SIXTH FRAMEWORK PROGRAMME: Structuring the European Research Area Specific Programme RESEARCH INFRASTRUCTURES ACTION

Contract for an INTEGRATING ACTIVITY implemented as

CO-ORDINATION ACTION

Black Sea SCENE-Black Sea Scientific Network Proposal/Contract no.: RICA-=2005-022868/ Start date of contract: 1 December 2005 Ending date of contract: 30 November 2008

DELIVERABLE NA3-1: Report on inventory of DQC/DQA methods in Black Sea countries and

EU member states December 2006

1. Data Quality Control methods within Black Sea organizations P.P. Shirshov Institute of Oceanology- Moscow-Russian Federation; Southern Branch of P.P. Shirshov Institute of Oceanology-Gelendzhik-Russian Federation DQC of biological parameters, methods of sampling are standardized with all Black Sea countries. The procedure of inter-calibration sampling was provided during international cruises. Net catchabilities were compared and coefficients of differences were estimated. The procedures for sampling and estimations of abundance and biomass were standardized during participation in the international programs COMSBlack, NATO-Tu Black Sea during 1992-1993. DQC procedures within the Southern Branch (physical and chemical oceanography) are based on

• “Guidance on the hydrological works in oceans and seas” of the General hydrographic and weather bureau of the Council of Ministers of USSR, Gidrometizdat 1977.

• ISO 5667-9:1992 Guidance on sampling from marine waters • Hydrochemistry: The Southern Branch of SIO has an accreditation certificate N POCC

RU.0001.512500 for the technical competence in the Analytical Laboratories Accreditation System, GOST R ISO/IEC 17025 (valid till 04/03/2009). In 2006 the Laboratory participated in the inter-calibration programme organized by BSERP: IAEA Laboratory of Marine Environment in Monaco.

Institute of Limnology-St. Petersburg-Russian Federation DQC of river runoff is measured by the National Hydrological or Hydro-meteorological Surveys, using international standard techniques of the International Association for Hydrological Research (IAHR) WORLDLAKE database: Much information within the WORLDLAKE database is based on limnological data from literature or personal communications. DQC was not applied.

State Oceanographic Institute-Moscow-Russian Federation For DQC of chemistry and pollution data SOI is applying the Russian “Manual on chemical analysis of marine waters” of Hydrometeoizdat, St. Petersburg 1993, RD 52.10.23-92. This manual is dealing with standard hydrochemistry (salinity, alkalinity, pH, oxygen saturation, H2S, phosphates/Total P, silicates, nitrites, nitrates, ammonium, total N, organic N) and pollution (petroleum hydrocarbons, phenols, chlorinated hydrocarbons-pesticides and PCBs-, heavy metals, dissolved Hg, detergents, sm-triasin herbicides, xantogenats, dithiophosphates). Each chapter of the manual is built up as follows:

• General description • Device, equipments, materials, chemicals • Sampling • Preparation to analysis

- chemical preparation - glass preparation - extraction - concentration

• analysis scheme • preparation of materials

- standards - calibration - linearity - chromatography preparation

• analysis

• Treatment of results - mathematical treatment - errors of methodology

• qualification of chemistry stuff • time consuming for analysis

DQC for bottom sediments pollution is based on the “Manual on determination of bottom sediments pollution” of Hydrometeoizdat 1979. Internal Data Quality Assessment procedures are based on: Internal - General instruction on inner laboratory control (VLK)

- Local instructions, mainly based on MI 2335-95 (Inner control of quality of chemical analysis) and RD 52.2.4.66-86 (inner control of quality of data of chemical analysis)

External - QUASIMEME - Monaco Laboratory

Technical DQC is related to technical errors like date, coordinates, units, dot/comma, decimals, detection limits, dissolved oxygen, nutrients) and abnormal data. All Russian Research Institute of Hydro-meteorological Information-World Data Centre B-Obninsk-Russian Federation RIHMI-WDC is dealing with oceanographic, marine meteorological and coastal station data. The principal stages of technical DQC are:

• check of data format • check of metadata • check of headers (coordinates, date and time) • check of parameters • duplicates checks

RIHMI applies a Data Quality Flag Scale: 0 value is correct 1 value has been recovered 2 value is doubtful 3 value is erroneous 4 value has been lost or not been observed 5 phenomenon did not occur 6 reserve 7 reserve (if unknown time was substituted by 0) 8 reserve 9 no quality control has been applied

Space Research Institute-Moscow-Russian Federation IKI is dealing with remote sensing images. DQC of the original images is carried out by ESA and is completely in line with European practice. For processing of the images (antenna pattern correction for balance in brightness over the picture, deleting of wrong pixels) specially developed ENVI software is used. Quality control of data interpretation: IKI applies 4 basic methods to validate the interpretations:

• sub-satellite field experiments including in situ measurements • joint use of data obtained by different satellite instruments operating in different ranges

and at different spatial resolutions • comparison with theoretical models • publication of results in peer-reviewed journals and at international conferences

Ukrainian Scientific Centre of the Ecology of Sea-Odessa-Ukraine UkrSCES presented a very detailed overview of DQC procedures applied within their organization. In the next figures the data streams and Quality Control “lines” are shown.

