REPORT ON THE NATIONAL MARINE CHEMICAL ANALYTICAL
QUALITY CONTROL SCHEME 20032

Presented to the June 200043 Meeting of the National Marine Monitoring Programme Working Group

Report prepared by:

Mrs J E Dobson

Senior Marine Chemist

Scottish Environment Protection Agency

Secretary of the NCC

NATIONAL MARINE CHEMISTRY ANALYTICAL QUALITY CONTROL SCHEME

REPORT FOR THE PERIOD JANUARY 2003 TO MARCH 2004

EXECUTIVE SUMMARY

This is the ninth report of the National Co-ordinating Committee (NCC) of the National Marine Chemical AQC scheme (NMCAQC). The report describes the actions taken during 2003 to ensure the quality assurance of data submitted to the UK National Marine Monitoring Programme (NMMP). The results of the implementation and operation of the Data Filter for samples analysed in 2003 are reported and trends in data quality summarised.

The data filter process has shown that, for a very large proportion of NMMP II data, contributing laboratories can provide a demonstration that they satisfy the basic NMMP performance requirements. Despite this, there are areas where improvements are desirable (both in performance achieved and in the extent to which performance can be demonstrated). The main areas where fitness for purpose is not consistently achieved by laboratories is for the determination of organochlorine substances and polycyclic aromatic hydrocarbons in biota.

During the period of this report, the NCC has:

·  Ensured that the quality standards achieved in previous years are maintained

·  Ensured scope of the scheme has been maintained and expanded to include new matrices e.g. seaweed and determinands e.g. TBT, through membership of the QUASIMEME Advisory Board.

·  Reviewed laboratory performance for PAH and made recommendations for improvements.

·  Maintained prudent financial management of the scheme

·  Implemented the data filter for 2003 data

·  Summarised contaminant data for the 2nd NMMP report

·  Started to collate information to audit the QC of data produced by field instruments

Future NCC activities will include:

·  Maintenance and development of the Quality Assurance approach through the data filter.

·  Ensuring that laboratories have Quality Assurance in place for supporting determinands.

·  Developing QC protocols for field instrumentation.

·  Review of Quality Assurance of sampling and sample handling.

·  Ensuring suitable test materials are available for all matrices in the NMMP.

TABLE OF CONTENTS

EXECUTIVE SUMMARY 2

TABLE OF CONTENTS 3

APPENDICES 4

TABLES 4

FIGURES 4

GLOSSARY OF TERMS 5

1. INTRODUCTION 6

2. REPORT OF THE NATIONAL CO-ORDINATING COMMITTEE 8

2.1. Membership 8

2.2. Finances 9

3. QUASIMEME PROGRAMME 10

3.1 Routine Programme 10

3.2 Development exercises 10

4.PERFORMANCE INDICATORS 12

5. DATA FILTER 13

6. LABORATORY IMPROVEMENT PLANS 15

7. REPORT FROM PAH EXPERT GROUP 16

8. SAMPLE HANDLING & SAMPLE PRESERVATION 17

9. 2nd NMMP REPORT 19

10. DATABASE ISSUES 20

11. QC OF FIELD INSTRUMENTATION 21

12. REFERENCES 22

APPENDICES

APPENDIX 1.2 Laboratories Analysing NMMP samples

APPENDIX 3.1 QUASIMEME Programme

APPENDIX 5 Data Filter paper for MON

APPENDIX 6. Laboratory Improvement Plans

APPENDIX 10. OSPAR BRCs and EACs

TABLES

1.  Laboratories in the NMCAQC Scheme

2.  NCC Membership

3.  NMCAQC Financial Summary

4.  Percentage of UK laboratories achieving IZI<2 in R31 and R33.

5.  Performance of UK laboratories in R34, percentage of IZI<2

FIGURES

1. Percentage of data meeting the data filter criteria 1999-2002
2. Current data submission arrangements

GLOSSARY OF TERMS

NMCAQC National Marine Chemical Analytical Quality Control

AQC Analytical Quality Control

DARDNI Department of Agriculture and Rural Development (Northern Ireland)

