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1 SITE CHARACTERIZATION TOOLS, SAMPLING TECHNIQUES, AND
2 LABORATORY ANALYTICAL METHODS SUMMARY FACT SHEET
3
4 REVIEW DRAFT
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6 DO NOT CITE OR QUOTE
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8 July 12, 2017
9 1 INTRODUCTION
10 This fact sheet is one of six developed by the Interstate Technology and Regulatory Council
11 (ITRC) to provide an overview of the site characterization tools, sampling techniques, and
12 analytical methods available for use when evaluating PFAS concentrations in environmental
13 samples. The fact sheets are tailored to the needs of state regulatory program personnel who are
14 tasked with making informed and timely decisions regarding PFAS-impacted sites. The content
15 is also useful to consultants and parties responsible for the release of these contaminants, as well
16 as public and tribal stakeholders. The information in this fact sheet is supplemented by others in
17 the series: Nomenclature Overview and Physical and Chemical Properties; History and Use;
18 Regulatory Summary; Environmental Fate and Transport (to be published late 2017); and
19 Remediation Technologies and Methods (to be published late 2017).
20 This Fact Sheet provides information and considerations for sites and sources of PFAS to the
21 environment that is special or unique to PFAS, including:
22 • Information about site characterization
23 • Sampling methods
24 • Analytical methods.
25 1.1 What are PFAS?
26 PFAS are a complex family of more than 3,000 manmade fluorinated organic chemicals (Wang
27 et al. 2017). These substances have a carbon chain structure containing at least one totally
28 fluorinated carbon atom. PFAS include both per- and poly -fluorinated chemicals. Perfluorinated
29 chemicals, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), are a
30 subset of PFAS with carbon chain atoms that are totally fluorinated, while polyfluorinated
31 chemicals have at least one carbon chain atom that is not totally fluorinated (Buck et al. 2011).
32 Due to unique physical and chemical properties (for example, surfactant, oil -repelling, water-
33 repelling), PFAS have been extensively manufactured and used worldwide. Some PFAS
34 molecules are environmentally stable, mobile, persistent, and bioaccumulative. Further
35 discussion is in the Nomenclature Overview and Physical and Chemical Properties, Regulatory
36 Summary and History and Use Fact Sheets.
37
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38 1.2 Why Are PFAS Important?
39 The scientific community is rapidly recognizing and evolving its understanding of PFAS in the
40 environment. PFAS in the environment are considered to be contaminants of emerging concern
41 (CECs). CECs are those chemicals that present known or potentially unacceptable human health
42 effects, or environmental risks, and either: (i) do not have regulatory cleanup standards, or (ii)
43 the regulatory standards are evolving due to new science, detection capabilities, or pathways, or
44 both (USDOD 2009).
45 PFAS are found globally in both remote and urban environments, and ar sent in various
46 matrices including: human blood (whole, plasma and serum), sedime ace and
47 groundwater, and wildlife (Kannan et al. 2004, Yamashita et al. 20 s et al. 2005,
48 Rankin et al. 2016). Due to their widespread uses in many co rod bility to bind to
49 blood -proteins, and long half-life in humans, scientists rout. d PFAS blood and
50 serum of both occupationally and non -occupationally exp people (Kannan 2004,
51 Karrman et al. 2006, Olsen et al. 2003). Both laborato ies using animals an
52 epidemiological studies of human show that expos some P may be associated with a
53 wide range of adverse health effects.
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2 SITE CHARACTERIZATION TO
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The fundamental objective of site characten o op_ a accurate picture of the
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sources of contamination, the contaminant fa
nd tr d potential exposures and risks
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posed by a site. The site charac ' ation tee
e d study principles for PFAS-contaminated
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sites are essentially the sam other
ecuted site investigation of any other type
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of hazardous substance minat ite. Gene
ite investigation principles and techniques
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will not be covered in ct �hee : here are
y existing guidance documents about how
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site investigation shoul
this section on characterization, the fact sheet
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will cover how the unique al characteristics, the unique uses, and the unique transport
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mechanisms 0 .uld ounted for when characterizing a PFAS contaminated site.
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2.1 Sotft* s and Site ficati
65 The un.q AS properti including both hydrophobic, lipophobic properties, and stability
66 under extre sical a hemical environments, has resulted in extensive surface coating
67 applications, pr ulations, and industrial uses. (3M, 1999; European Food Safety
68 Authority [EFSA], This widespread use has resulted in widespread contamination of the
69 environment by PFA PFAS contamination is both ubiquitous, creating anthropogenic derived
70 background concentrations in numerous areas around the globe, but also creating many point
71 sources of contamination. At this time (2017) there has not been an extensive accounting of the
72 many uses of PFAS nor has an extensive accounting of all the possible products and industries
73 where PFAS are found been created. The reader is directed to the History and Use fact sheet for
74 information on what is known of the uses of PFAS in the present and the past.
