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  • www.crccare.com

    Cooperative Research Centre for Contamination Assessment and Remediation of the Environment

    Assessment, management and remediation for PFOS and PFOAPart 4: application of HSLs and ESLs

    TEcHnicAL REPORT nO. 38

  • Cooperative Research Centre for Contamination Assessment and Remediation of the Environment, Technical Report series, no. 38 January 2017 Copyright CRC CARE Pty Ltd, 2017 This book is copyright. Except as permitted under the Australian Copyright Act 1968 (Commonwealth) and subsequent amendments, no part of this publication may be reproduced, stored or transmitted in any form or by any means, electronic or otherwise, without the specific written permission of the copyright owner. ISBN: 978-1-921431-56-2

    Enquiries and additional copies: CRC CARE, C/- Newcastle University LPO, PO Box 18, Callaghan NSW, Australia 2308 Tel: +61 (0) 2 4985 4941 Fax: +61 (0) 8 8302 3124 admin@crccare.com www.crccare.com

    This report should be cited as: CRC CARE 2017, Assessment, management and remediation guidance for perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) Part 4: application of HSLs and ESLs, CRC CARE Technical Report no. 38, CRC for Contamination Assessment and Remediation of the Environment, Newcastle, Australia.

    Disclaimer: This publication is provided for the purpose of disseminating information relating to scientific and technical matters. Participating organisations of CRC CARE do not accept liability for any loss and/or damage, including financial loss, resulting from the reliance upon any information, advice or recommendations contained in this publication. The contents of this publication should not necessarily be taken to represent the views of the participating organisations.

  • CRC for Contamination Assessment and Remediation of the Environment

    Technical Report no. 38d

    Assessment, management and remediation guidance

    for perfluorooctanesulfonate (PFOS) and

    perfluorooctanoic acid (PFOA)

    Part 4 application of HSLs and ESLs

    March 2017

  • CRC CARE Technical Report no. 38d i

    Assessment, management and remediation guidance for PFOS and PFOA. Part 4 appliation of HSLs and ESLs

    Important note to readers

    This guidance is to be regarded as both draft and interim, particularly in relation to

    health based screening values.

    The following caveats and limitations apply to this guidance:

    the health based values in this guidance are based on the interim TDI values

    endorsed by enHealth in 2016 for PFOS (+PFHxS) and PFOA, and

    should revised TDI values be endorsed by enHealth or another major national

    health based agency in Australia, then the health derived values in this guidance

    will be updated accordingly, and the guidance re-issued.

    It is recognised that there is much on-going research on the impacts of PFOS and

    PFOA on human health and the environment, the outcomes of which may improve the

    assessment, remediation and management of PFOS and PFOA. These developments

    will be monitored and this guidance will be updated, as appropriate.

    It is also recognised that PFAS compounds other than PFOS and PFOA may

    contribute to the impacts of PFAS on human health and the environment. When further

    research results for other PFAS compounds (or classes thereof) of sufficient

    robustness to be utilised in the formulation of guidance for those compounds (or

    classes thereof) become available, then that information will be used to extend the

    scope of this guidance.

    This guidance should therefore be regarded as both draft and interim.

    March 2017

  • CRC CARE Technical Report no. 38d ii

    Assessment, management and remediation guidance for PFOS and PFOA. Part 4 appliation of HSLs and ESLs

    Preamble

    CRC CARE has milestones in its Agreement with the Commonwealth Government

    relating to the development of guidance for contaminants of emerging concern in

    collaboration with end users. Priority contaminants were identified for CRC CARE

    through regulators and end users who met at a Forum held in February 2012. These

    contaminants included perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid

    (PFOA), which belong to a large group of compounds called per- and polyfluoroalkyl

    substances (PFAS). CRC CARE has undertaken the development of human health

    screening levels (HSLs) and ecological screening levels (ESLs) for PFOS and PFOA;

    these values provide a collective view of the available science and application of

    Australian approaches on the development of human health and ecological based

    screening levels

    The derivation of the HSLs and ESLs has followed the methodologies outlined in the

    National Environment Protection (Assessment of Site Contamination) Measure 1999

    (NEPM), as revised in 2013. HSLs and ESLs are subject to the assumptions,

    uncertainties and limitations outlined in the relevant parts of the guidance deviations

    from the assumptions used in their derivation may mean that a site specific

    assessment would be required. Further, HSLs for some exposures are calculated using

    a 100% relative source contribution. If more than one of these sources is relevant, use

    of the screening values would underestimate risks, and in this case, cumulative

    assessment of all relevant exposures must be made.

    The NEPM emphasises the importance of formulating a conceptual site model on

    which to base the assessment of soil and groundwater contamination, and guidance

    has been provided on the development of a conceptual site model for PFOS

    and PFOA.

    It is intended that the HSLs and ESLs that have been developed for PFOS and PFOA

    should be considered similarly to the NEPM HILs/HSLs and EILs/ESLs in forming

    generic screening levels which, if exceeded, would indicate that further more detailed

    investigation is required. The HSLs and ESLs and the information used in their

    derivation can assist in undertaking this more detailed investigation.

    It is emphasised that exceedance of the HSLs and ESLs does not necessarily imply

    that the contamination poses an unacceptable risk, and the HSLs and ESLs should not

    be used as remediation targets, as this could result in unnecessary remediation.

    The following limitations should be noted:

    The assessment and management of PFAS contamination in soil and groundwater

    is an emerging science in Australia and internationally and significant work

    continues to be undertaken. It is recommended that when using this guideline,

    more recent information is considered.

