application of lc-ms technique in environmental studies...aims ms nd go ls of env onmen l n ly s and...
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Application of LC-MS technique in environmental studiesin environmental studies
k N EŚNAgata KOT-WASIK, Jacek NAMIEŚNIK
Department of Analytical Chemistry Department of Analytical Chemistry, Chemical Faculty, Gdańsk University of Technology,
G. Narutowicza 11/12, 80-952 Gdańske-mail: [email protected]
1I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
AIMS AND GOALS OF ENVIRONMENTAL ANALYTICS AIMS AND GOALS OF ENVIRONMENTAL ANALYTICS MS ND GO LS OF ENV ONMEN L N LY S MS ND GO LS OF ENV ONMEN L N LY S AND MONITORINGAND MONITORING
Identification of sources of emission and evaluation of scale and impact assessment of emission
D f f llDetermination of mixing ration of pollutants
Studies of environmental fate of xenobiotics
Evaluation of toxicity and ecotoxicity of specific pollutants
Studies of bioaccumulation processes of pollutants by living organisms
2I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
AIMS AND GOALS OF ENVIRONMENTAL AIMS AND GOALS OF ENVIRONMENTAL MS ND GO LS OF ENV ONMEN L MS ND GO LS OF ENV ONMEN L ANALYTICS AND MONITORINGANALYTICS AND MONITORING
Low and even very low concentration level of analytes in samples y y pcharacterized by complex composition of the matrix
Possibility of time and space fluctuations of xenobiotics concentrationconcentration
Danger of interferences connected with presence of constituents characterized by similar physico-chemical properties
Lack of information on degradation path pollutants
Necessity of determination not only primary pollutants but also products of degradation and metabolism processesproducts of degradation and metabolism processes
Lack of suitable standards and reference materials
3I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
ENVIRONMENTAL POLLUTANTS
N l t d ll t tRegulated pollutants Nonregulated pollutants
............
.......
.......
...........
Dioxins(PCDD+PCDF)
P l ti
Metal complexes
Estrogens Polyaromatic hydrocarbons
(PAH’S)
Polichlorinated Biphenyls (PCB’s)
Estrogens
fitoestrogens
Bisfenol A
Brominated Flame Retardants (BFR’s)
Alkilofenole
Pesticides
Nonionic surfactants
Derivatives of phtalanes
ENDOCRINE DISRUPTING COMPOUNDS EDC’s
Pharmaceutical residues
Synthetic musk compounds
4I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
COMPOUNDS – EDC s
Personal Care Products (PCP’s)
Synthetic musk compounds
APPLICATION OF CHROMATOGRAPHIC TECHNIQUESAPPLICATION OF CHROMATOGRAPHIC TECHNIQUES
ttrri+2i+2In typical case chromatographic analysis constitutes a sources of two-
ttrri+1i+1
i+2i+2 ydimensional information (2D)
Generally it is a relationship between detector signal (first dimension) and nt
ensi
ty
ttrriig
retention time (secondd dimension).
Sign
al in
Time
Identification is based on comparison of retention times.
5I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
PROBLEMSPROBLEMSTWO DIMENSIONAL (2D) TWO DIMENSIONAL (2D) aanalysisnalysisTWO DIMENSIONAL (2D) TWO DIMENSIONAL (2D) aanalysisnalysis
Problem no 1 – overlapping of peaksProblem no 1 overlapping of peaksSolutions
Repeat analysis with use of second chromatographic Repeat analysis with use of second chromatographic column (character of interactions between analyte and stationary phase has to be different than in the case of first column)m )
Advantages: Disadvantages:g Disadvantages- Easy to realize- Low cost
- Time consuming task !!