Cgailllltt (RDl]: Point to other guidance such as UFP QAPP
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75 Notwithstanding the difficulty of knowing where PFAS contamination may be originating from,
76 any investigation of a site starts with review of site chemical use, processes, and history of
77 release of hazardous substance. It is likely the site history with timelines of processes, layouts
78 and chemical use compared against the timeline of PFAS development and use will give clues to
79 the types of PFAS that were released at the site. This is typically done at hazardous substance
80 release sites, however; this process takes on special importance at PFAS contaminated sites.
81 PFAS comes in complex mixtures and those mixtures changed over time. Also, mixtures of
82 PFAS included many different PFAS that have yet to be identified and comp unds for which
83 there are no developed analytical techniques. Even if the techniques are no _ vailable to the
84 research community, they have not been commercialized and standards n do not yet exist.
85 (See the section on Analytical Methods below). Also, the chemicals not have been identified
86 in site documents as the chemicals were thought to be inert and sderstanding of the
87 uses of PFAS and their history is critical to understanding wher AS m ve been released
88 at a site. At a typical site, it is likely that much of the mass P AS contam n will not be
89 measured because the analytical techniques are not yet av ' a le, so during the t'gation a
90 portion of the contamination will go undetected.
91 These facts need to be understood when looking for g arrizing source areas. There is
92 often a focus on only constituents of regulatory concern --ample, PFOS, PFOA and in some
93 cases PFBA and PFNA). However, these chemicals may n lye been in the original mixture,
94 but may be breakdown products of other P :' Additionally, "i ity evaluations of other PFAS
95 are in process at this time and it can be anti othm a _ years many more PFAS will
96 be of regulatory concern.
97 PFAS contamination can be resd to the en ent as a solid, liquid, gas or dust/ash. PFAS
98 movement in the environ 6 t-is`ri'` straightfo like many contaminants. Each PFAS has
99 one end of the molecul at e, esse pally inert 'le the other end of the molecule has been
100 designed for many dif Si1apph The act a end will react with enviromnental media
101 based upon its unique chfen icsftilb?tl perfluorinated end will react in a relatively
102 consistent way.
103 PFAS cogurination o
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Gomes film secondary sources. Prime examples are the watering of
lawnsPFAS contam ated water and application of contaminated biosoilds to farm land.
105 Air depds lion from mdus , _i1 and non -industrial use, burning of PFAS contaminates materials
106 creating P�� contaminatdash, and use of PFAS in transportation related products can lead to
107 non -point sou r6qs An unexpected source of PFAS contamination to the environment is septic
108 fields and mstitifti" Ctuse a great deal of some cleaning products. As a site investigation
109 proceeds and the site=is large in areal extent, it can be expected that these other sources of
110 contamination will be encountered. The Environmental Fate and Transport Fact Sheet includes
111 conceptual site models for different source scenarios.
112 2.2 Geologic and Hydrogeologic Framework
113 Once the likely source or sources of contamination are understood the normal techniques of
114 investigation are followed. Soils at the source are sampled and characterized. Pathways to
115 groundwater and surface water are investigated. Success for these studies, like all such studies,
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relies upon an adequate understanding of the geology and hydrogeology of the site. Some HAS
are relatively immobile in water. Some PFAS will be dispersed into the air as a gas, dust or ash.
Others readily dissolve in water and move with groundwater and surface water. Sediments may
act as a sink of PFAS contamination. No natural attenuation can be expected for these
contaminants other than dilution. Thus, the plumes of several HAS (for example, PFOA,
PFHxS, PFOS) can travel for many miles from the original source, with concentrations above
risk based levels of concern. At many sites the PFAS plume will be much more extensive than
plumes from other contaminants released at a site. A thorough under4sa
f the
geology/hydrogeology and hydrology of a site can reduce the requireby making the
selection of sampling locations more efficient. The expense of samplltiple
mobilizations make PFAS contamination characterization costly and investigation
planning is paramount to avoid any unnecessary investigation.
128 Although there numerous large and complex HAS contam' Ti sites, not site will be
129 highly complex. A site may be created by a onetime releldpVent such as tank3M that is
130 extinguished with AFFF.
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2.3 Risk Assessment
The objectives of site characterization and the
include enabling decision makers to makethf
both humans and the environment and the
Figure 1 is a generalized conceptual site mo
geologic media such as soils and rock, sedim
air. Through any of these im media, hu
these contaminants are so ter, site
drinking water, either s d from undwa
discovered through d ' water v
because PFAS plumes tr . R
opme accurate site conceptual model
decision t risks posed by the site to
1 need t aken to address those risks.
S contamination will impact
e t often impacts surface water and
biota can be exposed. Because many of
either discovered because of contaminated
surface water. Even if a site is not
s frequently tested immediately at many sites
not breakdown.
The main iss S coNch
on and risk assessment is simply the lack of sufficient
study on th , zicity o Ss. Almost allof the work to this point in time has been
on just S and PFOA. nd link to pathology, of these two compounds is complex
and stil ell understo eath Advisories and criteria development has been slow. Given
the fact tha AS come i mplex mixtures and the ecological system and in the human
population is - ed to a complex mixtures, makes evaluating the true risks as a site very
difficult. Some a d oose to only focus on the chemicals that have a regulatory standard or
have an issued hea visory. From a technical point of view, this is almost always inadequate
to evaluate the risks a site poses. More guidance is needed for risk assessors to be able to provide
an accurate assessment to decision makers and the public. Because of the above mentioned
challenges, it is incumbent upon the investigation team to identify data gaps and the impact that
they have on analysis of risks. Decisions will have to be made with only a partial understanding
of the site and risk conceptual site model. Those deficits must be documented so that future
researchers can reassess the site and the public can understand that the decisions are made
without believing that information is being suppressed.