    Uncertainties and limitations in the guidance values and their application are noted

    in the guidance document, and these should be considered when using the values.

    Some of the screening levels have assumed the occurrence of bioaccumulation

    and biomagnification based on international work - there is uncertainty as to the

    levels that will occur in Australian organisms. Where significant exceedances of

    HSLs and ESLs occur, consideration should be given to direct monitoring of

  • CRC CARE Technical Report no. 38d iii

    Assessment, management and remediation guidance for PFOS and PFOA. Part 4 appliation of HSLs and ESLs

    potentially affected organisms to determine if there are effects that can be

    distinguished. Further assessment would be would be required where

    bioaccumulation is an issue.

    This review has focussed on PFOS and PFOA. PFAS include a large number of

    compounds and analytical methods are reporting an increasing number of PFAS

    compounds. As this guidance document was being finalised, enHealth (2016) has

    advised that perfluorohexane sulfonate (PFHxS) should be considered to be

    additive to PFOS, The use of the HSLs and ESLs for PFOS and PFOA should

    recognise that other PFAS may contribute to potential effects and where present,

    these will need to be evaluated for potential cumulative risks in accordance with

    available information.

    Because of the evolving nature of the science relating to PFAS, these guidelines are

    considered to be Interim Guidance, and it is recommended that a review of this

    guidance is considered following any change in recommendation by enHealth or

    FSANZ.

    This guidance is intended for a variety of users within the contaminated sites industry,

    including site owners, proponents of works, contaminated land professionals, and

    regulators. It is assumed that readers are familiar with the NEPM 2013. While the aim

    of this guideline is to provide a resource that can be used at PFAS-contaminated sites

    across Australia, it does not replace specific laws, regulations and guidance provided

    at a local level.

  • CRC CARE Technical Report no. 38d iv

    Assessment, management and remediation guidance for PFOS and PFOA. Part 4 appliation of HSLs and ESLs

    Abbreviations

    CSM Conceptual site model

    CRC CARE Cooperative Research Centre for Contamination

    Assessment and Remediation of the Environment

    ESL Ecological screening levels

    HSL Health screening levels

    NEPM National Environment Protection (Assessment of Site

    Contamination) Measure 1999, as revised in 2013

    PFAS Per- and polyfluoroalkyl substances

    PFHxS perfluorohexane sulfonate

    PFOA Perfluorooctanoic acid

    PFOS Perfluorooctane sulfonate

  • CRC CARE Technical Report no. 38d v

    Assessment, management and remediation guidance for PFOS and PFOA. Part 4 appliation of HSLs and ESLs

    Table of contents

    Executive summary i

    1. Introduction 1

    1.1 Framework for assessing contaminated sites 2

    1.2 Site investigation 2

    1.3 Sampling and analytical methods and considerations 2

    1.3.1 Sample collection 2

    1.3.2 Laboratory analysis of soil and water samples 3

    1.4 Developing the conceptual site model 4

    2. Health screening level (HSLs) 8

    2.1 Soil HSLs 8

    2.2 Groundwater HSLs 9

    2.3 Water and sediment (human consumption of seafood) HSLs 11

    2.3.1 Multiple pathway exposure and cumulative risk 12

    3. Ecological screening levels (ESLs) 13

    3.1 Freshwater ecosystem ESLs 13

    3.2 Marine ecosystem ESLs 13

    3.3 Terrestrial ecosystem ESLs 13

    3.4 Considerations in the application of ESLs 14

    4. References 16

  • CRC CARE Technical Report no. 38d vi

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    Tables

    Table 1. Summary of soil HSLs for PFOS and PFOA (mg/kg) 8

    Table 2. Considerations in the application of soil HSLs 9

    Table 3. Summary of groundwater HSLs for PFOS and PFOA 10

    Table 4. Considerations in the application of groundwater HSLs for

    PFOS and PFOA

    10

    Table 5. Summary of derived surface water and sediment HSLs for

    PFOS and PFOA

    11

    Table 6. Considerations in application of surface water and sediment

    consumption of fish HSLs for PFOS and PFOA

    11

    Table 7. Default guidelines for PFOS and PFOA 13

    Table 8. Marine ESLs for fresh PFOS and PFOA 13

    Table 9. ESLs values for fresh PFOS and PFOA in soils 13

    Table 10. Considerations in the application of ESLs 14

    Figures

    Figure 1. Inputs to a site specific CSM 6

    Figure 2. Example CSM for PFAS-contaminated media 7

  • CRC CARE Technical Report no. 38d 1

    Assessment, management and remediation guidance for PFOS and PFOA. Part 4 appliation of HSLs and ESLs

    1. Introduction

    Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have been

    identified as contaminants of emerging concern in Australia. These contaminants

    belong to the broad group of chemicals referred to as per- and poly-fluoroalkyl

    substances (PFAS).

    PFAS are highly persistent and potentially toxic to humans and the environment, and

    some are bioaccumulative. PFOS and PFOA are considered to be the most widely

    studied of the PFAS due to historical production and in terms of breakdown of

    precursor compounds. PFAS have been detected at concentrations of potential

    concern at a number of sites, particularly where there has been use of firefighting

    foams. Industry and public awareness of the presence of PFOS and PFOA, is growing

    rapidly. Reporting of PFOS contamination problems in the media has raised particular

    concern regarding the risk that the contamination poses to the health of exposed

    persons and the environment.

