39
Appendix J - Data Validation

Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

  • Upload
    others

  • View
    6

  • Download
    0

Embed Size (px)

Citation preview

Page 1: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J - Data Validation

Page 2: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

1. Introduction

This data validation appendix summarises the data quality objectives (DQOs), established for the datato support residential produce sampling and then assesses the reliability of the field work proceduresand laboratory analytical results using the data quality indicators (DQIs).

1.1. Data Quality Objectives

The National Environment Protection Measure (NEPM, Schedule B2 Guideline on Site

Characterisation - 2013) states that the nature and quality of the data collected for a particular

assessment will be determined by the Data Quality Objectives (DQOs). The NEPM and the AustralianStandard AS4482.1-2005 reference the US EPA Guidance on Systematic Planning Using the Data

Quality Objectives Process (US EPA, 2006) which defines the DQO process. The US EPA defines

the process as ‘a strategic planning approach based on the Scientific Methods that is used to prepare

for a data collection activity. It provides a systematic procedure for defining the criteria that a data

collection design should satisfy, including when to collect samples, where to collect samples, the

tolerable level of decision errors for the study, and how many samples to collect.’

To define the purpose, type, quantity and quality of data required for the residential produce sampling,the seven step data quality objectives (DQOs) approach, as described in the NEPM 2013, wasadopted.

The seven steps of the DQO process for the current RAAF Base RAAF Base Tindal Investigationrelating to these works are summarised below:

Table 1: Data Quality Objectives

Quality objectives

1. State the Problem

PFAS contamination sources have been identified at RAAF Base Tindal and investigations to date have

identified contaminated soil and groundwater in the vicinity of known source areas. The nature and extent of

PFAS contamination to offsite areas within the Environmental Investigation Area (EIA) has identified PFAS in

groundwater, surface waters, sediment, animal biota (whole fish) and animal products (chicken and duck

eggs). The Ecological Risk Assessment (ERA) will utilise PFAS concentrations either measured or estimated

at the POE to estimate exposures to ecological receptors. The identified areas where PFAS concentrations in

media is not known or the CSM requires further refinement includes:

• Data are needed for the ERA to characterize PFAS concentrations in aquatic and terrestrial biota

across the EIA, and to estimate exposures and risk to upper trophic level receptors.

• Given the tropical climate of the Tindal/Katherine area, surface water flows and groundwater recharge

rates will have a strong seasonal variations that are likely to influence PFAS concentrations in

groundwater, surface water, sediments, food sources and receptor behaviours and exposures.

Page 3: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

Quality objectives

2. Identify the goal of the study

The purpose of the broader investigation is to understand the nature and extent of PFAS contamination as a

result of Defence activities.

The purpose of the ERA investigation is to understand the nature and extent of PFAS contamination in media

at the POE within the EIA where identified receptor populations may be exposed.

The ERA will rely on specific information that may be area or receptor specific, therefore data collected from

site media including surface water, sediment, soil, and biota tissue is essential.

The DSI will provide sufficient information on the sources of PFAS contamination, the migration pathways and

the current extent of contamination to enable a robust site model to be developed. The outcomes of the ERA

will guide management strategies where required.

3. Identify information inputs

• Recent and ongoing investigations will provide:

o CSM information relating to the site history, sources and use of PFAS contaminant

materials, and determine the nature and extent of contamination in soil, water, and

sediment.

o Surface water and groundwater flow regimes, to develop the conceptual site model

about the potential migration pathways of contamination from source areas towards

ecological receptors.

o Preliminary data relating to PFAS contamination of site biota including terrestrial and

aquatic plants, terrestrial invertebrates, small mammals, aquatic invertebrates, and fish.

o Relevant screening criteria, where established, to reflect plausible exposure routes.

4. Define the boundary of the study

Based on the potential for contaminated surface water or shallow groundwater to migrate west north-west

towards Katherine River, the broad study area includes land and waterways on RAAF Base Tindal and the

area between the Base and Katherine River. An approximate buffer of 1km across the western side of

Katherine River has been included.

Page 4: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

Quality objectives

5. Develop a decision rule

Primary environmental samples will be collected and analysed by the laboratories for the full suite of PFAScompounds.

Terrestrial biota samples

• Absolute concentrations to evaluate the exposure where ingestion of terrestrial biota (i.e.,

invertebrates, plants, amphibians, reptiles, small mammals) may occur, to allow the quantitative

assessment of ecological risk.

• Paired results (with amphibian biota) will be used to evaluate the potential for accumulation in

amphibians. Measured concentrations in amphibians will be used to assess the potential risk from

ingestion of amphibians to upper trophic level receptors (i.e., reptiles, mammals and birds).

• Paired results (with reptile biota) will be used to evaluate the potential for accumulation in reptiles.

Measured concentrations in reptiles will be used to assess the potential risk from ingestion of reptiles

to upper trophic level receptors (i.e., reptiles, mammals and birds).

• Paired results (with small mammal biota) will be used to evaluate the potential for accumulation in

small mammals. Measured concentrations in small mammals will be used to assess the potential risk

from ingestion of small mammals to upper trophic level receptors (i.e., reptiles, mammals and birds).

• Paired results (with reptile and bird egg data) will be used to evaluate the potential for accumulation in

reptile and bird eggs. Measured concentrations in reptile and bird eggs will be used to assess the

potential risk to upper trophic level receptors from ingestion of reptile and bird eggs.

Aquatic biota samples

• Absolute concentrations to evaluate the exposure where ingestion of aquatic biota (i.e., invertebrates,

plants, fish, amphibians) may occur, to allow the quantitative assessment of ecological risk.

• Paired results (with fish biota) will be used to evaluate the potential for accumulation in fish.

Measured concentrations in fish will be used to assess the potential risk from ingestion of fish to upper

trophic level (i.e., piscivorous amphibians, reptiles, mammals and birds).

• Paired results (with amphibian biota) will be used to evaluate the potential for accumulation in

amphibians. Measured concentrations in amphibians will be used to assess the potential risk from

ingestion of amphibians to upper trophic level receptors (i.e., reptiles, mammals and birds).

• Paired results (with reptile biota) will be used to evaluate the potential for accumulation in reptiles.

Measured concentrations in reptiles will be used to assess the potential risk from ingestion of reptiles

to upper trophic level receptors (i.e., reptiles, mammals and birds).

• Paired results (with small mammal biota) will be used to evaluate the potential for accumulation in

small mammals. Measured concentrations in small mammals will be used to assess the potential risk

from ingestion of small mammals to upper trophic level receptors (i.e., reptiles, mammals and birds).

Data set for POE will be sufficient to allow statistical analysis if required.

Page 5: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

Quality objectives

6. Specify performance of acceptance criteria

The assessment as a whole (including consideration of previous assessments) must reliably characterise the

sources of contamination from the Base and described the risk that the contamination may pose to human or

ecological receptors. In order to achieve that, there must be multiple lines of evidence to support location of

source areas; the characterisation of the nature and extent of the residual source and associated surface water

or ground water impact; the significance of the risk that that contamination currently poses to relevant

receptors; and predictions of future impacts.

The ERA assessment as a whole must reliably characterise the contaminant concentrations at the point of

exposure, either via direct measurement or calculation, to quantify the potential intake and associated risk to

ecological receptors within the EIA.

As consistent with NEPM guidance, the uncertainties associated with each step in the risk assessment

process, particularly site conditions, ecological exposure and chemical toxicity, will be discussed in terms of the

variability in the assumptions and associated influence on the estimates of risk.

7. Develop a plan for obtaining the data

The methodology and rationale for obtaining relevant data was developed and approved prior toimplementation.

1.2. Data Quality Indicators

An assessment of the reliability of field procedures and laboratory analytical results outlined throughthe DQOs has been undertaking using the DQIs of precision, accuracy, representativeness,completeness and comparability. A brief outline of the DQIs is presented below.

Precision – All Coffey field staff to implement Coffey standard operating procedures (SOPs) orproject specific procedures appropriate for the task being undertaken. All laboratories used toundertake analysis are NATA accredited for the analytes being tested for. An appropriate number ofintra-laboratory and inter-laboratory replicate samples were collected and analysed and are within theacceptable limits of 1 in 20.

Accuracy – All Coffey staff to follow the appropriate procedures for the tasks being undertaken. Tripblanks and equipment rinsate blank samples collected and results of which are to be satisfactory. Alllaboratories used are to be NATA accredited and the use of NATA endorsed methods, includingappropriate method blanks, laboratory control samples, laboratory spikes and duplicates, and theresults of which satisfy the defined criteria of acceptability.

Representativeness – A sufficient number of samples are to be collected and analysed from eachmedia to adequately achieve the overall DSI objectives.

Completeness – All Coffey staff to follow procedures appropriate to the task being performed, alongwith the appropriate documentation. All identified areas of environmental concern to be assessed withchemical analysis for relevant chemicals of potential concern from targeted and systematic samplinglocations. All samples to be under proper custody between the field and laboratory. The data obtainedfrom the laboratory is considered relevant and usable.

Comparability – All Coffey staff to follow the appropriate procedures for the task being undertakenand complete all sampling documentation. All analyte holding times to be complied with and samples

Page 6: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

properly and adequately preserved. All laboratory analysis to use the correct methods, along withappropriate limits of reporting (LORs).

The DQIs for the field works and laboratory analysis are presented in Table 2 and Table 3.

Table 2: Field Works Quality Control Criteria

Item Comments

Intra-laboratory

duplicates

Inter-laboratoryduplicates(triplicates)

Intra-laboratory field duplicates were collected at a minimum frequency of one sample per

twenty samples collected (5%). The analytical results of the primary sample and

duplicate/triplicate samples will be compared to assess the precision of the sampling

protocol and to provide an indication of variation in the sample source.

