MINISTRY OF ENVIRONMENT AND WATER BULGARIAN EXECUTIVE ENVIRONMENT AGENCY - Partner PP12 in the Project Danube WATER integrated management WATER MIS ETC 166 Sampling and testing activities of the General Directorate "Laboratory and analytical activities Phone: +359 2 955 90 11 Fax: +359 2 95590 15 e-mail: ncesd@eea.government.bg ; www.eea.government.bg/
Ruse Regional Laboratory and Montana Regional Laboratory took part in the water sampling and testing. The laboratories are structured as offices to testing laboratories in General Directorate "Laboratory and analytical activities" of the Executive Environmental Agency EEA. The laboratories were accredited in accordance with BS EN ISO 17025 from the 2006. Since 2011 the laboratories have been accredited as an offices of General Directorate "Laboratory and analytical activities" with certificate 135/ЛИ/30.09.2011 The laboratories carry out sampling and testing components and environmental factors water, air, soil and noise.
Quality Management System Testing Laboratories General Directorate "Laboratory and analytical activities" of the Executive Environmental Agency EEA operates under a single accreditation as a laboratory with 15 offices (laboratories) Central laboratory and 14 regional laboratories in accordance with BS EN ISO / IEC 17025: 2006 "General requirements for the competence of testing and calibration laboratories" since 2011 The scope of accreditation of the laboratory includes testing of water, air, noise, soil, sediment, waste products, plants, and GMOs.
Structure General Directorate "Laboratory and analytical activities" consists of 14 regional offices and a Central laboratory Head quarter with 8 departments. The total number of employs is 268. All of them are highly skilled engineers, physicists, chemists, biologists, technicians and other staff.
Where are our Laboratories?
Main Laboratory Quality Control Department Air Quality Laboratory Water Quality Laboratory Soil and West Characterization Laboratory Bio Monitoring Laboratory (including GMO) Radiation Measurement Laboratory Instrumental Analytical Methods Laboratory Emergency Situation Department Regional Laboratories Coordination
Quality Control Department prepares comprehend documentation regarding the procedures for accreditation of laboratories and new accreditation in accordance with the requirements of BDS EN ISO/IEC 17025: 2006; DG LAA has a system of internal laboratory control of all tested samples in comply with the requirements of good laboratory practice, as well as the instructions of the manufacturers of equipment and diagnostics; provides methodical assistance and control the quality of analyzes in regional laboratories; organizes regular courses and seminars for experts from the Directorate General with the aim of improving the qualification of staff; participates in interlaboratory comparison tests of national, European and international level: Qualco Danube, Aquacheck, Equate, Aguacom, BAM, AMOS, ILS-RIZA to ensure and control the quality of the analysis; Ensures authenticity and control of the quality data obtained by measurements on individual components of the environment.
Water Quality Laboratory The main activities are related to testing and ensuring data for quality of surface water, ground water, waste water, mineral water intended for drinking water, according to the monitoring programs. This activity is consistent with the requirements of the Water Framework Directive 2000/60/EEC establishing a framework of EU policy in the field of water
Sampling of surface water; Mobile water laboratory
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Bio Monitoring Laboratory Sampling and making hydro-biological analyzes for determination of the ecological status of water in biological quality elements (BEC) - macroinvertebrates, macrophytes, phytobenthos and chlorophyll "a" (the main characteristic of a biological element of quality phytoplankton). Microbiological analyzes for the characterization of sewage sludge for recovery in agriculture, plants and biologically treated waste. Assessment and determination of Escherichia coli, Salmonella and Clostridium perfringens.
Bio Monitoring Laboratory Sampling, detection, qualitative and quantitative determination of genetically modified DNA in plants. Control of genetically modified organisms (GMOs) into the environment and controlled conditions (according to Bulgarian GMO low and Directive EC/2001/18).
Radiation Measurements Laboratory The main task is to control the content of radionuclides in environmental components
Sampling and radiometric measurements in real conditions I.1. Environmental Sampling (soil, water, sediment, air, food and plant products, stone materials) for the subsequent radiological laboratory analysis. I.2. Measurement of gamma radiation dose in air (gamma background) with a portable gama dosimeter. I.3. Measurement of surface alpha and beta contamination - portable gama radiometer. I.4. Measurement of the concentration of radon in indoor air and outdoor.