6I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
TWO DIMENSIONAL (2D) analysisTWO DIMENSIONAL (2D) analysisProblem no 2 – identification of unknown compoundsp
Solution
Apply detector which permits to obtain information on the Apply detector which permits to obtain information on the structure of analyte (HYPHENATED TECHNIQUES)
Advantages: Disadvantages:- Possibility of identification of unknown species
- High cost of investmentS ifi i t th l l unknown species
-Availability of information on molecular mass and/or structure of analyte
-Possibility of confirmation of overlapping
-Specific requirements on the level of professional knowledge of personnel
7I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
y pp gpeaks effect
HYPHENATED TECHNIQUESHYPHENATED TECHNIQUESThanks to application of HYPHENATED TECHNIQUES analytical Thanks to application of HYPHENATED TECHNIQUES analytical information gains an additional dimension (STRUCTURE)information gains an additional dimension (STRUCTURE)
8000
6000
2000
4000
intensywność sygnału
14.5
15
15.5
16
8000
2000
12.5
13
13.5
14
400
500
600
700
czasm/z
8I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy11
11.5
12
100
200
300
APPLICATION RANGE OF DIFFERENT TYPES OF APPLICATION RANGE OF DIFFERENT TYPES OF HYPHENATED TECHNIQUES (GCHYPHENATED TECHNIQUES (GC--MS and LCMS and LC--MS)MS)HYPHENATED TECHNIQUES (GCHYPHENATED TECHNIQUES (GC--MS and LCMS and LC--MS)MS)
100000100000tes
100000ESI
100000
the
anal
yt
ESI (electospray)
10000
APCIFAB
10000
mas
s of
t
APCIFABTHERMOSPRAY
1000FAB
PBI
C/M
S
1000
Mol
ecul
ar FABTHERMOSPRAY
PBI
C/M
SGM
nonpolar
G
Very polar
9I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
Polarity of the analyte
THE MOST COMMON PHARMACEUTICAL
COMPOUNDS PRESENT IN
Antiinflammatory drugs/ analgesicsAcetylsalicylic acid (Aspirin)
DiclofenacIbuprofen
ENVIRONMENTAL SAMPLESAcetaminophenMetamizolCodeine
IndometacineNaproxen
Phenazone
AntibioticsErytromicynOfloxacin
ChlortetracyclineOxytetracyclineStreptomycinFl i
Lipid regulatorsBezafibrateFlumequine
CiprofloxacinTrimetoprim
SulfamethoxazoleLincomycinPenicillin
LincomycinAmoxicillin
BezafibrateGemfibrozil
Clofibric acidFenofibrate
Most common pharmaceuticals in
the environmentSpiramycin
Beta-blockersMetoprololPropranolol
NadololAtenololSotalol
Betaxolol
the environment
Steroids and related hormones
17 β estradiol
Cancer therapeuticsCyclophosphamide
Ifosphamide Betaxolol 17-β-estradiolEstrone
17 α-ethinyl estradiolDiethylstilbestrol
Diethylstilbestrol acetate
Ifosphamide
DiureticsFurosemide
AntieplepticsCarbamazepine
AntidepressantsMianserin
TranquillisersDiazepam
10I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
A. Nikolaou, S. Meric, D. Fatta, Anal. Bioanal. Chem., 387, 1225 (2007)
VETERINARY MEDICAL VETERINARY MEDICAL PRODUCTSPRODUCTS
I P l d ll bi l i ll i d d In Poland all biologically active compounds used as VETERNARY MEDICAL PRODUCTS can be divided into two groups:g p
GROUP A: substances having ANABOLIC EFFECTand UNAUTORIZED SUBSTANCESand UNAUTORIZED SUBSTANCES
GROUP B: VETERNARY DRUGS and CONTAMINANTCONTAMINANT
11I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
PHARMACEUTICAL RESIDUES IN THE ENVIRONMENT MILESTONESENVIRONMENT - MILESTONES
19811981 confirmation of the presence and quantitative determination of CLOFIBRIC ACIDp qIN ENVIRONMENTAL SAMPLES (USAUSA)
19971997 Determination of pharmaceutical residue in hospital sewages (GermanyGermany)
19971997 Studies related to the antibiotic toxicity in water environment (DenmarkDenmark)
19981998 Monitoring of river waters and sewage in Germany for the presence ofpharmaceutical residue (GermanyGermany)
19981998 Determination of antibiotic compounds in different water samples (GermanyGermany)
19991999 Elaboration of an analytical method allowing for the confirmation of the presence of19991999 Elaboration of an analytical method allowing for the confirmation of the presence ofestrogens in surface waters (USAUSA)
20022002 First method of simultaneous determination of residues of many pharmaceuticals insamples of the environment (DenmarkDenmark)
l20012001 –– 20022002 Determination of pharmaceutical residue in drinking waters (GermanyGermany)
20032003 Elaboration of appropriate mathematical models for predicting concentration andloss of individual pharmaceuticals in the environment (BelgiumBelgium)
20052005 Determination of pharmaceutical residue in steel samples (SpainSpain)
12I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
20052005 Determination of pharmaceutical residue in steel samples (SpainSpain)
HOW PHARMACEUTICALS HOW PHARMACEUTICALS ENTER DRINKING WATER ? ENTER DRINKING WATER ?