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157 2.3.1 Develop Initial Conceptual Site Model (CSM)
158 2.3.1.1 Human Receptors
159 The numerous sources and types of PFAS chemicals present a special challenge to risk
160 assessment. For example, exposure to PFOA results not just from exposure to PFOA and its
161 precursor compounds in soil and water from releases to the environment, but also from food (for
162 example, beef, vegetables), drinking water, packaging materials, treated carpets and personal
163 care products, among other ubiquitous sources. This means almost every In being has some
164 PFAS exposure. Exposure to PFOA and other PFAS chemicals can also, eur, and may be more
165 significant in occupational settings (for example, PFOS exposure by airy using AFFF, during
166 manufacturing).,,
167 PFOS is also known to bioaccumulate significantly in fish, ing0ding specie" _light for human
168 consumption. Another PFAS exposure scenario involvm ainsitive receptor e to the fact
169 that infants consume more fluid, as breast milk or form and that PFOA concen €ions in
170 breast milk have been detected at similar or higher co) ntratio s than in the mother's drinking
171 water. Serum PFOA levels in infants increase rapid y a er bi -This elevated, early life
172 exposure is of concern, as it can persist for many year ei, the slow rate of chemical clearance
173 from the body. ..".
174 2.3.1.2 Ecological Receptors"-
175 Persistent, bioaccumulative chemicals such aK FFAS 13eirks via direct exposure of
176 individual organisms to contaminant releases w hs to ecosystems via concentration and
177 distribution in the food chaA,�LO�nts to terre ;aquatic and aquatic -dependent species can
178 begin in contaminated s >arld sedi ent, with t estrial and benthic microorganism exposure.
179 This initial loading can %centrate d build up ough primary consumers as they eat plankton
180 or plants, up to and thrrto pretors (Yalding humans), all carrying an increasing body
191 burden in body fluids and tBoth wild and domestic species maybe affected, which has
182 implications forhih a ihealth sk from the consumption of fish, hunted animals and livestock.
183 Little haslieen done wiNf4gard to ecological risk assessment, but laboratory studies of animals
184 and various reports of PFA .levels in wildlife populations give rise to increasing concerns about
185 the impacfito biota. As A-iswriting there is little information on wildlife/ecological studies
186 being done Aor PFAS condminated sites.
187 2.3.2 Risk Assessment Evaluation
188 Although there are many PFAS contaminated site due to fire -fighting chemicals such as AFFF,
189 other everyday products can contain PFAS and serve as secondary sources of contamination. In
190 almost any urban setting where a medium to large size PFAS contamination site exists,
191 encountering other plumes or sources of soil, sediment and surface water contamination of PFAS
192 that are not associated with the site under investigation is likely during the remedial
193 investigation. All PFAS are anthropogenic in origin (maybe some very minor sources in nature).
194 Thus, these other HAS sites or background HAS contamination is anthropogenic in origin.
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195 Data analysis needs to be more robust in such situations. Identifying multiple sources may
196 require more reliance upon data analysis techniques not frequently used at other non-PFAS
197 contamination sites. This problem also underlies the need to analyze for the full suite of PFAS
198 chemicals that labs can usually perform Data Analysis and Interpretation. Upon the PFAS data
199 collection, the CSM can be refined by conducting more in depth ratio analysis for individual or
200 families of PFAS and/or isomer identification Forensic chemistry analysis is necessary at larger
201 PFAS contamination sites to differentiate sources and plumes, determine release history and
202 document data gaps in chemical site characterization and risk analysis.
203 Thousands of PFAS have been used in a wide range of consumer produ 'th many of the
204 PFAS being precursors that could partially degrade in the environme iota to other PFAS
205 have been found to be highly stable and persistent end products ( 2017). The ratios
206 of different individual or families of PFAS could indicate how to a 'al source zone
207 the sample was collected; if more than one product that con FAS mig been used, if
208 more than one source might be responsible of the PFAS c ination, and ho nt the
209 release in the environment might have occurred. Also g-chain sorption to soi sediments
210 have been found to be bind more strongly than sho n (Ahr et al., 2010; Higgins and
211 Luthy, 2006; Zhao et al., 2012). As a result, short-ch a expected to travel faster and
212 longer distances from the sources compared to long-cha S (See the Environmental Fate
213 and Transport Fact Sheet). The ratios between different P ould be used to better
214 understand and document how far from a ource a ce ple might have been taken.
215 2.4 Development of Site Cri[teri
216 The lack of regulatory criteria lth advis ns that at certain sites, site -specific
217 chemical criteria will nee oped. Gu ce should be developed for risk assessors on
218 accounting for risks of witho adequate ity data.