Database

Data StreamsInformationDepartament

ScientificVessels

AnalyticLaboratories

ScientificDepartaments

Database

Quality ControlsInformationDepartament

ScientificVessels

AnalyticLaboratories

ScientificDepartaments

Database

Quality ControlsScientificVessels

InformationDepartament

AnalyticLaboratories

ScientificDepartaments

in cruise and ship’s laboratories

UkrSCES applies DQC procedures for:

• Devices and equipment used for sampling of water, bottom sediments and biota from board of ships

• Analytical procedures, operation procedures, manuals and instructions are on board of UkrSCES ships

• Methodologies are on board of UkrSCES ships For technical quality control UkrSCES is using special software “OKEAN”: Each parameter in table TGM is accompanied by an attribute of quality. During the process an attribute of quality is automatically formed. Attributes of quality of chemical elements are formed during processing and entering the parameters in table TGM. The basic attributes of quality are: 0 - Value is correct; 1 - Value is restored; 2 - Value is doubtful; 3 - Value is rejected; 4 - Measurements were not carried out; 5 - Control was not carried out. When the expedition is fulfilled files MAINF, OSV, TGM are transferred to the Information Department for Quality control. Analytical works in ground laboratories are carried out in conformity to QA/QC requirements to procedures of intra laboratory quality control (standard techniques used in Ukraine, adapted to conditions of a certain laboratory). The main elements of Quality Assurance:

• Documented Quality System; • Suitable skilled staff; • Suitable environment; • Suitable Equipment and Standards; • Certified Reference Materials; • Training; • Validated Methods; • Reporting Procedures; • Record of Calibration, Training etc.; • Quality Audit and Review; • Complaints Procedure; • Proficiency Testing Schemes.

Marine Hydrophysical Institute-Sevastopol-Ukraine Oceanographic Data Quality check software provides:

• metadata control (duplicate cruises and profiles, data and chronology, ship velocity, location, sea depth, observation depth)

• hydrographic data control (density inversion check, spikes check, climatic check including checking of three standard deviations, density at standard depths and temperature and salinity on isopycnal surfaces)

Ukrainian Scientific and Research Institute of Ecological Problems-Kharkiv-Ukraine USRIEP presented a detailed overview of the DQC procedures applied by their organization for river water quality monitoring and internal and external laboratory control and assessment. National Normative documents used for methods development, approval and introduction into force:

• RD 52.24.51-85 «Meteorological attestation of methods for carry out of measurements of components of samples of surface waters». State Committee of USSR on Hydro-meteorology and Environmental Control

• Inter-state standard GOST 8.315-97 «Standard samples of composition and characteristics of substances and materials». Gosstandart of Ukraine1999

• Inter-state standard DSTU 27384-2002 «Water. Norms of errors (inaccuracies, bias) of measurements»

• DSTU 3215-95 «State system for provision of unity of measurements. Metrological attestation of measurement techniques»

• DSTU 1.7-2001 «Rules and methods of approval and introduction of international and regional standards»

• RD 52.24.66-86 «System of precision control for results of measurements of environmental pollution».

Method

Standardized method –state standards (GOST,

DSTU), inter-state methods, DSTU ISO

Attested method – methods those undergone an examination in State Standard of Ukraine (Gosstandart

of Ukraine) and have special numbers. These method can be named “Guiding document” (RD), “Methods for measurement carry

out” (MVI, MVV)

Special method -agreed and approved by Gosstandart – used

in special cases

The structure of the attested special procedures (=methods)

1. Scope1. Scope

2. Characteristics of inaccuracies of measurements

2. Characteristics of inaccuracies of measurements

3. Measurement tools and techniques, reagents and materials

3. Measurement tools and techniques, reagents and materials

4. Method4. Method

5. Safety requirements

5. Safety requirements

6. Qualification of operator

6. Qualification of operator

7. Conditions of analysis carry out

7. Conditions of analysis carry out

8. Preparation to analysis

8. Preparation to analysis

9. Carry out of measuring9. Carry out of measuring

10. Processing of results and paper work

10. Processing of results and paper work

11. Data quality control and assessment

11. Data quality control and assessment

12. References12. References

Institute of Biology of the Southern Seas-Sevastopol-Ukraine For biological data measured in the Black Sea are:

• no standard data formats • no standard sampling protocols • no standard taxonomic systems • no unified DQC procedures

In general:

• what is measured is equipment dependent • sampling processing requires human expert and hand processing • result electronic profile takes days to weeks (even months) to be prepared • metadata are very complex and of great importance

Odessa National University-Odessa-Ukraine In Odessa National University the work had been executed under the following scheme: Methods bottom sediments and water sampling When conducting geological and geochemical studies, sampling of water and bottom sediments was organised conformity with the following standards and methodical guidelines:

• GOST 17.1.5.01-80: Nature conservation. Hydrosphere, General requirements for sampling of bottom sediments of water objects for analysis of pollution. M. Gosstandart of the USSR. (in Russian)

• GOST 17.1.5.01-80: Nature conservation. Hydrosphere, General requirements for sampling of surface and seawaters, ice and rainfall. M. Gosstandart of the USSR. (in Russian

• Methodical guidelines on geological mapping of shelf areas. Sopot. 1987, (in Russian) • Temporary methodical guidelines on landscape & ecological to mapping at geological

survey of shelf. Ministry of Geology of the USSR. Leningrad, 1989. (in Russian) • Methodical guidelines on conducting geological surveys on the Black and Azov Seas • shelf. State Geological Enterprise "Prichernomorgeologia". Odessa. 2006. (in Russian)

After the fieldwork is finished the field materials are accepted in conformity with branch standards, representatives of samples and quality of sampling are assessed National Standards of Ukrainian sampling:

Parameter Method

Specific Conductance Determination of pH Dissolved Oxygen Phosphate Total Phosphorus Nitric nitrogen Total nitrogen Oil Phenol Chlorinated hadrocarbons Heavy metals Pesticides Ions composition of the nativ water Phytoplankton pigments: Chlorophyll a,

Chlorophyll b,Chlorophyll c,Pheophytin aPhytoplankton – numbers, biomass, spicies diversity Zooplankton – numbers, biomass, spicies diversity Zoobenthos – numbers, biomass, spicies diversity Radioactiv strontium Radioactiv caesium