PHARMACEUTICALS USED BY MAN
DIRECT DISPOSALOF
PHARMACEUTICALDISPOSED TO OF
PHARMACEUTICALTO SEWAGE
DISPOSED TOSEWAGE WITH
URINE
SEWAGE TREATMENT PLANTSEWAGE TREATMENT PLANT
SLUDGE DISPERSEDON FIELDS
WATER USED FORFIELD IRRIDATION
EFFECT ON SOILMICROORGANISMS
Many drugs are distributed, metabolised and finally excreted by the human and/or animal body to the environment. Very often they are
UNDERGROUNDWATER
SURFACEWATER
DRINKING
13I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
only slightly transformed or even unchanged and can contaminate the surface water, groundwater and even drinking water.
EFFECT ON LIVINGORGANISMS
WATER
APPLICATION OF LCAPPLICATION OF LC--MS TECHNIQUEMS TECHNIQUEAPPLICATION OF LCAPPLICATION OF LC--MS TECHNIQUEMS TECHNIQUE
Determination of residue of nonsteroid Determination of residue of nonsteroid anti-inflammatory drugs (NSAID’s) in environmental samples.
Biologically active compounds from NSAID group are present even in drinking water at ppt level. They are responsible for drug resistance.
Very often this compounds are quantitatively y p q ydetermined in surface waters.
14I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
ANALYTICAL PROCEDURESANALYTICAL PROCEDURESapplication of solid phase extraction technique (SPE)application of solid phase extraction technique (SPE)application of solid phase extraction technique (SPE)application of solid phase extraction technique (SPE)
off-line SPEoff line SPE
SPESPE on-line SPEpassive SPE
15I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
P
SAMPLING STEPS IN ANALYTICAL STEPS IN ANALYTICAL PROCEDURE FOR PROCEDURE FOR
PRETR
CONSERVATION
ISOLATION/PRECONCENTRATION
DETERMINATION OF DETERMINATION OF PHARMACEUTICAL PHARMACEUTICAL
RESIDUESRESIDUESVALI
REATM
ISOLATION/PRECONCENTRATION
DERIVATISATIONDATI
MENT
CLEAN-UP
S O GON
STORAGE
ANALYSIS
IDENTIFICATIONThere is no doubt that sample pre-treatment
operations are crucial for reliability of analytical
16I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
EVALUATION OF DATAreliability of analytical
results
SPE in off-line mode
MeOH H2O Sample H2O MeOH
conditioning sample deposit(sorption)
washing the sorbent
analyte elution (desorption)(sorption)
deposit( p )
solvent evaporation to dryness in the nitrogen stream
dissolution of the dry residue in the mobile phase
final indication with the help of
17I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
HPLC/DAD/MS
SPE w układzie SPE w układzie onon--linelineSPE w układzie SPE w układzie onon lineline
Analytical column DetectorsAnalytical column
SPE Column
DADMS
Detectors
Pump 2MS
Pump 1
LeakSAMPLE
St 1 l t d i l ti i h t i t lStage 1- analyte and isolation enrichment in water samples
18I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
SPE-HPLC-DAD-MSADVANTAGES AND DRAWBACKS
• Advantages
• The possibility of preparing
Drawbacks
• Difficulties with automating the offoff--lineline The possibility of preparing
several samples simultaneously• The possibility of the
optimization of individual stages• The elasticity of protocol steps
• Difficulties with automating the operation
• Work and time consuming• The necessity of working with a
large sample volume• The elasticity of protocol steps• Simple equipment
large sample volume• Risk of sample and extract
contamination and analyte loss
C li t d i tonon--lineline
• The possibility for process automation
• Analyzing the complete sample• The possibility of working with a
• Complicated equipment• Little procedure elasticity• Difficult or impossible
optimization of individual stepsp y gsmaller sample volume
• Shorter analysis time• Lowering the risk of analyte loss
and sample contamination