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220 3 SAMPLING
221 3.1 General
222 Sampling conducted for the purpose of determining PFAS compound concentrations in various
223 media and sources is in most ways similar to traditional chemical compounds. However, there
224 are additional considerations and protocol that are specific to PFAS samplin . The applicable
225 local, state, and federal rules and guidelines should be followed unless it 'termined that a
226 particular method or procedure is contrary to the specific needs of a P = sampling program, in
227 which case the applicable agency should be contacted directly to det'.. a mutually beneficial
228 approach or to determine if an exception can be made. The low fiat ,tection limits, state
229 and federal screening levels, and in some cases, cleanup cater `tII or exampl . Pw as) and
230 ubiquitous presence of PFAS compounds in the envit so requires ex pary
231 considerations during PFAS sampling.
232 Caution should be used to avoid direct contact withJngestioii`of sampling media that is
233 potentially contaminated with PFAS. As described in tItIjsry and Use section, various
234 adverse health effects from PFAS compounds are suspecfes <The American Cancer Society has
235 classified the PFAS compound, PFOA as • ossibly carcinog to to humans" (Group 213) as of
236 January 2016, based on limited evidence i ` juts that It can0.testicular and kidney
237 cancer, and limited evidence in lab animals ` ertd'alancer Society [ACS], 2016).
238 3.1.1 Equipment and Supplies
239 Many material used m th Course o 4anvironme ;investigation could potentially or do
240 knowingly contain PF�So far, t >e is no pub died research on how certain materials that
241 may be used by field staf ,effect s p% -re It erefore, a conservative approach is
242 recommended during execut iiib tthe sampling plan. All efforts must be taken to exclude
243 materials that arplatown to contain PFAS compounds. Various sources of PFAS are discussed in
`se it<heet 01tain and review all material Safety Data Sheets (SDS) before
244 the Historyt`[T
245 considerifig them for uess&#--. ng PFAS-'sampling. Anything with "fluoro" in the name or the
246 acronyf TPE, FEP, ET ;.and or PFA is suspect PFAS-containing material. Materials typically
247 used in P�sampling prjerts are provided in III(a)(i).
248 fable XX �dentlfibs matenals and equipment commonly used in the course of environmental
249 investigations that arOconsidered appropriate for use in PFAS focused investigations, as well as
250 materials that are known or suspected to be potential sources of PFAS and should be avoided if
251 possible. Further, this section will provide guidance to the environmental professional with
252 respect to what actions to take when a material that is known to or suspected to contain PFAS or
253 could potentially impact the PFAS analytical results (adsorption) cannot be avoided and must be
254 used
255 The ITRC PFAS team recognizes that there can be instances where it may not be possible to
256 completely eliminate the use material that may be able to contribute to or impact the result of
257 PFAS in your samples. These instances could include sites where hazards warrant the use of
258 specific PPE, or where PFAS are a co -contaminant or a secondary contaminant and the primary
7
Comment [YY7LCSL21: Provide link to ITRC Website where
table will be maintained and updated as data becomes available.
Comment [LH W3R2]: The table should be developed for the
team review. As noted by Janice, it can be provided as a separate file
from the fact sheet so that it is easily updated.
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259 contaminant requires the use of specific materials for proper sampling, or where the opportunity
260 to collect a sample presents itself prior to the establishment of a proper sampling program. In
261 these instances, it may not be possible for the environmental professional to avoid the use of
262 non -ideal or unacceptable material. In these situations, the development and application of a
263 thorough quality assurance and quality control (QA/QC) program is of the utmost importance.
264 3.1.2 Bottle Selection
265 Containers should be provided by the laboratory selected to perform the analyses, and should be
266 certified by the laboratory to be free of the PFAS that are to be quantified. UOPA Method 537,
267 Version 1.1 (September 2009) requires the use of a 250 milliliters (mL) ropylene containers
268 and caps/lids for drinking water sampling. Currently, there is no EPA ance/requirement for
269 bottle selection for any sample media other than drinking water. U
270 guidance/requirement are provided, it is recommended that a hi nsi ethylene (HDPE)
271 with a plastic cap containing no Teflon® liner, be utilized for her medi .
272 When selecting the size/volume of the sample to be col in addition to repre tiveness of
273 the site being considered, best practices in sample pr tion
st must be considered as well.
274 All plastic bottles (for example, HDPE, polypropyle en to adsorb PFAS at various
275 rates. In order to minimize this adsorption effect on sa Its, the laboratory must analyze
276 the entire sample and rinse the sample container. The prof eening and/or applicable
277 regulatory levels and the expected/potenti entration o alytes are also relevant. If the
278 sample is known to contain high concentra s (for e le, AFFF formulations), this
279 loss is negligible and therefore the entire s `le o n 1 to a used. Since the
280 concentration level of PFAS in aqueous sam wine whether the whole sample or an
281 aliquot is used in the laborato Aration, i "s ended that a small volume of each
282 sample be collected in a se iner. Th = a ple will allow for the laboratory to screen
283 the sample for high con tions out effe v the final sample result. In the case of soil or
284 sediment, obtaining a ' en— i $ub vnple i .` e laboratory is critical, therefore, the entire
285 sample should be homog prior to subsampling. For these reasons, it is
286 important to coordinate wit 4eaboratory on the appropriate container volume for
287 environmenainedi*tither tharng water.