SEPA Scottish Environment Protection Agency

EHS Environment and Heritage Service

LOD Limit of Detection

CEFAS Centre for Environment Fisheries and Aquaculture Science

MPMMG Marine Pollution Monitoring Management Group

NCC National Co-ordinating Committee

NLS National Laboratory Service (EA)

NMMP11 National Marine Monitoring Programme - Phase 11

NMMP National Marine Monitoring Programme

EA Environment Agency

NCEDS National Centre for Environmental Data and Surveillance

QUASIMEME Quality Assurance of Marine Environmental Monitoring in Europe

FRS Fisheries Research Services

DEFRA Department of the Environment, Fisheries and Rural Affairs

WRc Water Research Centre

NMMPWG National Marine Monitoring Programme Working Group

QA Quality Assurance

QUASH Quality Assurance of Sampling and Sample Handling

PCBs Poly-chlorinated biphenyls

TON Total oxidised Nitrogen

PAH Polycyclic Aromatic Hydrocarbons

BRC Background/Reference concentration

OSPAR Oslo and Paris Commission

TBT Tri-butyl-tin

EAC Ecotoxicological assessment criteria

1. INTRODUCTION

This report covers the activities of NMCAQC from January 2003 to March 20042. During this time the NMCAQC Scheme has continued to pursue its aims and objectives, namely:

(i)  To monitor and demonstrate the analytical accuracy achieved by laboratories which contribute data to the National Marine Monitoring Programme (NMMP);

(ii) To collate information on standards of quality control for NMMP determinands, to provide a screening tool for data submitted to the NMMP database; and

(iii)  To assist in achieving improved standards of accuracy, where appropriate.

(iv)  To collate QC information required by ICES for data assessments.

These aims and objectives are addressed through:

1. Analysis of test samples.


Laboratories are encouraged to participate in the QUASIMEME laboratory proficiency test scheme for determinand groups analysed for the NMMP. QUASIMEME provides two types of test samples:

a) proficiency tests

Laboratories are required to take part in interlaboratory proficiency tests at least twice per year for all determinands for which they report data to the NMMP. These tests provide a continuing check on comparability for the determinands and matrices required for the NMMP. The results of these tests are used to assess laboratory performance.

b) development exercises

Laboratories are required to participate in development exercises for new or difficult determinands. Development exercises are designed to help laboratories identify sources of uncertainty in the analysis.

2. Improvement Initiatives

Improvement initiatives are organised for new or problem determinands where performance is generally lower than required. Training workshops and expert group assessments are used to promote best practice.

a) training workshops

Training workshops are organised to exchange information concerning best analytical practices. The workshops are run in collaboration with QUASIMEME and are co-ordinated with the programme of development exercises.

b) expert group reports

A group of analysts from expert laboratories met to review performance for PAH in sediments and biota. Laboratories provided the group with copies of their analytical procedures and chromatograms. The group reviewed the procedures and provided a set of recommendations for improvement. This approach was found to work well and will be used for future assessments.

3. Maintenance of internal quality control procedures.
Laboratories are encouraged to maximise their score in the data filter, which awards points for internal quality control procedures (Appendix 1.1). The data filter criteria include accreditation for the determinand and the use of control charts to assess precision and bias.

This report is intended to inform the NMMP Working Group of the steps taken by participating laboratories (Table 1) to assure the quality of the data for NMMP samples analysed in 2003. NMMP samples analysed by laboratories in 2003 are summarised in Appendix 1.2.