Sampling. Part 2. Guidance on sampling techniques (ISO 5667-2:1991, IDT) DSTU ISO 5667-2:2003, Kiev Derzhspogzhvstsndart of Ukraine 2004 Part 3. Guidance on the preservation and handing of samples (ISO 5667-3:1994, IDT) DSTU ISO 5667-3:2001, Kiev Derzhspogzhvstsndart of Ukraine 2002

Bacterioplankton – numbers, biomass Sampling. Part 2. Guidance on sampling techniques (ISO 5667-2:1991, IDT) DSTU ISO 5667-2:2003, Kiev DERZHSPOGZHVSTSNDART OF UKRAINE 2004 Part 3. Guidance on the preservation and handing of samples (ISO 5667-3:1994, IDT) DSTU ISO 5667-3:2001, Kiev DERZHSPOGZHVSTSNDART OF UKRAINE 2002 Part 6. Guidance on sampling of rives and streams (ISO 5667-6:1990,IDT) DSTU ISO 5667-6:2001, Kiev DERZHSPOGZHVSTSNDART OF UKRAINE 2002

Ichthyofauna – numbers, spicies diversity Sampling. Part 3. Guidance on the preservation and handing of samples (ISO 5667-3:1994, IDT) DSTU ISO 5667-3:2001, Kiev DERZHSPOGZHVSTSNDART OF UKRAINE 2002

Bottom sediments Sampling. Part 12. Guidance on sampling of bottom sediments. (ISO 5667-12:1995,IDT) DSTU ISO 5667-12:2001, Kiev DERZHSPOGZHVSTSNDART OF UKRAINE 2002

Laboratory analyses were done in accordance with the methods corresponding to the international standards:

• Water quality. Determination of dissolved fluoride, chloride, nitrite, orthophosphate, bromide, nitrate and sulphate ions using liquid chromatography method. Part 1. Method for slightly polluted water (ІSО 10304-1: 1992, IDТ) DSTU ІSО 103041: 2003. Kiev, Derzhspogzhvstsndart of Ukraine, 2004. (in Ukrainian)

• Water quality. Determination of turbidity. DSTU ІSО 7027: 2003, Kiev, Derzhspozhivstsndart of Ukraine, 2003. (in Ukrainian)

• Water quality. Determination of рН (IS0 10523: 1994, МОD) . DSTU 4077-2001. Kiev. State Committee of Ukraine on Technical Regulation, 2003.

• Water quality. Determination of dissolved oxygen. Electrochemical a method, using a sound (ІSО 5814:1990. IDТ) DSTU ІSО 5814:2004. Kiev, Derzhspozhivstsndart of Ukraine, 2004. (in Ukrainian)

• Water quality. Determination of phosphorus. Method of spectrometry, using ammonium molibdate. (ІSО 6878:1998, GOTHA) DSTU ІSО 6878:2003. Kiev, Derzhspozhivstsndart of Ukraine, 2003. (in Ukrainian).

In case there was no national standard for laboratory analysis following guidelines were used:

• Guidelines chemical analysis of seawaters 52.10.243-92. St. Petersburg: Hydrometizdat. 1993. (in Russian)

• Guidelines for the geochemical analyses of marine sediments and suspended particulate mater/ Reference Methods for Marine Pollution studies, №71, UNEP, 1995

Institute of Oceanology-Varna-Bulgaria For DQC of biological data under development is a manual for phytoplankton sampling and analysis in the Black Sea. This manual will have the following table of content:

1. Introduction 2. Sampling 3. Sample preservation and storage 4. Phytoplankton enumeration and densities 5. Taxonomic identification 6. Biomass determination 7. Recording data 8. Phytoplankton related environmental status indicators 9. Quality control and quality assurance

Within the manual for quantitative sampling and sample treatment of marine soft bottom macrozoobenthos is included: Chapter 8: Recommendations for quality assurance Chapter 9: Quality control routines The phytoplankton manual is based on the contents of other phytoplankton manuals and documents, as well as experience from within the Black Sea Region itself. The following reports and documents have been of particular help in compiling this manual:

• Standard Operating Procedures for Algae and Aquatic Plant Sampling and Analysis North Carolina Department of Environment and Natural Resources Division of Water Quality January 2003 (JAN-03) Version Protocol for Monitoring Phytoplankton

• HELCOM Manual (http://www.helcom.fi/Monas/CombineManual2/PartC/CFrame.htm) • Standard Operating Procedures for Algae and Aquatic Plant Sampling and Analysis North

Carolina Department of Environment and Natural Resources Division of Water Quality January 2003 (JAN-03) Version Protocol for Monitoring Phytoplankton

• A report by the marine biodiversity monitoring committee (Atlantic maritime ecological science cooperative, Huntsman marine science center) to the ecological monitoring and assessment network of environment Canada by Jennifer L. Martin. The EMAN Ecosystem Monitoring Protocols and the Community-Based Monitoring Protocols for Marine and estuarine ecosystems, Canada.

• Phytoplankton guild sampling, preservation and laboratory analysis (prepared by Marina Cabrini, Laboratorio di Biologia Marina, via A. Piccard 54, 34010 Trieste, for a team of European phytoplankton experts working on the project TWReference-net).

• Guide to UK Coastal Planktonic Ciliates © 2001 DJS Montagnes, University of Liverpool http://www.liv.ac.uk/ciliate/.

• REPORT OF THE ICES/HELCOM Steering Group on Quality Assurance of Biological Measurements (SGQAB) in the Baltic Sea ICES Headquarters, Copenhagen 25–28 February 2003 Conseil International pour l’Exploration de la Mer, Palægade 2–4 DK–1261 Copenhagen K Denmark.

• ICES SGQAB REPORT 2005ACME:06 Ref. C, E, HICES/HELCOM Steering Group on Quality Assurance of Biological Measurements in the Baltic SeaICES Headquarters22 – 25 February 2005.