    In general, there is limited information on the occurrence, fate and toxicity of PFAS in

    the Australian environment. Australian screening levels for protecting human health

    and ecological systems are needed to assess the level of risk that the contamination

    poses.

    The Cooperative Research Centre for Contamination Assessment and Remediation of

    the Environment (CRC CARE) has developed human health and ecological screening

    levels (HSLs and ESLs) for PFOS and PFOA in soil, marine waters, groundwater and

    sediment, following the approach provided in the National Environment Protection

    (Assessment of Site Contamination) Measure 1999, as amended in 2013 (NEPM)

    (NEPC, 2013) and Australian Drinking Water Guidelines (NHMRC 2011), and provides

    information on the application of these screening levels. This guidance provides a

    practicable approach to the risk-based assessment, management and remediation of

    PFAS contamination. It comprises five stand-alone sections:

    Part 1: Background

    Part 2: Human health screening levels

    Part 3: Ecological screening levels

    Part 4: Application of human health and ecological screening levels (this

    report)

    Part 5: Risk based management and remediation of PFOS and PFOA

    This section, part 4, is an application document which provides a summary of the HSLs

    and ESLs, and considerations on how to apply them in the assessment of PFOS and

    PFOA contaminated soils, sediments and waters. It is strongly recommended that

    part 4 is read in conjunction with part 2 and part 3 of the guidance document, as these

    sections provide the background information, rationale and derivation of the screening

    levels.

  • CRC CARE Technical Report no. 38d 2

    Assessment, management and remediation guidance for PFOS and PFOA. Part 4 appliation of HSLs and ESLs

    1.1 Framework for assessing contaminated sites

    The process for the assessment of PFAS-contaminated sites should follow that

    outlined in the NEPM, which is recognised as the primary national guidance document

    for the assessment of site contamination in Australia.

    The NEPM includes two schedules:

    Schedule A provides a general process for assessment of site contamination, and

    Schedule B of the NEPM comprises 10 technical guidelines about site

    assessment, screening levels, site investigations, laboratory analyses, human

    health and ecological risk assessment, groundwater assessment, community

    consultation, consultants and auditors, and health and safety.

    Schedule A is of particular importance when making decisions as to the appropriate

    investigation and management of PFAS-contaminated sites. It is important this work is

    conducted by persons with a thorough understanding of contaminated site assessment

    and management, particularly with respect to PFAS.

    1.2 Site investigation

    The first step towards developing a management strategy for a PFAS-contaminated

    site is in understanding the extent and magnitude of contamination, and is a key step in

    site characterisation.

    Soil, sediment, surface water or groundwater sampling (as appropriate) and laboratory

    analysis is essential in delineating the extent and magnitude of the problem, and hence

    associated risks. As far as is practicable, sampling should be representative of the

    system being investigated. Sampling is likely to be an iterative process, commencing

    with a high level, preliminary sampling program and becoming more specific as the

    extent and magnitude of contamination is better understood.

    Schedule B2 of the NEPM provides detailed information on the design and

    implementation of a sampling and analysis plan.

    1.3 Sampling and analytical methods and considerations

    1.3.1 Sample collection

    Because of the unique chemical properties of PFOS and PFOA, consideration must be

    given to the low flow groundwater sampling setups which has been shown to leach

    long chain PFAS can adsorb to the surfaces of sample equipment (CONCAWE 2016).

    Additionally, it is recommended that Teflon-containing materials are avoided as a

    precautionary measure (ALS 2013, CONCAWE 2016). The implications of using

    Teflon-containing materials during sampling warrants further investigation, as it is

    currently unclear the extent to which, if any, cross contamination may occur. The effect

    of leaching from sampling materials or sample storage vessels on sample

    concentrations can become particularly important when working at the very low

    concentrations indicated by the fresh water ESLs and HSLs.

  • CRC CARE Technical Report no. 38d 3

    Assessment, management and remediation guidance for PFOS and PFOA. Part 4 appliation of HSLs and ESLs

    With respect to groundwater samples, if these are not filtered (investigation wells tend

    to draw in more sediments than wells constructed for other uses), consideration should

    be given to the sediment load in the sample and the possible effect on the measured

    PFOS and PFOA concentrations, as significant PFOS and PFOA may have adsorbed

    to the sediment material. It is important to take into consideration the quality of the

    water to which the receptor would actually be exposed.

    It may be useful to also include any supplementary information that could assist in

    understanding transformation rates of precursors to PFOS and PFOA, if possible (e.g.

    anaerobic/aerobic conditions may be a factor however the extent to which they affect

    transformation in real conditions is less understood at this time (Houtz et al. 2013).

    International studies have found some success with passive sampling of PFAS in water

    using a modified polar organic chemical integrative sampler (POCIS), although uptake

    and hence the reported concentration can be affected by water flow rate

    (Karsenzon et al. 2013). Passive sampling has not yet been widely implemented in

    Australia.

    1.3.2 Laboratory analysis of soil and water samples

    Internationally there are a range of standard methods utilised for the analysis of PFAS,

    mostly based on liquid chromatography with a tandem MS/MS detector

    (CONCAWE 2016).