Repeatability will be assessed by calculating the relative percentage difference (RPD)

between the primary and duplicate results. Where the RPD is greater than 30%, the

potential causes of variability has been reviewed.

Trip blanks Trip blanks are a check on sample contamination originating from containers, sample

transport, shipping and site conditions. The trip blank will be prepared in a clean

environment (office or warehouse) and remain with the sample containers during sampling

and during the return trip to the laboratory. At no time during these procedures will the

blanks be opened. Upon return to the laboratory the blank will be analysed, if needed, as

any other field sample. As PFAS is not volatile, a reduced blank frequency is considered

appropriate and a single trip blank per sample batch will be transported and analysed.

Detectable concentrations of PFAS in a trip blank sample will trigger review of sample

container types, transport procedures and UHP water quality. The concentration and

compound detected will be considered in reviewing the potential impact of transport related

cross-contamination of the assessment data quality.

Rinsate blanks Rinsate samples will be prepared in the field using empty bottles and the distilled

water/potable water used for the cleaning of non-disposable sampling equipment. These

samples will be a check of field decontamination procedures. A rinsate sample will be

collected and analysed for each day of field work, where non-disposable sampling

equipment has been used.

Detectable concentrations of PFAS in a rinsate blank sample will trigger review of

decontamination procedures, equipment materials, sample container types and UHP water

quality. The concentration and compound detected will be considered in reviewing the

potential impact of transport related cross-contamination of the assessment data quality.

Table 3: Laboratory Quality Control Criteria

Data Type Comments and Acceptable Control Limits

Sample Analysis All sample analyses were conducted using NATA certified laboratories which implementeda quality control plan in accordance with NEPM (2013).

Holding times Maximum acceptable sample holding times for PFAS in biota is 180 days.

Laboratorydetection limits

All laboratory detection limits to be less than the site investigation criteria.

Page 7: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

Data Type Comments and Acceptable Control Limits

LaboratoryBlanks

Laboratory blanks to be analysed at a rate of 1 in 20, with a minimum of one analysed perbatch.

Concentration of analytes to be less than the laboratory detection limits.

LaboratoryDuplicates

Laboratory duplicates to be analysed at a rate of 1 in 20, with a minimum of one analysedper batch. RPDs to be less than 30%.

LaboratoryControl Samples(LCS)

LCSs to be analysed at a rate of 1 in 20, with a minimum of one analysed per analyticalbatch.

Control limits: 50 to 150 % acceptable recovery

Matrix spikes Matrix spike duplicate prepared by dividing a field sample into two aliquots, then spikingeach with identical concentrations of the analytes at a rate of 1 in 20.

Matrix spikecontrol limits:

50–150 % acceptable recovery.

Matrix spikeduplicates:

RPDs <50%

1.3. Field Quality Assurance Quality Control

Field Quality Assurance Procedures

Field quality assurance involves all the planned actions, procedures, checks and decisions whichhave been made and undertaken through quality control measures to ensure the representativenessand integrity of collected samples is that of the true conditions.

Sample Collection

All Coffey environmental scientists/engineers were suitably qualified, trained and experienced for thesample collection undertaken. Sampling of each matrix was undertaken with reference to the projectspecific procedures.

Sampling Methodology

The adopted sampling methods for each media (e.g. biota, soil, sediments, groundwater and surfacewater) is presented in Appendix F.

All samples were collected using a new disposable nitrile glove. Each sample was collected in alaboratory supplied jar or bottle appropriate to the analysis required.

Each sample was labelled using a unique sample identifier, project reference and date of samplecollection, as directed by Defence.

Sample Transport and Preservation

To maintain sample integrity, all samples were placed into laboratory prepared containers suitable forPFAS and other non-PFAS analysis. Samples were immediately placed into an insulated ice chestcontaining ice, for storage and transportation to the laboratory.

All samples were sent to the laboratories under chain of custody (CoC) documentation.

Page 8: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

2. Terrestrial and Aquatic Vegetation

2.1. Samples Collected

Table 1. Type of Quality Assurance Quality Control (QA/QC) Samples Collected

Primary Samples 24

Days of sampling 3

Field Duplicates (at least 1 in 20 samples) 2 inter-laboratory

Trip Blanks (at least 1 per sampling event) -

Equipment Rinsate (at least

1/day/matrix/equipment)

1

2.1.1. Samples Analysed

24 samples were collected and sent to the primary laboratory over 3 days of sampling.

2.1.2. Inter-Laboratory and Intra-Laboratory Duplicates

ITEM QUESTION YES NO (Comment

below)

1 Were an Adequate Number of inter-laboratory and inter-laboratory

duplicates analysed for each chemical?

2 Were RPDs within Control Limits?

< 30% for concentrations

Comments

Duplicate samples of terrestrial and aquatic plant samples were reported within acceptable limits(<30%).

Page 9: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

2.1.3. Trip Blanks

ITEM QUESTION YES NO (Comment

below)

1 Was a trip blank collected on each day of sample?

2 Were the Trip Blanks free of contaminants?

(If no, comment whether the contaminants present are also detected

in the samples and whether they are common laboratory chemicals.)

Comments

No dedicated trip blank was collected during the sampling carried out through the sampling event.However, the rinsate blank that was collected was free of contamination. Therefore, this demonstratesthat cross contamination was unlikely to have occurred during sample storage and transport.

2.1.4. Rinsate Blanks

ITEM QUESTION YES NO (Comment

below)

1 Were Equipment Rinsates collected and analysed every

day/event/equipment?

2 Were the Equipment Rinsates free of contaminants?

(If no, comment whether the contaminants present are also detected

in the samples and whether they are common laboratory chemicals.)

Comments

Collection of terrestrial and aquatic plant samples was carried out in conjunction with terrestrialinvertebrate sampling. Batches of flora and fauna samples were sent together, with one rinsate blankfor the sampling event. Rinsate blank results are presented and discussed in the QAQC section forterrestrial invertebrates of this report.

Re-usable equipment was typically not used for collection of vegetation samples. Concentrations forall analytes were below the laboratory LOR for rinsate blanks where relevant.

The rinsate results indicated that the decontamination procedures, where relevant, were acceptableand it is considered that there is a low potential for cross-contamination to have impacted on thelaboratory results.

Page 10: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

In summary, the field QC results are considered generally acceptable for the purposes of thisinvestigation.

Field QA/QC was: Satisfactory

Partially Satisfactory

Unsatisfactory

2.2. Laboratory Quality Assurance Quality Control

2.2.1. Laboratories

ITEM QUESTION YES NO (Comment below)

1 Was a NATA registered laboratory used?

2 Did the laboratory perform the requested tests?

3 Were the laboratory methods adopted NATA endorsed?

4 Were the appropriate test procedures followed?

5 Were the reporting limits satisfactory?

6 Was the NATA Seal on the reports?

7 Were the reports signed by an authorised person?

Comments

Eurofins – Eurofins has been adopted as the primary laboratory for analysis of all matrices. Eurofins isa NATA accredited laboratory (NATA accreditation number 1261) for the media and analytes requiringanalysis.

Precision / Accuracy of the Laboratory Report Satisfactory

Partially Satisfactory

Unsatisfactory

2.2.2. Sample Handling

ITEM QUESTION YES NO (Comment

below)

1 Were the sample holding times met?

2 Were the samples in proper custody between the field and reaching

the laboratory?

3 Were the samples properly and adequately preserved?

This includes keeping the samples chilled, where applicable.

4 Were the samples received by the laboratory in good condition?

Page 11: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

Comments

Nil

Sample Handling was: Satisfactory

Partially Satisfactory

Unsatisfactory

2.2.3. Laboratory (Method) Blanks

The method blank allows assessment for potential method bias for relevant analytes. A method blankis the component of the analytical signal from each analytical method that is from laboratoryequipment (reagents, glassware and analytical instruments etc.). The method blank is determined bythe laboratories through running solvents and reagents in exactly the same manner as the samples.

At least one method blank should be run per 20 samples analysed, with a minimum of one methodblank per sample batch.

All laboratory method blank results reported concentrations of contaminants below the laboratoryreporting limits.

2.2.4. Laboratory Duplicates

To provide an estimate of the analysis method precision and duplicate sample heterogeneity, asample from the same batch is duplicated and analysed for a targeted analyte.

All internal laboratory duplicates analysed were within acceptable limits (<30% RPD).

2.2.5. Laboratory Control Samples

Laboratory control samples are prepared in the laboratory and comprise either a known analyteconcentration within a proven matrix or a control matrix spiked with analytes representative of thetarget analyte. The laboratory control sample percent recovery is reported along with the primarysample data to assess method accuracy for all targeted analytes.

Laboratory control samples are required to be processed per 20 samples analysed, with a minimum ofone laboratory control sample run per batch of samples.

All laboratory control sample analyses were within the acceptable range (>50%).

2.2.6. Matrix Spikes

A matrix spike is undertaken to document the effect of the matrix on the performance of the methodused. The matrix spike is the addition of a known analyte concentration to the target matrix prior toextraction or digestion. If a poor percentage recovery of a matrix spike is reported below the expectedanalytical method performance, the laboratory should investigate the likely cause. If, afterinvestigation, the poor matrix spike remains and is reported to the client, an explanation documentingthe limitations of the method for recovery of the target analyte from that particular matrix needs to beprovided. If the laboratory control sample recovery is acceptable for the same analyte, this mayindicate that it is the matrix causing the poor recovery and not the method.

All matrix spike analyses were within the adopted 50% – 150% acceptability criteria adopted.