Instrumental Analytical Methods Laboratory Performs testing of heavy metals and organic contaminants in environment: 12 of laboratories are equipped with ICP/MS and AAS and Hg analysts; performes measurement of heavy metals (lead, copper, zinc, cadmium, nickel, cobalt, chromium, arsenic, manganese, mercury etc.) in water, soil, waste, sediment arsenic, cadmium, nickel and lead in aerosols in the air; 8 of laboratories are equipped GC/FID, GC/MS, and 2 -GC/MS/MS, HPLC/MS/MS chromatographes.
Мeasured parameters : volatile organic compounds (VOCs) - benzene, toluene, xylenes, ethylbenzene, styrene, carbon tetrachloride, trichloromethane, dichloromethane, tetrachlorethylene, trichlorethylene, dichloroethane, trichlorobenzene, trichloroethane and others; pesticides - organochlorine, organophosphorus compounds, nitrogen and phosphorus containing pesticides; chlorobenzenes - pentachlorobenzene and hexachlorobenzene; alkylphenols - 4-n-nonylphenol and p-tert-octylphenol; petroleum products - C10 - C40; PAHs- (16 pieces incl. Benz (a) pyrene); PCBs - polychlorinated biphenyls number 9.
RL Ruse participated in Project "WATER MIS 161" in 2013 with sampling and testing of water samples from the river Danube - left bank, middle and right bank at Ruse, Tutrakan and Silistra town. Samples were tested for 34 characteristics. Samples were taken from 19 to 23.10.2013 at following points: Ruse right bank Ruse middle Ruse left bank Tutrakan right bank Tutrakan middle Tutrakan left bank Silistra right bank Silistra middle Silistra left bank
Sampling was done with a hydrographic ship "Vit" APPD- of Ruse. On 19/09/2013 River at the town Ruse, 20/09/2013 - River at the town Turtukan and 20/09/2013, River at the town Silistra, as samples were taken from the Bulgarian coast of the river environment, middle of the river and the Romanian coast, perpendicular to the current. Geographical coordinates were taken. Sampling was conducted by expert RL Ruse with job obligations of water sampling. Dates and times of sampling, that were pre-arranged with Romanian side of the project, were met. Measured characteristics at the sampling points are: active reaction ph, dissolved oxygen, dissolved oxygen saturation, temperature, conductivity, turbidity. Issued are relevant protocols for sampling of water. Ship "Vit" did provide the necessary conditions for the sample preparation of samples of water taken (filtration, conservation, appropriate storage conditions). Samples were delivered in RL Rousse on 21/9/2013. The samples were tested for 28 characteristics in the laboratory. These indicators were specified in advance by the organizers of the parallel sampling. Test results are reflected in the 12 test reports. Information about the results, methods and principles of testing, used basic technical resources and limits of determination are shown in Table 1. The test results has shown identical values at the sampling points of the river.