• ISO/IEC 17025. General requirements for the competence of testing and calibration laboratories and prEN 15204 (under Approval: 2005-11): Water quality - Guidance standard for the routine analysis of phytoplankton abundance and composition using inverted microscopy (Utermöhl technique).

For the Zoobenthos manual the following documents are used:

• This guideline has been adapted from established benthic grab sampling methods described in a range of documents the most important of which are:

• Davies et al. (2001), Gray et al. (1992), Holme and McIntyre (1984), • ISO 16665: 2005 (E), • the Manual for Marine Monitoring in the COMBINE Programme of HELCOM (2003), • Rees et al (1991), Rumohr (1990), Rumohr (1999) and UK NMMP Green Book (2003). • Further consideration has been given to quality assurance from other texts including

Rees (2004), ICES (2004) and ICES (2005). Institute of Fisheries and Aquaculture-Varna-Bulgaria Quality Assurance: set of guidelines that, if followed strictly for surveys, analyses, and reporting, will produce analytical results of known accuracy, precision, which are comparable, complete, and scientifically representative. Quality Assurance at IFA-Varna extends to areas of:

• Preparing of QA work plans: field and laboratory work design with all QA/QC elements. • Implementing a quality system including filed &laboratory quality manuals: organizational

level document to stipulate procedures to ensure data quality. • Documenting analytical methods by Standard Operating Procedures (SOPs): process level

document to outline procedures for a given method; • Documenting procedures for handling and analyzing samples; • Documenting procedures for data reporting and record keeping. • Providing reasonable facilities and suitable equipment; • Employing suitably trained staff.

Data quality control: implementation of additional checks to ensure adherence to the documented procedures:

• Field Duplicate: Collection of duplicate sample from the same sampling site. One FD is required for every 20 samples. The acceptance criteria is 20% Relative Percent Difference (RPD).

• Split Sample: Two or more samples produced when one sample has been divided or split. On a regular basis-10% of the samples yearly, are to be split. The acceptance criterion is 20% RPD.

• Archive sample: Some solid media samples are to be split, one of the splits is sent to the laboratory for analysis and the other is archived.

The laboratory preparation of biological samples includes:

• Skill Verification: Personnel performing a specific biological examination participates in a skill verification exercise.

• Sorting Statistic: A collected sample is sorted into specimens. A second examination of the material is performed by a second taxonomist to identify specimens missed during the initial sorting.

• Identification Consistency: An example specimen is examined separately by two individuals and identified to the lowest taxonomic level. The two identifications are compared and statistically evaluated.

National Institute of Marine Geology and Geo-ecology-Bucharest-Romania DQC metadata:

• using predefined values from dictionary tables (whenever is possible) • using unique value types for some parameters (as cruise ID) • checking the position against the lower left and upper right working rectangle • the metadata are input by dedicated personnel (experienced) • the final check is made by visualization when the maps are drafted

DQC data:

• using predefined values from dictionary tables (whenever is possible) • using unique value types for some parameters (as cruise ID) • checking the values against the lower and upper detection limits, specific to the analyzing

equipment • checking the values against the lower and upper accepted limits, specific to the working

area • the data are input by dedicated personnel (experienced) • the final check is made by visualization when the maps are drafted

National Institute for Marine Research and Development-Constanta-Romania DQC Monitored physical parameters: datasets are validated by scientific researchers based on their experience. DQC measured chemical parameters: datasets are validated by the scientific researchers based on their experience. DQC measured marine biology & microbiology parameters: datasets are validated by the scientific researchers based on their experience. DQC coastal dynamics & sedimentology parameters: datasets are validated by the scientific researchers based on their experience. DQC for laboratory for physical-chemical measures and quality analysis:

• DQC chart on reference material • Inter-comparison exercises organized by QUASISEME and IAEA-MEL (International

Agency for Atomic Energy – Marine Environmental Laboratories) • Inter-calibration between laboratories – reference laboratory of Monaco (Oceanographic

Institute of Monaco) • Extension of DQC procedures (accreditation) for other existing monitored parameters

Black Sea Technical University of Marine Sciences-Trabzon-Turkey No overview was shown of DQC procedures applied. Only overview measurements were presented.

Middle East Technical University Institute of Marine Sciences-Erdemli-Turkey By METU-IMS only technical DQC is executed.

Collection of samples

The scheme employed for data reported in real-time has been chosen, as given in the GETADE Formatting Guidelines for Oceanographic Data Exchange, proposed by the IOC's Group of Experts on the Technical Aspects of Data Exchange (GETADE). This scheme is universal and can be applied to the types of data in the project database. It uses a one character field with the following interpretation:

• 0 = data are not checked • 1 = data are checked and appear correct • 2 = data are checked and appear inconsistent but correct • 3 = data are checked and appear doubtful • 4 = data are checked and appear to be wrong • 5 = data are checked and the value has been altered • 6 = data are checked and appear to be assigned to the wrong depth

Flag 6 was added according to request of the NATO TU-Black Sea project’s (1993-1997) Project Expert Groups. It can be considered as the code 2 if necessary. Flags are compatible with MEDAR and MEDATLAS data quality control procedures. Sinop Fisheries Faculty of Ondokuz Mayis University-Sinop-Turkey DQC procedures are based on guidelines of TUBITAK (Turkish Scientific and Technical Research Council), DPT (Turkish Prime Minister State Planning Organization) and OMU Research Foundation Projects. Black Sea NGO Network-Varna-Bulgaria BSNN consulted the Black Sea NGOs to get end-users requirements and feedback on the nature of data and thematic maps as well as the quality of data including availability and accessibility. In general most data requirements are realated to climate, physical environment, hydrology, hydrophysics, hydrochemistry, geology, flora and fauna. The Black Sea NGOs are very interested in quality controlled data. SAKNAPIRDATSVA Georgian Coastal Protection Scientific Industrial Centre of Research and Governance of Coastal Formation Processes-Tbilisi-Georgia