    The National Measurement Institute (NMI) conducted a pilot proficiency study in 2015

    to compare the performances of 11 laboratories, evaluate their test methods, and

    assess their accuracy in measuring total and linear PFOS and PFOA in soil and water

    matrices. Nine of the laboratories used a detection method of LC-MS/MS, but a variety

    of extraction methods were adopted. There was no correlation found between results

    and method. Results varied between individual samples, and between laboratories. A

    spiked water sample with a PFOS concentration of 3.2 g/L resulted in a maximum

    concentration detected of 5.7 g/L and a minimum concentration of 2.3 g/L. The

    results of a water sample spiked with 3.7 g/L of PFOA resulted in a maximum

    concentration detected of 8.7 g/L and a minimum concentration of 3.4 g/L. Water

    was sampled from a contaminated site and the results for the PFOS concentration

    were reported ranging from 0.001 to 0.0031 g/L and PFOA from 0.0036 to 0.0040

    g/L with some laboratories reporting non detected with a detection limit of 1 g/L.

    Spiked soil concentrations also showed variability, with soil spiked with 8.6 g/kg PFOS

    showing a range of 5 to 18 g/kg and soil spiked with 251 g/kg PFOS showing a

    range of 163 to 352 g/kg. Soil spiked with PFOA also showed a similar range of

    detections with a spike of 8.9 g/kg recorded from 5.4 to 20 g/kg (NMI 2015).

    Laboratories were requested to report a measure of uncertainty for results, which

    ranged between 0.9% and 100% of the reported value (NMI 2015).

    From this it is evident there is variability in the analytical results reported for PFOS and

    PFOA within, and between laboratories in Australia. NMI noted, however, that the

    performance of laboratories was similar to that observed in other NMI pilot trials for

    organic pollutants1. It has been hypothesised that the variability observed in PFOS

    results may in part be due to some laboratories using linear standards, and others

    using mixed standards (i.e. linear and branched) for PFOS (ALS 2015). This is being

    1 End user discussion, held by NMI across Australia on 14 August 2015

  • CRC CARE Technical Report no. 38d 4

    Assessment, management and remediation guidance for PFOS and PFOA. Part 4 appliation of HSLs and ESLs

    further investigated, and NMI has recommended further studies. The variability could

    also in part be due to the low levels being analysed.

    A second proficiency testing study on the analysis of PFOS and PFOA in soil, water

    and fish was conducted in June 2016 with 26 laboratories (NMI 2016). The data from

    both proficiency testing studies show a wide variety of results for the same sample,

    therefore it is important to understand what is being reported. The 2016 participants

    reported up to 72% of the reported value. A variety of methods for extraction were

    used, with no correlation between results and method the analytical detection method

    used was LCMS/MS.

    The results reported by different laboratories also showed a variety of detection limits,

    particularly with the water samples. In many cases the detection limits were above

    drinking water/groundwater guidelines commonly used at the time of testing. When

    detection limits exceed screening levels it is necessary to err on the side of caution and

    assume the screening level is exceeded, thus resulting in the requirement of

    management actions when they may not be necessary. For example, the typical

    detection limit for PFOS in water can be 100 ng/L, which is greater than the

    concentration of interest when evaluating fish uptake and suitability for human

    consumption. In such a situation requesting a trace method of analysis may be able to

    reduce the detection limit to less than 1 ng/L (perhaps to 0.2 ng/L). Therefore, when

    requesting analysis of PFOS and PFOA in soil and water the following should be

    included on the chain of custody form:

    Request for the uncertainty estimate (if this is not requested the laboratory is not

    required to provide it)

    Request that the method of analysis is reported for ease of comparison of results,

    and

    Request an appropriate detection limit that will allow the sample to be compared to

    screening levels.

    With respect to interpreting laboratory analytical results for PFOS and PFOA-

    contaminated soil, sediment and water samples, it is important to be aware of the

    possible uncertainty range in results reported, particularly when concentrations are

    reported of similar magnitude to the HSLs or ESLs. Undertaking sufficient quality

    assurance/quality control sampling, such as collection of samples for interlaboratory

    analysis is important in evaluating the accuracy of analytical results.

    1.4 Developing the conceptual site model

    Schedule B2 of the NEPM provides information on the development of a conceptual

    site model (CSM). Development of a site-specific CSM is an iterative process, with the

    complexity of the CSM corresponding to the scale and complexity of the known or

    potential impacts. As more information is gathered about a site and the contamination,

    the CSM can be further refined to allow remediation and management actions to be

    defined that are commensurate with the scale of the problem and are most cost

    effective.

    The essential elements of a CSM are outlined in section 4.3 of Schedule B2 of the

    NEPM. Briefly these include:

  • CRC CARE Technical Report no. 38d 5

    Assessment, management and remediation guidance for PFOS and PFOA. Part 4 appliation of HSLs and ESLs

    Known and potential sources of contamination and contaminants of concern and

    precursors, including the mechanism of contamination (e.g. surface spill top down

    which is most commonly the case for PFAS-contaminated sites, or a subsurface

    release such as from a corroded pipe).

    The media contaminated (e.g. soil, groundwater, surface water, sediments, and

    air).

    Potential human and ecological receptors, such as site works or the general public,

    users of groundwater at or removed from the site, and terrestrial and surface water

    ecological receptors.

    Potential exposure pathways, how humans or ecological receptors may become

    exposed to PFAS (e.g. direct contact through handling contaminated soil, ingestion

    of contaminated soil/dust, surface water runoff or contaminated groundwater

    discharge to surface water bodies). Once current and potential future exposure

    pathways have been identified it needs to be determined whether the pathways

    are complete (refer to NEPM schedule B6). If a pathway is incomplete the risk to

    receptors may be low despite the presence of contamination.