Project WATER MIS 161- sampling in September 2013 Results Water quality parameter Unit Tutraka n-left Tutrakan -middle Method used Ruse-left Rusemiddle Ruseright Tutrakanright Silistra-left Silistramiddle Silistra-right MQL Sample ID Sample ID Sample ID Sample ID Sample ID Sample ID Sample ID Sample ID Sample ID 2408/2409 2410/2411 2406/240 7 2416/24 17 2414/241 2412/2413 2422/2423 2420/2421 2418/2419 5 1 рн рн БДС EN ISO 10523:2012 7,9±0,1 8,0±0,1 7,9±0,1 7,9±0,1 7,9±0,1 7,9±0,1 8,0±0,1 8,0±0,1 7,9±0,1 2 2 Temperature ºС БДС 17.1.4.01: 1977 19,6±0,2 19,6±0,2 19,5±0,2 16,9±0, 2 17,0±0,2 16,9±0,2 19,8±0,2 19,8±0,2 19,7±0,2 0,1 3 Dissolved oxygen mg/dm 3 БДС EN ISО 5814:2012 6,4±0,1 6,4±0,1 6,4±0,1 6,7±0,1 6,4±0,1 6,5±0,1 6,5±0,1 6,6±0,1 6,4±0,1 0,4 4 Dissolved oxygen saturation % БДС EN ISО 5814:2012 70,2±1,1 70,5±1,1 70,4±1,1 68,9±1, 0 66,4±1,0 67,8±1,1 71,6±1,1 72,5±1,1 70,5±1,1 4
5 Conductivity μs/cm БДС ЕN 27888:2000 369±37 359±36 358±36 358±36 356±36 341±34 362±36 366±37 355±36 5 6 Suspended solids mg/dm 3 БДС EN 872:2006 1,0±0,1 1,0±0,1 1,0±0,1 1,0±0,1 1,0±0,1 4,0±0,1 7,0±0,1 6,0±0,1 2,0±0,1 2 7 Chlorides mg/dm 3 ISO 9297:1989 30,3±1,1 24,8±0, 9 25,6±0,9 27,4±0,9 27,8±1,0 23,7±0,8 27,0±0,9 24,8±0,9 24,1±0,8 5 8 Ammonium ( аs N-NH4) mg/dm 3 БДС ISO 7150-1:2002 0,022±0, 002 0,026±0 0,034±0, 0,030±0,0 0,259±0, 0,020±0, 0,083±0,0,003 003 03 012 002 07 0,030±0,0 03 0,022±0,00 2 0,005 9 Nitrites (as N- NO2) mg/dm 3 БДС EN 26777:1997 0,008±0, 001 0,008±0 0,007±0, 0,008±0,0 0,008±0, 0,007±0, 0,011±0,0,001 001 01 001 001 01 0,008±0,0 01 0,008±0,00 1 0,002 10 Nitrates (as N-NO3) mg/dm 3 БДС ISO 7890-3:1998 0,982±0, 032 1,06±0, 03 1,10±0,0 4 1,030±0,0 33 1,04±0,0 34 1,05±0,0 3 1,010±0,0 33 0,973±0,0 32 1,08±0,035 0,1 11 Total Nitrogen mg/dm 3 БДС EN 12260:2004 1,4±0,1 1,3±0,1 1,4±0,1 1,30±0,10 1,60±0,1 0 1,30±0,1 0 1,50±0,10 1,40±0,10 1,20±0,10 0,14
12 Orthophosphates mg/dm 3 БДС EN ISO 6878:2005 0,027±0,0 02 0,037±0,0 03 0,026±0,0 02 0,058±0,0 0,048±0,00 0,048±0,0 0,095±0,0 05 4 04 08 0,077±0,003 0,091±0,00 8 0,002 13 Total Phosphorous mg/dm 3 БДС EN ISO 6878:2005 0,087±0,0 08 0,096±0,0 09 0,077±0,0 03 0,069±0,0 0,066±0,00 0,076±0,0 0,100±0,0 06 6 07 09 0,097±0,009 0,091±0,00 8 0,01 14 Magnesium mg/dm 3 БДС ISO 6059:2002 14,6±0,7 13,6±0,7 14,4±0,7 17,3±0,9 14,6±0,7 14,2±0,7 15,0±0,8 16,1±0,8 15,9±0,8 1,21 15 Calcium mg/dm 3 БДС ISO 6058:2002 49,5±1,0 49,7±1,0 51,0±1,0 46,0±0,9 49,0±1,0 49,6±1,0 48,8±1,0 47,6±1,0 49,1±1,0 2 16 Alkalinity mmol/dm БДС EN ISO 3 9963-1:2000 2,86±0,10 2,76±0,09 3,07±0,10 2,86±0,10 2,86±0,10 2,76±0,09 2,86±0,10 2,86±0,10 2,76±0,09 0,4 17 COD mg/dm 3 ISO 6060:1989 <10* <10* <10* <10* <10* <10* <10* <10* <10* 10
