Caspian MAP

Regional Water Quality Monitoring Plan

For the development of the Regional Water Quality Monitoringplan two activities are/will be carried out:

1. Proficiency test, to define the relative weaknesses and strengths of the regional Laboratories
2. Pilot Pollution surveys: to demonstrate …

Both activties are building stones to prepare an optimal and sustainable Regional Water Quality Monitoring Plan

Proficiency Test 2008

1. Introduction

A fundamental requirement for the monitoring and assessment of marine contamination is accurate analytical data for pollutant concentrations in the various environmental compartments. While trueness (accuracy) cannot be compromised, an acceptable level of precision may varydepending on the use to be made of the data.

The International Standards Organisation defines key termsas follows:

• Accuracy – the closeness of agreement between a test result and the accepted reference value.
• Trueness – the closeness of agreement between the average value obtained from a series of test results and the accepted reference value.
• Precision - the closeness of agreement between independent test results obtained under stipulated conditions.

Quality Control / Quality Assurance (QA/QC) procedures mustbe established in laboratories as key components of an overall qualitymanagement programme. QC procedures commonly comprise the analysis of referencematerials (RMs) and certified reference materials (CRMs) to assess precisionand trueness. QA procedures are usually realized through participation inproficiency tests that compare and evaluate analytical performance.

Proficiency Testing has several synonyms: Proficiency Test,Round Robin, Inter-comparison Exercise, Inter-calibration Exercise,Inter-laboratory Study, and Laboratory Performance Study (LPS). The later termis the one most currently favoured in the literature.

What is a Proficiency Test? Under the supervision of aqualified reference laboratory:

• A test sample is carefully prepared and bottled in a manner to ensure the material is homogeneous and stable.
• The test sample is distributed to laboratories for analysis of a specified set of parameters.
• Participating laboratories return data to the reference laboratory.
• The reference laboratory interprets data, both individually and collectively.
• Individual laboratory performance for each determination is assessed.
• Advice on remedial action is given to laboratories.
• Laboratory participation is generally anonymous, but laboratories can use their results as proof of external QA when submitting monitoring data to a third party database.

Proficiency Testing is very important for a variety ofreasons. One-off participation in a blind, external QA programme permits an independent assessment of data quality from an individual laboratory or alaboratory network. PT participation helps ensure comparability between results, either due to multiple laboratories generating data or due to the same laboratory performing measurements over time. Ongoing involvement can identify trends, normally towards improving data quality. Thus, PTs have been shown to stimulate improved analytical performance at the individual laboratory level. 

2. The IAEA PT2005

The International Atomic Energy Agency conducted proficiency tests in the Caspian Sea Region in 2005 for both metals and organic contaminants in a sediment sample. The test materials were well-characterized reference materials, namely IAEA-356 and IAEA-417 for metals and organic contaminants, respectively. All test materials were dispatched by DHL in March 2005, with a deadline for submission of results at the end of June 2005 that had to be extended until the end of July. For metals, only 7 of 10 laboratories receiving the test material submitted data. For organic contaminants, 12 sets were distributed but only 3 laboratories submitted results, of which only 2 reported OCPs.

The conclusions were disappointing, but very informative. Notably there was very poor participation in proficiency tests (7 out of 10 formetals; 3 out of 12 for organics) and poor performance on the part of laboratories. For the determination of metals, there were 2 very good laboratories, 3 very poor laboratories, and 2 with mixed results. Regarding organic contaminants, no laboratories able to analyse OCPs, but 1 laboratory could measure PAHs.

3. The Tacis PT2008

Based on the poor results of the IAEA PT 2005, a number of improvements for a new PT were recommended:

• Use sediment from the Caspian Sea
• Parameters to include radionuclides
• Involve only national laboratories (max 2 per country) that are willing and able to participate, and guarantee to submit results 

The Test Sample for the Tacis PT 2008 was prepared using asediment core collected near the mouth of the Kura River during the IAEA mission in 2006. The material in situ comprised a homogeneous mixture based on radionuclide measurements. Thus, layers from one core were combined to give onesample (1.15.kg) that was dried, milled, and sieved to give a fraction <125µm. The test material was bottled: Metals: 20g aliquots in plastic bottles with Teflon-lined plastic caps; Organics: 40 g aliquots in amber glass bottleswith aluminium caps. Homogeneity tests will be based on analyses of Cd, Cu,DDT, ¹³⁷Cs, and ⁴⁰K.

The test material will be characterized by three reference laboratories:

• Ukrainian Centre for Marine Ecology (UCME), Odessa, Ukraine
• Scientific Industrial Association “Typhoon” (SIA Typhoon), Obninsk, Russian Federation
• IAEA - Marine Environment Laboratory (IAEA-MEL), Monaco

The selection of parameters to be determined was based onthe conclusion of the pollution assessment from the CEP sediment surveys conducted in 2000-2001 and 2005. During the 2000-2001 CEP Survey, the pollution observed based on 105 surface sediment samples comprised petroleumhydrocarbons, DDT-related compounds, lindane, Hg, Cu, and Zn. For the 2005 CEPSurvey, the pollution observed based on 105 surface sediment samples comprised PCBs,  DDT - related compounds, hexachlorocyclohexanes (HCHs), notably lindane, Hg, and Cu.