    In developing and refining the CSM it is important to ensure that the available data are

    representative (i.e. provides an accurate picture of the contamination, without biasing

    high or low), and to understand where variability and uncertainty may lie (is the extent

    and magnitude of contamination sufficiently well defined), and the significance of data

    gaps.

    Further detail regarding aspects to be considered when developing a site-specific CSM

    for PFOS- and PFOA- contaminated sites is provided in part 1 and part 5 of this

    guidance document. A brief summary of aspects to consider is provided in figure 1, and

    an example CSM is provided in figure 2.

    Because of the persistence and bioaccumulative properties of PFOS and PFOA, the

    CSM will need to consider scenarios and pathways that may not be normally

    considered for other contaminants. Example pathways that may need to be examined

    include:

    Leaching from soil to groundwater

    Groundwater discharge into surface water bodies

    Adsorption onto and leaching from sediments

    Bioaccumulation/biomagnification through the food chain, particularly in seafood

    Discharge to the sewerage system, with potential for accumulation in biosolids and

    discharge in the treated effluent

    Irrigation with uptake by plants, and possible accumulation in soil

    Ingestion of contaminated plant material and soil by livestock during grazing

    Uptake by garden produce and ingestion by persons or animals

    Consumption by persons of meat and animal products (e.g. milk and eggs), and

    Consumption of breast milk by infants.

    This list is by no means exhaustive, and each site will need to be evaluated on a case

    by case basis. A discussion on how these aspects should be considered in the

    application of the HSLs and ESLs is provided in section 2 and section 3 respectively.

    Further detail is provided in part 2 and part 3 of the guidance.

  • CRC CARE Technical Report no. 38d 6

    Assessment, management and remediation guidance for PFOS and PFOA. Part 4 appliation of HSLs and ESLs

    Figure 1 Inputs to a site specific CSM

  • CRC CARE Technical Report no. 38d 7

    Assessment, management and remediation guidance for PFOS and PFOA. Part 4 appliation of HSLs and ESLs

    Figure 2 Example CSM for PFAS-contaminated media

  • CRC CARE Technical Report no. 38d 8

    Assessment, management and remediation guidance for PFOS and PFOA. Part 4 appliation of HSLs and ESLs

    2. Health screening level (HSLs)

    The background information and derivation of HSLs is provided in part 2 of this

    guidance document. This section provides a brief summary of the land and

    groundwater use scenarios, potential receptors, and the HSLs. The limitations of the

    HSLs and receptor populations for which HSLs have not been developed but that

    require consideration are also discussed. For a discussion about the derivation and

    limitations of these screening levels, refer to part 2.

    2.1 Soil HSLs

    Consistent with the NEPM, HSLs have been developed for four land use scenarios,

    summarised in table 1.

    Table 1 Summary of soil HSLs for PFOS and PFOA (mg/kg)

    Land use PFOS

    (+PFHxS) PFOA

    Low density residential (HSL-A) Residential scenario with garden/accessible soil (home-grown produce

  • CRC CARE Technical Report no. 38d 9

    Assessment, management and remediation guidance for PFOS and PFOA. Part 4 appliation of HSLs and ESLs

    Table 2 Considerations in the application of soil HSLs

    Aspect Commentary

    Consumption of home grown garden produce

    Although the uptake of PFOS and PFOA by garden produce may occur, and be significant, it is difficult to derive a generalised screening criterion. The likelihood of this exposure pathway should be reviewed on a site-specific basis, and direct sampling of plants may be required.

    Protection of groundwater/surface water quality

    Leaching of PFOS and PFOA from contaminated soils to groundwater systems frequently occurs. The soil HSLs do not account for the leaching potential of PFOS and PFOA, as attempting to predict the groundwater concentrations that will arise from soil contamination is highly complex and site specific. Where groundwater contamination has occurred, direct measure of groundwater concentrations should be undertaken, and compared against the relevant groundwater HSLs. Additionally, leaching potential of PFAS from soil samples may be tested using the Australian Standard Leaching Procedure (ASLP) test (Australian Standard 4439). This test measures how much of a chemical can move from soil into water using conditions similar to rain events. Other types of leaching tests are available which are designed to be used to evaluate leaching in landfills under more extreme conditions and are less relevant for the initial screening of these sites. The trigger points in leachate as measured in an ASLP test should consider the dilution that will occur as the leachate moves from the soil into the underlying groundwater; this will depend on the relative rates of rainfall and groundwater movement, absorption in the soil, local concentration in groundwater, and the depth of groundwater into which the leachate mixes. Note US EPA recommend a default factor of 20. (Reference should be made to the relevant jurisdiction which may have specific requirements for the protection of groundwater/surface water quality)

    Sensitive receptors in commercial properties

    For commercial properties an adult worker has been identified as the primary receptor. It is assumed that the public, including children would visit commercial properties for short periods only, and hence the risk to the public would be less than for workers present at the site on a full-time basis. The commercial/industrial HSLs may not adequately protective of more sensitive land uses that may be permissible under commercial/industrial zoning in some jurisdictions (e.g. schools, childcare centres, health care facilities, nursing homes, hospitals). If such developments are present or proposed, consideration should be given to more conservative screening levels (i.e. HSL-A) or a site-specific risk assessment. Occupational exposures may be best addressed separately.

    Open grounds Given that PFAS chemicals are non-volatile, exposure is limited to direct contact with soil contamination. Vapour intrusion is not a significant factor in exposure and therefore the presence of buildings is not a limitation in the use of industrial/commercial HSLs. Industrial properties such as fire training grounds should still be based on commercial/industrial screening levels (HSL-D) provided access by the general public is prohibited.

