Environmental Monitoring & Technology Certificate 4 - Trainee Learner Resource Environmental Fieldwork Study Module 6 – Quality control cffet.net/env Environmental Fieldwork Study Module 6 Assessment details Purpose This subject covers the ability to site and set up basic ‘ground level’ meteorological equipment and collect and record reliable data. It also includes the ability to assess data quality, interpret significant data features and use the data to ensure the validity of air and noise monitoring measurements. Instructions ◗ Read the theory section to understand the topic. ◗ Complete the Student Declaration below prior to starting. ◗ Attempt to answer the questions and perform any associated tasks. ◗ Email, phone, book appointment or otherwise ask your teacher for help if required. ◗ When completed, submit task by email using rules found on last page. Student declaration I have read, agree to comply with and declare that; ◗ I know how to get assistance from my assessor if needed… ☐ ◗ I have read and understood the SAG for this subject/unit… ☐ ◗ I know the due date for this assessment task… ☐ ◗ I understand how to complete this assessment task… ☐ ◗ I understand how this assessment task is weighted… ☐ ◗ I declare that this work, when submitted, is my own… ☐ Details Student name Type your name here Assessor Marker’s use only Class code EF Assessment name SM6 Due Date Total Marks Available 50 (by assignment) Marks Gained Marker’s use only Final Mark (%) Marker’s use only Marker’s Initials Marker’s use only Date Marked Click here to enter a date. Weighting This assessment contributes 5% to the overall mark for this subject Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 1 Environmental Fieldwork Study Module 6 Introduction Let’s review what we are up to so far. You have; ◗ Got a basic understanding of the overall survey and reasons for the sampling, ◗ You understand the concept of Data Quality Objectives ◗ You know the field protocols and sample regime ◗ You know how to take samples that are representative ◗ You know how to test water in the field Now you need to make sure you are doing it properly Consider this; You are out in the field sampling and testing for water. You stick a DO probe in and the DO meter states the result as 7.68 mg/L. Is it? Is that the actual concentration? How confident are you? Imagine that at a later date, for whatever reason, the data is called upon in the Land and Environment Court. You are told by your manager that the sampler, you, is to testify about the samples collected and the testing that is done in the field (the lab analysis is covered by the lab staff). Could you stand up in court and prove that the results are accurate? Let’s find out! Just because the meter reads that on the display in no way means that it is correct. You need to validate the results of every sample and every field and laboratory test that you undertake, otherwise you are just guessing, and that is simply unacceptable. Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 2 Environmental Fieldwork Study Module 6 Quality Assurance (QA) and Quality Control (QC) You will learn about these concepts in other units of study and subjects throughout your course, so this is just a simple explanation. Quality Assurance Quality Assurance (QA) is a way of preventing mistakes or defects and avoiding problems when delivering processes. Quality Assurance refers to administrative and procedural activities implemented in a quality system so that requirements and goals for a product, service or activity will be fulfilled. QA is designed to avoid defective results It is the systematic measurement, comparison with a standard, monitoring of processes and an associated feedback loop that confers error prevention. This can be contrasted with quality control, which is focused on process output. Two principles included in Quality Assurance are Fit for purpose, i.e. what you are doing should be suitable for the intended purpose and right first time, i.e. mistakes should be eliminated. QA includes management of the quality of raw materials, assemblies, products and components, services related to production, and management, production and inspection processes. QA in fieldwork With reference to the example involving being taken to court above, if samples are to be the basis for later legal proceedings, the following areas are likely to be under challenge: ◗ Exactly where was the sample taken from? ◗ Was the person taking the sample competent to do so? ◗ How was the sample labelled to ensure that no possibility of mix-up or substitution occurred? ◗ Was there any possibility of contamination of the sample during collection? ◗ Did the sample deteriorate after collection? ◗ Was sample storage adequate to avoid losses? Once sampling sites have been determined, their locations must be specified accurately, preferably using a geographic positioning system. Where transects are sampled, the location range should be specified if this is within the precision of the positioning instrument. The exact location of sampling sites and any sub-sites must be recorded in the sampling protocol. Field notebooks must contain an accurate description of where samples were collected to allow cross-checking with those specified in the sampling protocol. Taking note of the time when samples were taken (standard or daylight savings time) is an obvious but frequently overlooked requirement of rigorous sample definition. Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 3 Environmental Fieldwork Study Module 6 Where automatic sampling devices are used, their timing mechanism must be calibrated to ensure that samples are acquired at the specified intervals. This is especially critical where hydrologic or other conditions result in significant short-term concentration variations. Transfer of results to a database should be automated where possible, with checking of the printout against the field and analysis register. Validation of entries can be achieved by electronic screening against expected range, other analytes for the same site, and sampling date and field measurements. Chain-of-custody documentation is the formal means of recording the people who have been in contact with a sample from collection to analysis. This is mandatory in legal cases, and is discussed in the next module. A field-sampling sheet is mandatory if parameters are to be measured in the field. All field data are recorded on this sheet, as well as instrument calibration data. All field records must be completed before a sampling site is left. Any observations or information on the conditions at the time of sampling that may assist in interpretation of data should be entered on the field-sampling sheet or in a field notebook. This information may explain unusual data, which may have been attributed to problems in sampling or analysis. All equipment and field instruments should be kept clean and in good working order, with records kept of calibrations and preventative maintenance. Records should be kept of all repairs to equipment and instruments and of any incidents that may affect the reliability of equipment Quality control Quality control (QC) is a process by which allows the review of the quality of all factors involved in whatever it is you are doing (in our case, fieldwork). This approach relies on controls, well managed integrity criteria, and identification of records as well as competence checks of the technicians. Quality control is designed to discover defective results QC in fieldwork The objective of a field quality control program is to control sampling errors to acceptable levels. Thus procedures are designed to prevent, detect, and correct problems in the sampling process and to statistically characterize errors through quality control samples. Major errors to be avoided are faulty sampling device operation, incorrect sample collection and labelling, and sample changes before measurement (e.g., contamination or chemical/biological changes). Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 4 Environmental Fieldwork Study Module 6 Calibration Calibration and standardization of analytical systems are necessary to ensure that the produced data are accurate. Calibration Stock Solutions Calibration stock solutions are either commercially available or “house prepared” by the laboratory. Records should be maintained for both types of stock solutions. Calibration stock solutions used for metals analysis are stored at room temperature. In the case of purchased stock, the applicable holding time is indicated by the given expiration date. House-prepared stock should be renewed when instrument response is not satisfactory. Calibration standard solutions are prepared from calibration stock solutions by appropriate dilution. Figure 6.1 – Example of a calibration process from Horiba U50 Series manual. Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 5 Environmental Fieldwork Study Module 6 Field QA/QC program The field QA/QC program consists of the following areas and corresponding documentation: 1. Sample collection plan or procedure 2. Field QC requirements 3. Procedures to record and process data 4. Procedures to review and reduce data based on QC results 5. Processes to validate field measurement data for reporting purposes 6. Procedures to calibrate and maintain field instruments and equipment 7. Qualification and training of sampling personnel to attain proficiency in the following areas: ◗ Determination of the best representative sample site ◗ Use of proper sampling techniques ◗ Use of appropriate data recording techniques and reporting form ◗ Calibration and maintenance of field instruments and equipment ◗ Use of QC samples such as duplicate, split, and spiked samples After the training program, the fresh-sample collector must be involved in sampling activities