Dr.PANKAJ MEHTA Assistant Professor Department of Environmental Sciences

1. LIFELINE OF AN ANALYTICAL LAB: VALIDATION, QA/QC, CERTIFICATION IN ACHIEVING PROFESSIONAL EXCELLANCE Dr.PANKAJ MEHTA Assistant Professor Department of Environmental Sciences Central University of Jammu, Jammu. Email:drpankajmehta79@gmail.com

2. FRAMEWORK 1. Introduction to Environmental Lab Quality Data & Professional Research (Two sides of the same Coin) 2. Environmental Sampling, Monitoring & Analytical Techniques 3. Calibration, QA/QC and Proficiency Testing 4. Certification

3. INTRODUCTION The Environmental laboratory undertakes analysis of soil, sediment, rock, water and plant materials for environmental, ecological, geological and agricultural investigations. The laboratory is equipped with sophisticated modern equipment, such as atomic absorption spectrometry, ion chromatography, elemental combustion analysis, UV-visible spectrometry, ICP-OES, ICP-MS, GC and X-ray fluorescence, XRDetc. Sample preparation is required, prior to the final analysis, for soil and plant samples which involves drying, crushing, extraction and digestion of the samples. Source: Dr.Pankaj Mehta/personalpics AAS ICP-OES Source: Dr.Pankaj Mehta/personalpics

4. INTRODUCTION Compact, fully automatic elemental analyzer for the determination of total wt% C, H and N in soil, plant and solid samples. Sample requirements: solid samples 8-10 g Source: Dr.Pankaj Mehta/personalpics Ion chromatograph is used for analysis of anions in aqeous matrices.Typical analytes are nitrate (NO3-), nitrite(NO2-), chloride(Cl-), sulfate (SO42-), Phosphate (PO43-) and fluoride (F-). Detection limits are typically in the ppm range and calibration is performed with certified reference materials (CRM’s) which are used for routine quality control. Sample requirements: Liquid 8-10 ml, Solids 15g C,H,N Analyzer Source: Dr.Pankaj Mehta/personalpics Ion Chromatograph

5. Environmental Laboratory: Services • The Environmental laboratory serves the environmental community by offering the following analyses in water, air and soil: • Basic environmental tests in air, water and soil (Chemical, Heavy Metals, VOC, PAH, PCB, Pesticides etc). • Basic Sewage water tests (pH, COD, BOD, Heavy Metals, TSS etc) • Basic and Specialised microbiological testing specific to water(MPN coliform, • Pseudomonas spp., Klebiella spp., Surface counts, Microcystis toxicity / toxins) • Eutrophication test package specific to water (N,P, DO, TOC, DOC etc) • Trace and ultra-trace element analysis in air,water and soil (ICP-OES, ICP-MS )

6. Sampling and Analysis – can’t have one without the other Objectives of environmental sampling and analysis Vary depending on the specific task at hand Source: http://slideshare.net Sampling, Analysis and Interpretation determines the overall quality of the study. • Determining pollutant emissions from smoke stacks, wastewater discharge, etc. in order to comply with regulatory requirements • 2) To study the fate and transport of contaminants and to evaluate the efficiency of remediation systems

7. Analysis – requires reporting of analytical errors (precision, accuracy, reproducibility, etc.) • Legally defensible data is critical in industrial and governmental work • Components which include: • Custody or control • Documentation • Traceability (paper trail) – accuracy of standards with certificate of analysis • Examples of scientifically defective data: • Incorrect sampling protocol • Incorrect analytical protocol • Lack of good laboratory practice (GLP) • Falsification of results • Two types of errors: • Determinate errors (systematic) – errors that can be traced to their source • Indeterminate errors (random) • Random error is dealt with by applying statistics to the data

