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Project Funding
This project was funded by the American Water Works Association (AWWA), utilizing the Water
Industry Technical Action Fund (WITAF), Project # 327.
Contents
Executive Summary....................................................................................................................................... 4
Acronyms, Abbreviations and Units.............................................................................................................. 6
Radionuclide Methods and Compliance Challenges ..................................................................................... 8
Obtaining Reliable Data for Decision Making about SDWA Compliance .................................................... 15
Utility guidance to Enhance Data Reliability ............................................................................................... 16
Method Proficiency Testing ........................................................................................................................ 22
Recommendations for review and action based on analytical results ....................................................... 29
Appendix A: Discussion of ERA Proficiency Testing (PT) Data .................................................................... 32
Appendix B: Calculations Used to Assess Method Performance ................................................................ 42
Appendix C: How Does Measurement Uncertainty Impact Compliance Decisions? .................................. 43
References .................................................................................................................................................. 47
Executive Summary
Utilities in many parts of the country are challenged by compliance issues associated with the
Radionuclide Rule, in large part due to the performance limitations associated with the existing
approved analytical methods for radionuclides such as gross alpha activity, radium-226 (226Ra),
and radium-228 (228Ra). When utilities are supplying water that is low in radium and/or gross
alpha, the method limitations do not typically affect compliance. However, when source waters
contain these analytes near decision levels (e.g. 5 pCi/L as a trigger for 226Ra or 15 pCi/L for
adjusted gross alpha (alpha activity minus uranium and radon, but including radium) or 5 pCi/L
for 226Ra, 228Ra or combined radium), selection of appropriate analytical methods and ensuring
that laboratories are performing those methods in a manner to minimize uncertainty is critical.
This guidance document is limited to 226Ra and 228Ra, with discussion of gross alpha as it
relates to 226Ra, but also points out the general issues with the current gross alpha analytical
methods. It provides background on the relevant radionuclide methods that are commonly
used for compliance monitoring for these constituents. It provides criteria by which utilities can
a) evaluate performance of laboratories as pre-qualifications for bids when maximum accuracy
is important; b) set requirements for bid documents to ensure that labs understand the
requirements; and c) let utilities evaluate the data upon receipt to ensure that the laboratory met
the requirements.
The document does not suggest options for utilities which have high adjusted gross alpha
results that cannot be explained by either 226Ra alone or uranium. The document assumes that
uranium measurements are not as problematic as the gross alpha and radium methods. The
guidance document also provides recommendations for selection of the most appropriate
methods and sample handling techniques for compliance monitoring, to assist utilities in
specifying methods that are most likely to provide higher quality results.
To ensure maximum accuracy for gross alpha measurements, in situations where 224Ra
is not a consideration, the document recommends that utilities hold samples for 2-3
weeks before submittal to the laboratory to allow short lived radionuclides such as 224Ra
to decay, and then have the lab count gross alpha immediately (ideally within 24-48
hours) after sample preparation to minimize ingrowth.
For selection of methods, EPA is currently revising Method 900.0, but as it is currently
written it does not result in the most accurate measurements, in part due to the
requirement that samples be held for at least 72 hours after preparation and before
counting.
The co-precipitation method (7110 C) is recommended for samples with high dissolved
solids.
For radium isotopes, the document strongly recommends the use of the gamma
counting methods developed by Georgia Tech, as they demonstrate better precision and
accuracy in proficiency testing (PT) studies.
The document provides flow charts and tables that should assist utilities in obtaining the best
quality data, given limitations of existing methods, when radionuclide activity is near various
compliance points.
Note that actual compliance with the Safe Drinking Water Act (SDWA) adjusted gross alpha
Maximum Contaminant Level (MCL) is based on a running quarterly annual average, but
individual gross alpha measurements may be highly inaccurate and impact this compliance
decision, whereas the major focus of this document is on the radium measurements and the
gross alpha measurement itself. A utility should keep both issues in mind when evaluating
data.