The proficiency test investigated the following parameters:

• Cu, Hg, Zn (Al and Fe optional)
• Total Petroleum Hydrocarbons (TPH)
• PCBs
• DDT - related compounds (DDT, DDD, DDE)
• Hexachlorocyclohexanes (HCHs), notably Lindane
• ⁴⁰K, ¹³⁷Cs, ²¹⁰Pb, ²²⁶Ra, ²³⁸U

The countries selected the laboratories (see below) to beinvolved in the proficiency test on the understanding that such laboratories would also participate in the subsequent sampling campaign and analysis of sediment samples. It was stressed that test material for metals and organic contaminants would be in separate bottles, but that only two sets of test samples would be available for each country. The same laboratory did not have to analyze both metals and organic contaminants. The countries nominated two orthree laboratories that would participate in both the proficiency test and the monitoring programme.

Table 3: Laboratories participatedin the Proficiency Test and Monitoring Programme

AZ-1	Caspian Complex Env. Monitoring Administration
AZ-2	AzEcolab
IR-1	Department of Environment-Central Laboratory
IR-2	Iranian National Center for Oceanography / Plant Protection Research Center
KZ-1	Aktau-Port HMC Laboratory /Central Laboratory
KZ-2	Atyrau Municipal Analytical Environment Protection Lab.
RU-1	SOI Branch St. Petersburg1
RU-2	Shirshov OI| Astrakhan Caspian Center
TK-1	CaspEcontrol Laboratory
TK-2	TurkmenGeology Laboratory

¹replaced SOI/ Dagestan HMC, after their negative response toparticipate

The Proficiency Test took place between February-July 2008,

The report, prepared by CMSET, was presented at a meeting in late June 2008. The assessment of the performance of the regional laboratory network is incorporated in the plan for the Pollution Surveys.

Pilot pollutionsurveys

The CaspianMAP project will develop an enhanced hotspot-specific Regional Water QualityMonitoring Program (RWQMP). The project will assist in the design planning and support for implementation of enhanced pilot RWQP over a two year period with relevant specifically justified tasks, based on main principles agreed by theP-RAGs and resulting in execution of four surveys:

1.Parameters

The monitoring programme will focus on bottom sediments from the coastal Caspian Sea. Sampling will be by grabs, although theremay be scope at some locations to collect sediment cores, which would be veryuseful in order to evaluate pollution histories at river mouths. The key contaminants that all countries will analyze comprises: Total Petroleum Hydrocarbons (TPH);some Organochlorinated pesticides (OCPs), notably DDTs and lindane; PCBs; keytrace metals (Hg, Cu, Zn); artificial and natural radionuclides: ⁴⁰K,¹³⁷Cs, ²¹⁰Pb, ²²⁶Ra, ²³⁸U. Complementary parameters that should be determined, particularly to help withdata interpretation includes grain size, Total Organic Carbon (TOC), carbonate,Al and Fe.

Thesampling campaign will include measurement of some surface water parameters(temperature, salinity, chlorophyll-a, suspended sediment load) with a view to provide ground truth data for satellite imagery.

2. Sampling Locations

Some criteria were set for the selection of sampling sites. They should be coast allocations near known hot spots, based on previously sediment surveys in the Caspian Sea. The number in each country varied between 10and 15.

The national sample collection will examine the following APCs. The number of samples to be collect at each location ois indicated in brackets.

AZ	BakuBay (5) Kura Avandelta (5), coastal area (3)
KZ	Ural River (2), Agip platforms (5), Bautino (2) Aktau (3), Fetisovo (3)
IR	SefidRood River(3), Bandar Anzali (3), Chalus/Noshahr (3), Gorgan Bay(3)
RU	Volga avandelta (4), Dagestan North (3), Central (3), Samur (3)
TM	Turkmenbashi (3), Cheleken (3), Ekerem (1), Gasan-Kuli (1), Bekdash (2)

4.Timetable for the collection and analysis of samples

 

The countries agreed to the following timetable for the collection and analysis ofsamples. Notably, they intend to conduct the missions at about the same time –late August / early September, thereby avoiding the hottest part of the summer but still at a time to expect good weather.

Table 2: Timetable for thecollection and analysis of samples

5.Laboratories

The countries nominated on the First Regional Workshop, two or three laboratories that would participate in both the proficiency test and the monitoring programme.

Table 3: Laboratories to participate in the Proficiency Test and Monitoring Programme

AZ-1	Caspian Complex Env. Monitoring Administration
AZ-2	AzEcolab
IR-1	Department of Environment-Central Laboratory
IR-2	Iranian National Center for Oceanography. Plant Protection Research Center
KZ-1	Aktau-Port HMC Laboratory/Central Laboratory
KZ-2	Atyrau Municipal Analytical Environment Protection Lab.
RU-1	SOI/ Dagestan HMC
RU-2	Shirshov OI| Astrakhan Caspian Center<
TK-1	CaspEcontrol Laboratory
TK-2	TurkmenGeology Laboratory

6.Sampling Mission

As shown in table 4, the countries have made tentative plans with respect to thedates and vessel to be used for sample collection.

Table 4: Dates and Vessel forSampling Campaign

Country	Mission Dates	Vessel
AZ	Sept 8-15	Halif Gajiev; 4+2 person
IR	unknown	Gilan
KZ	Sept 7-19	Elen; 4+2 person
RU	Aug 15 - 23	Briz; 4+1 person
TK	Oct. 27 – Nov 10	Rented2; 4+2 person

²rented from Ministry of Fisheries Turkemistan