8. Environmental Sampling • Scope of Environmental Sampling • Steps in a sample’s life: • Sample is planned • Identification of sampling point • Collection of sample • Transfer to a laboratory • Sample is analyzed (destructive/non-destructive) • Sample expires and is discarded • Sample is represented as a data point Objective: Collect a portion of material small enough in volume to be transported and large enough for analysis while still accurately representing the material being sampled RSPM Sampler Water Sampling Source: Dr.Pankaj Mehta/personalpics Source: Dr.Pankaj Mehta/personalpics

9. Environmental Sampling • Where, When, What, How, and How Many • Where (spatially) and When (temporally) to take samples should be based on sound statistics (judgmental, systematic, random, stratified, systematic, composite, etc.) • Best sample number is the largest possible! • Quantity should not be increased at the expense of quality. Source: APHA, 21 EDN. 2005

10. Lab or Field Analysis? What are the relative merits of lab and field analyses? Soil Sampling Lab Pros: analyses performed under optimum conditions, leading to maximum accuracy, precision will also be maximized Cons: transport, time delay in getting results, changes to sample during storage, cost to operate lab Field Pros: instantaneous results, no errors due to storage, possible to analyze in-situ, possible to use continuous monitoring Cons: conditions may not be optimum, lower precision and accuracy, Source: Dr.Pankaj Mehta/personalpics

11. Can you guess which of the following water quality determinations are best made in the lab or in the field? Field Temperature pH DO Lab Metals Nitrate Organics 22nd Edition 2012 Standard analytical methods should be used wherever possible Regulatory agencies require very specific protocols to be followed

12. Environmental Analysis • Uniqueness of Modern Environmental Analysis • Sample matrices are complex, matrix interferences are variable and not predictable • Chemical concentrations are usually very low, requiring increasingly more sophisticated instruments to detect ppm, ppb, ppt levels • Some analyses have to be done in-situ (on site) continuously • Analysts need both technical background and knowledge of regulations for regulatory compliance and enforcement Classical and Modern Analytical Monitoring Techniques Classical methods – include gravimetric and volumetric methods (wet chemical) Modern methods – include spectrometric, electrometric and chromatographic techniques etc. Source: Dr.Pankaj Mehta/personalpics

13. Environmental Sampling Techniques General Guidelines of Environmental Sampling Techniques • Sequence of Sampling Matrices and Analytes • Use following sequence: • Collect from least to most contaminated sampling locations • If sediment and water is being collected, collect water first to minimize effects from suspended bed materials • For shallow streams, start downstream and work upstream to minimize sediment effects due to sampling disturbances • If sampling at different depths, collect surface samples first and then proceed deeper • Always collect VOCs first, followed by SVOCs (e.g. pesticides, PCBs, oil, etc.), then total metals, dissolved metals, microbiological samples, and inorganic nonmetals

14. Sample Preservation and Storage • Refrigeration is a universally accepted method to slow down loss processes • Container choice (material type and headspace) is critical to reduce • Volatilization • Adsorption • Absorption • Diffusion • Photodegradation • Addition of preservatives is critical to reduce losses due to chemical reactions and bacterial degradation Source:APHA, 21 Edn 2005

15. Selection of Sampling Equipment • Surface Water and Wastewater Sampling • Grab sampler, weighted bottle sampler, Kemmerer bottle

16. Selection of Sampling Equipment • Groundwater Sampling • Collected from wells using a bailer or by pumps (peristaltic and bladder) • Samples do not come into contact with mechanical components of the pump • Soil Sampling • Soil depth and whether or not each soil horizon is necessary to sample are main considerations • Scoops and trowels, tube sampler, augers, split spoon sampler (drilling)

17. Calibration of Instruments and Standard Laboratory Calibration process The purpose of calibration is to ensure that the measuring accuracy is known over the whole measurement range under specified environmental conditions for calibration. Calibration of Instrument ·   Measurement of Accuracy · Establishment the relation of an instrument’s accuracy to the international standard

18. Table 1. A typical format for instrument record Further details about the procedures for calibration of instrument is covered by BS 5781.

