modern laboratory equipment for water quality wfd...
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Republic of Serbia Ministry of Agriculture and Environmental Protection Serbian Environmental Protection Agency
Modern laboratory equipment for water quality
monitoring – WFD request
Country visit Serbia, Belgrade, March 22nd, 2017
History of implementation of water monitoring in Serbia
Result on reports of water quality
testing dated from 1965
source: Serbian Environmental Protection Agency
History of implementation of water monitoring in Serbia
2000 – Water Framework Directive
2008 – EQS Directive
2010 – Serbian Water Law
2011-2012 – Several bylaws adopted
2013 – new EQS Directive (August)
2014 – Regulation on limit values of priority and priority hazardous substances polluting surface
water and deadlines for their achievement (February)
Harmonization of surface water status monitoring in the Republic of Serbia with Water Framework Directive (2000/60/ЕC) requirements
• The first Programe of surface water monitoring status in Serbia harmonized with the WFD requirements was carried out in 2012 • In Republic of Serbia 498 surface water bodies were determined and grouped
into the following categories: rivers, heavily modified water bodies (HMWB), artificial water bodies (AWB) and lakes
• The stations for operational and surveillance monitoring were selected (WFD,
Annex V, 1.3.1; 1.3.2) • 50 surveillance monitoring stations represent “the basis” of water monitoring
network with main goal to provide the whole water status survey within the catchment areas (Morava, Sava and Danube River)
Surface Water Monitoring Network in 2012-2016
During the period 2012-2016,
monitoring of surface water
status in 181 water bodies were
covered.
IPA 2012 Establisment of an integrated environmental monitoring system for air and water quality
2011 – Project idea and application
2012 - 2014 – Tender procedure and evaluation
March 2015 – Contract signed with supplier
September 2015 – Arrival of the equipment
October/November 2015 – Equipment instalation
December 2015/January2016 – Preparation of Training Program
February – November 2016 Trainings in SEPA and EU laboratories
December 2016 –Audit by Jaroslav Slobodnik, project supervisor
IPA 2012 – List of donation
2.1 Gas chromatograph - time-of-flight - mass spectrometer (GCxGC-TOF-MS) for comprehensive gas
chromatography with automated sample preparation/sample introduction facility and auto sampler system
fully compatible with SBSE and LVI techniques, LECO Instruments
2.2 Gas chromatograph – triple quadrupole - mass spectrometer GC7890/7000MSD (GC-MS/MS) with
automated sample preparation/sample introduction, Agilent Technologies
2.3 Ultra High Performance Liquid Chromatograph (UHPLC) 1290 with Diode Array UV Detector (DAD UV)
and high resolution MS/MS spectrometer 6550 with on-line SPE sample preparation system, Agilent