under the direction of a more experienced person. Field sample QC The quality of data resulting from sampling activities depends on the following major activities: ◗ Collecting representative samples ◗ Use of appropriate equipment ◗ Proper sample handling and preservation ◗ Proper chain-of-custody and sample identification procedure ◗ Proper QA and QC in the field Testing for sample and preservation contamination In simple terms, whenever we measure something, we need to have a reference point or line from which to measure (ignoring scale at this stage). Quite often this will be zero (such as measuring distance), but with analytical chemistry, zero is impossible (because nothing is pure), so we need to define what zero really is. The amount of contamination will be small, most times effectively approaching zero, but it won’t be zero, so we need to work out what the level of contamination is and then ‘subtract’ it from the analytical result. Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 6 Environmental Fieldwork Study Module 6 A reminder about decontamination Decontamination is particularly important when collecting samples for microbiological, organic, metals or low concentration analysis. It is also of key importance when the data from the samples is being used for legal reasons. Decontamination agents come in a variety of forms including; ◗ Chelating agents (similar to EDTA) ◗ Detergents ◗ Caustic substances Blanks, duplicates and spikes A blank is a ‘sample’ of laboratory water, specifically, the same water (or from the same source) that will be used in any subsequent analysis. If the water is not from the same source, it needs to have documented evidence about its purity. The blank is then ‘treated’ in different ways and the results indicate the inclusion of analytes that are not part of the sample. They are an essential aspect of any QC field procedure and if not carried out, their absence allows for many questions about the sample integrity to occur. Figure 6.2 – Preparing field blanks. Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 7 Environmental Fieldwork Study Module 6 Container blanks “Is the sample container contaminated?” Prior to sampling, containers of each type to be used for sampling (about 1 in 10) are selected at random and filled with high-purity deionized water or seawater and preserved in the same manner as field samples. Analysis of these blanks is used to detect contamination during container preparation Equipment blanks “Does the sampling equipment allow for contamination?” Equipment blanks are used to detect contamination from sampling equipment. At least one equipment blank should be collected for every 20 samples per parameter group.. Each type of equipment used in sampling must be accompanied by an equipment blank. This blank is prepared in the field before sampling begins by using the pre-cleaned equipment and filling the appropriate container with laboratory water. Preservation and documentation should be the same as for the collected samples. If equipment is cleaned on site, then additional equipment blanks should be collected for each equipment group. Trip blank “Was the sample contaminated during the field sampling trip?” The purpose of trip blanks is to verify contamination that may occur during sample collection and transportation, as a result of improperly cleaned sampling containers, contaminated reagents, airborne contamination during transportation, and so on. Trip blanks are blanks of analyte-free water prepared by the laboratory and transported to the field that remain unopened during the sampling and are then transported back to the laboratory with the collected samples. These blanks should be properly labelled and documented. Trip blanks are usually collected with volatile organic compound (VOC) samples. Field filter blanks “Does filtering a sample introduce contamination?” Blanks should be prepared by passing a sample of high-purity water through a pre-cleaned filter. A preservative may have to be added to the water sample in the field. This allows estimation of contamination by filtration in the field. Field blank “Does the sampling allow atmospheric ingress of contaminants?” The purpose of collecting field blanks is to evaluate the potential that exists for environmental samples to be contaminated by airborne (and other) contaminants during Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 8 Environmental Fieldwork Study Module 6 the sample collection process. Once the field blank sample bottles are full, they are capped and then sent to the laboratory to be analysed for the same parameters that environmental samples are to be tested for at the site. Example A field blank may determine that airborne organic vapours in the vicinity of a sampling site may potentially be contaminating the environmental groundwater samples being collected. Field blanks are collected at the end of the sampling