    Agriculture and grazing

    A site specific assessment may be required which could include sampling of crops and biota.

    2.2 Groundwater HSLs

    Potential beneficial uses of groundwater and HSLs (where derived) are provided in

    table 3, and considerations for their application are detailed in table 4. Note the

    relevant beneficial uses of groundwater that require consideration differs between

    jurisdictions and local regulations and guidelines should be consulted.

  • CRC CARE Technical Report no. 38d 10

    Assessment, management and remediation guidance for PFOS and PFOA. Part 4 appliation of HSLs and ESLs

    In its June 2016 statement, enHealth recommended drinking water guidelines of

    0.5 g/L and 5 g/L for PFOS (+PFHxS) and PFOA respectively, based on 10% of the

    EFSA (2008) tolerable daily intake allocated to drinking water.

    Table 3 Summary of groundwater HSLs for PFOS and PFOA

    Groundwater beneficial use PFOS (+PFHxS) PFOA

    Drinking water 0.5 g/L* 5 g/L *

    Primary contact recreation 5 g/L* 50 g/L *

    Stock water Not derived Not derived

    Irrigation/agriculture Not derived Not derived

    Maintenance of ecosystems (marine)

    Refer ESLs Refer ESLs

    Aquaculture (fresh water) 21 ng/L (refer to section 2.3) 210 ng/L (refer to section 2.3) * Based on enHealth (2016) interim drinking water quality guideline

    Table 4 Considerations in the application of groundwater HSLs for PFOS and PFOA

    Groundwater beneficial use

    Commentary and considerations

    Drinking water Drinking water quality guidelines presented by enHealth (2016) apply to all sources of drinking water, including extracted groundwater.

    Primary contact recreation

    NHMRC 2008 specifies that it may be appropriate to apply a factor for 10 to drinking water standards to account for limited ingestion of recreational waters during swimming activities. Recreational water quality guideline presented by enHealth (2016) has adopted this approach.

    Stock water for protection of animal products (milk, meat, eggs)

    PFOS and PFOA can biomagnify in the food chain to varying extents. Limited data and information on this issue makes the derivation of a screening level that will avoid contamination of food products difficult. Drinking water HSLs do not apply (an important consideration is that water ingestion rates differ for animals).

    Assessment on a site-specific basis may include direct sampling of PFOS and PFOA in animal products where animals have been exposed through drinking contaminated water.

    Irrigation/agriculture

    Uptake of PFOS and PFOA by plants is possible, however this is highly variable and a screening level for irrigation and protection of agricultural products has not been derived. Drinking water HSLs do not apply.

    Assessment required on a site-specific basis, and may include direct sampling of PFOS and PFOA in flora and biota.

    Consumption of seafood

    Assessment of groundwater impact on surface water bodies with regard to bioaccumulation and biomagnification in seafood should be undertaken on a site-specific basis.

    If HSLs for surface water (human consumption of fish) are applied to groundwater, considerations may be made for issues such as complexities of groundwater-surface water interactions, benthic-biota bioaccumulation factors, the mass flux of the groundwater discharge to the surface water, and the flowthrough rate of surface water body. Where possible, direct sampling of PFOS and PFOA in fish can be considered.

    Refer to section 2.3 for surface water and sediment HSLs.

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    2.3 Water and sediment (human consumption of seafood) HSLs

    HSLs have been derived for surface waters (fresh and marine waters) and sediment for

    the protection of human consumption of seafood. The HSLs are summarised in table

    5Table 5, and considerations for their application are provided in table 6.

    Table 5 Summary of derived surface water and sediment HSLs for PFOS and PFOA

    Media PFOS (+PFHxS) PFOA

    MPCfish 270 g/kg 2,700 g/kg

    HSLfresh water, fish consumption 21 ng/L 210 ng/L

    HSLmarine water, fish consumption 616 ng/L 6,100 ng/L

    HSLsediments 22 g/kg 220 g/kg

    MPC maximum permissible concentration

    Table 6 Considerations in application of surface water and sediment consumption of fish HSLs for

    PFOS and PFOA

    Aspect Consideration

    Nature of surface water body

    HSLs for consumption of edible fish and crustaceans are only applicable to water bodies where fishing or harvesting of edible crustaceans occurs (associated habitats/niches of such species, including locations of their nurseries, may also be of interest in risk assessments). The HSLs do not typically apply to water bodies such as small drains, ponds and creeks where these activities do not occur, unless they are connected to other water bodies (in which instance the HSLs would apply in the receiving water).

    Groundwater

    HSLs for consumption of fish and crustaceans should not be applied directly to groundwater. The exception is where aquaculture is considered as a relevant beneficial use by the local jurisdiction.

    The HSLs may be applied to the connected surface water body to reflect the exposure that will be relevant to the edible fish and crustaceans. The sediment HSLs are applied to the sediments where fish, crustaceans and benthic organisms of interest are in contact with the sediments. (Refer to part 3, section 3.4. regarding considerations for pore water)

    Direct measurement applies to edible portions, typically muscle flesh although there exceptions such as roe and small fish such as sardines where the whole fish is eaten.

    Groundwatersedimentsurface water interactions

    If the fish are pelagic (living in the middle depths and surface water), then the concentration of the contaminant in the water body and food ingestion likely to be relevant, rather than the concentration in the sediment or at the point of discharge (see below regarding benthic-biota interactions). Estimates of the mass flux discharge to the receiving water that will occur may provide a useful indicator of the receiving water concentration.