Utility Challenges
The current Radionuclide Rule, coupled with the precision and accuracy of existing approved
radioanalytical methods, and inherent variability in the way individual laboratories perform the
testing, present potential compliance challenges to utilities. This is particularly true for utilities
which have 226Ra and/or 228Ra present in their source waters. The method variability noted above
impacts the reported gross alpha activity, possibly more even than it does the test results for 226Ra
or 228Ra. Examples of this variability are shown below. The purpose of this guidance document
is to assist utilities in maintaining compliance with the Radionuclide Rule by minimizing method
inaccuracies and imprecision and selecting labs based on performance capabilities that support
these concepts.
Some of the variability seen by utilities is attributable to a lack of specific guidance to laboratories
that would help them navigate the complexity and options available when performing commonly
used approved methods. This would range from the selection of methods, and the size of samples
being processed, to decisions about the timing of sample counts. This all ultimately impacts the
uncertainty in radioanalytical measurement results. Failure to minimize uncertainty can
significantly increase the rate of incorrect decisions about whether drinking water is determined
to be compliant with Safe Drinking Water Act (SDWA) regulations. Decision errors about
compliance can have quite significant consequences. They may result in potential public health
issues associated with failing to identify water with levels of radionuclides that are above
compliance limits. Alternatively, incorrectly deciding that a water system is out of compliance may
result in costly treatment. Either example can result in a concern that is nearly as serious, loss of
public confidence in the water supply.
Gross alpha methods should be designed to reliably identify waters that could contain 226Ra in
excess of an amount that would be compliant with the SDWA maximum contaminant level (MCL)
for combined radium (226Ra + 228Ra). The SDWA allows gross alpha results to be substituted for
226
Ra to demonstrate compliance with the combined radium MCL if the sum of the gross alpha
and 228Ra is less than or equal to 5 pCi/L. When the sum of the gross alpha and 228Ra exceeds
the combined radium MCL, a utility is not automatically out of compliance. Rather a radionuclide-
specific method for 226Ra is run that presumably will not overestimate the 226Ra activity (see further
discussion of 226Ra methods below). The results of this analysis are then used to determine
compliance with the combined radium MCL. These results may be used to determine compliance
with the combined radium MCL and may increase the frequency of required testing. Both cases
will result in higher overall costs for radioanalytical testing.
EPA has also established an MCL for alpha particle emitters (including 226Ra but excluding radon
and uranium), referred to as adjusted gross alpha. When the gross alpha result (“adjusted” by
subtracting the uranium activity) exceeds the MCL of 15 pCi/L, the drinking water is determined
to be out of compliance. This can have consequences that range from additional testing to
implementation of treatment.
Approved methods for gross alpha involve concentrating the sample by evaporation or co-
precipitation, followed by analysis of alpha emissions from the test source in a low-background
gas flow proportional counter. Although turn-around times as rapid as 1-3 days are possible,
depending on regulatory requirements, as will be discussed later, the most accurate screening
results for 226Ra will be obtained by delaying preparation of the sample for 2-3 weeks after
collection.
Water utilities should be careful in their interpretation of gross alpha results. It is crucial to keep
in mind that this method is a screen and that it is not specific for 226Ra. It also assumes that the
utility has measured the uranium level, which is also a source of alpha, but is subtracted in
determining the adjusted gross alpha. If alpha emitters other than 226Ra are present, the result
protectively overestimates the activity of 226Ra present. In addition to the presence of alpha
emitters not related to 226Ra, other uncontrolled factors associated with approved methods can
artificially increase the bias and uncertainty associated with measurements of alpha activity.