Instrument Laboratory Inter-laboratory calibration analysis comparisons

Data analysis control

Data base

DQC is based on equipment precise: • Calibration of equipmrnt locally carried out • Echo sounding device: calibration is based on observation methodology, errors are

corrected by the layer density and equipment errors • Theodolite: coordinates of points are determined with 3 theodolites by triangle method;

also GPS (non stationary, mobile) in use Department of Meteorology of the Ministry of Environmental Protection and Natural Resources, Centre for Monitoring and Prognostication-Tbilisi-Georgia Meteorological DQC: From the establishment of the meteorological stations (more than 70 stations with more than 90 years records existing) data processing quality control until 1972 carried out by experts in NMHS of Georgia. from 1972 until 1993 data processing and DQC were carried out Data Processing World Center (Obninsk, Russia) based on the software Program “PERSONA MIS”. Since 1993 the meteorological data processing and QC are carried out in NMHS of Georgia based on the same software and expert knowledge. DQC is carried out step by step: Syntax-oriented – identification of syntax-oriented, accidental mistakes (PERSONA MIS ); Semantic – identification of outrage mistakes (in the 2 stages, Expert knowledge): 1st Stage: identification of logical mistake (human-factor mistake); 2nd Stage: statistical errors (method of semantic tableaux). The identification of statistical errors are revealed by the experts (meteorologist) through the Critical Control Method - the analysis of meteorological elements distribution in space and time and make a comparison with mean monthly norm of analogous stations. Hydrological DQC: From the establish of the stations until 1985 hydrological regime data were send to the National Data Center in Obninsk (Russia) and there were created the annual reference books - state water cadastre. Since 1985 data quality control occur by experts through the methodical guidance of the National Data Center of Obninsk. Hydrological data control occurs first on the station from the observer-technician who controls the observations method and then is made the work complex diagrams: (Q,H): discharge, depth; (Q,G): discharge, bottom drift; (Q,R): discharge, suspended drift; (vav, H): mean speed of flow, depth; (ρav, ρc): mean turbidity of river, controlled sample turbidity, etc. In the stations are mare the tables – KH-1 and sent to the centre where are made the data quality control through the hydrological characteristic chronological graphs of adjacent stations where is united the variation of water depth, discharge, temperature, turbidity and etc. After the quality control are made TH-1 tables through them is made state water cadastre. DQC of monitoring data: Until 1992 Quality Control of surface waters characteristics were carried out according to methodological of the Hydrochemical Institute of Rostov, (Russia) based on so called inter-laboratory control. On the basis of inter-laboratory control is carried out:

• Assessment of Recurrence accuracy of the analysis; and

• Control of adequacy of analysis. Inter laboratory Control of recurrence of errors made by assessment of accidental component and its interpretation. Therefore it provides determination of recurrence of accidental error by 95 % reliability. For that some amount of hydro chemical samples are repeatedly estimated determination of accidental error mean square deviation from standard. This method is called determination of controlled pair as the part of earlier analyzed sample is used.

• Inter-laboratory calibration exercises were continuously made in Former Soviet Union With Laboratory Gidromet (Russia) aiming testing of the analyses quality and methodology reliability e.g. periodically the amount of pesticides in control samples from water and soil were received from Russia for attestation of professional qualification and reliability of the results.

• In frames of the international project “Project: 977991 Science for Peace River

Monitoring” (OSCE/NATO) /2002-2005/ in collaboration with the laboratories: the Institute of Ionosphere Researches Academy of Sciences (Armenia) and the Center of Physical Researches of Environment, Institute of Radiation Problems Academy of Sciences (Azerbaijan) were created the unified Standard Operational Procedures (SOP) on the basis of ISO and EPA. The special methodologies for Quality Assurance of Received Results are established for all stakeholders. More information see in webpage http://www.kura-araks-natosfp.org.

• In frames of the INTAS project “Study of the Transport of Pollutants through Small

Polluted Rivers to the Sea (1998-2000) in collaboration with the laboratories (Vigo University (Spain) and University of Athens (Greece)) conducted joint sampling of small rivers surface waters and to carry out the analysis on common bases.

• In frames of the international project “Joint River Monitoring in South Caucasus”(TACIS)

/2002-2003/ in collaboration with the laboratories: “Kaspi” (Azerbaijan) and the Environment Pollution Monitoring Center of the Center of Hydrometeorology of the Ministry of Environment (Armenia) was carried out joint sampling of river Kuras and the analysis on common methodology aiming harmonization transboundary river quality management.

• In frames of the international project “Water Resources Management in South Caucasus”

(USAID/DAI) /2002-2004/ in collaboration with the Environment Pollution Monitoring Center of the Center of Hydrometeorology of the Ministry of Environment (Armenia) were made inter-laboratory calibration exercises aiming assessment of the role of the several pollutant objects.

2. DQC in Europe Oslo Paris Commission-OSPAR Oslo-Paris Convention (1992) for the protection of the North-East Atlantic. Update of earlier convention on dumping waste at sea and land-based sources of marine pollution and includes 15 countries and EU (www.ospar.org). OSPAR is organised under six strategies and working groups:

• Protection and Conservation of Marine Biodiversity and Ecosystems • Eutrophication • Hazardous Substances

• Offshore Oil and Gas Industry • Radioactive Substances • Monitoring and Assessment

Large amounts of data to EEA (European Environment Agency) go via OSPAR (processed by ICES). EEA have no QA/QC guidelines on their own, but rely on the guidelines given by OSPAR/ICES. HELCOM, and most probably MEDPOL and the Black Sea Commission have adopted the same QA/QC guidelines.