19I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
p• Improved analysis precision
DETERMINATION OF NSAID RESIDUE FROM WATER SAMPLESDETERMINATION OF NSAID RESIDUE FROM WATER SAMPLES
Sample Volume Sample Volume1000 mL
Initial sample preparationt= 2 min
100 mL
Initial sample preparationt= 2 min
OFF LINE SPE ON LINE SPEColumn Preparation
t= 18 min
SPE Extraction 70 i
SPE Extractiont 35 i
Column Preparationt= 8 min
OFF-LINE SPE ON-LINE SPE
t= 70 min
Drying the deposit in the SPE column
t= 5 minValve switch
t= 35 min
Analyte elutiont= 20 min
Solvent evaporationt 200 i
HPLC-DAD-MSANALYSIS
t= 25 min
Total time: 70 minutesTotal time:
70 minutes
t= 200 min
Dissolution of the residuet= 30 min
20I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
HPLC-DAD-MSANALYSIS
t= 25 min
Total time: 370 minutesTotal time:
370 minutes
METROLOGICAL ASPECTSMETROLOGICAL ASPECTS
Proposed analytical approach permits to detect Proposed analytical approach permits to detect analytes from NSAID group at the level of ppt in analytes from NSAID group at the level of ppt in water sampleswater sampleswater sampleswater samples
Off-line On-lineRSD% < 11 < 7
Reproducibility % 30-100 89-105Reproducibility % 30 100 89 105
Limit of detection 20-950 0,7-50
21I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
AD
)5
N
OHH
Cl
O
F
F
OH
COOH
STUDIES OF na
l int
ensi
ty (D
A
2
Cl
OCH3
COOH
OHCH3
SURFACE WATERSSAMPLES
Sig
n
1
3
46
CH3
OH
O
CH3
CH3
OH
MeO
NCH3 CH2COOH
O
CH
min2 4 6 8 10 12 14 16 18Time
CH3
y (E
SI-M
S)
1
2
3
4
5 6 1 = tolmetin 2 = naproksen 3 = fenoprofen 4 difl i l
Sig
nal i
nten
sity 4 = diflunisal
5 = diklofenak 6 = ibuprofen
22I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
min2 4 6 8 10 12 14 16 18Time
DETERMINATION OF NSAID RESIDUE IN WATER DETERMINATION OF NSAID RESIDUE IN WATER SAMPLESAMPLE
Analyte
Type of water sample
Drinking water
Sea water River water Lake water
Ground water
Sample no 1
Sample no 1
Sample no 2
Sample no 1
Sample no 1
Sample no 1
Sample no 1
Tolmetin n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Naproksen n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Fenoprofen n.d. n.d. n.d. 55 84 24 n.d.
Diflunisal n.d. 38 62 95 123 28 n.d.
Diklofenak n.d. n.d. n.d. 300 390 528 n.d.
Ibuprofen n.d. n.d. 17 n.d. n.d. 10 n.d.
2,3-DHBA n.s. n.d. n.d. n.s. n.s. n.d. n.s.
2,5-DHBA n.s. n.d. n.d. n.s. n.s. n.d. n.s.
SA n.s. n.d. n.d. n.s. n.s. n.d. n.s.
23I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
n.d. – non detected (below LOQ)
n.s. –non studied
DETERMINATION OF VETERNARY DRUGS IN DIFFERENT TYPES OF DRUGS IN DIFFERENT TYPES OF
SAMPLES
24I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
The most commonlThe most commonlyy used coccidiostaticsused coccidiostaticsThe most commonlThe most commonlyy used coccidiostaticsused coccidiostatics
• Ionophore antibiotics
(salinomycin, narasin, monensin, lasalocid)
• Vitamin antagonists
(amprolium, trimethroprim, pirymethamine)• Sulphonamides
(sulfadimethoxine, sulfamethoxine sulfanitron)• Nitroimidazoles
( it f l i b i di t id l)(nitrofural, nicarbasin,dimetridazol)• Other coccidiostatics
(robenidine clopidol)
25I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
(robenidine, clopidol)
NAJWAŻNIEJSZE CECHY ZASTOSOWANYCH W NAJWAŻNIEJSZE CECHY ZASTOSOWANYCH W TRAKCIE BADAŃ TECHNIK EKSTRAKCJI ANALITÓWTRAKCIE BADAŃ TECHNIK EKSTRAKCJI ANALITÓWTRAKCIE BADAŃ TECHNIK EKSTRAKCJI ANALITÓWTRAKCIE BADAŃ TECHNIK EKSTRAKCJI ANALITÓW
Shaking UAE ASE MAE Soxhlet Soxtec
Full time of extraction per one sample (include heating and cooling and filtration)
40 min 30 min 20 min 45 min 6.5 h 45 min
V l f l t d 60 l 25 l 30 l 10 l 45 l 25 lVolume of solvent used 60 ml 25 ml 30 ml 10 ml 45 ml 25 ml