19. TAGS FOR CALIBRATION, EQUIPMENT & PREVENTIVE MAINTENANCE

20. Traceability As shown in Fig.2, calibration has a chain-like structure in which every instrument in the chain is calibrated against a more accurate instrument immediately above it in the chain. The knowledge of the full chain of instruments involved in the calibration procedure is known as traceability, and is specified as a mandatory requirement in satisfying the ISO 9000 standard. Documentation must exist which shows that process instruments are calibrated by standard instruments which are linked by a chain of increasing accuracy back to national reference standards. Fig.2

21. General process for evaluation/validation of methodology. • The process of Validation involves: • selectivity • linearity • accuracy • precision • sensitivity • range • limit of detection (LOD) • limit of quantitation (LOQ) • Standard reference materials (SRMs) are best for determining accuracy.

22. Documentation of Calibration • An essential element in the operation of calibration is the provision of full documentation that consists of the following: • Measurement requirements (such as environmental conditions) • Instruments used • Calibration system and procedures operated • Calibration record • Traceability of the calibration system back to national reference standards must be defined and supported by calibration certificates. • Training programmes • The above-mentioned are also important to the maintenance of measurement system and form a necessary part of the quality manual.

23. Quality Assurance (QA) for environmental measurement • Why do we need quality assurance (QA) for environmental measurement? • To Understand data reliability • To Quantify areas of analytical uncertainty • To Standardize measurement to allow for repeatable and comparable data across time and place QA ensures that data will meet defined standards of quality with a standard level of confidence

24. ISO Documents - Laboratory ISO 9001:2000 Quality Management System Requirements Model for QA in design, development production, installation, and servicing ISO/IEC 17025:2005 General requirements for the competence of testing and calibration laboratories To Summarize Quality management is not new. Quality management grew from the good works of innovators who defined quality over a span of 80 years. Quality management is as applicable for the Environmental laboratory as it is for manufacturing and industry.

25. QC in the laboratory • Standardized laboratory method programs • EPA Methods • State Modified Methods • APHA Methods • ASTM • IS Methods

26. QC: Internal vs. external measures • Internal quality control • “controllable” by those responsible for undertaking the project or directly “involved in the program” • External quality control • a “set of measures” established for and conducted by those people and organizations “outside of the program”

27. Laboratory Assessment Internal External Proficiency testing Inspections Accreditations Quality indicators Audit program Audit review

28. Proficiency testing by interlaboratory comparisons • To determine the competence of individual laboratories to perform specific tests or measurements • To monitor the performance of laboratories overtime PT Scoring System Z score = A measure of an observation’s distance from the mean.

29. Assigned Value, The assigned value may be the “true” or the consensus value. True value may be a theoretical value or known value from “spiking’ of known quantity of a known quantity of analyte to a sample. Consensus value based on the results of the participants. The consensus value is determined by the application of robust statistics (eg median value, mean interquartile range). Z-score ≼ 2 satisfactory ≽ 2≼ 3 questionable > 3 unsatisfactory

30. Maintenance of Accreditation of a Laboratory Mandatory reassessments are conducted one year after the granting of accreditation and at two-year intervals thereafter Surveillance visits, announced or unannounced, are also conducted. Accredited laboratories are visited at least once a year and are required to participate in proficiency testing activity at least once every four years for each major sub-area of major disciplines for establishing National and International competency and recognition

31. Maintenance of Accreditation of a Laboratory Indian Labs can go for NABL, BIS and MoEF Certification. To achieve confidence in the goods and services which move across national boundaries, international agreements have established the equivalence of the different accreditation schemes in existence. There are various International agencies for Accreditation such as International Accreditation Forum (IAF), International Laboratory Accreditation Cooperation (ILAC),Pacific Accreditation Cooperation (PAC) and Asia Pacific Laboratory Accreditation Cooperation (APLAC).

32. … THANK YOU LAB AND RESEARCH ARE INTERDEPENDENT QUALITY DATA IS THE BASIS OF PROFESSIONAL RESEARCH