Page 12: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

2.2.7. Surrogate Recoveries

Surrogate spikes are a means of the laboratory checking that no gross errors have taken placethroughout the analysis procedure, causing losses of the target analytes. The laboratory undertakessurrogate spikes by adding a known quantity of compounds with similar properties and behaviour tothe target compounds, but which are not expected to be found in field samples.

Surrogate spikes are only appropriate for organic analysis and are added to all samples beinganalysed prior to the extraction process. A percent recovery is calculated for each surrogate,providing the analytical method accuracy of extraction of the target analytes from samples.

The collated laboratory data for surrogate recoveries reported 337 surrogates out of a total of 552surrogate analyses undertaken outside of the acceptable recovery limits (50% to 150%). A total of39% of surrogate recoveries were within acceptable limits. These discrepancies were for a number ofPFAS compounds. For the three primary compounds of concern (PFOS, PFOA & PFHxS), a total of57% (31 out of 72) of surrogate recoveries were within acceptable limits.

The surrogate outliers for key compounds were all reported below the lower acceptable limit of 50%,or were not reported due to interference. When surrogate outliers occur, the laboratory apply acorrection factor adjustment to the result, which can result in the laboratory over-reporting theconcentration. For this reason, and because maximum concentrations of plant material have beenadopted for the modelling in this ERA, mean that a conservative approach has been applied whenassessing ecological risks to terrestrial and aquatic plants.

2.2.8. Summary of Internal Laboratory Quality Control

A summary of the internal laboratory quality control results is provided in the following tables

ITEM QUESTION YES NO (Comment

below)

1 Were the laboratory blanks/reagents blanks free of contamination?

2 Were the spike recoveries within control limits?

3 Were the RPDs of the laboratory duplicates within control limits?

4 Were the surrogate recoveries within control limits?

Table 2. Summary of internal laboratory QC results

QC test Total Analyses Number outside of

Acceptable Criteria

% of analyses acceptable

Method Blanks 28 0 100%

Laboratory

Duplicates

56 0 100%

Laboratory

Control Samples

28 0 100%

Matrix Spikes 28 0 100%

Surrogates 552 337 38.9%

Totals 692 337 51.3%

Page 13: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

The review of the laboratory internal quality control testing undertaken indicated that the overallcompleteness for the internal laboratory quality control results was 51.3%. As discussed in Section1.3.7, the low surrogate recoveries reported have likely added a level of conservatism to the results.The data is therefore considered of an acceptable quality to use in the report.

Laboratory internal QA/QC was: Satisfactory

Partially Satisfactory

Unsatisfactory

2.3. Summary of Vegetation Data Quality Review

In general, the data quality of the terrestrial and aquatic plant sampling was considered to beacceptable in relation to low potential for cross contamination during sampling, followed by suitabletransport to a NATA certified laboratory for analysis within holding times. The surrogate recoverieswere typically low and many were below the acceptance target of 50% or labelled as “Interference”.This may indicate low confidence in the absolute values of PFAS compounds in native vegetation. Toaccount for this potential variability, results should be applied conservatively.

Page 14: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Ecological Risk Assessment

Aquatic and Terrestrial Plant Tissue

Quality Control - RPDs

DoD, RAAF Base Tindal

Chem_Group ChemName Units

PFAS Perfluoro-n-octanoic acid (PFOA) µg/kg

Perfluoro-n-hexane sulfonic acid (PFHxS) µg/kg

Perfluoro-n-octane sulfonic acid (PFOS) µg/kg

Perfluorobutane sulfonic acid (PFBS) µg/kg

Perfluoro-n-decanoic acid (PFDA) µg/kg

Perfluoro-n-dodecanoic acid (PFDoDA) µg/kg

Perfluoro-n-heptanoic acid (PFHpA) µg/kg

Perfluoro-n-hexanoic acid (PFHxA) µg/kg

Perfluoro-n-nonanoic acid (PFNA) µg/kg

Perfluoro pentanoic acid (PFPeA) µg/kg

Perfluoro-n-undecanoic acid (PFUnDA) µg/kg

1H.1H.2H.2H-perfluorooctanesulfonic acid (6:2 FTS) µg/kg

1H.1H.2H.2H-perfluorodecanesulfonic acid (8:2 FTS) µg/kg

Page 15: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Ecological Risk Assessment

Aquatic and Terrestrial Plant Tissue

Quality Control - RPDs

DoD, RAAF Base Tindal

Lab Report Number 578707 RN1184142 578707 RN1184142

Field ID

0990_VG173_1

71211

0990_VG173_

171211RPD

0990_VG173_1

71211

0990_VG173_

171211RPD

Sampled Date 13/12/2017 13/12/2017 13/12/2017 13/12/2017

EQL

0.5 <0.5 <0.5 0 <0.5 <0.5 0

0.3 <0.3 <0.3 0 <0.3 <0.3 0

0.3 0.4 <0.3 28 <0.3 <0.3 0

0.5 <0.5 <0.5 0 <0.5 <0.5 0

0.5 <0.5 <0.5 0 <0.5 <0.5 0

0.5 <0.5 <0.5 0 <0.5 <0.5 0

0.5 <0.5 <0.5 0 <0.5 <0.5 0

0.5 <0.5 <0.5 0 <0.5 <0.5 0

0.5 <0.5 <0.5 0 <0.5 <0.5 0

0.5 <0.5 <0.5 0 <0.5 <0.5 0

0.5 <0.5 <0.5 0 <0.5 <0.5 0

0.5 <0.5 <0.5 0 <0.5 <0.5 0

0.5 <0.5 <0.5 0 <0.5 <0.5 0

Page 16: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

3. Terrestrial Invertebrates

3.1. Samples Collected

Table 3. Type of Quality Assurance Quality Control (QA/QC) Samples Collected

Primary Samples 25

Days of sampling 1

Field Duplicates (at least 1 in 20 samples) 3 intra-laboratory and 2 inter-laboratory

Trip Blanks (at least 1 per sampling event) -

Equipment Rinsate (at least

1/day/matrix/equipment)

1

3.1.1. Samples Analysed

25 samples were collected and sent to the primary laboratory over one day of sampling. Threeduplicate samples were collected and submitted for laboratory analysis.

3.1.2. Inter-Laboratory and Intra-Laboratory Duplicates

ITEM QUESTION YES NO (Comment

below)

1 Were an Adequate Number of inter-laboratory and inter-laboratory

duplicates analysed for each chemical?

2 Were RPDs within Control Limits?

< 30% for concentrations

Comments

Where RPDs were outside the acceptable range, sampling procedures, laboratory analytical methodsand laboratory results were investigated.

There were 84 intra-laboratory and 26 inter-laboratory duplicate pair analyses for PFAS compoundsand 95.5 % were reported within the acceptance target of less than 30 % RPD.

The RPD results from the terrestrial invertebrate sampling were generally considered acceptable andable to be relied on for the report.

Page 17: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

3.1.3. Trip Blanks

ITEM QUESTION YES NO (Comment

below)

1 Was a trip blank collected on for each batch of samples?

2 Were the Trip Blanks free of contaminants?

(If no, comment whether the contaminants present are also detected

in the samples and whether they are common laboratory chemicals.)

Comments

No dedicated trip blank was collected during the sampling carried out through the sampling event.However, the rinsate blank that was collected was free of contamination. Therefore, this demonstratesthat cross contamination was unlikely to have occurred during sample storage and transport.

3.1.4. Rinsate Blanks

ITEM QUESTION YES NO (Comment

below)

1 Were Equipment Rinsates collected and analysed every

day/event/equipment?

2 Were the Equipment Rinsates free of contaminants?

(If no, comment whether the contaminants present are also detected

in the samples and whether they are common laboratory chemicals.)

Comments

Rinsate samples were collected from the field equipment after decontamination. Equipment rinsatesamples were collected by pouring laboratory prepared deionised water over the equipment andcollecting the ‘rinse’ into sample containers. Concentrations of PFOS were reported for three of thefour samples collected, however these concentrations were marginally below the laboratory LOR forrinsate blanks.

The rinsate results indicated that the decontamination procedures were acceptable and it isconsidered that there is a low potential for cross-contamination to have impacted on the laboratoryresults.

Page 18: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

In summary, the field QC results are considered generally acceptable for the purposes of thisinvestigation.

Field QA/QC was: Satisfactory

Partially Satisfactory

Unsatisfactory

3.2. Laboratory Quality Assurance Quality Control

3.2.1. Laboratories

ITEM QUESTION YES NO (Comment below)

1 Was a NATA registered laboratory used?

2 Did the laboratory perform the requested tests?

3 Were the laboratory methods adopted NATA endorsed?

4 Were the appropriate test procedures followed?

5 Were the reporting limits satisfactory?

6 Was the NATA Seal on the reports?

7 Were the reports signed by an authorised person?

Comments

Eurofins – Eurofins has been adopted as the primary laboratory for analysis of all matrices. Eurofins isa NATA accredited laboratory (NATA accreditation number 1261) for the media and analytes requiringanalysis.

Precision / Accuracy of the Laboratory Report Satisfactory

Partially Satisfactory

Unsatisfactory

Page 19: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

3.2.2. Sample Handling

ITEM QUESTION YES NO (Comment

below)

1 Were the sample holding times met?

2 Were the samples in proper custody between the field and reaching

the laboratory?

3 Were the samples properly and adequately preserved?

This includes keeping the samples chilled, where applicable.

4 Were the samples received by the laboratory in good condition?

Comments

Nil

Sample Handling was: Satisfactory

Partially Satisfactory

Unsatisfactory

3.2.3. Laboratory (Method) Blanks

The method blank allows assessment for potential method bias for relevant analytes. A method blankis the component of the analytical signal from each analytical method that is from laboratoryequipment (reagents, glassware and analytical instruments etc.). The method blank is determined bythe laboratories through running solvents and reagents in exactly the same manner as the samples.