Table 1. Laboratories in the NMCAQC Scheme

BGS, KEYWORTH

SEPA WEST, EAST KILBRIDE

DARDNI, BELFAST

SEPA EAST, EDINBURGH

EHS, LISBURN

CEFAS BURNHAM

CEFAS LOWESTOFT (nutrients only)

ENVIRONMENT AGENCY NLS NOTTINGHAM

ENVIRONMENT AGENCY NLS EXETER

ENVIRONMENT AGENCY NLS LLANELLI

ENVIRONMENT AGENCY NLS LEEDS

FRS, ABERDEEN

ENVIRONMENT AGENCY SHIPBOARD LABORATORIES (Nutrients only)

2. REPORT OF THE NATIONAL CO-ORDINATING COMMITTEE

2.1. Membership

The NCC is made up of representatives from all participating organisations (Table 2). Membership of the group did not change in 2003 until the November meeting when Dave Gazzard replaced John Fardon as the Environment Agency NLS representative. Lynda Webster joined the group to represent FRS, there were no other changes in 2002.

Table 2. NCC Membership

Dr B Miller / SEPA West Region / Chair
Mrs J Dobson / SEPA East Region
/ Fund Manager
& Secretary
Mr D McMullan / EHS / EHS
Represenative
Mr C Allchin / CEFAS / CEFAS
Representative
Dr J Cook / BGS / BGS
Representative
Mr D Wright / EA National Marine Service / EA NMS
Representative
Mr T Oliver / DARDNI / DARD
Representative
Mr J Fardon / EA National Laboratory Service, Leeds / EA NLS
Representative
(until November 2003)
Dr M Gardner / WRc / AQC Advisor
Dr L Webster / FRS / FRS
Representative
Dr D Wells / QUASIMEME Project Manager / FRS
Representative
Mr D Gazzard / EA National Laboratory Service, Llanelli / EA NLS
Representative
(from November 2003)

The NCC continues to promote participation in external interlaboratory proficiency testing schemes whilst maintaining in-house AQC as a continuing check of daily performance. The international interlaboratory proficiency testing scheme QUASIMEME continues to be the main provider of external QC. Laboratories purchase proficiency test samples direct from QUASIMEME and forward their results to the NMCAQC database at the EA National Centre for Environmental Data and Surveillance (NCEDS). The Chairman of the NCC sits on the QUASIMEME Advisory Board to ensure that external AQC is available for all determinands in NMMP. The NCC met four times in 2003/4 to review NMCAQC laboratory performance in QUASIMEME and discuss ways to improve performance as required.

The main activities of the NCC throughout 2003/4 were:

  1. Summarising 1999-2001 contaminant data for the 2nd NMMP report.
  2. Establishing an expert group to review performance for PAH in sediments and biota.
  3. Collating QC information for implementation of the data filter on 2002 data.
  4. Discussing developments in OSPAR and the Water framework Directive.
  5. Developing methods for QC of in situ instrumentation

2.2. Finances

Laboratories purchase proficiency test materials direct from QUASIMEME and Defra fund a contract to run the data filter and provide expert advice to the NCC. There are sufficient funds available to cover annual expenditure which arises from attendance at QUASIMEME Advisory Board meeting, expert group meetings and hospitality at NMCAQC meetings (Table 3)::

Table 3. NMCAQC Financial Summary 2003/4

2003/4
INCOME / EXPENDITURE
Income carried forward / £ 15344.57 / Hospitality / £ 130.00
Interest / £ 374.67 / Expenses / £ 753.20
Total / £ 15719.24 / Total / £ 883.20
Balance carried forward / £ 14836.04

3. QUASIMEME PROGRAMME

3.1 Routine Programme

QUASIMEME continue to provide a comprehensive range of determinands covering NMMP requirements (Appendix 3.1).

Determinand groups are distributed twice per year and there are generally two samples per group covering low range and high range concentrations. Additional low salinity samples were included in 2003/4 to satisfy the requirements of laboratories analysing Baltic waters. A new determinand group for trace metals in seaweed was added and provides PT data for laboratories analysing this matrix in the NMMP.

3.2 Development exercises

QUASIMEME organises development exercises for new or problem determinands. There were five development exercises during 2003/4:

1. Organotins in biota, seawater and sediments (3 separate exercises). - The analysis of TBT in biota is required to complement imposex analysis and the analysis of TBT in sediments became a mandatory monitoring requirement in 2003.