Technologies
2.4 Fully automated analyzer for the determination of mercury in liquid samples Mercury plus BU, Analytik
Jena AG
2.5 Gel Permeation Chromatograph 1260 for preparation of sediment and biota samples, Agilent
Technologies
IPA 2012 – List of donation
2.6 Lyophylizer for preparation of sediment and biota samples Lyoquest, Telstar Technologies, S.L.U.
2.7 Vibratory Sieve Shaker with set of sieves (0,063-2,000 mm) for preparation of sediment samples AS200,
Retsch GmbH
2.8 Mortar grinder with PTFE scraper for preparation of sediment samples RM200, Retsch GmbH
2.9 Inverted microscope with dark and light field and phase contrast with camera and image analysis for
phytoplankton analysis Axio Observer D1, Carl Zeiss GmbH
2.10 Stereomicroscope with gooseneck type cold light with camera and image analysis for analysis of
benthic invertebrates SteREO Discovery V8, Carl Zeiss GmbH
2.11 Chemicals – Standards and reagents
2.12 Trainings for 2.1, 2.2 & 2.3 in duration of 175 days
2013/39/EU – Environmental Quality Standards Directive - priority and priority hazardous substances
No. CAS Number Priority substance Analytical method Biota
1 15972-60-8 Alachlor GC-MS
2 120-12-7 Anthracene GC-MS
3 1912-24-9 Atrazine GC-MS/LC-MS
4 71-43-2 Benzene GC-MS
5 not applicable Brominated diphenylethers GC-MS *
6 7440-43-9 Cadmium and its compounds AAS/ICP-MS
7 85535-84-8 Chloroalkanes, C10-13 GC-MS
8 470-90-6 Chlorfenvinphos GC-MS
9 2921-88-2 Chlorpyrifos (Chlorpyrifos-ethyl) GC-MS
10 107-06-2 1,2-dichloroethane GC-MS
11 75-09-2 Dichloromethane GC-MS
2013/39/EU – Environmental Quality Standards Directive - priority and priority hazardous substances
No. CAS Number Priority substance Analytical method Biota
12 117-81-7 Di(2-ethylhexyl)phthalate (DEHP) GC-MS/LC-MS
13 330-54-1 Diuron LC-MS
14 115-29-7 Endosulfan GC-MS
15 206-44-0 Fluoranthene GC-MS *
16 118-74-1 Hexachlorobenzene GC-MS *
17 87-68-3 Hexachlorobutadiene GC-MS *
18 608-73-1 Hexachlorocyclohexane GC-MS
19 34123-59-6 Isoproturon LC-MS
20 7439-92-1 Lead and its compounds AAS/ICP-MS
21 7439-97-6 Mercury and its compounds AAS
22 91-20-3 Naphthalene GC-MS
2013/39/EU – Environmental Quality Standards Directive - priority and priority hazardous substances
No. CAS Number Priority substance Analytical method
Biota
23 7440-02-0 Nickel and its compounds AAS/ICP-MS
24 not applicable Nonylphenols GC-MS
25 not applicable Octylphenols GC-MS
26 608-93-5 Pentachlorobenzene GC-MS
27 87-86-5 Pentachlorophenol GC-MS
28 not applicable Polyaromatic hydrocarbons (PAH) GC-MS *
29 122-34-9 Simazine LC-MS
30 not applicable Tributyltin compounds
31 12002-48-1 Trichlorobenzenes GC-MS
32 67-66-3 Trichloromethane (chloroform) GC-MS
33 1582-09-8 Trifluralin GC-MS
2013/39/EU – Environmental Quality Standards Directive - priority and priority hazardous substances
No. CAS Number Priority substance Analytical method
Biota
34 115-32-2 Dicofol GC-MS *
35 1763-23-1 Perfluorooctane sulfonic acid and its derivatives (PFOS) LC-MS *
36 124495-18-7 Quinoxyfen GC-MS
37 not applicable Dioxine & dioxine like compounds GC-MS *
38 74070-46-5 Aclonifen GC-MS
39 42576-02-3 Bifenox GC-MS
40 28159-98-0 Cybutryne GC-MS
41 52315-07-8 Cypermethrin GC-MS
42 62-73-7 Dichlorvos GC-MS