At least one method blank should be run per 20 samples analysed, with a minimum of one methodblank per sample batch.

All laboratory method blank results reported concentrations of contaminants below the laboratoryreporting limits.

3.2.4. Laboratory Duplicates

To provide an estimate of the analysis method precision and duplicate sample heterogeneity, asample from the same batch is duplicated and analysed for a targeted analyte.

100% of internal laboratory duplicates analysed were within acceptable limits (<30% RPD).

Page 20: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

3.2.5. Laboratory Control Samples

Laboratory control samples are prepared in the laboratory and comprise either a known analyteconcentration within a proven matrix or a control matrix spiked with analytes representative of thetarget analyte. The laboratory control sample percent recovery is reported along with the primarysample data to assess method accuracy for all targeted analytes.

Laboratory control samples are required to be processed per 20 samples analysed, with a minimum ofone laboratory control sample run per batch of samples.

All laboratory control sample analyses were within the acceptable range (>50%).

3.2.6. Matrix Spikes

A matrix spike is undertaken to document the effect of the matrix on the performance of the methodused. The matrix spike is the addition of a known analyte concentration to the target matrix prior toextraction or digestion. If a poor percentage recovery of a matrix spike is reported below the expectedanalytical method performance, the laboratory should investigate the likely cause. If, afterinvestigation, the poor matrix spike remains and is reported to the client, an explanation documentingthe limitations of the method for recovery of the target analyte from that particular matrix needs to beprovided. If the laboratory control sample recovery is acceptable for the same analyte, this mayindicate that it is the matrix causing the poor recovery and not the method.

All matrix spike recoveries were within acceptable limits.

3.2.7. Surrogate Recoveries

Surrogate spikes are a means of the laboratory checking that no gross errors have taken placethroughout the analysis procedure, causing losses of the target analytes. The laboratory undertakessurrogate spikes by adding a known quantity of compounds with similar properties and behaviour tothe target compounds, but which are not expected to be found in field samples.

Surrogate spikes are only appropriate for organic analysis and are added to all samples beinganalysed prior to the extraction process. A percent recovery is calculated for each surrogate,providing the analytical method accuracy of extraction of the target analytes from samples.

The collated laboratory data for surrogate recoveries reported 115 surrogates (out of a total of 575surrogate analyses undertaken) outside acceptance targets. These discrepancies were for a numberof PFAS compounds, however only one of these discrepancies was for a key compounds (PFOS)indicating that the data set was acceptable for the purposes of supporting the outcomes of the report.

3.2.8. Summary of Internal Laboratory Quality Control

A summary of the internal laboratory quality control results is provided in Table 4 and Table 5.

Page 21: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

Table 4: Summary of Internal Laboratory Quality Control

ITEM QUESTION YES NO (Comment

below)

1 Were the laboratory blanks/reagents blanks free of contamination?

2 Were the spike recoveries within control limits?

3 Were the RPDs of the laboratory duplicates within control limits?

4 Were the surrogate recoveries within control limits?

Table 5: Summary of internal laboratory QC results

QC test Total Analyses Number outside of

Acceptable Criteria

% of analyses acceptable

Method Blanks 28 0 100%

Laboratory Duplicates 84 0 100%

Laboratory Control Samples 28 0 100%

Matrix Spikes 56 0 100%

Surrogates 575 235 (1 for PFOS,

PFOA or PFHxS)

60% (99%)

Totals 771 235 69.7%

The review of the laboratory internal quality control testing undertaken indicated that the overallcompleteness for the internal laboratory quality control results was 69.7%. However as most of thesurrogate outlies are not for key PFAS compounds and without the precursor and fluorotelemersurrogate outliers reported, over 99% of internal laboratory quality control results were acceptable.The data is therefore considered of an acceptable quality to use in the report.

Laboratory internal QA/QC was: Satisfactory

Partially Satisfactory

Unsatisfactory

3.3. Summary of Terrestrial Invertebrate Data QualityReview

In general, the data quality of the terrestrial invertebrate sampling was considered to be acceptable.Surrogate recoveries were poor for precursor compounds and fluorotelemers, but suitable for PFOSand PFOA, which are the compounds applied quantitatively in this risk assessment.

Page 22: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Ecological Risk Assessment

Terrestrial Invertebrates

Quality Control - Blanks

DoD, RAAF Base Tindal

Lab Report Number 578676

Field ID 0990_QC3IV_171213

Sampled_Date/Time 13/12/2017

Sample Type Rinsate - bug sorting tray

Chem_Group ChemName Units EQL

PFAS Perfluoro-n-octanoic acid (PFOA) µg/L 0.01 <0.01

Perfluoro-n-hexane sulfonic acid (PFHxS) µg/L 0.01 <0.01

Perfluoro-n-octane sulfonic acid (PFOS) µg/L 0.01 <0.01

PFHxS and PFOS (Sum of Total) µg/L 0.01 <0.01

Perfluorobutane sulfonic acid (PFBS) µg/L 0.01 <0.01

Perfluorobutanoic acid (PFBA) µg/L 0.05 <0.05

Perfluoro-n-decane sulfonic acid (PFDS) µg/L 0.01 <0.01

Perfluoro-n-decanoic acid (PFDA) µg/L 0.01 <0.01

Perfluoro-n-dodecanoic acid (PFDoDA) µg/L 0.01 <0.01

Perfluoropentane sulfonic acid (PFPeS) µg/L 0.01 <0.01

Perfluoro-n-heptane sulfonic acid (PFHpS) µg/L 0.01 <0.01

Perfluoro-n-heptanoic acid (PFHpA) µg/L 0.01 <0.01

Perfluoro-n-hexanoic acid (PFHxA) µg/L 0.01 <0.01

Perfluoro-n-nonanoic acid (PFNA) µg/L 0.01 <0.01

Perfluorooctan esulfonamide (PFOSA) µg/L 0.05 <0.05

Perfluoro pentanoic acid (PFPeA) µg/L 0.01 <0.01

Perfluoro-n-tetradecanoic acid (PFTeDA) µg/L 0.01 <0.01

Perfluoro-n-tridecanoic acid (PFTriDA) µg/L 0.01 <0.01

Perfluoro-n-undecanoic acid (PFUnDA) µg/L 0.01 <0.01

2-(N-ethylperfluoro-1-octane sulfonamide)-ethanol µg/L 0.05 <0.05

2-(N-methylperfluoro-1-octane sulfonamide)-ethanol µg/L 0.05 <0.05

N-Ethyl perfluorooctane sulfonamidoacetic acid µg/L 0.05 <0.05

N-Methyl perfluorooctane sulfonamidoacetic acid µg/L 0.05 <0.05

1H.1H.2H.2H-perfluorohexanesulfonic acid (4:2 FTS) µg/L 0.01 <0.01

1H.1H.2H.2H-perfluorooctanesulfonic acid (6:2 FTS) µg/L 0.05 <0.05

1H.1H.2H.2H-perfluorodecanesulfonic acid (8:2 FTS) µg/L 0.01 <0.01

1H.1H.2H.2H-perfluorododecanesulfonic acid µg/L 0.01 <0.01

N-Ethylperfluoro-1-octane sulfonamide (N-EtFOSA) µg/L 0.05 <0.05

N-methylperfluoro-1-octane sulfonamide (N-MeFOSA) µg/L 0.05 <0.05

Page 23: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Lab Report Number 578759 578759 578759 578759 578759 578759 578759 RN1184145 578759 RN1184145

Field ID

0990_IV148_

171213 - A

0990_IV148_1

71213 - BRPD

0990_IV153

_171213 - B

0990_IV153

_171213 - CRPD

0990_IV161

_171213 - A

0990_IV161_

171213 - BRPD

0990_IV143_

171213

0990_IV143

_171213RPD

0990_IV151_

171213

0990_IV151_

171213 RPD

Sampled Date 13/12/2017 13/12/2017 13/12/2017 13/12/2017 13/12/2017 13/12/2017 13/12/2017 13/12/2017 13/12/2017 13/12/2017

Chem_Group ChemName Units EQL

PFAS Perfluoro-n-octanoic acid (PFOA) µg/kg 0.5 <0.5 <0.5 0 0.5 0.6 19 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 0.53 0

Perfluoro-n-hexane sulfonic acid (PFHxS) µg/kg 0.3 <0.5 <0.5 0 46 82 56 <0.3 <0.3 0 <0.3 <0.3 0 6.9 9.9 36

Perfluoro-n-octane sulfonic acid (PFOS) µg/kg 0.3 3.5 4 13 160 150 6 <0.3 <0.3 0 0.7 1.1 44 64 68 6

Perfluorobutane sulfonic acid (PFBS) µg/kg 0.5 <0.5 <0.5 0 3.6 3.4 6 <0.5 <0.5 0 <0.5 <0.5 0 0.9 0.81 11

Perfluorobutanoic acid (PFBA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

Perfluoro-n-decane sulfonic acid (PFDS) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

Perfluoro-n-decanoic acid (PFDA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 0.76 0

Perfluoro-n-dodecanoic acid (PFDoDA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

Perfluoropentane sulfonic acid (PFPeS) µg/kg 0.5 <0.5 <0.5 0 7.9 6.4 21 <0.5 <0.5 0

Perfluoro-n-heptane sulfonic acid (PFHpS) µg/kg 0.5 <0.5 <0.5 0 1.8 1.9 5 <0.5 <0.5 0

Perfluoro-n-heptanoic acid (PFHpA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

