PBA-2008, Gdańsk 8-12.06.2008 1 ADVANCES IN NSAID RESIDUE ANALYTICS IN AQUEOUS ENVIRONMENT Agata KOT-WASIK, Jacek NAMIEŚNIK Deopartment of Analytical Chemistry, Chemical Faculty, Gdańsk University of Technology G. Narutowicza 11/12, 80-952 Gdańsk E-mail: [email protected]
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PBA-2008, Gdańsk 8-12.06.20081
ADVANCES IN NSAID RESIDUE ANALYTICS IN AQUEOUS
ENVIRONMENT
Agata KOT-WASIK, Jacek NAMIEŚNIKDeopartment of Analytical Chemistry, Chemical Faculty,
Gdańsk University of TechnologyG. Narutowicza 11/12, 80-952 Gdańsk
Identification of sources of emission and evaluation of scale and impact assessment of emission
Determination 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
PBA-2008, Gdańsk 8-12.06.20083
ANALITYKA I MONITORING ŚRODOWISKA PROBLEMY I WYZWANIA
Low and even very low concentration level of analytes in samples characterized by complex composition of the matrix
Possibility of time and space fluctuations of xenobioticsconcentration
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 processes
Lack of suitable standards and reference materials
PBA-2008, Gdańsk 8-12.06.20084
ENVIRONMENTAL POLLUTANTS
Regulated pollutants Nonregulated pollutants
...........
............
.......
.......
Dioxins(PCDD+PCDF)
Polyaromatichydrocarbons
(PAH’S)
PolichlorinatedBiphenyls (PCB’s)
Metal complexes
Brominated FlameRetardants (BFR’s)
Alkilofenole
Estrogens
Pesticides
fitoestrogens
Bisfenol A
Derivatives of phtalanes
ENDOCRINE DISRUPTING COMPOUNDS – EDC’s
Nonionic surfactants
Pharmaceutical residues
Personal Care Products(PCP’s)
Synthetic muskcompounds
PBA-2008, Gdańsk 8-12.06.20085
MOTTO
„Pollution from pharmaceuticals in surface and groundwaters is becoming recognised as an
environmental concern in many countries leading to the area of study labelled PIE”
PHARMACEUTICALS IN THE ENVIRONMENT
S. K. Khetan, T. J. Collins, Chem. Rev., 107, 2319-2364 (2007)
PBA-2008, Gdańsk 8-12.06.20086A. Nikolaou, S. Meric, D. Fatta, Anal. Bioanal. Chem., 387, 1225 (2007)
Antiinflammatorydrugs/ analgesics
Acetylsalicylic acid (Aspirin)DiclofenacIbuprofen
AcetaminophenMetamizolCodeine
IndometacineNaproxenPhenazone
AntibioticsErytromicynOfloxacin
ChlortetracyclineOxytetracycline
StreptomycinFlumequine
CiprofloxacinTrimetoprim
SulfamethoxazoleLincomycinPenicillin
LincomycinAmoxicillinSpiramycin
Lipid regulatorsBezafibrateGemfibrozil
Clofibric acidFenofibrate
Beta-blockersMetoprololPropranolol
NadololAtenololSotalol
Betaxolol
Most common pharmaceuticals in the environment
Steroids and related hormones17-β-estradiol
Estrone17 α-ethinyl estradiol
DiethylstilbestrolDiethylstilbestrol acetate
Cancer therapeuticsCyclophosphamide
Ifosphamide
DiureticsFurosemide
AntieplepticsCarbamazepine
AntidepressantsMianserin
TranquillisersDiazepam
THE MOST COMMON PHARMACEUTICAL
COMPOUNDS PRESENT IN ENVIRONMENTAL SAMPLES
PBA-2008, Gdańsk 8-12.06.20087
MAIN SOURCES OF DISCHARGES OF BIOLOGICALLY ACTIVE COMPOUNDS TO
THE ENVIRONMENT
• Production of pharmaceuticals (human drugs and veterinary drugs)
• Discharge to the environment a large amount of overdue drugs both from households and hospitals
• Excretion of non changed forms of biologically active compounds and their metabolites by humans and animals
PBA-2008, Gdańsk 8-12.06.20088
1. France, 2. Poland, 3. Germany, 4. USA, 5. Japan
AMOUNT OF DRUGS, WHICH ARE BOUGHT IN DIFFERENT COUNTRIES
BY PATIENT IN ONE YEAR
32
22 20
7
29
1 2 3 4 5
PBA-2008, Gdańsk 8-12.06.20089
PHARMACEUTICAL RESIDUES IN THE ENVIRONMENT - MILESTONES
19811981 confirmation of the presence and quantitative determination of CLOFIBRIC ACID IN ENVIRONMENTAL SAMPLES (USAUSA)
19971997 Determination of pharmaceutical residue in hospital sewages (GermanyGermany)