2. Brominated flame retardants – these are not currently included in NMMP II but are on the Water Framework Directive Priority list and may be in a revised JAMP.

3. Shellfish toxins – analysis of these compounds is required by the Shellfish Hygiene directive, their analysis is not required by the current NMMP.

Laboratory Performance in QUASIMEME

A review of performance in interlaboratory proficiency test schemes (Gardner and Dobbs 2004, in press) recommended that a minimum of 75% pass in LPT schemes demonstrated fitness for purpose. This criterion has been used to assess laboratory performance in QUASIMEME.

Summaries of UK laboratories performance in Rounds 31, 33 and 34 were discussed at NMCAQC meetings and the number of laboratories achieving Z scores of >90% and >75% of results reported were quantified. Rounds 31 and 33 contained aqueous samples analysed for trace metals and trace organic compounds. Six UK laboratories received trace metal samples and five received trace organic samples although not all laboratories returned data. Results for rounds 31 and 33 are summarised in Table 4.

Table 4. Percentage of UK laboratories achieving IZI<2 in R31 and R33

R31 / R33
Z >90% / Z >75% / Z >90% / Z >75%
Trace metals / 100% / 100% / 83% / 83%
Hg / 75% / 75% / 75% / 75%
OCPs / 100% / 100% / 0% / 75%
volatiles / 50% / 50% / 100% / 100%
PCP / 75% / 75% / 100% / 100%
herbicides / 100% / 100% / 75% / 75%

On average performance was good for all aqueous determinands.

Round 34 contained sediments and biota for trace metals and trace organic analyses and aqueous samples for nutrient analysis. Results show that laboratories are excellent at analysing nutrients and most had >75% of Z scores <2 (Table 5). Performance for trace metals is also good with only one laboratory failing to achieve the 75% pass rate. Results for trace organic compounds in sediments and biota are generally poor with only 2 laboratories achieving 75% pass for organochlorine compunds in sediments and in biota. The average percentage of IZI<2 for PAH in sediments and biota were better than results for organochlorine compounds in biota but were below 75.

Table 5. Performance of UK laboratories in R34, Percentage of IZI <2.

LAB
code / AQ1
nutrients / AQ2
nutrients / MS1
metals / MS2
OCs / MS3
PAH / BT1
metals / BT2
OCs / BT4
PAH
Q152A / 100 / 5 / 86 / 86 / 17 / 64 / 94
Q153A / 100 / 100 / 96 / 83 / 83 / 86 / 76 / 65
Q153B / 100
Q154A / 100 / 95 / 63 / 90
Q156A / 79 / 81 / 100 / 38 / 90 / 56
Q157A / 78 / 59 / 100 / 54 / 71 / 100 / 75 / 8
Q158A / 100 / 96 / 92 / 31
Q234A / 94 / 97
Q235A / 83
Q237A / 93 / 100 / 100 / 77 / 65 / 82
Q239A / 100 / 27 / 86
Q240A / 83 / 41 / 63 / 77 / 35 / 90
Q240B / 89 / 100
Q242A / 31 / 50 / 0 / 40
Q243A / 92
Q247B / 93 / 100
Q247C / 93 / 95
Q247D / 93 / 100
Q248A / 60
Ave. / 92 / 90 / 85 / 49 / 73 / 76 / 53 / 71
Key
>90%
>75%
<75%

4.PERFORMANCE INDICATORS

Following the NMMP workshop on Performance Indicators in May 2001 Defra funded a contract to develop BRCs applicable to the UK. Data from clean sites were used to derive a set of UK BRCs (Davies, I.M. 2004). Although the proposed BRCs were more comprehensive than the OSPAR BRCs they could not be used to assess data in the 2nd NMMP report as they had not been approved by OSPAR. The information in the report was used to inform an OSPAR meeting about background concentrations in January 2004. The meeting agreed to review existing OSPAR BRCs and EACs.