18 BOD 5 mg/dm3 БДС EN 1899-2:2004 1,2±0,1 1,1±0,1 1,4±0,1 1,4±0,1 1,4±0,1 1,3±0,1 1,5±0,1 1,5±0,1 1,4±0,1 0,5 19 Total Chromium mg/dm3 БДС EN ISO 17294-2:2005 <2* <2* <2* <2* <2* <2* <2* <2* <2* 2 20 Nickel mg/dm3 БДС EN ISO 17294-2:2005 <2* <2* 2,08±0,25 <2* <2* <2* <2* <2* <2* 2 21 Cuprum mg/dm3 БДС EN ISO 17294-2:2005 <2* <2* 2,44±0,20 <2* 2,02±0,17 <2* 3,61±0,31 3,69±0,32 2,32±0,19 2 22 Zink mg/dm3 БДС EN ISO 17294-2:2005 <10* <10* <10* <10* <10* <10* <10* 52,1±1,2 12,3±1,6 10 23 Arsenic mg/dm3 БДС EN ISO 17294-2:2005 2,36±0,14 2,41±0,14 2,47±0,14 2,32±0,14 2,39±0,14 2,54±0,15 2,35±0,14 2,32±0,14 2,46±0,14 2
24 Cadmium mg/dm3 25 Lead mg/dm3 26 4,4 -ДДТ µg/dm3 27 γ-hch µg/dm3 28 Atrazine µg/dm3 29 30 Benzo(b) fluoranth en+ Benzo(k) fluoranth en Fluoranth en µg/dm3 µg/dm3 БДС EN ISO 17294-2:2005 БДС EN ISO 17294-2:2005 ВВЛМ 1014/201 0 ВВЛМ 1014/201 0 ВВЛМ 1015/201 0 ВВЛМ 1016/201 0 ВВЛМ 1016/201 0 <0,08* <0,08* <0,08* <0,08* <0,08* <0,08* <0,08* <0,08* <0,08* 0,08 <1* <1* <1* <1* <1* <1* <1* <1* <1* 1 <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* 0,01 <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* 0,01 <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* 0,01 <0,004* <0,004* <0,004* <0,004* <0,004* <0,004* <0,004* <0,004* <0,004* 0,004 <0,02* <0,02* <0,02* <0,02* <0,02* <0,02* <0,02* <0,02* <0,02* 0,02
31 Benzo (a)pyrene µg/dm3 ВВЛМ 1016/2010 <0,02* <0,02* <0,02* <0,02* <0,02* <0,02* <0,02* <0,02* <0,02* 0,02 32 Indeno(1,2,3-cd) pyrene µg/dm3 ВВЛМ 1016/2010 <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* 0,01 33 Benzo(g,h, i) perylene µg/dm3 ВВЛМ 1016/2010 <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* <0,01* 0,01 34 Mercury µg/dm3 ВВЛМ 1012/2010 <0,3 <0,3 <0,3 <0,3 <0,3 <0,3 <0,3 <0,3 <0,3 0,3 35 Turbidity FNU БДС EN ISO 7027:2003 5,31 5 5,55 7,26 7,06 5,12 6,81 5,24 5,48 1
In 2015 RL Ruse and RL Montana took part in the sampling of two points on the Danube. 1.Sampling section: Silistra-Chiciu River km: 374 Sampling date: 08.06.2015 2. Sampling section: r. Dunav - s. Novo selo River km: 833,7 Sampling date: 16/06/2015
Silistra-Chiciu River km: 374 Sampling date: 08.06.2015 Water Quality Parameter Unit Left Middle Right LOD LOQ Uncertainty of measurement Method analysis Water temp. 0 C 22,3 21,5 21,3-0,1 1,00% БДС 17.1.4.01:1977 Suspended solids mg/l 29,0 27,0 43,0 0,7 2 4,50% БДС EN 872:2006 Dissolved Oxygen Concentration mg/l 8,3 8,3 8,2-0,4 4,80% БДС EN ISО 5814:2012 Dissolved Oxygen Saturation % 94,7 