Overview data flow

OSPAR

ICES

HELCOM

MEDPOLData

processing centre

Black Sea Commision

Data repository

Water-base

EEA

Web

Member country

Recommendations DQA/DQC, given by the OSPAR guidelines: “...contractor must be accredited according to ISO standards...” (1) “...accreditation shall include all activities unless no approval exist..” (1) “...DQA should be applied in field and laboratory...” (RID) (2) “...laboratory work should be carried out by experienced analysts...” (RID) (2) “...Laboratories should participate in relevant national or international inter-comparison exercises...” (RID) (2) (1) From OSPAR Guidelines on Oil and Gas activities (2) RID, Riverine Input and Direct Discharges Recommendations DQA/DQC from JAMP - Joint Assessment and Monitoring Programme: “...DQA should include periodic inspection of test facilities, DQA documentation, inter-laboratory performing testing exercises and ...” ”...apply methods which are referenced... ... following internationally agreed protocols...” ”...staff should be trained...” ”...regular internal (within laboratory) calibration...” ”...inter-laboratory performance assessment...” Detailed:

• Oxidative stress (fish): Details on handling of reference materials (liver) related to inter-calibration

• Cytochrome P4501A activity (fish): Details on handling reference materials related to inter-calibration

• PAH (fish): Details on handling reference material related to inter-calibration • TBT (biota): Few certified reference materials available. It should be possible to establish

Shewart control charts...... • Etc

There can be concluded:

• Most of the recommendations are general and based on common sense (calibration and laboratory standards, trained staff, etc)

• Some guidelines provide more specific DQA, depending on the type of data (sediment samples, biota, etc)

• Analyses of ‘new’ pollutants can be very challenging and the establishment of appropriate DQA procedures can be very difficult and expensive

• DQA is also provided by proposing strategy for sampling (frequency, location, storage of samples, equipment, reporting, etc)

• Guidelines provide recommendations. In real life, end-users (eg. ICES, EES) of data more or less accept and use the data that is available

Key questions Black Sea SCENE: How to DQC-label EDMED, EDMERP, etc in a consistent, flexible and understandable way, which includes data that are:

• varying in degree of QA • heterogeneous • incomplete

Possible Solution? Document overall standards applied (if any)

• ISO • CEN • Accreditation • GLP (good laboratory practice) • Part of inter-calibration exercises • Competence of staff • Etc

Helsinki Commission-HELOM DQC objectives:

• Liabastre et al. (1992) identified four stages in the quality assurance of environmental assessment activities: - establishment of Data Quality Objectives (DQOs) - design of the sampling and analytical plan, - execution of the sampling and analytical plan, - data assessment.

• The DQC process provides a logical and quantitative framework for establishing an

appropriate quality level defined as the tolerable total measurement uncertainty in different sets of data in order to achieve an acceptable level of confidence in final decisions

• DQC methods are defined as “interactive management tools used to interpret and communicate the data users’ needs to the data supplier such that the supplier can develop the necessary objectives for QA and appropriate levels of quality control”.

THE MANUAL FOR THE MARINE MONITORING IN THE COMBINE PROGRAMME OF HELCOM adopted 26 March 1998: THE COMMISSION RECOMMENDS to the Governments of the Contracting Parties to the Helsinki Convention that: a) the monitoring of the state of the marine environment of the Baltic Sea should be

performed from 1 January 1998 onwards in accordance with the Manual for the Marine Monitoring in the COMBINE Programme of HELCOM adopted by the Environment Committee of HELCOM

b) the Manual should be applied also for monitoring the coastal waters covering also aspects of biodiversity, as soon as finalized;

c) the annual monitoring data, as committed by the Contracting Parties in the Manual, should be made available for the Commission by 1 May of the following year for hydrographic and hydrochemical data and by 1 September of the following year for biological data and harmful substances; and

d) the national data reports and other relevant additional information concerning monitoring and quality assurance should be submitted annually together with the data submission.

Working groups of HELCOM

ICES/HELCOM:SGQAC -chemistrySGQAB - biology

Procedures and guidelines

QUALITY ASSURANCE RULES OF THE HELSINKI COMMISSION

1. All Contracting Parties have to nominate persons responsible for quality assurance in all laboratories reporting to the monitoring programmes.

2. If alternative methods of sampling, analyses are being used, proof shall be given that the results are comparable with results generated from methods described in the Manual. SGQAC/SGQAB are responsible for evaluation of the method and give advice to EC MON on data incorporation within HELCOM Data Bank.

3. All institutes/laboratories should participate in regular (annual) inter-comparison exercises, arranged in the Baltic community and laboratories should take part in proficiency testing schemes, e.g. the QUASIMEME-II.

4. The results of inter-comparison exercises and the analyses of certified standards should be reported together with the monitoring data according to procedures to be decided by EC MON.

5. The requirements of ISO/IEC/EN 17025 'General Requirements for the Competence of Testing and Calibration of Laboratories' (formerly EN 45001 and ISO Guide 25).

Principal elements of Quality Assurance • A knowledge of the purpose of the investigation is essential to establish the required data

quality. • Provision and optimization of appropriate laboratory facilities and analytical equipment. • Selection and training of staff for the analytical task in question. • Establishment of definitive directions for appropriate collection, preservation, storage and

transport • Procedures to maintain the integrity of samples prior to analysis. • Use of suitable pre-treatment procedures prior to analysis of samples, to prevent

uncontrolled contamination and loss of the determinant in the samples. • Validation of appropriate analytical methods to ensure that measurements are of the

required quality to meet the needs of the investigations. • Conduct of regular intra-laboratory checks on the accuracy of routine measurements, by

the analysis of appropriate reference materials, to assess whether the analytical methods are remaining under control, and the documentation and interpretation of the results on control charts.