event. Fill an appropriate sample container with analyte-free water and preserve (if required) and document in the same manner as the collected samples. The exact nature of the use of field blanks can vary slightly from project to project, but will generally follow this principle. Testing for reproducibility and accuracy Duplicate samples Duplicates are samples collected at the same time from the same source (called field duplicates) or aliquots of the same sample that are prepared and analysed at the same time (laboratory duplicates). Duplicate samples are analysed to calculate measurement precision. During each independent sampling event, at least one sample or 10% of the samples, whichever is greater, must be collected for duplicate analysis. This requirement applies to each parameter group and each matrix sampled. Field spikes Field-spiked samples are environmental samples that contain specific added concentrations of various parameters of interest. Spiked samples are used to measure the performance of the complete analytical system, including interference from the sample matrix. Field preparation and transportation to the laboratory of a spiked sample should be similar to other samples, and the spiked sample can either be marked (as FSp or similar) or left blind for the laboratory. Replicates (split samples) Split samples are replicas of the same sample. Split samples are usually given to two independent laboratories for analysis, but can be sent ‘blind’ to one laboratory. The reason they are used is to make relative judgements about the precision of the laboratories analytical accuracy, but they also tell us about the quality of the sampling technique itself (although further investigation is required). Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 9 Environmental Fieldwork Study Module 6 Field instrument QC The QC techniques used in determining if the sample is collected correctly and without contamination are carried through to the field testing, sometimes literally in the sense that the same water can be used for QC testing of probe responses. Quality control solutions The solutions we use in calibration can be used on the meters and probes to test their ability to measure accurately. This is done by using the ‘measure mode’ and not putting the instrument into calibration mode. Common QC solutions and techniques for field test equipment are stated below; Temperature Use a calibrated glass thermometer in the field to check the temperature of the measured water. If the meter registers the same temperature for the meter, then the temperature has passed your QC test. pH QC for pH is very simple, you just measure the buffers used in the calibration procedure. Dissolved Oxygen Dissolved oxygen QC can be as simple as an ‘air’ test or as complex as a reproduction of the calibration, i.e. using two solutions where one is the zero (sodium sulphite) and the other is saturated with atmospheric oxygen, or anything in-between. Our method is to measure air and zero. This ensures that the probe span is still at large. Turbidity A known sample of turbidity measured in NTU, FTU, JTU FAU or any other unit (it does not matter because they are all the same!) is used to measure the probe response. The concentration of the QC should fall inside the range of expected for the samples being measured. Conductivity Use the same solutions as for calibration which is typically 0.5, 0.005 and 0.005 molar. ORP Is really tricky. Solutions need to be fresh as they change with time quite rapidly. Also, the results are arguable as to their accuracy due to the nature of the ORP science itself when applied to natural systems. Two common techniques are to; Calibrate ORP before and after sampling, or, Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 10 Environmental Fieldwork Study Module 6 Use the calibration solution to run QC, but be aware that accuracy will be an issue. Recording and reporting results All results need to be recorded on the appropriate record sheets, which will vary from place to place. This is covered by us in the next module. When QC fails So you have employed an extensive QA and QC system. You have all the procedures, training, equipment and solutions you need. As far as you are aware, you have done everything properly. And then it fails. So what do you do? Quality control charts for testing equipment Quality control needs to be assured, and graphing the results of your QC tests is the easiest way of determining whether there is a problem with the instruments. An example of the run charts used by our section can be seen in the badly designed graph below (the aim is 2 mg/L). Figure 6.3 – example of a run chart used in QC. Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 11 Environmental Fieldwork Study Module 6 Laboratory Analysis Once samples are collected, preserved and transported, they are generally ‘logged’ at the laboratory for analysis. Sample receipt Every laboratory will have its own procedures for the receipt of samples. This process is controlled by several factors, including; ◗ The type of laboratory (i.e. commercial versus ‘in-house’) ◗ The number of samples received, ◗ The type of sample received ◗ The use of receipt software (such as LIMS) ◗ Barcoding systems and requirements ◗ The dissemination of samples once the samples are processed. And many other factors. The key point to remember is that if a sample is not received in accordance with workplace protocols, the sample may not make it ‘through the system’ and could result in customer complaints! Sample preparation Once the sample is received and registered for analysis, it will generally be prepared for testing or analysis. Again, the list of preparation techniques is somewhat endless, but could include; ◗ Sample size reduction; ◗ Sub sampling ◗ Filtering ◗ Preserving ◗ Addition of reagents The degree of sample preparation is governed by the analysis and the specific technique that will be used on the sample. Sample analysis So, once more we end up with a list that never ends. The specific analysis that can be performed depends on the customers’ requirements, but generally speaking the following lists the common tests performed. Suspended Solids Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 12 Environmental Fieldwork Study Module 6 Suspended solids are a physical measure of particulate matter in water. The sample is filtered through a glass fibre filter paper (pore size 1.2um), the residue is weighed and the suspended solids calculated. The main thing to remember is that the volume required by the Laboratory is dependent on the expected final result. For very clean waters it may be necessary to filter up to one litre of sample to be able to report an accurate low result. In cases of water filter systems, we have had to filter up to 2.5 Liters of sample to give the required detection limit. Total Dissolved Solids Total dissolved solids are a measure of the solids that pass through a glass fibre filter paper (pore size 1.2um). This includes the dissolved salts and fine colloidal particles, which are less than 1.2um. A related measure called Total dissolved salts is a measure of the dissolved salts in a sample, which is calculated from the conductivity. Biochemical Oxygen Demand Biochemical oxygen demand (BOD) is a measure of the amount of oxygen used in the biochemical oxidation of organic matter, over a given time at a given temperature. It is determined entirely by the availability of the material as a biological food source and by the amount of oxygen used by microorganisms during the oxidation process. The standard test is conducted over 5 days at 20°C. Chemical Oxygen Demand Chemical oxygen demand (COD) is a measure of the amount of oxygen used in the chemical oxidation of carbonaceous organic matter in wastewater using dichromate or permanganate salts as oxidants. The organic material is oxidised at high temperature and the COD is determined by the loss of colour of the oxidising salt solution. Nutrients Nutrients' testing usually refers to nitrogen and phosphorus. These can exist in a number of different forms, and therefore may be measured in these different forms. Nitrogen may be measure as ammonia, total oxidised nitrogen (nitrate and nitrite), total nitrogen, organic nitrogen (total nitrogen - total oxidised nitrogen and ammonia) and Kjeldahl nitrogen (total nitrogen - total oxidised nitrogen). Phosphorus may be measured as ortho or reactive phosphorus and total phosphorus. Nutrient levels may be a useful indicator for the prediction of algal growths and potential pollution sources. Sewage is usually rich in nutrients, but it must be remembered that vegetation is also rich in nutrients, and these will be released upon decay. MBAS Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 13 Environmental Fieldwork Study Module 6 Methylene blue active substances (MBAS) are usually anionic surfactants. Anionic surfactants are found in common detergents that are used in household and general cleaning products. MBAS therefore gives an indication of the amount of detergents in a sample. Coliforms Thermotolerant - Faecal Faecal Coliforms are used as a potential indicator of faecal related contamination, usually sewage or warm-blooded animal in origin. This is commonly measured in STP effluent related samples. E coli These are a sub group of faecal Coliforms believed to be a more robust indicator of "Faecal" contamination. This is used commonly for drinking water guidelines. Total Coliforms Coliforms are used as an indication of bacterial activity and total Coliforms are measured in drinking water, as a measure of the effectiveness of the sterilisation process: Algae and Chlorophyll a Algal growth is seasonal and generally occurs in spring and summer. There is a wide range of algal groups, which can be difficult to identify with the naked eye. Of particular interest is blue-green algal group, some of which have the potential to release toxins into the water body. There are a number of Algae groups which contribute to taste and odour problems. Chlorophyll a is used as an indicator of biomass in water samples. The analysis involves extracting the green pigment from algae. Samplers need to be aware that macrophytes and other vegetation also contain chlorophyll. Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 14 Environmental Fieldwork Study Module 6 Assessment Task After reading the theory above, answer the questions below. Note that; ◗ Marks are allocated to each question. ◗ Keep answers to short paragraphs only, no essays. ◗ Make sure you have access to the references (last page) ◗ If a question is not referenced, use the supplied notes for answers Answer the following questions 1. You will be given an assignment task for this study module based on a case study. Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 15 Environmental Fieldwork Study Module 6 Assessment Submission Answers ◗ Attempt all questions and tasks ◗ Type your answer into the text fields provided. Submission Use the documents ‘Save As…’ function to save the document to your computer using the file name format of; name-classcode-assessmentname Note that class code and assessment code are on Page 1 of this document. ◗ email the document back to your teacher Penalties If this assessment task is received greater than seven (7) days after the due date (located on the cover page), it may not be considered for marking without justification. Results Your submitted work will be returned to you within 3 weeks of submission by email fully graded with feedback. You have the right to appeal your results within 3 weeks of receipt of the marked work. Problems? If you are having study related or technical problems with this document, make sure you contact your assessor at the earliest convenience to get the problem resolved. The name of your assessor is located on Page 1, and the contact details can be found at; www.cffet.net/env/contacts References Note that some of these resources might be available from your teacher or library Bates, G. (2010). Environmental Law in Australia. Australia: LexisNexis-Butterworths. Bratram, J. E. (1996). Water Quality Monitoring - A Practical Guide to the Design and Implementation of Freshwater Quality Studies and Monitoring Programmes. New York?: UNEP/WHO. Burden, F. E. (2002). Environmental Monitoring Handbook. McGraw-Hill Professional. CFFET. (2012). Practical Laboratory Skills - supplementary results sheet. Newcastle: Hunter TAFE. Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 16 Environmental Fieldwork Study Module 6 EPA, N. (1996). Environmental Guidelines: Solid Waste Lanfills. Chatswood: Environmental Protection Authority. EPA, S. (2007). EPA Guidelines: Regulatory monitoring and testing - water and wastewater sampling. Adelaide: Environment Protection Authority (South Australia). ESDSC. (1992). National Strategy for Ecologically Sustainable Development. Canberra: Department of Sustainability, Environment, Water, Populations and Communities. Ferrier, R. C. (2010). Handbook of Catchment Management. Oxford: Wiley-Blackwell. Hauer, F. R. (2007). Methods in Stream Ecology, 2nd Ed. Burlington: Academic Press. Jorgensen, S. E. (2005). Handbook of Ecological Indicators for Assessment of Ecosystem Health. Boca Raton: CRC Press. Manahan, S. (2000). Environmental Chemistry. Boca Raton: Lewis Publishers. Newton, A. (2007). Forest Ecology and Conservation. Oxford: Oxford University Press. StandardsAustralia. (2004). AS/NZS ISO 14001:2004 Environmental Management Systems: Requirements with guidance for use. Australia: Standards Australia. U.S.GeologicalSurvey. (Variously dated). National field manual for the collection of water quality data: U.S. Geological Survey Techniques of Water Resources Investigation, book 9, chaps. A1-A9. available online at http://pubs.water.usgs.gov/twri9A. vanLoon, G. W. (2011). Environmental Chemistry: a global perspective. New York: Oxford University Press. Vogel, A. (1987). Vogel's textbook of quantitative inorganic analysis, 4th Ed. London: Longman Group Limited. Workplace Health and Safety Act 2011. (n.d.). Workplace Health and Safety Regulation 2011. (n.d.). Other resources If they exist, the items listed below are for general information only. If you know of a good resource that other students might find useful let your teacher know and we shall add it to the list. http://www.epa.gov/QUALITY/dqos.html Where to get help Contact your teacher if you run into any trouble this unit. You would be surprised how flexible we are at accommodating your needs, but communication is the key. If you don’t let us know you are having trouble, we may have trouble trying to help you. Chemical, Forensic, Food & Environmental Technology [cffet.net] Version 1.0 30/05/2016 Page | 17