95,3 92,6-4 4,80% БДС EN ISО 5814:2012 ph - 8,0 8,1 8,0-2 1% БДС EN ISO 10523:2012 Conductivity (@ 20 0 C) µs/cm 353 337 335-5 10% БДС EN ISO 9963-1:2000 Alkalinity mmol/l 2,74 2,74 2,84 0,13 0,4 3,30% БДС EN 27888:2000 Ammonium (NH 4 + -N) mg/l N 0,024 0,009 0,023 0,001 0,005 14,60% БДС ISO 7150-1:2002 Nitrites (NO 2 - -N) mg/l N 0,025 0,020 0,021 0,0006 0,002 6,40% БДС EN 26777:1997 Nitrates (NO 3 - -N) mg/l N 1,61 1,71 1,69 0,011 0,1 3,90% БДС ISO 7890-3:1998 Total Nitrogen mg/l N 2,40 2,40 2,60 0,057 0,4 4,90% БДС EN 12260:2004 Ortho-phosphates (PO 4 3- -P) mg/l P 0,033 0,037 0,042 0,001 0,005 17,70% БДС EN ISO 6878:2005 Total Phosphorous mg/l P 0,170 0,170 0,158 0,004 0,01 13,90% БДС EN ISO 6878:2005
Water Quality Parameter Unit Left Middle Right LOD LOQ Uncertainty of measurement Method analysis COD-Cr mg/l O 2 <10 <10 <10 3 10 - ISO 6060:1989 BOD 5 mg/l O 2 1,1 1,1 1,1-0,5 5,60% БДС EN 1899-2:2004 Calcium (Ca 2+ ) mg/l 49,0 47,2 47,1 0,7 2 2,00% БДС ISO 6058:2002 Magnesium (Mg 2+ ) mg/l 9,44 10,7 10,7 0,4 1,21 5,40% БДС ISO 6059:2002 Clorides (Cl - ) mg/l 21,5 20,1 20,8 1,5 5 3,40% ISO 9297:1989 Cadmium µg/l <0,08 <0,08 <0,08 0,02 0,08 - БДС EN ISO 17294-2:2005 Lead µg/l <1 <1 <1 0,3 1 - БДС EN ISO 17294-2:2005 Mercury µg/l <0,05 <0,05 <0,05 0,017 0,05 - own method BBЛM 1012/2010 Nickel µg/l <2 <2 <2 0,5 2 - БДС EN ISO 17294-2:2005 Copper µg/l 2,12 2,38 2,04 0,6 2 4,14% БДС EN ISO 17294-2:2005 Zinc µg/l <10 <10 <10 3 10 - БДС EN ISO 17294-2:2005 Chromium µg/l <2 <2 <2 0,5 2 - БДС EN ISO 17294-2:2005 Arsenic µg/l 1,72 1,75 1,82 0,06 0,2 3,10% БДС EN ISO 17294-2:2005
Water Quality Parameter Unit Left Middle Right LOD LOQ Uncertainty of measurement Method analysis Arsenic µg/l 1,72 1,75 1,82 0,06 0,2 3,10% БДС EN ISO 17294-2:2005 Atrazin µg/l <0,01 <0,01 <0,01 0,003 0,01 - own method BBЛM 1015/2010 Lindan µg/l <0,01 <0,01 <0,01 0,003 0,01 - own method BBЛM 1014/2010 pp-ddt µg/l <0,01 <0,01 <0,01 0,003 0,01 - own method BBЛM 1014/2010 Chlorophyll a µg/l 9,21 8,88 6,9 0,5 1,5 10% БДС ISО 10260:2002
Novo Selo River km: 833,7 Sampling date: 16/06/2015 No. Water Quality Parameter Unit Left Middle Right LOD LOQ 1 Water temp. Uncertainty of measurement Method analysis 0 C 23,6 23,8 23,8 0,1 0,3 BDS 17.1.4.01 2 Suspended solids mg/l 58 55 60 1,6 5 8% BDS EN 872 3 Dissolved Oxygen Concentration mg/l 6,9 6,6 6,5 0,1 0,3 5,50% BDS EN ISO 5814 4 Dissolved Oxygen Saturation % 82 80 78 1 3 5,50% BDS EN ISO 5814 5 ph - 8,05 8,06 8,06 0,01 0,03 1% BDS EN ISO 10523 6 Conductivity (@ 20 0 C) µs/cm 383 378 388 14 5% BDS EN 27888 7 Alkalinity mmol/l 3,2 3,1 