P,
288 3.1.3 J9 ple Preservatt Shipp"g, Storage, and Hold Times
v
289 USEPA 81537, Verq 1.1 (September 2009) contains specific requirements for sample
290 preservation, shtppmg s _ ge and hold times. Currently, there is no EPA guidance/requirement
291 for other sampf6e*, ka . or most PFAS samples (non -drinking water) the only preservation
292 needed is thermal.)" I ervatives such as Trizma® are not needed since free chlorine in the
293 media is not expected. EPA guidance/requirements are published or laboratory validated studies
294 are conducted, it is recommended that thermal preservation, shipping, storage, and hold times
295 contained in USEPA Method 537, Version 1.1 (September 2009) be adhered to for all other
296 sample media, with the exception of biota. For biota samples such as fish, it is recommended
297 that the samples be frozen upon receipt at the laboratory until sample preparation. It should be
298 noted however, that current information does not suggest that sample storage above 6°C, or even
299 above 10°C, for a brief period of time (for example, several hours to a few days) renders the
300 results invalid. Perfluoroalkyl substances are resistant to degradation under typical conditions
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301 and, if anything, the results could be biased high due to the degradation of precursor compounds
302 to the perfluorinated compounds of current regulatory interest.
303 Note that the ambient water temperature may be higher than 10°C depending on the site location,
304 type of water (for example, surface water, groundwater), and season; the ambient air temperature
305 may also be significantly higher than IOT during the sampling. In addition, in some cases the
306 samples may be hand delivered to the laboratory, rather than being shipped overnight. In these
307 situations, it is important to chill the samples quickly.
308 3.1.4 Decontamination Procedures
309 Sampling equipment should be thoroughly decontaminated before mobilisation to each
310 investigation area and between sample locations at each investigattiigdi6 or as required in the
311 site -specific work plan. Field sampling equipment, including oiUACiter ii orface meters and
c
312 water level indicators, and other non -dedicated equipment uscdt each sam location, will
313 require cleaning between uses. Alconox® and Liquinox® is acceptable atse since the
314 Safety Data Sheets do not list fluoro-surfactants as an i lent. Water used fore"f[nal rinse
315 during decontamination of sampling equipment will la6oratorcertified "PFAS free" water.
316 For larger equipment (for example, drill rig and larg tloovnho drilling and sampling
317 equipment), decontamination will be conducted with p1e`ater using a high-pressure washer
318 and then rinsed using potable water. Decontamination of s`6 11 heavy equipment is best conducted
319 within a decontamination facility or other eaus of contai`gnt (for example, bermed, lined pad
320 and sump or a portable, self-contained dec� taiX4tii�t on booth). Ppt6b water sources should be
321 analyzed ahead of time for concentration of ,FAS constitttents, Wherever possible, a "PFAS
free" free" water rinse shall be conducted immedia ply predtn the equipment use.
323 3.1.5 Field QC (frequency;}cni,6ri , procedure
324 Field Quality Control sample are a means of assessing quality from the point of collection.
325 Such QC samples include; but are not limited to trip blanks, field blanks, equipment rinse blanks,
326 and Sample Duplicates. They can provide valuable information on the heterogeneity of the
327 media, and possible biases due contamination (for example, insufficient rinsing of sampling
328 cquipment) USEPA iu ethod 53-,, Version 1.1 (September 2009) contains specific requirements
329 for theyleld Quality Coh"l (QC) samples that must accompany drinking water samples. For all
pec
330 other sA*le media, the sific field QC samples utilized is dependent on the type of sample
331 media collected, PFAS concentrations expected, and type (for example, single use, resusable,
332 HAS containing) of equipment used. Although the collection and analysis of QC samples adds
333 cost to the sampling and analysis program, these samples can be especially important for PFAS
334 analyses due to thievery low detection limits of the analysis methods and because of the
335 widespread use (historical and current) of fluorinated compounds (including perfluoroalkyl
336 substances and their precursors) in commerce.
337 3.2 Sampling Procedure
338 Sampling a "potable water source", as defined by the EPA Safe Drinking Water Act (Section
339 1401(4), August 1998), is conducted according to protocol established in the USEPA Method
340 537, Version 1.1 (September 2009). Per this method, the drinking water source must be from a
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341 public drinking water supply, as opposed to a private drinking water supply for this method to be
342 applicable.
343 Currently, there is no EPA guidance or requirement for other sample media, however, general
344 guides such as ASTM Standard Guide for Sampling Ground -Water Monitoring Wells, D 4448-01
345 (ASTM, 2007), Pore Water Sampling Operating Procedure (EPA, 2013), and the Compendium
346 of Superfund Field Operations Methods (EPA, 1987) are good sources for general information.