43 not applicable Hexabromocyclododecane (HBCDD) GC-MS *
44 76-44-8/1024-57-3 Heptachlor & heptachlor epoxide GC-MS *
45 886-50-0 Terbutryn GC-MS
2.1 Gas chromatograph - time-of- flight - mass spectrometer (GCxGC-TOF-MS)
Gas chromatograph - time-of- flight - mass
spectrometer (GCxGC-TOF-MS) for comprehensive
gas chromatography with automated sample
preparation/sample introduction facility and
autosampler system fully compatible with SBSE and
LVI techniques
Analytical methods:
1. Pesticides
2. Industrial pollutants
3. PAHs
2.1 Gas chromatograph - time-of- flight - mass spectrometer (GCxGC-TOF-MS)- PAH
2.1 Gas chromatograph - time-of- flight - mass spectrometer (GCxGC-TOF-MS)-PAHs
PAH analytes as in the EQS Directive µg/l
Compound MAC Max conc Postive results
Naphtalene 130 0.003 48
Fluorene 0.0002 6
Anthracene 0.1 0.0002 8
Phenanthrene 0.0002 16
Pyrene 0.0002 2
Benzo(a) anthracene 0.0008 30
Chrysene 0.0008 30
Benzo(b) fluoranthene 0.017 0.0007 14
Benzo(k) fluoranthene 0.017 0.0002 24
Benzo(a) pyrene 0.27 0.0008 14
Indeno(1,2,3,-cd) pyrene 0.0006 15
2.1 Gas chromatograph - time-of- flight - mass spectrometer (GCxGC-TOF-MS), Pesticides
Compund MAC Min conc Max conc Postive results
Alpha HCH 0.002 0.0002 0.002 30
Simazine 4 0.0002 0.001 15
Atrazine 2 0.0002 0.001 24
Lindane 0.002 0.0002 0.0008 3
Delta /-HCH 0.002 0.0006 0.0060 32
Alachlor 0.7 0.0002 0.0006 50
Heptachlor 3*10-5 0.0002 0.002 36
Terbutryn 0.034 0.0002 0.004 16
Chlorpyrifos 0.1 0.0002 0.0006 40
Pesticide/biocide analytes as in the EQS Directive µg/l
2.1 Gas chromatograph - time-of- flight - mass spectrometer (GCxGC-TOF-MS), Pesticide
Compound MAC Min conc Max conc Postive results
Dicofol 0.0012
AA-EQS
0.0002 0.003 12
Endosulfan alfa 0.0004 0.007 18
p,p'-DDE, p,p'-DDD, o,p'-DDT, p,p'-DDT total 0.025 0.004-total 0.01-total 16
Dieldrin 0.0002 0.0016 12
Endrin 0.0002 0.0006 5
Endosulfan beta 0.0002 0.001 15
Pesticide analytes as in the EQS Directive µg/l
2.1 Gas chromatograph - time-of- flight - mass spectrometer (GCxGC-TOF-MS) IPS
Compound MAC Min conc Max conc Postive results
Phenol, 4-(1,1,3,3-tetramethylbutyl)- 0.01 AA-EQS 0.0002 0.005 8
Phenol, 4-(1,1-dimethylpropyl)- 0.001 0.2 34
4-Nonylphenol 2 0.0006 0.002 8
Industrial pollutant analytes as in the EQS Directive µg/l
2.2 Gas chromatograph – triple quadrupole - mass spectrometer (GC-MS/MS) with
automated sample preparation/sample introduction
Gas chromatograph – triple quadrupole - mass
spectrometer (GC-MS/MS) with automated sample
preparation/sample introduction facility for analysis of
WFD priority substances and identification of river basin
specific pollutants.
Analytical methods:
1. Pesticides and biocides
2. Polyaromatic hydrocarbons
3. Industrial pollutants
4. Volatile organic compounds
5. Pentachlorophenol
6. Brominated diphenylethers
7. Chloroalkanes C10-13
8. Dioxini, furani and PCB-DLs
2.2 Gas chromatograph – triple quadrupole - mass spectrometer (GC-MS/MS) with automated sample preparation/sample introduction
Pesticides and biocides
Analyzed compounds:
Atrazine
Alachlor
Chlorfenvinphos
Chlorpyrifos
Aldrin
Isodrin
Dieldrin
Endrin
Endosulfan-alpha
Endosulfan-beta
4,4’-DDE
4,4’-DDD
2,4’-DDT
4,4’-DDT
Alpha-HCH
Beta-HCH
Gamma-HCH(Lindan)