Perfluoro-n-hexanoic acid (PFHxA) µg/kg 0.5 <0.5 <0.5 0 0.8 0.8 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 0.51 0

Perfluoro-n-nonanoic acid (PFNA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

Perfluorooctan esulfonamide (PFOSA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

Perfluoro pentanoic acid (PFPeA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

Perfluoro-n-tetradecanoic acid (PFTeDA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

Perfluoro-n-tridecanoic acid (PFTriDA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

Perfluoro-n-undecanoic acid (PFUnDA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

2-(N-ethylperfluoro-1-octane sulfonamide)-ethanol µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

N-Ethyl perfluorooctane sulfonamidoacetic acid µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

N-Methyl perfluorooctane sulfonamidoacetic acid µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

1H.1H.2H.2H-perfluorohexanesulfonic acid (4:2 FTS) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

1H.1H.2H.2H-perfluorooctanesulfonic acid (6:2 FTS) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

1H.1H.2H.2H-perfluorodecanesulfonic acid (8:2 FTS) µg/kg 0.5 <0.5 <0.5 0 0.7 0.5 33 <0.5 <0.5 0 <0.5 <0.5 0 1.6 3.0 61

1H.1H.2H.2H-perfluorododecanesulfonic acid µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

N-Ethylperfluoro-1-octane sulfonamide (N-EtFOSA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

N-methylperfluoro-1-octane sulfonamide (N-MeFOSA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

N-Me perfluorooctanesulfonamid oethanol µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0

Page 24: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

4. Terrestrial Vertebrates

4.1. Samples Collected

Table 6. Type of Quality Assurance Quality Control (QA/QC) Samples Collected

Primary Samples 63

Days of sampling 3

Field Duplicates (at least 1 in 20 samples) 5 inter lab + 1 intra lab

Trip Blanks (at least 1 per sampling event) -

Equipment Rinsate (at least

1/day/matrix/equipment)

3

4.1.1. Samples Analysed

63 samples were collected and sent to the primary laboratory over three days of sampling. Fiveprimary laboratory duplicate samples and one secondary laboratory were collected and submitted forlaboratory analysis.

4.1.2. Inter-Laboratory and Intra-Laboratory Duplicates

ITEM QUESTION YES NO (Comment

below)

1 Were an Adequate Number of inter-laboratory and inter-laboratory

duplicates analysed for each chemical?

2 Were RPDs within Control Limits?

< 30% for concentrations

Comments

Where RPDs were outside the acceptable range, sampling procedures, laboratory analytical methodsand laboratory results were investigated.

There were 140 intra-laboratory duplicate pair analyses for PFAS compounds and 95% were reportedwithin the acceptance target of less than 30 % RPD.

There were 28 inter-laboratory duplicate pair analyses for PFAS compounds and 53.6% werereported within the acceptance target of less than 30 % RPD.

The RPD discrepancies observed between the primary laboratory samples and secondary laboratoryduplicate samples be attributable to the laboratory methodologies. It is noted that the secondarylaboratory consistently reported concentrations lower than the primary laboratory sample. As theprimary sample reported higher concentrations and these more conservative results have beenadopted for the ERA, this is not considered to have impacted the outcome of the assessment.

The RPD results from the terrestrial vertebrate sampling were generally considered acceptable andable to be relied on for the report.

Page 25: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

4.1.3. Trip Blanks

ITEM QUESTION YES NO (Comment

below)

1 Was a trip blank collected on for each batch of samples?

2 Were the Trip Blanks free of contaminants?

(If no, comment whether the contaminants present are also detected

in the samples and whether they are common laboratory chemicals.)

Comments

No dedicated trip blank was collected during the sampling carried out through the sampling event.However, the rinsate blanks that were collected were free of contamination. Therefore, thisdemonstrates that cross contamination was unlikely to have occurred during sample storage andtransport.

4.1.4. Rinsate Blanks

ITEM QUESTION YES NO (Comment

below)

1 Were Equipment Rinsates collected and analysed every

day/event/equipment?

2 Were the Equipment Rinsates free of contaminants?

(If no, comment whether the contaminants present are also detected

in the samples and whether they are common laboratory chemicals.)

Comments

Rinsate samples were collected from the field equipment after decontamination. Equipment rinsatesamples were collected by pouring laboratory prepared deionised water over the equipment andcollecting the ‘rinse’ into sample containers. Concentrations of PFAS in all rinsate samples werereported below the laboratory limit of reporting.

The rinsate results indicated that the decontamination procedures were acceptable and it isconsidered that there is a low potential for cross-contamination to have impacted on the laboratoryresults.

In summary, the field QC results are considered generally acceptable for the purposes of thisinvestigation.

Field QA/QC was: Satisfactory

Partially Satisfactory

Unsatisfactory

Page 26: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

4.2. Laboratory Quality Assurance Quality Control

4.2.1. Laboratories

ITEM QUESTION YES NO (Comment below)

1 Was a NATA registered laboratory used?

2 Did the laboratory perform the requested tests?

3 Were the laboratory methods adopted NATA endorsed?

4 Were the appropriate test procedures followed?

5 Were the reporting limits satisfactory?

6 Was the NATA Seal on the reports?

7 Were the reports signed by an authorised person?

Comments

Eurofins – Eurofins has been adopted as the primary laboratory for analysis of all matrices. Eurofins isa NATA accredited laboratory (NATA accreditation number 1261) for the media and analytes requiringanalysis.

ALS Environmental – ALS has been adopted as the secondary laboratory for analysis. ALS is a NATAaccredited laboratory (NATA accreditation number 825) for all the analytes requiring analysis.

Precision / Accuracy of the Laboratory Report Satisfactory

Partially Satisfactory

Unsatisfactory

4.2.2. Sample Handling

ITEM QUESTION YES NO (Comment

below)

1 Were the sample holding times met?

2 Were the samples in proper custody between the field and reaching

the laboratory?

3 Were the samples properly and adequately preserved?

This includes keeping the samples chilled, where applicable.

4 Were the samples received by the laboratory in good condition?

Comments

Nil

Page 27: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

Sample Handling was: Satisfactory

Partially Satisfactory

Unsatisfactory

4.2.3. Laboratory (Method) Blanks

The method blank allows assessment for potential method bias for relevant analytes. A method blankis the component of the analytical signal from each analytical method that is from laboratoryequipment (reagents, glassware and analytical instruments etc.). The method blank is determined bythe laboratories through running solvents and reagents in exactly the same manner as the samples.

At least one method blank should be run per 20 samples analysed, with a minimum of one methodblank per sample batch.

All laboratory method blank results reported concentrations of contaminants below the laboratoryreporting limits.

4.2.4. Laboratory Duplicates

To provide an estimate of the analysis method precision and duplicate sample heterogeneity, asample from the same batch is duplicated and analysed for a targeted analyte.

100% of internal laboratory duplicates analysed by Eurofins and ALS were within acceptable limits(<30% RPD).

4.2.5. Laboratory Control Samples

Laboratory control samples are prepared in the laboratory and comprise either a known analyteconcentration within a proven matrix or a control matrix spiked with analytes representative of thetarget analyte. The laboratory control sample percent recovery is reported along with the primarysample data to assess method accuracy for all targeted analytes.

Laboratory control samples are required to be processed per 20 samples analysed, with a minimum ofone laboratory control sample run per batch of samples.

All laboratory control sample analyses were within the target acceptable range (>50%).

4.2.6. Matrix Spikes

A matrix spike is undertaken to document the effect of the matrix on the performance of the methodused. The matrix spike is the addition of a known analyte concentration to the target matrix prior toextraction or digestion. If a poor percentage recovery of a matrix spike is reported below the expectedanalytical method performance, the laboratory should investigate the likely cause. If, afterinvestigation, the poor matrix spike remains and is reported to the client, an explanation documentingthe limitations of the method for recovery of the target analyte from that particular matrix needs to beprovided. If the laboratory control sample recovery is acceptable for the same analyte, this mayindicate that it is the matrix causing the poor recovery and not the method.

All matrix spike analyses were within the 50% - 150% acceptance target adopted. Recoveries weretypically poorer for precursors and fluorotelemers than for PFOS, PFHxS and PFOA.

Page 28: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

4.2.7. Surrogate Recoveries

Surrogate spikes are a means of the laboratory checking that no gross errors have taken placethroughout the analysis procedure, causing losses of the target analytes. The laboratory undertakessurrogate spikes by adding a known quantity of compounds with similar properties and behaviour tothe target compounds, but which are not expected to be found in field samples.

Surrogate spikes are only appropriate for organic analysis and are added to all samples beinganalysed prior to the extraction process. A percent recovery is calculated for each surrogate,providing the analytical method accuracy of extraction of the target analytes from samples.

The collated laboratory data for surrogate recoveries reported 398 surrogates (out of a total of 1,334surrogate analyses undertaken) outside acceptable limits. These discrepancies were for a number ofPFAS compounds, however only 35 of these discrepancies were for key compounds (PFOS, PFOA &PFHxS) indicating that the data set was acceptable for the purposes of supporting the outcomes ofthe report based on PFOS and PFOA toxicity.

4.2.8. Summary of Internal Laboratory Quality Control

A summary of the internal laboratory quality control results is provided in Table 7 and Table 8.