347 These standard procedures sampling can be used with some exceptions and/or additional
348 considerations to be taken to address issues associated with the potential use of HAS containing
349 sampling equipment and supplies. Table XX should be consulted to minirrl&lhe use of HAS
350 containing equipment and supplies as well as those with PFAS adsorpti ues.
351 3.2.1 Groundwater
352 The most inert material (for example, stainless steel, silicone igh-dens ethylene),
-353 with respect to known or anticipated contaminants in the should be us never
354 possible. Dedicated sampling equipment installed in ex' wells prior to the P
355 investigation should not be used without identifying aterial and within the equipment
356 and reviewing their chemical properties to ensure th PF ee. For longer term
357 investigations, samples may be collected in duplicate ithout existing dedicated
358 equipment. If HAS analyses show that the equipment do mpact results, the equipment
359 may be kept and used long term. Howeve deternminatio pendent upon project -specific
360 requirements and should only be allowed b ee p anager ' -dull disclosure to all
361 stakeholders.:
362 3.2.2 Surface Water
363 Generally, the outside o vappe ple con ers shall be triple rinsed with the surface
364 water being sampled filling containers ss'th the sample to be analyzed. Where required
365 by site conditions, remo ph o ontainers will be allowed by clamping the
366 container onto the end of a xtension ro The extension rod must be made of material that
367 does not me FA3,gnd ha through decontamination.
368 3.2.3 1* Water
and HDPE tubing are typically used for pore water sample
369 Peristalticpnnnpstyith sih
370 collection A with pusW*int samplers, pore water observation devices (PODS), and/or drive
371 point piezomet;6 PusJafioint samples and drive point piezometers are construction of stainless
372 steel and inherentl` lac any PFAS-containing material. PODs are constructed of slotted PVC
373 pipe and silicon tubih and will not contribute PFAS to the samples. PODs and drive point
374 piezometers are permanent, or dedicated, sample points typically installed and used for multiple
375 sample events, whereas push point samplers are used for a temporary sampling location. If non-
376 dedicated sampling equipment is to be used and contaminant histories of the sample locations are
377 known, it is advisable to sample in order of the least contaminated area first and sample the area
378 of highest known contamination last.
379 3.2.4 Soil/Sediment
380
10
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381 Core samplers and grab samplers are two types of soil and sediment sampling devices that are
382 typically used. Most of these devices are constructed of stainless steel, and some core samplers
383 allow a sleeve, which should be made of HDPE, to be inserted into the core barrel to retain the
384 sample. PPE may be required for sampling personnel such as waders and personal floatation
385 devices. Ensure that these materials that will come in contact with the sampling media do not
386 consist of water-resistant coatings or other PFAS containing materials or substances.
387 3.2.5 Fish
388 Proper procedures are necessary to assure the quality and integrity of anal ig�l results and that
389 appropriate fish samples are collected according to the project -specific o iives. The species of
390 fish collected as well as the portion of the fish prepared (whole versu et) depends on the
391 project goals (ecological risk vs human health). Studies have sho . z; "AS bioaccumulation
392 rate vary depending on the PFAS studied and the species of fish,. r"dies g also shown the
393 majority of the PFAS bioaccumulated in fish is stored in the o_gns, not the b , Because of
394 this, communication of the project objectives with the ana - 1 laboratory is a n�nportant
395 prior to the field work in order to determine the quanti 'd quality of tissue nec Sry, fish
396 handling requirements, laboratory sample preparati(�i'cludingAingle fish or composite fish
397 samples and whole or fillet preparation), packing an t§l f pin equirements.
398 3.2.6 Potential high concentration samples
399 The conceptual site model (CSM) or prevr6"s s tng may in�Fl to areas of high PFAS
400 concentrations. In these cases, the samples) foul-U- 4 ected'th additional care taken to
401 avoid damage that can occur to laboratory eq j�ment doe tralysis of high concentration
402 samples using standard methods Some proje fs ma eq ire the analysis of AFFF product that
403 has been used at the site. A11� _product sa ples must be considered high concentration
s gregated fr other samples during the sampling event as
404 samples. These samples sl&i� be
405 well as during shipmelohi;entrati&is
a the laboAlky in ordee'to avoid cross contamination. The samples
406 that may contain high of"AS should be clearly identified on the Sample Chain
407 of Custody (CoC) that is shtpop#'with the samples to the laboratory. Field test kits are available
408 for PFAS compound but have bt been fully evaluated at the time of this Fact Sheet release and
409 cannot achieve low dett(otions limits that may be necessary. However, when such kits become
410 availabjd they could be �i ' helpful`in screening for potential high concentrations of PFAS in
411 the field:-, _ 1-
412 4 ANALYTICAL METHODS
413 4.1 Quantitative
414
USEPA Method 537, Version 1.1 (September 2009) contains specific requirements for sample
415
416
417
preparation and analysis of drinking water samples. Currently, there are no EPA methods the
preparation and analysis of other sample media, however, other method have been published.
See C able YNI for a list of current published methods for PFAS analysis
comment iWJLCSL4l: Link to list of methods on ITRC website
--
-- Comment{LHW5R4]: The table should be developed for the
418
The following information is based on current best practices and is recommended until additional
team review. As noted by Janice, it can be provided as a separate file
from the fact sheet so that it is easily updated.