Parameters assisted of extraction shaking ultrasonic temperature
pressure microwave temperature temperature
Level of difficulty low low medium medium low medium
Number of sample, which can be extracted simultaneously
One sample or
series
One sample or
series
One sample or series
One sample or
seriesone 6
Level of automatisation low low high high low medium
Cost of instruments low low high high low medium
26I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
TECHNIKI EKSTRAKCJI ROBENIDYNY Z PRÓBEK PASZYTECHNIKI EKSTRAKCJI ROBENIDYNY Z PRÓBEK PASZY
SHAKING UAE SOXHLET SOXTEC MAE ASE
sample preparation before extraction
K E
8 g spiked poultry feed + 8 g pure quartz
5 g spiked poultry feed + 5 g pure quartz
4 g spiked poultry feed
2.5 g spiked poultry feed
0.5 g spiked poultry feed
8 g spiked poultry feed + 5 g pure quartz
ambient
60 ml acidified methanol
25 ml acidified methanol
ambient
45 ml acidified methanol
extraction at
25 ml acidified methanol
extraction in
9 ml acidified methanol
extraction at
25 ml acidified methanol
extraction at
solvent used for extraction
extraction temperatureambient
temperatureambient
temperatureextraction at
elevated temperature
extraction in boiling solvent
extract on at 60, 80, 100, 120, 140oC
microwave power 300W
60, 80, 100, 120, 140oC
extraction pressure 1000, 1500 2000
temperature
additional parameters used for extraction1500, 2000,
2500psifor extraction
extract + molecular sieve, shaking vigorously 5 min
2 ml li t
drying step
2 ml aliquot column filled with 1g of aluminium oxide (activity grade I)
elution with 10 ml of methanol, careful mixing
clean-up step
chromatographic analysis20 μl aliquot of the purified extract
HPLC – DAD – MS analysis
27I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
HPLC DAD MS analysis
RECOVERY OF ROBENIDYNE FROM SAMPLES OF ANIMAL RECOVERY OF ROBENIDYNE FROM SAMPLES OF ANIMAL FOODSTUF (with addition of standard)FOODSTUF (with addition of standard)
120
80
100
y[%
]
próbkiskażone
próbkirzeczyw iste
Samples
without standard
Samples
40
60
Rec
over
y rzeczyw istewith standard
0
20
0
ASE
MAE
Soxte
c
Soxhl
et
Shaki
ng
UAE
28I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
CHROMATOGRAPHIC SEPARATION OF CHROMATOGRAPHIC SEPARATION OF ROBENIDYNE (LC ROBENIDYNE (LC DAD DAD MS)MS)ROBENIDYNE (LC ROBENIDYNE (LC –– DAD DAD ––MS)MS)
Chromatographic column:Chromatographic column:
125 x 4.0, 5 µm LiChrosphere ODS (Merck)
Mobile phase flow-rate: 1 ml/min
Temperature of the chromatographic column: 30 oC
Mobile phase: isocratic conditions: (70% methanol +30% water with addition (1% v/v) ofTFAA
29I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
DETECTIONDETECTION 6000
8000
40
60
80
100
334.0
336.0
ktor
a M
S
widmo SCAN
S
Spectrum SCAN
DETECTIONDETECTION
2000
4000
6000
m/z
100
200
300
400
20
40
335.0
Sygn
ał d
etek
Detector DAD
Sign
al o
f M
S
min
0
2
4
6
8
10
12
14
16
18
0
Detector DADMonitored wavelength: 317 nm
Mass spectrometerMass spectrometerIonisation type: electrospray (ESI), mode: positive ions
Drying gas flow rate: 12 l/minDry ng gas flow rate l/m n
Pressure: 45psi
Drying gas temperature: 350 oCy g g pMode of ions monitoring: SIM,
Monitored ions: 334 m/z and 336 m/z
30I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
PASSIVE TECHNIQUES OF ANALYTES SAMPLINGQ
SPMD LDPE strips MESCO POCIS
UPTAKE OF ANALYTES occurs as a free transport of massacross the membrane to the receiving medium and results fromthe difference of CHEMICAL POTENTIALS of analytes in thisthe difference of CHEMICAL POTENTIALS of analytes in thismedium and in the aqueous environment in which the sampler isplaced.