Table 7: Review of Internal Laboratory Quality Control

ITEM QUESTION YES NO (Comment

below)

1 Were the laboratory blanks/reagents blanks free of contamination?

2 Were the spike recoveries within control limits?

3 Were the RPDs of the laboratory duplicates within control limits?

4 Were the surrogate recoveries within control limits?

Table 8: Summary of internal laboratory QC results

QC test Total Analyses Number outside of

Acceptable Criteria

% of analyses

acceptable

Method Blanks 28 0 100%

Laboratory Duplicates 165 0 100%

Laboratory Control Samples 28 0 100%

Matrix Spikes 112 0 100%

Surrogates 1334 397 70.2%

Totals 1667 298 76.2%

The review of the laboratory internal quality control testing undertaken indicated that the overallcompleteness for the internal laboratory quality control results was 76.2%. However as most of thesurrogate outliers are not for key PFAS compounds and without the non-target compound surrogateoutliers reported, over 95% of internal laboratory quality control results were acceptable. The data istherefore considered of an acceptable quality to use in the report.

Page 29: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

Laboratory internal QA/QC was: Satisfactory

Partially Satisfactory

Unsatisfactory

4.3. Summary of Terrestrial Vertebrate Data QualityReview

In general, the data quality of the terrestrial vertebrate biota analysis was considered to beacceptable. Minor QC deficiencies in field duplicates (elevated RPDs for some paired samples)indicated a high variability in environmental concentration, indicating that results should be appliedconservatively. Poor surrogate recovery was also noted for many samples and may result in lowerconfidence in the precision of the results, but is considered unlikely to impact on the outcome of thereport when results are applied conservatively.

5. Aquatic Invertebrates, reptiles and mammals(August 2018)

5.1. Samples Collected

Table 9. Type of Quality Assurance Quality Control (QA/QC) Samples Collected

Primary Samples 18

Days of sampling 2

Field Duplicates (at least 1 in 20 samples) 1

Trip Blanks (at least 1 per sampling event) 2

Equipment Rinsate (at least

1/day/matrix/equipment)

1

5.1.1. Samples Analysed

18 samples were collected and sent to the primary laboratory over two day of sampling. Threeduplicate samples were collected and submitted for laboratory analysis

Page 30: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Ecological Risk Assessment

Terrestrial Vertebrates

Quality Control - RPDs

DoD, RAAF Base Tindal

Lab Report Number 592572 592572 592572 592572 592572 592572 592572 592572 592572 592572 592572 ES1810307

Field ID

0990_TV015_1

80328

0990_TV016_1

80328 RPD

0990_TV034_18

0328

0990_TVC15_18

0328 RPD

0990_TV048_1

80328

0990_TV049_1

80328 RPD

0990_TV051_1

80328

0990_TV052_18

0328 RPD

0990_TV108_1

80328

0990_TV110_1

80328 RPD

0990_TVC10_1

80328

0909_TVC11_

180328 RPD

Sampled Date/Time 28/03/2018 28/03/2018 28/03/2018 28/03/2018 28/03/2018 28/03/2018 28/03/2018 28/03/2018 28/03/2018 28/03/2018 28/03/2018 28/03/2018

Chem_Group ChemName Units EQL

PFAS Perfluoro-n-octanoic acid (PFOA) µg/kg 0.5 <0.5 <0.5 0 0.7 1.0 35 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 4.1 <1.0 122

Perfluoro-n-hexane sulfonic acid (PFHxS) µg/kg 0.3 0.5 0.5 0 75.0 70.0 7 <0.3 <0.3 0 0.7 4.2 143 0.4 <0.3 29 31.0 16.0 64

Perfluoro-n-octane sulfonic acid (PFOS) µg/kg 0.3 9.8 11.0 12 440.0 510.0 15 5.5 7.6 32 21.0 49.0 80 21.0 <0.3 194 1800.0 1330.0 30

Perfluorobutane sulfonic acid (PFBS) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 6.8 1.0 149

Perfluorobutanoic acid (PFBA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 24.0 <5.0 131

Perfluoro-n-decane sulfonic acid (PFDS) µg/kg 0.5 <0.5 <0.5 0 7.9 8.1 2 <0.5 <0.5 0 1.8 1.3 32 7.0 <0.5 173 72.0 167.0 79

Perfluoro-n-decanoic acid (PFDA) µg/kg 0.5 <0.5 <0.5 0 2.9 3.0 3 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 6.5 7.0 7

Perfluoro-n-dodecanoic acid (PFDoDA) µg/kg 0.5 <0.5 0.6 18 3.7 3.9 5 <0.5 <0.5 0 <0.5 <0.5 0 2.7 <0.5 138 31.0 26.0 18

Perfluoropentane sulfonic acid (PFPeS) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 26.0 5.0 135

Perfluoro-n-heptane sulfonic acid (PFHpS) µg/kg 0.5 <0.5 <0.5 0 13.0 11.0 17 <0.5 <0.5 0 1.0 1.4 33 <0.5 <0.5 0 <0.5 <1.0 0

Perfluoro-n-heptanoic acid (PFHpA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 9.8 2.0 132

Perfluoro-n-hexanoic acid (PFHxA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 3.1 <1.0 102

Perfluoro-n-nonanoic acid (PFNA) µg/kg 0.5 <0.5 <0.5 0 2.4 3.1 25 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <5.0 0

Perfluorooctan esulfonamide (PFOSA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 9.5 <2.0 130

Perfluoro pentanoic acid (PFPeA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 7.0 8.0 13

Perfluoro-n-tetradecanoic acid (PFTeDA) µg/kg 0.5 <0.5 0.6 18 0.7 0.8 13 <0.5 <0.5 0 <0.5 <0.5 0 0.5 <0.5 0 20.0 15.0 29

Perfluoro-n-tridecanoic acid (PFTriDA) µg/kg 0.5 <0.5 <0.5 0 1.0 1.1 10 <0.5 <0.5 0 <0.5 <0.5 0 2.3 <0.5 129 18.0 13.0 32

Perfluoro-n-undecanoic acid (PFUnDA) µg/kg 0.5 <0.5 <0.5 0 3.0 3.5 15 <0.5 <0.5 0 <0.5 <0.5 0 0.9 <0.5 57 <0.5 <2.0 0

2-(N-ethylperfluoro-1-octane sulfonamide)-ethanol µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <1.0 0

N-Ethyl perfluorooctane sulfonamidoacetic acid µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <1.0 0

N-Methyl perfluorooctane sulfonamidoacetic acid µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0

1H.1H.2H.2H-perfluorohexanesulfonic acid (4:2 FTS) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0

1H.1H.2H.2H-perfluorooctanesulfonic acid (6:2 FTS) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 5.9 2.0 99

1H.1H.2H.2H-perfluorodecanesulfonic acid (8:2 FTS) µg/kg 0.5 <0.5 <0.5 0 2.5 3.6 36 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 1.1 <2.0 0

1H.1H.2H.2H-perfluorododecanesulfonic acid µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0

N-Ethylperfluoro-1-octane sulfonamide (N-EtFOSA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <5.0 0

N-methylperfluoro-1-octane sulfonamide (N-MeFOSA) µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 3.7 <1.0 115

N-Me perfluorooctanesulfonamid oethanol µg/kg 0.5 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0

Page 31: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Ecological Risk Assessment

Terrestrial Vertebrates

Quality Control - Blanks

DoD, RAAF Base Tindal

Lab Report Number 592492 592492 592492

Field ID 0990_QCTV001_180328 0990_QCTV002_180328 0990_QCTV003_180328

Sampled_Date/Time 28/03/2018 28/03/2018 28/03/2018

Sample Type Rinsate - Scissors Rinsate - Knife Rinsate - Scalpel

Chem_Group ChemName Units EQL

PFAS Perfluoro-n-octanoic acid (PFOA) µg/L 0.01 <0.01 <0.01 <0.01

Perfluoro-n-hexane sulfonic acid (PFHxS) µg/L 0.01 <0.01 <0.01 <0.01

Perfluoro-n-octane sulfonic acid (PFOS) µg/L 0.01 <0.01 <0.01 <0.01

PFHxS and PFOS (Sum of Total) µg/L 0.01 <0.01 <0.01 <0.01

Perfluorobutane sulfonic acid (PFBS) µg/L 0.01 <0.01 <0.01 <0.01

Perfluorobutanoic acid (PFBA) µg/L 0.05 <0.05 <0.05 <0.05

Perfluoro-n-decane sulfonic acid (PFDS) µg/L 0.01 <0.01 <0.01 <0.01

Perfluoro-n-decanoic acid (PFDA) µg/L 0.01 <0.01 <0.01 <0.01

Perfluoro-n-dodecanoic acid (PFDoDA) µg/L 0.01 <0.01 <0.01 <0.01

Perfluoropentane sulfonic acid (PFPeS) µg/L 0.01 <0.01 <0.01 <0.01

Perfluoro-n-heptane sulfonic acid (PFHpS) µg/L 0.01 <0.01 <0.01 <0.01

Perfluoro-n-heptanoic acid (PFHpA) µg/L 0.01 <0.01 <0.01 <0.01

Perfluoro-n-hexanoic acid (PFHxA) µg/L 0.01 <0.01 <0.01 <0.01

Perfluoro-n-nonanoic acid (PFNA) µg/L 0.01 <0.01 <0.01 <0.01

Perfluorooctan esulfonamide (PFOSA) µg/L 0.05 <0.05 <0.05 <0.05

Perfluoro pentanoic acid (PFPeA) µg/L 0.01 <0.01 <0.01 <0.01

Perfluoro-n-tetradecanoic acid (PFTeDA) µg/L 0.01 <0.01 <0.01 <0.01

Perfluoro-n-tridecanoic acid (PFTriDA) µg/L 0.01 <0.01 <0.01 <0.01

Perfluoro-n-undecanoic acid (PFUnDA) µg/L 0.01 <0.01 <0.01 <0.01

2-(N-ethylperfluoro-1-octane sulfonamide)-ethanol µg/L 0.05 <0.05 <0.05 <0.05

2-(N-methylperfluoro-1-octane sulfonamide)-ethanol µg/L 0.05 <0.05 <0.05 <0.05

N-Ethyl perfluorooctane sulfonamidoacetic acid µg/L 0.05 <0.05 <0.05 <0.05

N-Methyl perfluorooctane sulfonamidoacetic acid µg/L 0.05 <0.05 <0.05 <0.05

1H.1H.2H.2H-perfluorohexanesulfonic acid (4:2 FTS) µg/L 0.01 <0.01 <0.01 <0.01

1H.1H.2H.2H-perfluorooctanesulfonic acid (6:2 FTS) µg/L 0.05 <0.05 <0.05 <0.05

1H.1H.2H.2H-perfluorodecanesulfonic acid (8:2 FTS) µg/L 0.01 <0.01 <0.01 <0.01

1H.1H.2H.2H-perfluorododecanesulfonic acid µg/L 0.01 <0.01 <0.01 <0.01

N-Ethylperfluoro-1-octane sulfonamide (N-EtFOSA) µg/L 0.05 <0.05 <0.05 <0.05

N-methylperfluoro-1-octane sulfonamide (N-MeFOSA) µg/L 0.05 <0.05 <0.05 <0.05

Page 32: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

5.1.2. Inter-Laboratory and Intra-Laboratory Duplicates

ITEM QUESTION YES NO (Comment

below)