• Participation in inter-laboratory quality assessments (proficiency testing schemes, ring-tests, training courses) to provide an independent assessment of the laboratory's capability of producing reliable measurements.

• The preparation and use of written instructions, laboratory protocols, laboratory journals, etc., so that specific analytical data can be traced to the relevant samples and vice versa.

PRINCIPAL COMPONENTS OF A DQC MANUAL:

• The quality system should be formalized in a quality manual which must be maintained and kept up-to-date.

• The person responsible for authorization and compilation of the quality manual should be identified. A distribution list of the quality manual and identification of holders of controlled copies of the quality manual should be included.

• The quality manual should contain, for example, the following items or their equivalent: 1. Scope 2. References. 3. Definitions. 4. Statement of quality policy. 5. Organization and management. 6. Quality system audit and review. 7. Personnel. 8. Accommodation and environment. 9. Equipment and reference material. 10. Measurement, traceability and calibration. 11. Calibration and test methods. 12. Handling of calibration and test items. 13. Records. 14. Certificates and reports. 15. Sub-contracting of calibration or testing. 16. Outside support services and supplies. 17. Complaints.

VALIDATION OF AN ESTABLISHED ANALYTICAL METHOD FOR CHEMISTRY

• According to ISO17025, Section 5.4.5.2 “The laboratory shall validate non-standard methods, laboratory-designed/developed methods, standard methods used outside their intended scope, and amplifications and modifications of standard methods to confirm that the methods are fit for the intended use… The laboratory shall record the results

obtained, the procedure used for the validation, and a statement as to whether the method is fit for the intended use.”

• The procedure described for full method validation will generate information on: - Detection limit (LOD) - Accuracy - Precision (repeatability and reproducibility) over the concentration range - Linearity - Sensitivity - Range - Selectivity - Measurement uncertainty - Robustness/interference

DQC Marine Data in the Netherlands (TNO B&O) Review of standards and protocols for seabed habitat mapping (MESH Interreg 2005 Report) is available on www.searchmesh.net/default.aspx MESH is an international marine habitat mapping programme that started in spring 2004 and will last for 3 years. A consortium of 12 partners across the UK, Ireland, the Netherlands, Belgium and France gained financial support from the EU INTERREG IIIB fund for this international programme. The MESH partnership covers all five countries in the Interreg (IIIb) north-west Europe area, drawing together scientific and technical habitat mapping skills, expertise in data collation and its management, and proven practical experience in the use of seabed habitat maps for environmental management within national regulatory frameworks. MESH aims to produce seabed habitat maps for north-west Europe (see MESH study area) and develop international standards and protocols for seabed mapping studies. The end products will be a meta database of mapping studies, a web-delivered geographic information system (GIS) showing the habitat maps, guidance for marine habitat mapping including protocols and standards, a report describing case histories of habitat mapping, a stakeholder database and an international conference with published proceedings. MESH is an international marine habitat mapping programme that started in spring 2004 and will last for 3 years. A consortium of 12 partners across the UK, Ireland, the Netherlands, Belgium and France gained financial support from the EU INTERREG IIIB fund for this international programme. The MESH partnership covers all five countries in the Interreg (IIIb) north-west Europe area, drawing together scientific and technical habitat mapping skills, expertise in data collation and its management, and proven practical experience in the use of seabed habitat maps for environmental management within national regulatory frameworks. MESH aims to produce seabed habitat maps for north-west Europe (see MESH study area) and develop international standards and protocols for seabed mapping studies. The end products will be a meta database of mapping studies, a web-delivered geographic information system (GIS) showing the habitat maps, guidance for marine habitat mapping including protocols and standards, a report describing case histories of habitat mapping, a stakeholder database and an international conference with published proceedings. Standards apply to data and ensure quality assurance of data, common terminology and formats, and compatibility of data between different techniques and technologies. Protocols apply to methods and ensure consistency in survey methodology, consistency in data interpretation, and common methods for extrapolation, interpolation and aggregation of data across spatial scales. Standards and protocols need to be established for each of the main mapping techniques, together with various combinations of techniques.

The standards and protocols proposed will be tested through a range of field-testing scenarios involving trans-national co-operation between all the Partners to ensure they are robust (see Testing Protocols). Wherever possible and relevant, stakeholders will be encouraged to contribute to these testing programmes to ensure the wider acceptability of the outputs. A series of research cruises and mapping studies are planned for this testing phase, and will also help fill some of the gaps identified during the data collation phase to extend the area of seabed mapped in north-west Europe. As a consequence of this action a catalogue of seabed acoustic signatures for varying habitat types will be published. DQC procedures for oceanographic data in Greece (HNODC-HCMR) HNODC follows DQC procedures to manage oceanographic data according to international standards and recommendations:

• UNESCO/IOC/IODE and MAST, 1993, Manual and Guides 26 • Data Type guidelines - ICES Working Group of Marine Data Management

Automatic Check of Cruise and Stations headers: Vertical Profiles

• duplicates cruises within a preset space-time radius • date of the stations • ship velocity between two consecutive stations • bottom sounding (ETOPO5) • land position (GEBCO)

Time Series

• duplicates entries • Sensor depth check • Series duration check • land position (GEBCO)

Automatic check of parameters of vertical profiles and time series of fixed moorings:

• at least two parameters required for the qc (vertical reference + measurement) • constant profiles or times series (sensor stuck) • data out of regional values • comparison with pre-existing climatologically statistics (LEVITUS, MODB, MEDATLAS). • ime series are compared with internal statistics. • decreasing reference parameter (pressure or time) • pressure must not exceed the bottom depth • spikes • vertical instability (for vertical profiles)