19971997 Studies related to the antibiotic toxicity in water environment (DenmarkDenmark)
1998 1998 Monitoring of river waters and sewage in Germany for the presence of pharmaceutical residue (GermanyGermany)
19981998 Determination of antibiotic compounds in different water samples (GermanyGermany)
1999 1999 Elaboration of an analytical method allowing for the confirmation of the presence of estrogens in surface waters (USAUSA)
2002 2002 First method of simultaneous determination of residues of many pharmaceuticals in samples of the environment (DenmarkDenmark)
2001 2001 –– 20022002 Determination of pharmaceutical residue in drinking waters (GermanyGermany)
2003 2003 Elaboration of appropriate mathematical models for predicting concentration and loss of individual pharmaceuticals in the environment (BelgiumBelgium)
20052005 Determination of pharmaceutical residue in steel samples (SpainSpain)
PBA-2008, Gdańsk 8-12.06.200810
BIOLOGICALLY ACTIVE COMPOUNDS ON THE LIST OF PRIORITY POLLUTANTS
(the Netherlands)
ConcentrationCompounds
Presence in WWTP
effluent min [µg· l-1] max [µg· l-1]
Hormone disruptors
17 α-ethinyloestradiolBisphenol AOestrone
+++++
n.d.0,040,00
<0,014,090,01
Medical substances
IbuprofenAnhydro-erythromecine
SulfomethoxazoleCarbamazepine
SotalolAmidotrizoic acid
++++++++++++++++++
0,120,150,060,330,970,23
0,760,520,131,001,61,2
n.d. non detected+ found in 5% to50% of studied samples of effluent++ found in 50% to 95 % of studied samples of effluent+++ found in more than 95% of studied samples of effluent
P. De Jong, J. F. Kramer, W. F. Slotema, K. A. Third, STOWA REPORT 2005-34, ISBN 90.5773.316.1
PBA-2008, Gdańsk 8-12.06.200811
APPLICATION OF LC-MS TECHNIQUE
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 determined in surface waters.
PBA-2008, Gdańsk 8-12.06.200812
STEPS IN ANALYTICAL PROCEDURE FOR
DETERMINATION OF PHARMACEUTICAL
RESIDUESVALIDATION
PRETREATMENT
There is no doubt that sample pre-treatment
operations are crucial for reliability of analytical
results
SAMPLING
CONSERVATION
ISOLATION/PRECONCENTRATION
DERIVATISATION
CLEAN-UP
STORAGE
ANALYSIS
IDENTIFICATION
EVALUATION OF DATA
PBA-2008, Gdańsk 8-12.06.200813
DIFFERENT APPROACHES IN THE FIELD OF APPLICATION OF LC-MS TECHNIQUE
1. SCREENING (direct injection of aqueous sample)
2. SHORT-TERM MONITORING (SPE technique in OFF-LINE or ON-LINE mode)
3. LONG TERM (passive sampling of analytes)
PBA-2008, Gdańsk 8-12.06.200814
SCREENING OF NSAID RESIDUE IN AQUEOUS SAMPLES
• Usual samples volume inRPLC ~20μl.
• LARGE VOLUMES OF WATER SAMPLES (500μl, 1000 μl i 2000 μl) WERE INTRODUCED TO INJECTION PORT
PBA-2008, Gdańsk 8-12.06.200815
COMPARISON OF CHROMATOGRAPHIC PARAMETERS during analysis of large
samples of water with standard addition of analytes from NSAID group
UPTAKE OF ANALYTES occurs as a free transport of mass across the membrane to the receiving medium and results from the difference of CHEMICAL POTENTIALS of analytes in this medium and in the aqueous environment in which the sampler is placed.
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
PBA-2008, Gdańsk 8-12.06.200831
CONFIGURATION OF CHEMCATCHER PASSIVE SAMPLER
LCLC--DAD DAD --MSMSLCLC--DADDAD--MSMSLCLC--DADDAD--MSMSLCLC--DADDAD--MSMSFinal determination
• List of publications• Lectures presented during conferences
• Courses and expertises
PBA-2008, Gdańsk 8-12.06.200839
COURSES AND EXPERTISES
Individual courses (on demand)HPLC (basic and advanced)GC (basic and advanced)Sample preparation for analysisABC of the SPE techniqueApplication of HPLC in food analysisHyphenated techniquesBiotests in environmental studiesQuality Control and Quality Assurance (QC/ QA) of analytical results
PBA-2008, Gdańsk 8-12.06.200840
QUALITY CONTROL AND QUALITY ASSURANCE OF ANALYTICAL RESULTS