419
methods are published by the EPA.
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420 4.1.1 Sample Preparation
421 Care must be taken to prevent sample contamination during preparation and extraction. All
422 supplies must be checked and confirmed as PFAS-free prior to sample preparation. Intermittent
423 contamination can occur due to vendor supplies or manufacturing changes, therefore it is
424 recommended that each lot of supplies be verified prior to use.
425 Ensuring a representation sample/subsample is utilized by the laboratory for analysis is critical.
426 In order to do this, entire aqueous sample received by the laboratory must be prepared and the
427 sample container appropriately rinsed. Sample filtration is not recommend rice problems
428 with adsorption of PFAS onto filters have been noted. Instead, techniqu ch as centrifuging
429 are often used. Due to limitations in technology (Solid Phase Extract' PE) cartridge
430 capacity and instrumentation sensitivities), the exception to this is ma. ing high
431 concentrations of PFAS. The laboratory should screen the samp ng Illholl volume sample
432 that was received in order to determine if the sample contain S at cone ons too high
433 for SPE sample preparation and analysis. Samples that ar ared using the sample
434 must be extracted using SPE while high concentration es must be prepared serial
435 dilution techniques. For solid samples, the entire sa receiv ust be homogenized and
436 extracted using SPE. In order to account of biases re f eparation steps, internal
437 standards (isotopically -labeled analogs of each analytes, ercially available) should be
438 added to the whole sample/sample aliquot prior to the nex n the process. For samples
439 prepared by serial dilution, internal standa uI I be adde final sample dilution.
440 Clean-up procedures (such as ENVI-Carb T on ch as on samples when matrix
441 interferences (for example, bile salts, gasolin ge n could be present. Clean-up
442 procedures should always be for prep soil, sediment, and biota. ENVI-Carb TM
443 cleanup will remove choli own inte nce in fish sample.
444
Batch QC samples su : ethod _ c ), l iratory control sample (LCS), laboratory
445
control sample duplicate
p e (SD), matrix spike (MS), and matrix spike
446
duplicate (MSD) should be
' d based on the type of sample (for example, high
447
concentratio '
bei ared. For sample with high concentrations of PFAS, it is
448
recomme at m ` of
,'r
a M3"MSD, a LCSD and SD be prepared. The SD should be
449
prepar in ad cr n
' not from the same sample bottle to create a second set of serial
450
dilutions ;
451 4.1.2
452 The currently the analytical detection method of choice for PFAS analysis is liquid
453 chromatography -mass spectrometry -mass spectrometry (LC/MS/MS), which is especially suited
454 for analysis of the ionic compounds, such as the PFSAs and PFCAs. GCMS can also be used for
455 PFAS analysis, specifically the neutral and nonionic analytes, such as the fluorotelomer alcohols,
456 fluorooctane sulfonamides (FOSAs) and sulfonamidoethanols (FOSEs). Currently, LCMSMS
457 analysis of PFAS is widely commercially available where are GCMS analysis has limited
458 commercial availability.
459 LCMSMS methods developed by laboratories are typically modified versions of USEPA Method
460 537, Version 1.1 (September 2009). The EPA method does not contain steps to alleviate matrix
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461
462
463
464
465
466
467
468
469
470
471
472
473
474
475
476
477
478
479
480
interference issues potentially found in other sample media and does not contain steps to prepare
solid sample media. Modifications typically include inclusion of such steps, utilization of
isotope dilution for more accurate quantification, and the addition of other PFAS analytes to the
scope of the method. Because these modifications are not standardized, laboratory modified
methods can result in data of greatly varying representativeness, precision, and accuracy. The
DoD Environmental Data Quality Workgroup (EDQW) has attempted to standardize a
significant number of these modifications through the requirements contained in the DoD
Environmental Laboratory Accreditation Program (DoD ELAP) document, the DoD Quality
Systems Manual for Environmental Laboratories (DoD QSM), Version 5.1, 4,ppendix B, Table
B-15.
Chemical standards are available from several manufacturers. Care gt lie taken in product
selection as these products may have variable purity and isomer pr at may negatively
impact the accuracy, precision and reproducibility of data. Only, ified`�tndards of the highest
purity available (for example, American Chemical Society (.) grade) ca used for accurate
quantitation. Standard containing linear and branched iso ef5 are not commer . ly vaiiable
for all applicable analytes. Currently, such standards a 4rily available for PFOSd PFHxS.
Technical grades which contain branched and linear ers are.46ilable for other PFAS.
These standards do not have the accuracy needed to pdoquantitation purposes, but can be
usefull in verifying the location of branched isomers.tlon of individual HAS should
include all isomers. ...
481 Isotope dilution quantitation technique is r v ' t ShdeA Isotope ilution is the technique of
482 quantifying the analytes of interest against t ' isoto iMally lai 10 analogs of the analytes,
483 which are added to the sample prior to and a sam�i reparation. Addition prior to
484 preparation helps to account�for loss of analyt dttrig4the preparation process whereas addition
t .,.