DQC flag scale (MEDATLAS Quality Flags values; GTSPP Project Flag Scale definition) 0: No QC 1: Correct value 2: Out of statistics but not obviously wrong 3: Doubtful value 4: Bad value Real Time QC in Operational Oceanography (such as Argo, GTSPP and GOSUD Programmes of IOC/IODE): Managed data sets are mainly T-S profiles and time series from:

• CTD • XBT

• Profiling floats • Thermosalinographs • Drifting and moored buoys • Gliders

References DQC procedures:

• Data Type guidelines: ICES Working Group of Marine Data Management (12 data types). • QC procedures for real time data: described in the IOC MANUALS AND GUIDES #22. • In-situ data quality con rol procedures, COR-DO/DTI-RAP/04-047, V1.3 t• Gosud data management, Real-time QC, go-um-03-01, V1.0

Automatic (real-time) DQC: Vertical profiles Time series Trajectories

- Platform Identification - Impossible date tests - Impossible location tests - Impossible speed tests - Position on land test - Global, Regional range tests - Pressure increasing test - Spike test - Gradient test - Digit rollover Test - Stuck Value Test - Density inversion - Grey list - Gross S or T sensor drift

- Platform Identification - Impossible date tests - Impossible location tests - Impossible speed tests - Position on land test - Global range tests - Regional range tests - Spike test - Climatology

- Platform Identification - Impossible date tests - Impossible location tests - Impossible speed tests - Position on land test - Global range tests - Regional range tests - Spike test - Gradient test - Climatology - Instrument comparison

DQC Marine Biology DATA in European Union Legislative and policy backgrounds

• EU Birds Directive 1979 • EU Habitats Directive 1992 • EU Water Framework Directive 2000 • Common Fisheries Policy • EC Biodiversity Strategy and Action Plan 2002 • EC Communication (2006) on Halting the Loss of Biodiversity by • Proposed Marine Strategy Directive (passed by EU Parliament on 14 November 2006

NATURA 2000 EU member states have adopted the Birds and Habitats Directives. Among other obligations, they have to identify, protect and manage representative areas in their countries for the terrestrial, freshwater, coastal and marine habitats and species listed in the Directive Annexes. These obligations are reinforced by the Water Framework Directive. Areas designated for birds are called Special Protection Areas (SPAs) and those designated for other fauna and flora are called Special Areas of Conservation (SACs). Natura 2000 takes account of bio-geographical variation, and requires a detailed knowledge of species and habitat status in each country European Environment Agency EEA

• The EEA aims to … provide timely, targeted, relevant and reliable information to policy making agents and the public.

• Reportnet is group of web applications and processes developed by the EEA to support international environmental reporting, in particular for the CORE SET of INDICATORS.

• The main mechanism for data flow is the European Information and Observation Network (EIONET)

Core Indicators for seas and coasts

• Threatened and protected species • Designated areas • Species diversity • Nutrients in transitional, coastal & marine waters • Bathing water quality • Chlorophyll in transitional, coastal & marine waters • Status of marine fish stocks • Aquaculture production • Fishing fleet capacity

European Topic Centre on Nature Protection and Biodiversity (Paris)

• Assists the European Environment Agency in reporting on Europe's environment by addressing state and trends of biodiversity in Europe

• Provides relevant information to support the implementation of environmental and sustainable development policies in Europe

• Builds capacity for reporting on biodiversity in Europe, mainly through EIONET – especially DQC

3. Summary and evaluation by Scientific Coordinator 1. Two types of presentations:

- presentations by the Black Sea partners concerning datasets of the Black Sea that are managed by the partners, and the DQC procedures that are applied on these datasets

- general presentations by EU partners regarding DQC procedures that are applied at national level in EU countries, or that are applied in international projects in the EU.

Comments:

- the datasets that are presented by the Black Sea partners mainly concern basic parameters of the water (physical, chemical, biological), whereas the international programmes in the EU mainly concern “products” that are relevant for environmental monitoring purposes. This is particularly the case for the biological programmes considering preferentially “habitats” instead of particular species.

- The datasets presented by the Black Sea partners on the one hand concern datasets related to parameters (physical, chemical, biological) from open waters, on the other hand data from on-land monitoring stations. Limited datasets are related to the coastal zones.

- A limited number of datasets presented by the Black Sea partners are related to specific environmental parameters.

- Many basic (physical and chemical) parameters appear to be spatially overlapping with different partners.

- The request has been made by the NGO representative for giving priority to data related to the “living environment”. These data are limited within the presented datasets.

2. Origin of the datasets: There are different categories of data managers among the Black Sea partners:

- data managers in Institutes that are responsible for monitoring programmes: within the same institute they consequently collect the data, process them and are responsible for storage of data and database management. DQC procedures are consequently more easily applied and controlled.

Moreover, data from monitoring programmes favor the application of standardized DQC procedures.

- data managers that assemble data originated by external data producers: DQC is more difficult to apply.

- Databases that originate from scientific projects (mainly in Universities): the DQC is commonly applied based on internally defined procedures.

Comments: The evaluation of the DQC has to take into account the professional environment from which the data originate. 3. DQC procedures: All Black Sea partners have presented the DQC procedures that they apply on their datasets. In most cases they rely on the directives that were imposed by the legislation of the USSR. In most cases, their application results in datasets that are officially certified as well for sampling as for analytical procedures. Nevertheless it has been mentioned that when the samples are submitted to inter-laboratory comparisons, the results are bad. In a few cases (mainly universities), own DQC procedures are applied. Comments: The negative results of inter-laboratory comparisons make the validity of (certain) datasets questionable. Moreover, it concerns only one step of the DQC, namely the laboratory analyses, and gives no information on other steps such as sampling procedures and data handling. This problem has to be considered.