Delta-HCH
Simazine
Trifluralin
Bifenox
Cybutryne
Cypermethrin
Dicofol
Dichlorvos
Heptachlor
Heptachlor epoxide
Quinoxyfen
Terbutryn
Aclonifen
Lindan
Chlorfenvinphos
Chlorfenvinpho
s
Lindan
Compound MAC Min conc Max conc Postive results
Atrazine 2.0 0.0041 0.0162 37
Alachlor 0.7 0.0412 1
Terbutryn 0.34 0.0024 0.0193 2
Alpha-HCH
sum 0.04 Beta-HCH 0.0040 1
Gamma-HCH(Lindan)
Delta-HCH
Simazine 4 0.0051 0.0113 6
Cypermethrin 6x10-4 0.0001 0.0056 93
Dicofol NA 0.0014 0.0016 1
2.2 Gas chromatograph – triple quadrupole - mass spectrometer (GC-MS/MS) with automated sample preparation/sample introduction
Pesticide/biocide analytes as in the EQS Directive µg/l
Compound MAC Min conc Max conc Postive results
Anthracene 0.1 0.001 0.006 6
Fluoranthene 0.12 0.002 0.004 3
Benzo(a)pyrene 0.27 0.001 2
Benzo(a)anthracene / 0.001 6
Benzo(b)fluoranthene 0.017 0.001 100
2.2 Gas chromatograph – triple quadrupole - mass spectrometer (GC-MS/MS) with automated sample preparation/sample introduction
PAH analytes as in the EQS Directive µg/l
Industrial pollutants
Analyzed compounds:
Hexachlorobenzene
Pentachlorbenzene
4-n-Nonylphenol
4-Nonylphenols
(technical)
4-tert-Octylphenol
DEHP (Phthalic acid, bis-2-ethylhexylester)
Hexachlorobenzene
Hexachlorobenzene
2.2 Gas chromatograph – triple quadrupole - mass spectrometer (GC-MS/MS) with automated sample preparation/sample introduction
Compound AAC Min conc Max conc Postive results
DEHP (Phthalic acid, bis-
2-ethylhexylester) 1,3 0.025 8.303 100
Industrial pollutant analytes as in the EQS Directive µg/l
Compound MAC Min conc Max conc Postive results
Benzen 50 0.149 11.954 75
Carbon tetrachloride NA 0.122 5.065 78
Hexachloro-1,3-butadien 0.6 0.125 0.423 78
Naphtalene 130 0.267 12.995 78
Tetrachloroethene NA 0.154 3.754 7
Trichloromethane NA 3.406 7.155 5
1,3,5-Trichlorobenzene
NA
0.196 0.526 68
1,2,4-Trichlorobenzene 0.120 0.641 62
1,2,3-Trichlorobenzene 0.184 0.590 74
2.2 Gas chromatograph – triple quadrupole - mass spectrometer (GC-MS/MS) with automated sample preparation/sample introduction
VOC analytes as in the EQS Directive µg/l
Pentachlorphenol
Analyzed compounds:
Pentachlorphenol
Pentachlorphenol
2.2 Gas chromatograph – triple quadrupole - mass spectrometer (GC-MS/MS) with automated sample preparation/sample introduction
Compound MAC Min conc Max conc Postive results
PCHP 1 / / 0
PCHP analyte as in the EQS Directive µg/l
Brominated diphenylethers
Analyzed compounds:
Pentabromodiphenylether
Pentabromodiphenylether
2.2 Gas chromatograph – triple quadrupole - mass spectrometer (GC-MS/MS) with automated sample preparation/sample introduction
Compound MAC Min conc Max conc Postive results
BDE 0.14 0.002 1
BDE analyte as in the EQS Directive µg/l
2.3 Ultra High Performance Liquid Chromatograph (UHPLC) with Diode Array UV Detector (DAD UV) and high resolution MS/MS spectrometer with on-line SPE sample preparation
Ultra High Performance Liquid Chromatograph (UHPLC)
with Diode Array UV Detector (DAD UV) and high resolution
MS/MS spectrometer with on-line SPE sample preparation
system, chromatographic control and data management
station with software for analysis of WFD priority
substances and identification of river basin specific
pollutants.