485 after preparation to an al�ttot of the sample extract accounts for the bias associated with the
486 instrumentation.
487 Mass calibration should dccur at the frequency recommended by the instrument manufacturer
488 and as needed based, on QC`ttidicators such as calibration verifications. The instrument blanks,
489 calibration curve; initial and cotilinual calibration verification requirements should consistent
490 with those published for_other LCMSMS methods. The lowest calibration point should be a
491 concentration at or below;the limit of quantitation. It is also recommended that a standard at the
492 limit of quantitation concentration be analyzed periodically to document the instrument's ability
493 t&quantitafe eocurately down to that concentration. Instrument blanks are critical in determining
494 if the instrum`ld is potentially biasing PFAS concentrations in samples. Acceptance criteria for
495 all of these analytical QC elements must be set at levels that meet the project's data quality
496 objectives (DQOs).`'For DoD projects, these criteria can be found in the DoD Quality Systems
497 Manual for Environmental Laboratories (DoD QSM), Version 5.1, Appendix B, Table B-15.
498 4.1.3 Data Evaluation
499 Data should be generated from a currently accredited laboratory to ensure the laboratory is
500 capable of performing the analyses required and has a quality management system in place to
501 ensure the data will be generated properly. Industry recognized accreditations include National
502 Environmental Laboratory Accreditation Program (NELAP) or Department of Defense
503 Environmental Laboratory Accreditation Program (DoD ELAP). Evaluation of data generated
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504 by a laboratory, even data generated by a certified laboratory, is recommended because
505 accreditation doesn't tell you how well the laboratory performed on your specific samples. The
506 overall quality of the data includes laboratory analytical performance as well as sample
507 collection techniques and complexity of the sample matrix.
508 PARCCS (Precision, Accuracy, Representativeness, Comparability, Completeness, and
509 Sensitivity) parameters should be assessed during the data evaluation. PARCCS guide you
510 through the process of looking at your data (field collection and laboratory information) with a
511 critical eye. Data are reviewed in a systematic way by looking at the results of each Quality
512 Control (QC) indicator of the PARCCS parameters (for example, spike rec 'es, method
513 blanks, etc.) to obtain an understanding about the overall quality of the The most important
514 goal of Data Evaluation is to ensure that you understand whether the any limitations to your
515 HAS data (i.e., confidence that the data are usable to meet your n rder to perform this
516 evaluation you need to know how the samples were collected, t w w there were any
517 problems encountered during collection, and have a report fr e laborato laining how
518 the samples were analyzed, including the sample results a C performance s es.
519 Ideally, before you send samples to a laboratory, you s specify to them exac hat
520 compounds you need, whether there are specific re ry leve concern for the compounds
521 (for example, must meet Vermont Regulatory Limits u want the data reported, or in
522 laboratory terms, what type of "data deliverable" you re ata deliverables range from
523 simple data sheets that report only sample results to "full iverables" containing all sample
524 and QC results with raw data (i.e., ins trum uts). The la ry can also provide your data
525 in a variety of electronic formats (called El elive s or EDDs). At a minimum,
526 we recommend that you request a report tha tain tter (or Narrative) explaining
527 sample receipt, analytical methods, and any ed s data sheets containing results for
528 compounds and method QC - urrogat ries). With this simple deliverable, you
529 will be able to assess PA o ide con ce in the data.
530 For large public projec uali 3 Prct Plan (QAPP) such as Intergovernmental
531 Data Quality Task Force, . for Quality Assurance Project Plans,
532 Optimized UFP- Wor - s (March 2012)
533 [https:// /pro pn/files/documents/ufp_gapp_worksheets.pdfJ will specify
534 the proje - uiremen demo tion and documentation of Data Quality Objective
535 (DQO - the PARCCameters: If developing a QAPP is not feasible, the Consolidated
536 Quality 4 s Manual ( v1) for Environmental Laboratories, Version 5.1 (DOD/DOE, 2017)
537 [http:// ` ` osd.mi edgw/documents/documents/qsm-version-5-1-final/] outlines standard
538 protocols for c ettng d performing analysis of samples for PFAS. Table B-15 of the QSM
539 5.1 can serve as t r=j i laboratory scope of analysis for samples when negotiating cost and
540 placing sampling ki orders. Table 13-15, with its specifications of quality control criteria, can
541 also serve as a guide for your evaluation of data.
542 4.2 Qualitative Analysis
543 Several methodologies have been developed that attempt to assess a broader range of the PFAS
544 contamination at a site. These methodologies attempt determine either total precursor content or
545 total fluorine instead of quantifying concentrations of specific individual compounds. Such
546 methods are not standardized through a published EPA method therefore they are not widely
547 commercially available and to date have not undergone multi -laboratory validation. Such
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548 methods include Total Oxidizable Precursors (TOP), Adsorbable Organic Fluorine (AOF) or
549 Combustion Ion Chromatography (CIC) or AOF/CIC and Proton Induced Gamma -ray Emission
550 (PILE).
551 5 REFERENCES
552 <currently a separate file ITRC SCSA Fact Sheet References(6-12-17).doc>
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