Modern laboratory equipment for water quality WFD...

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


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


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


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


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


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


Pesticide/biocide analytes as in the EQS Directive µg/l


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


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


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


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


VOC analytes as in the EQS Directive µg/l

Pentachlorphenol

Analyzed compounds:

Pentachlorphenol

Pentachlorphenol



PCHP 1 / / 0

PCHP analyte as in the EQS Directive µg/l

Brominated diphenylethers

Analyzed compounds:

Pentabromodiphenylether

Pentabromodiphenylether



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


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


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




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



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


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


Erythromycin

Pharmaceuticals – macrolide antibiotics

Analyzed compounds: Azithromycin

Clarithromycin

Erythromycin

Diclofenac


Azithromycin 0.09 0.0710 3

Clarithromycin 0.13 <0.0003 0

Erythromycin 0.20 <0.0003 0

Diclofenac 0.050 0.0065 35


Pharmaceutical analytes as in the EQS Directive µg/l


Alpha and beta

estradiol

Estrogens

Analyzed compounds: Alpha estradiol

Beta estradiol

Estrone

Ethynyl estradiol

Alpha estradiol Beta estradiol


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


Estrogen analytes as in the EQS Directive µg/l


PFOS and PFOA

PFOS

Analyzed compounds: PFOS

PFOA

PFOS PFOA


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


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

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Modern laboratory equipment for water quality WFD...

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