31I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
CHEMCATCHER CHEMCATCHER PASSIVE SAMPLER DESIGNPASSIVE SAMPLER DESIGN
-Sampler body
-Diffusion limiting bmembrane
-Receiving phase
MPLER h b d i d d l d h U i i f P h SAMPLER has been designed and evaluated at the University of Portsmouth within the STAMPS project.STAMPS = Standardised Aquatic Monitoring of Priority Pollutants by Passive Sampling
32I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
Sampling
CONFIGURATION OFCONFIGURATION OF CHEMCATCHERCHEMCATCHER PASSIVE SAMPLERPASSIVE SAMPLER
Extraction Extraction Extraction discExtraction discExtraction discExtraction discExtraction discExtraction discReceiving
Chemcatcher4
Chemcatcher3
Chemcatcher2
Chemcatcher1
Version of the sampler
Extraction Extraction discdisc
(SDB(SDB--XC) XC)
Extraction discExtraction disc(SDB(SDB--RPS )RPS )
Extraction discExtraction disc(C18)(C18)
Extraction discExtraction disc(C18 )(C18 )
Receiving phase
(trapping medium)
------polyethersulfonepolyethersulfoneMembrane
LCLC--DAD DAD --MSMSLCLC--DADDAD--MSMSLCLC--DADDAD--MSMSLCLC--DADDAD--MSMSFinal determination
technique
33I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
CALIBRATION OF CHEMCATCHER IN A FLOWCALIBRATION OF CHEMCATCHER IN A FLOW--THROUGH SYSTEMTHROUGH SYSTEMTHROUGH SYSTEMTHROUGH SYSTEM
ov
Chemicalsin MeOH
Waterreservoir
verhead sti
waste
rrer
Samplers
Water
water
AnalytesIn MeOH
Peristaltic pumpPeristaltic pumpStirrer
34I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
30 ml/minPeristaltic pump
100 μl/min Exposure tank
CONDITIONS OF SEPARATION AND FINAL CONDITIONS OF SEPARATION AND FINAL DETRERMINATIONDETRERMINATION ((HPLC HPLC –– DAD DAD ––MSMS))(( ))
Elements of measuring system Parameters
Li id h t h HPLC 1100 A il tLiquid chromatograph HPLC 1100, Agilent
Column Altima HPLC - 18 EPS 250mm x 4.6 mm x 5µm
Mobile phase A: H2O + 1% HCOOHMobile phase A: H2O + 1% HCOOHB: MeOH/ACN (1:1, v:v) + 1% HCOOH
Mobile phase flow-rate 0.9 ml/min
G di t s %A %BGradient czas %A %B
0 60 40
7.5 45 55
10 45 55
20 0 100
35I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
Analysis time 20 min
MONITORED IONSMONITORED IONS
MS(SCAN 20 - 280) Ionisation mode: ELECTROSPRAY
SIMtolmetin 212
naproxen 229ELECTROSPRAY naproxen 229
fenoprofen 241
ibuprofen 205
diklofenak 294
diflunisal 249
DAD 275nmDAD 275nm
36I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
CONCLUSIONSCONCLUSIONSCONCLUSIONSCONCLUSIONS
SPESPE Low level concentration
Complex and varied composition of the
of analytesp
sample matrix
37I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
CONCLUSIONSCONCLUSIONSCONCLUSIONSCONCLUSIONSDRINKING WATER NATURAL WATERS WASTE WATERS
l Eon-line SPE
off-line SPE
38I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
passive sampling (SPE)
DEPARTMENT OF ANALYTICAL CHEMISTRYCHEMISTRY
http://www.pg.gda.pl/chem/Katedry/Analityczna/analit.htmy
• List of publications• List of publications• Lectures presented during conferences
d • Courses and expertises
39I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
COURSES AND EXPERTISESCOURSES AND EXPERTISES
I di id l ( d d)Individual courses (on demand)HPLC (basic and advanced)GC (basic and advanced)( )Sample preparation for analysisABC of the SPE techniqueApplication of HPLC in food analysisApplication of HPLC in food analysisHyphenated techniquesBiotests in environmental studiesQ li C l d Q li A Quality Control and Quality Assurance (QC/ QA) of analytical results
40I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
QUALITY CONTROL AND QUALITY UR NCE OF N LYT C L RE ULTASSURANCE OF ANALYTICAL RESULTS
EDITED BY: P. Konieczka and J. Namieśnik
ISBN: 978-83-204-3255-8 ISBN: 978-83-204-3255-8
41I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
ISEAC’08ISEAC 08
42I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
DEPARTMENT OF ANALYTICAL CHEMISTRY
43I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy
Dr inż. Agata KOT-WASIK
THANK YOU FOR YOUR ATTENTION!ATTENTION!
44I Konferencja Polskiego Towarzystwa Spektrometrii Mas, 16 – 18.04.2008, Puławy