1 Were an Adequate Number of inter-laboratory and inter-laboratory

duplicates analysed for each chemical?

2 Were RPDs within Control Limits?

< 30% for concentrations

Comments

The RPD results from the August 2018 biota sampling were considered acceptable and able to berelied on for the report.

Page 33: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

5.1.3. Trip Blanks

ITEM QUESTION YES NO (Comment

below)

1 Was a trip blank collected on for each batch of samples?

2 Were the Trip Blanks free of contaminants?

(If no, comment whether the contaminants present are also detected

in the samples and whether they are common laboratory chemicals.)

Comments

The trip blank results indicate that there is a low potential for cross contamination to have occurredduring sample transport.

5.1.4. Rinsate Blanks

ITEM QUESTION YES NO (Comment

below)

1 Were Equipment Rinsates collected and analysed every

day/event/equipment?

2 Were the Equipment Rinsates free of contaminants?

(If no, comment whether the contaminants present are also detected

in the samples and whether they are common laboratory chemicals.)

Comments

Rinsate samples were collected from the field equipment after decontamination. Equipment rinsatesamples were collected by pouring laboratory prepared deionised water over the equipment andcollecting the ‘rinse’ into sample containers.

The rinsate results indicated that the decontamination procedures were acceptable, and it isconsidered that there is a low potential for cross-contamination to have impacted on the laboratoryresults.

Page 34: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

In summary, the field QC results are considered generally acceptable for the purposes of thisinvestigation.

Field QA/QC was: Satisfactory

Partially Satisfactory

Unsatisfactory

5.2. Laboratory Quality Assurance Quality Control

5.2.1. Laboratories

ITEM QUESTION YES NO (Comment below)

1 Was a NATA registered laboratory used?

2 Did the laboratory perform the requested tests?

3 Were the laboratory methods adopted NATA endorsed?

4 Were the appropriate test procedures followed?

5 Were the reporting limits satisfactory?

6 Was the NATA Seal on the reports?

7 Were the reports signed by an authorised person?

Comments

Eurofins – Eurofins has been adopted as the primary laboratory for analysis of all matrices. Eurofins isa NATA accredited laboratory (NATA accreditation number 1261) for the media and analytes requiringanalysis.

Precision / Accuracy of the Laboratory Report Satisfactory

Partially Satisfactory

Unsatisfactory

Page 35: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

5.2.2. Sample Handling

ITEM QUESTION YES NO (Comment

below)

1 Were the sample holding times met?

2 Were the samples in proper custody between the field and reaching

the laboratory?

3 Were the samples properly and adequately preserved?

This includes keeping the samples chilled, where applicable.

4 Were the samples received by the laboratory in good condition?

Comments

Nil

Sample Handling was: Satisfactory

Partially Satisfactory

Unsatisfactory

5.2.3. Laboratory (Method) Blanks

The method blank allows assessment for potential method bias for relevant analytes. A method blankis the component of the analytical signal from each analytical method that is from laboratoryequipment (reagents, glassware and analytical instruments etc.). The method blank is determined bythe laboratories through running solvents and reagents in exactly the same manner as the samples.

At least one method blank should be run per 20 samples analysed, with a minimum of one methodblank per sample batch.

All laboratory method blank results reported concentrations of contaminants below the laboratoryreporting limits.

5.2.4. Laboratory Duplicates

To provide an estimate of the analysis method precision and duplicate sample heterogeneity, asample from the same batch is duplicated and analysed for a targeted analyte.

100% of internal laboratory duplicates analysed were within acceptable limits (<30% RPD).

Page 36: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

5.2.5. Laboratory Control Samples

Laboratory control samples are prepared in the laboratory and comprise either a known analyteconcentration within a proven matrix or a control matrix spiked with analytes representative of thetarget analyte. The laboratory control sample percent recovery is reported along with the primarysample data to assess method accuracy for all targeted analytes.

Laboratory control samples are required to be processed per 20 samples analysed, with a minimum ofone laboratory control sample run per batch of samples.

54 out of 56 (96.4%) of laboratory control sample analyses were within the acceptable range (>50%).

5.2.6. Matrix Spikes

A matrix spike is undertaken to document the effect of the matrix on the performance of the methodused. The matrix spike is the addition of a known analyte concentration to the target matrix prior toextraction or digestion. If a poor percentage recovery of a matrix spike is reported below the expectedanalytical method performance, the laboratory should investigate the likely cause. If, afterinvestigation, the poor matrix spike remains and is reported to the client, an explanation documentingthe limitations of the method for recovery of the target analyte from that particular matrix needs to beprovided. If the laboratory control sample recovery is acceptable for the same analyte, this mayindicate that it is the matrix causing the poor recovery and not the method.

82 out of 84 (98%) of matrix spike recoveries were within acceptable limits.

5.2.7. Surrogate Recoveries

Surrogate spikes are a means of the laboratory checking that no gross errors have taken placethroughout the analysis procedure, causing losses of the target analytes. The laboratory undertakessurrogate spikes by adding a known quantity of compounds with similar properties and behaviour tothe target compounds, but which are not expected to be found in field samples.

Surrogate spikes are only appropriate for organic analysis and are added to all samples beinganalysed prior to the extraction process. A percent recovery is calculated for each surrogate,providing the analytical method accuracy of extraction of the target analytes from samples.

The collated laboratory data for surrogate recoveries reported 109 surrogates (out of a total of 690surrogate analyses undertaken) outside acceptance targets. These discrepancies were for a numberof PFAS compounds, however only two of these discrepancies were for key compounds (one forPFOS and one for PFOA) indicating that the data set was acceptable for the purposes of supportingthe outcomes of the report.

5.2.8. Summary of Internal Laboratory Quality Control

A summary of the internal laboratory quality control results is provided in Table 4 and Table 5.

Page 37: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Appendix J – Data Validation

Table 10: Summary of Internal Laboratory Quality Control

ITEM QUESTION YES NO (Comment

above)

1 Were the laboratory blanks/reagents blanks free of contamination?

2 Were the spike recoveries within control limits?

3 Were the RPDs of the laboratory duplicates within control limits?

4 Were the surrogate recoveries within control limits?

Table 11: Summary of internal laboratory QC results

QC test Total Analyses Number outside of

Acceptable Criteria

% of analyses acceptable

Method Blanks 28 0 100%

Laboratory Duplicates 84 0 100%

Laboratory Control Samples 56 2 96.4%

Matrix Spikes 84 2 98%

Surrogates 690 109 (2 for PFOS,

PFOA or PFHxS)

84% (99%)

Totals 970 113 (6) 89% (99%)

The review of the laboratory internal quality control testing undertaken indicated that the overallcompleteness for the internal laboratory quality control results was 69.7%. However as most of thesurrogate outlies are not for key PFAS compounds and without the precursor and fluorotelemersurrogate outliers reported, over 99% of internal laboratory quality control results were acceptable.The data is therefore considered of an acceptable quality to use in the report.

Laboratory internal QA/QC was: Satisfactory

Partially Satisfactory

Unsatisfactory

5.3. Summary of August 2018 aquatic invertebrates,reptiles and mammals data quality review

In general, the data quality of the terrestrial invertebrate sampling was considered to be acceptable.Surrogate recoveries were poor for precursor compounds and fluorotelemers, but suitable for PFOSand PFOA, which are the compounds applied quantitatively in this risk assessment.