Analytical methods:
1. Triazine and phenylureate herbicides
2. Neoicotinoide pesticides
3. Pharmaceuticals – macrolide antibiotics
4. Estrogens
5. Phtalates
6. PFOS
2.3 Ultra High Performance Liquid Chromatograph (UHPLC) with Diode Array UV Detector (DAD UV) and high resolution MS/MS spectrometer with on-line SPE sample preparation
Atrazine
Isoproturon
Triazine and phenylureate herbicides
Analyzed compounds: Desethylatrazine
Methabenthiazuron
Monolinuron
Isoproturon
Sebuthylazine
Metobromuron
Diuron
Chlorotoluron
Metazachlor
Terbutylazine
Linuron
Metolachlor
Simazine
Hexazinon
Metoxuron
Cyanazine
Atrazine
Compound MAC Max conc Postive results
Desethylatrazine N/A <0.0001 0
Simazine 4.000 <0.0001 0
Hexazinon N/A <0.0001 0
Metoxuron N/A <0.0001 0
Cyanazine N/A <0.0001 0
Atrazin 2.000 0.0041 37
Methabenzthiazuron N/A 0.0104 0
Monolinuron N/A 0.0065 62
2.3 Ultra High Performance Liquid Chromatograph (UHPLC) with Diode Array UV Detector (DAD UV) and high resolution MS/MS spectrometer with on-line SPE sample preparation
Pesticide analytes as in the EQS Directive µg/l
Compound MAC Max conc Postive results
Isoproturon 1.000 0.0076 58
Sebuthylazine N/A 0.0015 0
Metobromuron N/A 0.0021 0
Diuron 1.800 0.0038 8
Metazachlor N/A 0.0033 16
Terbutylazine N/A 0.013 67
Linuron N/A 0.014 2
Metolachlor N/A 0.0021 25
Chlorotoluron N/A 0.0007 12
2.3 Ultra High Performance Liquid Chromatograph (UHPLC) with Diode Array UV Detector (DAD UV) and high resolution MS/MS spectrometer with on-line SPE sample preparation
Pesticide analytes as in the EQS Directive µg/l
Compound PNEC Max conc Postive results
Thiamethoxam 0.140 0.015 4
Clothianidin 0.130 0.012 5
Imidacloprid 0.009 0.016 39 (8 over limit)
Acetamiprid 0.500 0.019 9
Thiacloprid 0.050 0.047 6
2.3 Ultra High Performance Liquid Chromatograph (UHPLC) with Diode Array UV Detector (DAD UV) and high resolution MS/MS spectrometer with on-line SPE sample preparation
The Predicted No Effect Concentration (PNEC) is the concentration of a chemical which marks the limit at which below no
adverse effects of exposure in an ecosystem are measured
Neonicotinoide analytes as in the EQS Directive µg/l
2.3 Ultra High Performance Liquid Chromatograph (UHPLC) with Diode Array UV Detector (DAD UV) and high resolution MS/MS spectrometer with on-line SPE sample preparation
Erythromycin
Pharmaceuticals – macrolide antibiotics
Analyzed compounds: Azithromycin
Clarithromycin
Erythromycin
Diclofenac
Compound PNEC Max conc Postive results
Azithromycin 0.09 0.0710 3
Clarithromycin 0.13 <0.0003 0
Erythromycin 0.20 <0.0003 0
Diclofenac 0.050 0.0065 35
2.3 Ultra High Performance Liquid Chromatograph (UHPLC) with Diode Array UV Detector (DAD UV) and high resolution MS/MS spectrometer with on-line SPE sample preparation
Pharmaceutical analytes as in the EQS Directive µg/l
2.3 Ultra High Performance Liquid Chromatograph (UHPLC) with Diode Array UV Detector (DAD UV) and high resolution MS/MS spectrometer with on-line SPE sample preparation
Alpha and beta
estradiol
Estrogens
Analyzed compounds: Alpha estradiol
Beta estradiol
Estrone
Ethynyl estradiol
Alpha estradiol Beta estradiol
Compound PNEC Max conc Postive results
Alpha estradiol N/A 0.00034 55
Beta estradiol N/A 0.00033 53
Estrone 0.0036 0.00016 65
Ethynyl estradiol N/A 0.0007 44
2.3 Ultra High Performance Liquid Chromatograph (UHPLC) with Diode Array UV Detector (DAD UV) and high resolution MS/MS spectrometer with on-line SPE sample preparation
Estrogen analytes as in the EQS Directive µg/l
2.3 Ultra High Performance Liquid Chromatograph (UHPLC) with Diode Array UV Detector (DAD UV) and high resolution MS/MS spectrometer with on-line SPE sample preparation
PFOS and PFOA
PFOS
Analyzed compounds: PFOS
PFOA
PFOS PFOA
Compound MAC Max conc Postive results
PFOS 36 0.0034 20
PFOA 36 0.0022 26
PFOS analytes as in the EQS Directive µg/l
2.4 Fully automated analyser for the determination of mercury in liquid samples, Analytik Jena AG Mercur plus BU
Compound MAC Min conc Max conc Postive results
Hg 0.07 0.005 0.08 1
