed the separate determination of
contaminant in the particulate fraction The blank situation of this method showed that experiencecontaminant in the particulate fraction The blank situation of this method showed that experiencecontaminant in the particulate fraction. The blank situation of this method showed that experience contaminant in the particulate fraction. The blank situation of this method showed that experience is needed to cope with laboratory and field artefactsis needed to cope with laboratory and field artefacts. .
Method comparison(SPM = 45 mg/L)
15 00
20,00
0,20
0,25sum of 8 PAH sum of 6 PBDE
10,00
15,00
sum
(ng/
L)
0,15
PBD
E sum
5,00
PAH
s
0,05
0,10
m (ng/L)
0,00
E20
L
226 L
D45
L
2.3 L
E2 L
4160
L
0,00
GF/F +
LLE
2GFC
+ X
AD 22
GF/F +
XAD
4SP
EEDIS
K 2.
LLE
2EN
TRIFU
GE 41
6
G G
CEN
Po river: PAH sum whole water results(SPM = 45 mg/L)
LLE40
135
30SPEEDISK
WITHOUT /L
SPECENTRIFUGE
SPM
AVERAGE OF 5
REFERENCE
20 SPEWITH
FILTRATION FILTR + LLE SPM+DISS
FILTRATION
ng/
LLEWITHOUT
FILTRATION
< 10 < 10
METHODS
SPM+DISS
10 DISSSPM+DISS
0CMA00 CMA01 CMA02 CMA03 CMA04 CMA05 CMA06 CMA07
Grey bars are the blank value determined LOQs of the labs.
Po river: PBDE sum whole water results(SPM 45 /L)(SPM = 45 mg/L)
1 FILTR + LLE
0.8
1 SPM+DISS
0.6
L]
SPEEDISK
WITHOUT FILTRATION
AVERAGE OF 5
REFERENCE
0.4[ng/
L REFERENCE METHODS
SPM+DISSFILTR + LLECENTRIFUGE
0.2
FILTR + LLE SPM+DISS
CENTRIFUGE
SPM
0CMA00 CMA03 CMA04 CMA05 CMA06
Po river: Nonylphenol in whole water(SPM = 45 mg/L)(SPM = 45 mg/L)
120
SPE WITH FILTRATION
DISSContamination
f filt ?100
SPE
DISS
FILTRATION
SPM
from filters?
80
L
WITHOUT FILTRATION
SPE
WITHOUT
SPM
40
60
ng/L WITHOUT
FILTRATION
SPECENTRIFUGE
20
40
< 22
< 10< 105 1
LLE WITHOUT FILTRATION
SPM
0
CMA00 CMA01 CMA02 CMA03 CMA04 CMA05 CMA06 CMA07
5.1
Grey bars are the blank value determined LOQs of the labs.
ConclusionsConclusionsConclusionsConclusions
•Further work is needed to develop suitable and robust methods for PS monitoring in natural surface “whole” waters and harmonise labs at EC level waters and harmonise labs at EC level
•There is not a suitable and straightforward alternative th d t id th ti f di l d d SPM method to avoid the separation of dissolved and SPM
fractions in order to determine “whole water” concentration for high and medium hydrophobic compounds
••Alternative methods for time integrating sampling Alternative methods for time integrating sampling g g p gg g p g(e.g. (e.g. passive samplers) are not directly intended for passive samplers) are not directly intended for compliance checking in whole water samplescompliance checking in whole water samples
AcknowledgmentsAcknowledgmentsAcknowledgmentsAcknowledgments
I will thank my coworker Sara Valsecchi I will thank my coworker Sara Valsecchi (CNR(CNR--IRSA) and Georg Hanke, Jan IRSA) and Georg Hanke, Jan (( ) g ,) g ,Wollgast and Robert Loos from the JRC Wollgast and Robert Loos from the JRC team for collaboration informationteam for collaboration informationteam for collaboration, information team for collaboration, information exchange and helpful discussions exchange and helpful discussions