Page 38: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Ecological Risk AssessmentAugust 2018 SamplingQuality Control - RPDs

DoD, RAAF Base Tindal

Lab Report Number 612989 612989 612989 612989 612989 612989 612989 ES1824883 612989 ES1825854

Field ID0990_FH557_

1808150990_FH559_

180815 RPD0990_TV112_

1808140990_TV113_

180814 RPD0990_SD276

_1808140990_SD277

_180814 RPD0990_TV118_

1808150990_TV119_

180815 RPD0990_FH555_

1808150990_FH555_

180815 RPDSampled Date/Time 15/08/2018 15/08/2018 14/08/2018 14/08/2018 14/08/2018 14/08/2018 15/08/2018 15/08/2018 15/08/2018 15/08/2018

Chem_GroupChemName Units EQL

PFAS 2-(N-ethylperfluoro-1-octane sulfonamide)-ethanol µg/kg 0.5 (Primary): 2 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0 <0.5 <2.0 0 <0.5 <2.0 01H.1H.2H.2H-perfluorohexanesulfonic acid (4:2 FTS) µg/kg 0.5 (Primary): 2 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0 <0.5 <2.0 0 <0.5 <2.0 01H.1H.2H.2H-perfluorooctanesulfonic acid (6:2 FTS) µg/kg 0.5 (Primary): 2 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0 <0.5 <2.0 0 <0.5 <2.0 01H.1H.2H.2H-perfluorodecanesulfonic acid (8:2 FTS) µg/kg 0.5 (Primary): 2 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0 <0.5 <2.0 0 <0.5 <2.0 01H.1H.2H.2H-perfluorododecanesulfonic acid µg/kg 0.5 (Primary): 2 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0 <0.5 <2.0 0 <0.5 <2.0 0Perfluoro-n-octanoic acid (PFOA) µg/kg 0.5 (Primary): 1 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <1.0 0 <0.5 <1.0 0 <0.5 <1.0 0Perfluoro-n-hexane sulfonic acid (PFHxS) µg/kg 0.3 (Primary): 1 (Interlab) <0.3 <0.3 0 <0.3 <0.3 0 <0.3 <1.0 0 <0.3 <1.0 0 0.6 <1.0 0Perfluoro-n-octane sulfonic acid (PFOS) µg/kg 0.3 (Primary): 1 (Interlab) 12.0 16.0 29 <0.3 <0.3 0 <0.3 <1.0 0 <0.3 <1.0 0 14.0 13.0 7Perfluorobutane sulfonic acid (PFBS) µg/kg 0.5 (Primary): 1 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <1.0 0 <0.5 <1.0 0 <0.5 <1.0 0Perfluorobutanoic acid (PFBA) µg/kg 0.5 (Primary): 5 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <5.0 0 <0.5 <5.0 0 <0.5 <5.0 0Perfluoro-n-decane sulfonic acid (PFDS) µg/kg 0.5 (Primary): 2 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0 <0.5 <2.0 0 <0.5 <2.0 0Perfluoro-n-decanoic acid (PFDA) µg/kg 0.5 (Primary): 1 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <1.0 0 <0.5 <1.0 0 <0.5 <1.0 0Perfluoro-n-dodecanoic acid (PFDoDA) µg/kg 0.5 (Primary): 2 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0 <0.5 <2.0 0 <0.5 <2.0 0Perfluoro-n-heptane sulfonic acid (PFHpS) µg/kg 0.5 (Primary): 1 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <1.0 0 <0.5 <1.0 0 <0.5 <1.0 0Perfluoro-n-heptanoic acid (PFHpA) µg/kg 0.5 (Primary): 1 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <1.0 0 <0.5 <1.0 0 <0.5 <1.0 0Perfluoro-n-hexanoic acid (PFHxA) µg/kg 0.5 (Primary): 1 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <1.0 0 <0.5 <1.0 0 <0.5 <1.0 0Perfluoro-n-nonanoic acid (PFNA) µg/kg 0.5 (Primary): 1 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <1.0 0 <0.5 <1.0 0 <0.5 <1.0 0Perfluorooctan esulfonamide (PFOSA) µg/kg 0.5 (Primary): 5 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <5.0 0 <0.5 <5.0 0 <0.5 <5.0 0Perfluoro pentanoic acid (PFPeA) µg/kg 0.5 (Primary): 2 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0 <0.5 <2.0 0 <0.5 <2.0 0Perfluoro-n-tetradecanoic acid (PFTeDA) µg/kg 0.5 (Primary): 2 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0 <0.5 <2.0 0 <0.5 <2.0 0Perfluoro-n-tridecanoic acid (PFTriDA) µg/kg 0.5 (Primary): 2 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0 <0.5 <2.0 0 <0.5 <2.0 0Perfluoro-n-undecanoic acid (PFUnDA) µg/kg 0.5 (Primary): 1 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <1.0 0 <0.5 <1.0 0 <0.5 <1.0 0N-Ethyl perfluorooctane sulfonamidoacetic acid µg/kg 0.5 (Primary): 1 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <1.0 0 <0.5 <1.0 0 <0.5 <1.0 0N-Methyl perfluorooctane sulfonamidoacetic acid µg/kg 0.5 (Primary): 1 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <1.0 0 <0.5 <1.0 0 <0.5 <1.0 0N-Ethylperfluoro-1-octane sulfonamide (N-EtFOSA) µg/kg 0.5 (Primary): 2 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0 <0.5 <2.0 0 <0.5 <2.0 0N-methylperfluoro-1-octane sulfonamide (N-MeFOSA) µg/kg 0.5 (Primary): 5 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <5.0 0 <0.5 <5.0 0 <0.5 <5.0 0Perfluoropentane sulfonic acid (PFPeS) µg/kg 0.5 (Primary): 1 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <1.0 0 <0.5 <1.0 0 <0.5 <1.0 0N-Me perfluorooctanesulfonamid oethanol µg/kg 0.5 (Primary): 2 (Interlab) <0.5 <0.5 0 <0.5 <0.5 0 <0.5 <2.0 0 <0.5 <2.0 0

*RPDs have only been considered where a concentration is greater than 0 times the EQL.**High RPDs are in bold (Acceptable RPDs for each EQL multiplier range are: 50 (0-10 x EQL); 50 (10-20 x EQL); 30 ( > 20 x EQL) )***Interlab Duplicates are matched on a per compound basis as methods vary between laboratories. Any methods in the row header relate to those used in the primary laboratory

Page 39: Appendix J - Data Validation - Department of Defence€¦ · Appendix J – Data Validation Quality objectives 6. Specify performance of acceptance criteria The assessment as a whole

Ecological Risk AssessmentAugust 2018 SamplingQuality Control - Blanks

DoD, RAAF Base Tindal

Lab Report Number 612989 612989 612989Field ID 0990_QC300_180815 0990_QC301_180815 0990_QC302_180815Sampled_Date/Time 15/08/2018 15/08/2018 15/08/2018Sample Type Rinsate Trip_B Trip_B

Chem_Group ChemName Units EQL

PFAS 2-(N-ethylperfluoro-1-octane sulfonamide)-ethanol µg/L 0.05 <0.05 <0.05 <0.051H.1H.2H.2H-perfluorohexanesulfonic acid (4:2 FTS) µg/L 0.01 <0.01 <0.01 <0.011H.1H.2H.2H-perfluorooctanesulfonic acid (6:2 FTS) µg/L 0.05 <0.05 <0.05 <0.051H.1H.2H.2H-perfluorodecanesulfonic acid (8:2 FTS) µg/L 0.01 <0.01 <0.01 <0.011H.1H.2H.2H-perfluorododecanesulfonic acid µg/L 0.01 <0.01 <0.01 <0.01Perfluoro-n-octanoic acid (PFOA) µg/L 0.01 <0.01 <0.01 <0.01Perfluoro-n-hexane sulfonic acid (PFHxS) µg/L 0.01 <0.01 <0.01 <0.01Perfluoro-n-octane sulfonic acid (PFOS) µg/L 0.01 <0.01 <0.01 <0.01Perfluorobutane sulfonic acid (PFBS) µg/L 0.01 <0.01 <0.01 <0.01Perfluorobutanoic acid (PFBA) µg/L 0.05 <0.05 <0.05 <0.05Perfluoro-n-decane sulfonic acid (PFDS) µg/L 0.01 <0.01 <0.01 <0.01Perfluoro-n-decanoic acid (PFDA) µg/L 0.01 <0.01 <0.01 <0.01Perfluoro-n-dodecanoic acid (PFDoDA) µg/L 0.01 <0.01 <0.01 <0.01Perfluoro-n-heptane sulfonic acid (PFHpS) µg/L 0.01 <0.01 <0.01 <0.01Perfluoro-n-heptanoic acid (PFHpA) µg/L 0.01 <0.01 <0.01 <0.01Perfluoro-n-hexanoic acid (PFHxA) µg/L 0.01 <0.01 <0.01 <0.01Perfluoro-n-nonanoic acid (PFNA) µg/L 0.01 <0.01 <0.01 <0.01Perfluorooctan esulfonamide (PFOSA) µg/L 0.05 <0.05 <0.05 <0.05Perfluoro pentanoic acid (PFPeA) µg/L 0.01 <0.01 <0.01 <0.01Perfluoro-n-tetradecanoic acid (PFTeDA) µg/L 0.01 <0.01 <0.01 <0.01Perfluoro-n-tridecanoic acid (PFTriDA) µg/L 0.01 <0.01 <0.01 <0.01Perfluoro-n-undecanoic acid (PFUnDA) µg/L 0.01 <0.01 <0.01 <0.01N-Ethyl perfluorooctane sulfonamidoacetic acid µg/L 0.05 <0.05 <0.05 <0.05N-Methyl perfluorooctane sulfonamidoacetic acid µg/L 0.05 <0.05 <0.05 <0.05N-Ethylperfluoro-1-octane sulfonamide (N-EtFOSA) µg/L 0.05 <0.05 <0.05 <0.05N-methylperfluoro-1-octane sulfonamide (N-MeFOSA) µg/L 0.05 <0.05 <0.05 <0.05PFHxS and PFOS (Sum of Total) µg/L 0.01 <0.01 <0.01 <0.01Perfluoropentane sulfonic acid (PFPeS) µg/L 0.01 <0.01 <0.01 <0.01N-Me perfluorooctanesulfonamid oethanol µg/L 0.05 <0.05 <0.05 <0.05Sum of PFAS µg/L 0.1 <0.1 <0.1 <0.1Sum of PFAS (WA DER List) µg/L 0.05 <0.05 <0.05 <0.05