    Because of the potential for magnification along the food web, accumulation within organisms that are in contact with the sediments and are then consumed by fish may be of interest (note that PFOA biomagnification in marine food chains has not usually been found to be a significant issue). Where there is uncertainty as to the situation that applies, sampling and direct measurement of contamination in the fish or crustaceans of interest may provide a more direct measure of the situation. PFOS and PFOA concentrations measured in fish should be compared to the MPCfish values presented in table 5. Direct measurement applies to edible portions, typically muscle flesh although there exceptions such as roe and small fish such as sardines where the whole fish is eaten.

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    2.3.1 Multiple pathway exposure and cumulative risk

    Schedule B(4) of the NEPM (2013) specifies that when assessing the risk of combined

    exposure, all relevant exposure routes must be included. This is important in the

    context of PFAS investigations as exposure to PFAS contamination can occur through

    soil, groundwater and the food chain, through more than one mechanism due to its

    persistence, mobility and bioaccumulation properties.

    In addition, the recent toxicological information suggests an additive effect between

    PFAS and their derivatives, and therefore assessment should be made for cumulative

    risks of the chemicals. A specific example of this is enHealths 2016 statement that the

    EFSA (2008) tolerable daily intake for PFOS should apply to PFOS and PFHxS, and

    the derived drinking water quality guideline should apply to the sum of PFOS and

    PFHxS.

    The HSLs presented in preceding sections were derived independent of other

    exposure routes. For example, the estimate of exposure occurring through soil

    ingestion (direct contact with soil) does not consider whether there might also be

    exposure through groundwater used for domestic (including potable) use or to water

    stock.

    HSLs for some exposures are calculated using a 100% relative source contribution. If

    more than one of these sources is relevant, use of the screening values would

    underestimate risks, and in this case, cumulative assessment of all relevant exposures

    must be made. To evaluate the overall risk the cumulative fraction should be

    calculated as follows:

    =

    That is, the PFAS concentration in soil, groundwater and surface water, is divided by

    the relevant HSL for the relevant media and use. A fraction above 1 of any one of the

    media indicates an exceedance of the HSL. The sum of these fractions is the

    cumulative fraction and a result above 1 indicates an exceedance when all routes are

    considered. This calculation can also help with the investigation and management of

    risk as the pathways which pose the more significant risk can be identified.

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    3. Ecological screening levels (ESLs)

    The background information and derivation of ESLs is provided in part 3 of this

    guidance document. This section provides a brief summary of the ESLs for terrestrial

    and aquatic ecosystems, and considerations in the application of the ESLs. For a

    discussion about the derivation and limitations of these screening levels, refer to part 3.

    3.1 Freshwater ecosystem ESLs

    Screening levels for PFOS and PFOA are currently being derived by the

    Commonwealth Department of Agriculture and Water Resources for inclusion in the

    revision of the ANZECC/ARMCANZ (2000) water quality guidelines. At the time of

    preparation of this report, these guidelines were currently under review and were in

    draft form. Table 7 shows the draft PFOS default guideline for each percent species

    protection value. The 95% confidence limits were not provided in the draft documents.2

    Table 7 Default guidelines for PFOS and PFOA

    % Species protection PFOS g/L PFOA g/L

    99 0.00023 19

    95 0.13 220

    90 2.0 632

    80 31 1,824

    3.2 Marine ecosystem ESLs

    A summary of ESLs derived for PFOS and PFOA in marine environments is provided in

    table 8.

    Table 8 Marine ESLs for fresh PFOS and PFOA

    % Species protection PFOS g/L PFOA mg/L

    99 0.29 3

    95 7.8 8.5

    90 32 14

    80 130 22

    3.3 Terrestrial ecosystem ESLs

    The ESLs derived for protection of terrestrial ecosystems are summarised in table 9.

    Table 9 ESLs values for fresh PFOS and PFOA in soils

    Land use % Species protection

    PFOS (mg/kg)

    % Species protection

    PFOA (mg/kg)

    Commercial and industrial 65 60 60 48

    Urban residential and public open space

    85 32 80 17

    National parks/areas with high ecological values

    99 6.6 99 0.65

    2 Perfluorooctanoic Acid (PFOA) Fresh. Default Guideline Values for Toxicants. Australian and New Zealand Guidelines for Fresh and Marine Water Quality. November 2015. Final Draft Perfluorooctane Sulphonate (PFOS) Fresh. Default Guideline Values for Toxicants. Australian and New Zealand Guidelines for Fresh and Marine Water Quality. August 2015. Final Draft

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    3.4 Considerations in the application of ESLs

    Aspects that should be considered in the application of ESLs are summarised in

    table 10.

    Table 10 Considerations in the application of ESLs

    Aspect Commentary

    Contaminant aging and soil properties

    At present there is insufficient information to predict the influence of contaminant aging or soil properties on PFOS and PFOA bioavailability. The terrestrial ESLs assume 100% bioavailability, and are appropriate for non-aged PFOS and PFOA contamination. Studies suggest that the toxicity of PFOS and PFOA reduces with time (although there is insufficient information to quantify this), and a line of evidence approach could be adopted whereby consideration may be given to soil properties (e.g. TOC, pH, CEC, particle size, clay content, meso-pore fractions, organic carbon to total nitrogen ratio). Soil results are then compared with the ESLs following the NEPM ecological risk assessment procedure. This can be expected to provide a conservative assessment of the bioavailable fraction of PFOS and PFOA for use in an ecological risk assessment, and avoids the need to determine either an aging factor or a factor based on soil property effects.

