The water is not too deep:
Our approach to implementing new demands for analysing environmental contaminants in the laboratory.
Robert Carter BSc (Hons) MIScT CSci National Laboratory Service Product Manager
Identifying, buying & developing…
BEST AVAILABLE TECHNOLOGY
(Not Entailing Excessive Cost)
Background
Directives
Analytical gap analysis
Funding, Procurement Process including Tendering
Method Development
What next
3 Laboratories:
Solids Waste Water Clean Waters
Water Quality Instrumentation Facility - Reading Water Framework Directive (2000/60/EC) (WFD)
Environmental Quality Standards (Directive 2008/105/EC) (EQSD) and 2013 revision
Quality Assurance Quality Control Directive (Directive 2009/90/EC) (QAQC)
UKTAG CTT guidance on QAQC Directive
• The Limit of Quantification (LoQ) must ≤ ⅓ of the Environmental Quality Standard (EQS).
• As the LoQ is a function of the Limit of Detection (LoD), i.e. 10xsd or 2.15xLoD, 1 the LoD will need to be ≤ ⁄7 EQS
EQS for B( )P in water is 0.00017µg/l so LoD = α ~0.00002µg/l
EQS for Cypermethrin is 0.00008µg/l so LoD = ~0.00001µg/l
Precision (2x%RSD) at EQS must be ≤ 50%
Method must be demonstrated to be in control at the LoQ
Alconifen cis and trans Permethrin Triclosan Alachlor Surface Cypermethrin Heptachlor Bifenox (fresh) Cybutryne Heptachlor EpoxideSaline Benzo(a)pyrenewaters Diazinon Hexachlorocyclohexane(TRAC) Benzo(b)fluoranthene Dicofol Methiocarbwaters Benzo(ghi)perylene Dichlorovos Biota Pentachlorobenzene Endosulfan A&B Benzo(k)Fluoranthene (Mytilus, PFOS & PFOA HBCDD Fluoranthene crayfish & Terbutryn Oestrone Nonylphenol fish) Tributyl tin chloride 17-alpha-ethinylstradiol Octylphenol Tri-phenyl tin 17-beta-estradiol Benzyl butyl Phthalate Cr VI Toxic 6 metals
Cypermethrin
1ng-L 0.01ng-L
Benzo(α)pyrene
1ng-L 0.02ng-L
PFOS
5ng-L 0.09ng-L
HBCDD n/a 0.2ng-L
HBCDD in biota
n/a 24µg-kg
Dicofol in biota n/a 5µg-kg
Heptachlor in water
1ng-L 0.00008ng-L
Heptachlor in biota n/a 0.001µg-kg
Workloads:-
PAH’s 800 spm
Organo tins 600 spm
Cypermethrin 300 spm
Nonylphenols & Triclosan 600 spm
Misc Pesticides 600 spm
PFOS & PFOA 100 spm
Biota (various test) 250 pa
Sampling workloads renegotiated every year based on govt. funding
Regulation Oct 2013
Budget Develop Estimation & methods go ahead! Feb 2014
New methods Funding Identify BAT
Monitoring & Reporting Procurement cycles
and a sceptical customer!
A sceptical supplier(s)
Evaluating new instrument
• Price 50% • Quality 50% • BAT? • LoD equivalent solutions trialled before awarding contract • Install and “sign off” purchase
Regulation Oct 2013
Budget Develop Estimation & methods Funding Feb 2014
New methods Identify BAT Funding Jun-Nov 2014
Monitoring & Procurement Reporting Nov 2014- cycles April 2015 Monitoring and Budgetary cycles
2019 all water bodies and TRaC waters – “Good Chemical Status”
Monitoring to start April 2014 – conceptual gap in capability
No money assigned to development including equipment
April 2014 - Start development in existing equipment (Nonyl / Octyl Phenol and Biota)
April 2014 - start procurement / tender process
June2014 - reassign limited money and prioritise PAH development
November 2014 award contract to instrument companies and start buying equipment. 2xGCQQQ
Monitoring and Budgetary cycles – cont.
November 2014 start bidding process for DEFRA GiA for more equipment and development costs
April 2015 - Agency reports first Chemical Status data to DEFRA/Europe Insert large April 2015 – due to funding delays earlier in 2014 miss opportunity to develop sufficient methods in time to make a full bidpicture for the water ofindustry the CIP programme.
Monitoring of the majority of contaminants smiling for faces the Environment of Agency can now not start until April 2016 (e.g. PFOS, Cpermethrin, Misc pesticides) Paul Gribble and Remaining funding is awarded and remaining instrumentation can be purchased. Mixture of GC and LC QQQ John Quick
Methods developed
April 2016 remaining methods go live Regulation Oct 2013
Develop Budget methods Estimation & Up to Mar Funding 2016 Feb 2014
New methods Funding Identify BAT April 2015 for Jun-Nov 2014 bulk
Monitoring & Procurement Reporting cycles Nov 2014- April 2015 2015 - 2019 Validation Requirements
11x2 in UHP, River Water, Saline Water, Biota & some sediments
Detection Limit – preferred approach to spike at the target.
Limit of Quantification – UKTAG requires government labs to demonstrate control. Method to validate a QC at the LoQ followed by embed the level in the curve.
Precision & BIAS measured at:-
LoQ (2x target LoD)
EQS or below
15-20% range
75-80% range
0,9 0,8 Limit of Detection 0,7 Validation Data 0,6 Benzo ( ) pyrene 0,5 α ngl-1 River LoD 0,4 UHP LoD
0,3
0,2
0,1
0 1 2 3 4 5 6 7 8 9 -l Benzo(α)pyrene (3ng ) C o n t a i n e r
W a l l
Benzo( )pyrene (0.02ng-l) α
0,9 0,8 Limit of Detection 0,7 Validation Data 0,6 Benzo (α) pyrene -1 River LoD 0,5 ngl UHP LoD 0,4 River LoD UHP LoD 0,3
0,2
0,1
0 1 2 3 4 5 6 7 8 9 10 11 Water Biota Dichlorovos BAT Nonylphenol PFOS Endosulfan Cypermethrin (saline) Octylphenol HBCDD Alconifen Heptachlor Benzo(a)pyrene Heptachlor Alachlor Heptachlor Epoxide Benzo(b)fluoranthene Heptachlor Epoxide Bifenox Benzo(ghi)perylene Dicofol Terbutryn Benzo(k)Fluoranthene Quinoxifen Hexachlorocyclohexane Fluoranthene April 1st Methiocarb PFOS Cypermethrin Pentachlorobenzene HBCDD cis and trans Permethrin Drins Tributyl tin chloride Cybutryne Methiocarb
Diazinon Pentachlorobenzene
Dicofol
Regulation Regulation Budget Develop Estimation & methods Funding
New methods Funding Identify BAT
Monitoring & Reporting Procurement cycles RegulationRegulation
Budget Develop Estimation & methods Funding
New methods Funding Identify BAT
Monitoring & Reporting Procurement cycles Chloroalkanes (SCCP) in water and biota
Bis(2-ethylhexyl) phthalate (DEHP) in biota
Investigation in effect of particulates on PAH, PFOS & HBCDD
2008 EQS – 2013 lowered the LoD’s
2018?
Mercury 10ng to 0.07ng/l
Questions?