Hg as in the EQS Directive µg/l
2.9 Inverted microscope with dark and light field and phase contrast with camera and image analysis for phytoplankton analysis, Carl Zeiss GmbH, Axio Observer D1
Biological Quality Elements investigation
-Phytoplankton (including Cyanobacteria) and phytobenthos
-Identification of pressures: eutrophication and organic pollution
-Ecological status/potential assessment according to the Water Framework Directive 2000/60/EC
Diatom indices calculation (OMNIDIA v. 5.5)
Diatom indices used in ecological status/potential assessment according to
the National Monitoring Programme
0,01,02,03,04,05,06,07,08,09,0
10,011,012,013,014,015,016,017,018,019,020,021,0
0 50000
100000
150000
200000
250000
300000
350000
400000
450000
500000
550000
600000
650000
700000
dep
th (
m)
аbundance (cell ml-1)
Planktothrix agardhii species abundance with
regard to depth of the water column in the
Garaši Reservoir in 2016
May
August
-Algal blooms in the Garaši Reservoir
caused by the species Planktothrix agardhii
in 2016 (this is potentially toxic species can
produce microcystin-LR (hepatotoxin)
Phytoplankton (including Cyanobacteria) - eutrophication indicator
Parameters: Phytoplankton Abundance and Phytoplankton Biomass (chlorophyll a)
-The presence of Euglena species indicate high
organic pollution
bad ecological potential
2.10 Stereomicroscope with gooseneck type cold light with camera and image analysis for
analysis of benthic invertebrates, Carl Zeiss GmbH, SteREO Discovery V8
-Benthic invertebrate community composition and structure
analysis
-Identification of pressures: organic pollution and
hydromorphological degradation
-Ecological status/potential assessment according to the
Water Framework Directive 2000/60/EC
-ZEN 2 Microscope and Imaging
Software
-Zelinka & Marvan Saprobic Index, BMWP Score, ASPT,
Shannon-Wiener Diversity Index, Total No. of Taxa, EPT Taxa,
No. of Sensitive Taxa (Austrian list), Percentage Participation
of Oligochaeta/Tubificidae
-Sampling according to the AQEM protocol
ASTERICS v. 4.0.4 Software for benthic invertebrate metrics
Future – Guidelines on further harmonization of surface water monitoring to the WFD
Defining a list of the specific polluting substances and their Environmental Quality Standards
(EQS)
Monitoring of priority and priority hazardous substances in Biota/Sediment
Defining a clear methodology to determine appropriate values in ecological and chemical status
assessment
Revising the criteria considering the level of confidence and precision in ecological status
classification
Amendment the Regulation on reference conditions of surface water types
Amendment the Regulation on the parameters of ecological and chemical status of surface
waters and parameters of chemical status and quantitative status of groundwater
Revision the list of parameters and ecological status class boundaries
Future – Establishing functional Regional Monitoring Centers within the SEPA
Quality Control - Quality management system
Quality management system is
established 2006 by acceptance of
general requirements specified in
SRPS ISO/IEC 17025:2006.
It covers testing and calibration
performed using standard methods,
non-standard methods and
laboratory-developed methods.
Acknowledgement
Ministry of Agriculture and Environment Protection, Republic of Serbia
Rainer Freund, ing. PhD, Project Manager, EU Delegation in Serbia
Ivan Špánik, ing. PhD, Faculty of Chemical and Food Technology, Bratislava, Slovakia
Olga Vyviurska, ing. PhD, Faculty of Chemical and Food Technology, Bratislava, Slovakia
Jaroslav Slobodnik, ing. PhD, Masaryk University, Brno, Czech Republic
Thanks for your attention
Republic of Serbia
Ministry of Agriculture and Environmental Protection
Serbian Environmental Protection Agency
Mirjana Balać, chemist Aleksandra Djurkovic, biologist
Daliborka Popadić, physical chemist Snežana Čadjo, biologist
Ivana Dersek Timotić, chemist Ana Vujović, physical shemist
Katarina Nedeljković, chemist Boris Novaković, biologist
Zoran Stojanović, chemist