    Sample extraction methods for evaluating impact on terrestrial and aquatic organisms

    The concentrations of PFOS and PFOA determined in sediment samples can vary depending on the type of desorbant used, with methanol extraction resulting in significantly higher concentrations than water extraction for PFOS, but similar concentrations for PFOA (Victor et al. 2015). It is possible that the use of a methanol desorbant may overestimate the amount of PFOS that is bioavailable to aquatic organisms. Similar considerations apply when determining the bioavailability of PFOS in soil.

    Location and extent of potentially affected area

    The ESLs apply to soil where the soil interacts with ecological systems, or may interact in the future. If soil is permanently contained under a structure or building, for example, the ESLs may have less relevance if the leaching potential is limited. Local regulators guidance on the application of the ESLs should be referred to.

    Australian regulatory agencies generally require that, where groundwater discharges through a shoreline or bed of a river, that the benthic organisms at the point of discharge (prior to dilution in the bulk receiving water) be protected. Aquatic ecosystem protection is prescribed for groundwater dependent ecosystems (e.g. stygofauna) as a protected environmental value of groundwater.

    Because of the potential for PFAS to bioaccumulate, concentrations within the sediments at the point of discharge may be elevated. When evaluating such areas, the environmental values of the receiving environment must be taken into consideration. The extent of shoreline or sediment that is potentially affected and its significance with respect to the whole of the water body and associated sediment may be considered. If the area of effect and contaminant loading are small and the environmental values are not affected to any significant degree, it may be appropriate to conclude that it is a low risk situation (this excludes the consideration of intentional release of pollutants which would be unacceptable and subject to jurisdictional legislation). However, such a conclusion would need to consider local regulatory requirements and it may be necessary to consult with the relevant agency or auditor in finalising a conclusion relating to such areas. For example, the ESLs do not consider other environmental values such as public amenity and cultural and spiritual values that may apply.

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    Bioaccumulation

    PFOS is bioaccumulative, and the ESLs for protection of ecosystems take this into account as follows:

    For aquatic ecosystems, in the case of moderately modified freshwater and marine ecosystems, the guideline for 99% protection of species for PFOS is recommended to be applied rather than the criterion for protection of 95% of species.

    For terrestrial ecosystems, an increase of 5% species protection is added to the standard species protection levels for PFOS.

    Given the variability of ecosystems, it may be appropriate conduct site-specific assessments using suitable data (see considerations for bioaccumulating chemicals in ANZECC/ARMCANZ (2000).

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    4. References

    ALS 2013, Testing of extended Perfluorinated Compounds (PFCs), EnviroMail #67,

    viewed 22 January 2016, .

    ALS 2015, PFOS/PFOA analysis why do my laboratory results not always agree and

    which number is correct?, EnviroMail #94, viewed 14 January 2016,

    .

    Conservation of Clean Air and Water in Europe (CONCAWE) 2016, Environmental fate

    and effects of poly- and perfluoroalkyl substances (PFAS), Report no. 8/16, prepared

    by Arcadis.

    CRC CARE & NMI 2015, Proficiency study AQA 15-03 PFOS/PFOA in soil and water,

    National Measurement Institute and CRC for Contamination Assessment and

    Remediation of the Environment, New South Wales, Australia.

    enHealth 2016, Interim national guidance on human health reference values for per-

    and poly-fluoroalkyl substances for use in site investigations in Australia,

    Environmental Health Standing Committee, Australia.

    Houtz, E 2013, Oxidative measurement of perfluoroalkyl acid precursors: implications

    for urban runoff management and remediation of AFFF-contaminated groundwater and

    soil, PhD dissertation, University of California, Berkeley, USA.

    Kaserzon, SL, Vermeirssen, ELM, Hawker, DW, Kennedy, K, Bentley, C, Thomspon, J,

    Booij, K & Mueller, JF 2013, Passive sampling of perfluorinated chemicals in water:

    Flow rate effects on chemical uptake, Environmental Pollution, vol. 177, pp. 5863.

    National Environment Protection Council 2013, National Environment Protection

    (Assessment of Site Contamination) Measure, as amended 2013, National

    Environmental Protection Council, Australia.

    National Health and Medical Research Council (NHMRC) 2008, Guidelines for

    managing risks in recreational waters 2008, National Health and Medical Research

    Council, viewed 23 March 2015,

    .

    National Health and Medical Research Council (NHMRC) 2011, Australian Drinking

    Water Guidelines Paper 6 National Water Quality Management Strategy, National

    Health and Medical Research Council, National Resource Management Ministerial

    Council, Commonwealth of Australia, Canberra, Australia.

    NMI 2016, Proficiency Test report AQA 16-06 PFOS/PFOA in fish, soil and water,

    National Measurement Institute, New South Wales, Australia.

    Victor, A, Arias, E, Mallavarapu, M & Naidu, R 2015, Identification of the source of

    PFOS and PFOA contamination at a military air base site, Environmental Monitoring

    and Assessment, vol. 187, pp. 411.

  • CRC CARE ATC Building University of Newcastle Callaghan NSW 2308 Australia

    Postal C/- Newcastle University LPO PO Box 18 Callaghan NSW 2308 Australia

    Contact usP: +61 2 4985 4941 E: admin@crccare.com

    www.crccare.com

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