3,2 0,03 0,1 6% BDS EN ISO 9963-1 8 Ammonium (NH 4 + -N) mg/l N 0,021 0,059 0,063 0,004 0,013 7% BDS ISO 7150-1 9 Nitrites (NO 2 - -N) mg/l N 0,018 0,022 0,021 0,001 0,003 11% BDS EN 26777 10 Nitrates (NO 3 - -N) mg/l N 1,19 1,22 1,19 0,007 0,02 7% BDS ISO 7890-3 11 Total Nitrogen mg/l N 1,6 1,5 1,8 0,2 0,5 14% BDS EN 12260 12 Ortho-phosphates (PO 4 3- -P) mg/l P 0,054 0,058 0,099 0,002 0,005 14% BDS EN ISO 6878 13 Total Phosphorous mg/l P 0,058 0,071 0,104 0,002 0,005 15% BDS EN ISO 6878 14 COD-Cr mg/l O 2 10,8 10,6 10,8 1,3 4 5% ISO 15705 15 BOD 5 mg/l O 2 3,2 3 3,2 0,2 0,5 10% BDS EN 1899-2 16 Calcium (Ca 2+ ) mg/l 33,6 48,1 52,8 0,7 2 5% BDS ISO 6058 17 Magnesium (Mg 2+ ) mg/l 22,7 15 13,3 0,6 2 18% BDS ISO 6059 18 Clorides (Cl - ) mg/l 17,5 17,5 17,5 1,5 5 5% ISO 9297
Novo Selo River km: 833,7 Sampling date: 16/06/2015 Uncertainty of No. Water Quality Parameter Unit Left Middle Right LOD LOQ Method analysis measurement 13 Total Phosphorous mg/l P 0,058 0,071 0,104 0,002 0,005 15% BDS EN ISO 6878 14 COD-Cr mg/l O 2 10,8 10,6 10,8 1,3 4 5% ISO 15705 15 BOD 5 mg/l O 2 3,2 3 3,2 0,2 0,5 10% BDS EN 1899-2 16 Calcium (Ca 2+ ) mg/l 33,6 48,1 52,8 0,7 2 5% BDS ISO 6058 17 Magnesium (Mg 2+ ) mg/l 22,7 15 13,3 0,6 2 18% BDS ISO 6059 18 Clorides (Cl - ) mg/l 17,5 17,5 17,5 1,5 5 5% ISO 9297 19 Cadmium µg/l <0,02 <0,02 0,03 0,006 0,02 20% BDS EN ISO 17294-2 20 Lead µg/l <0,08 <0,08 <0,08 0,027 0,08 - BDS EN ISO 17294-2 21 Mercury µg/l <0,05 <0,05 <0,05 0,017 0,05 - own method BBЛM 1012/2010 22 Nickel µg/l 1,11 1,09 1,37 0,023 0,07 5% BDS EN ISO 17294-2 23 Copper µg/l 1,8 1,8 4,07 0,023 0,07 5% BDS EN ISO 17294-2 24 Zinc µg/l 11,5 6,64 22,8 0,33 1 5% BDS EN ISO 17294-2 25 Chromium µg/l 0,203 0,205 0,233 0,02 0,06 15% BDS EN ISO 17294-2 26 Arsenic µg/l 1,98 2,02 2 0,017 0,05 5% BDS EN ISO 17294-2 27 Atrazin µg/l <0,01 <0,01 <0,01 0,003 0,01 - own method BBЛM 1015/2010 28 Lindan µg/l <0,01 <0,01 <0,01 0,003 0,01 - own method BBЛM 1014/2010 29 pp-ddt µg/l <0,01 <0,01 <0,01 0,003 0,01 - own method BBЛM 1014/2010 30 Chlorophyll a µg/l 3 3,6 3,7 0,5 1,6 6% BDS ISO 10260
RESUME OF THE MEASURMENTS The results of the measured indicators of the samples in 2013 and 2015 show insignificant difference. The are no significant differences between the values in Silistra city and Novo Selo village. The results of the organic compounds and heavy metals are about the limits of quantification determination. The two laboratories have used same methods and equipment. That is a good base for a comparison. General, the results show good environmental status of Donau river.