When 226Ra is present in a sample, the length of time between the preparation and the counting
will dramatically impact the sample result. Radium-226 decays into a noble gas familiar to many
as a radionuclide of concern for indoor air, radon-222 (222Rn), with a half-life of 3.8 days. Since
the evaporation used to prepare samples drives off any dissolved gases, including 222Rn, the
concentration of radon (and its decay progeny) upon completion of sample preparation, will
essentially be zero. The sample at this point has been converted by the preparation process to a
thin layer of solid salts on a 2-inch planchet. From this point, 226Ra continues to decay forming
new atoms of 222Rn. The newly generated radon has limited capability to escape from the solid
salt matrix, which allows it to build up over time. As 222Rn and its short-lived alpha-emitting decay
products, polonium-218 and polonium-214, build up in the sample, the alpha activity in the sample
actually increases. The activity doubles in the first three to four days after preparation and
continues to increase until it reaches a maximum of four times the initial concentration of 226Ra
(See Figure 1) after about four weeks. For example, if a sample containing 4 pCi/L of 226Ra (as
the sole contaminant) is counted immediately after evaporation, the alpha activity will be
approximately 4 pCi/L (less than 1/3 the gross alpha MCL), whereas if the sample count occurs
three weeks after evaporation, the activity could be as high as 16 pCi/L which would be out of
compliance with the MCL for adjusted gross alpha. However, bear in mind that compliance is
determined by the running average of quarterly samples, so even under these circumstances, a
sampling point may or may not be out of compliance based on an individual result.
Figure 1: Four-fold Increase in Alpha Activity after Sample Preparation due to 226Ra
Decay Products
Ra-226 Activity
2
1.5
0.5
0
0.0 3.8 7.6 11.4 15.2 19.0 22.8 26.6
Days Elapsed Since Evaporation
SDWA-approved gross alpha methods have different requirements regarding the minimum time
that must elapse between the preparation and counting of samples. One of the major sources of
interlaboratory variability is associated with labs counting samples containing short-lived
radionuclides at different points after sample collection. For example, the most commonly used
method, EPA Method 900.0, requires delay of the sample count for 72 hours after evaporation
whereas SM 7110B or SM 7110C allow the sample to be counted immediately following
preparation. Depending on the choices made about when the sample is counted, a Method
900.0 result could arbitrarily be 2-4 times that of a Method 7110B or 7110C result. It should be
noted that there are no method restrictions that require samples to be counted more quickly
than is needed to meet holding time restrictions1.
In contrast to 226Ra, 224Ra has a very short half-life of 3.7 days. Although 224Ra is produced through
decay of its parent, thorium-228 (228Th), the solubility of thorium in water is extremely low and
228
Th is rarely present in drinking water. Lacking a radioactive parent, 224Ra begins to decay as
soon as the sample is collected. Following preparation, the alpha emitters in the decay chain
below 224Ra (220Rn, 216Po and 212Po) very quickly reach equilibrium (minutes to hours). After this
point these radionuclides decay as a group over the next several weeks following the half-life
characteristic of 224Ra (see Figure 2).
1
A regulatory hold-time restriction for gross alpha of 180 days from collection to analysis is the upper limit for
delay of the count of a sample. Note that this hold-time is not protective when medium-lived radionuclides such as
210
Po with its 138 day half-life, since it could allow considerable decay of these radionuclides prior to analysis. The
State of New Jersey has implemented much more stringent requirements than the EPA and has prescribed specific
methods gross alpha and radium. Two counts of each sample are required, one quickly (within 24 hours if possible)
to capture the activity of short-lived 224Ra plus unsupported 212Po from unsupported 212Pb (in addition to 226Ra),
and one after 48 hours to protectively capture the activity of short-lived 224Ra plus supported 212Po while accepting
that this will introduce a positive bias in the screening estimate is 226Ra is present in the sample. If the gross alpha
activity exceeds 5 pCi/L, specific 226Ra analysis is required.
224
Figure 2: Rapid Decay after Sample Collection of Alpha Activity from Ra and Decay
Progeny
3.5
Analogous to 226Ra, when 224Ra is present in a sample, the timing of the count will have a
substantial impact on gross alpha results. Since radium is not lost during preparation of the
sample (as was radon with 226Ra), it is the length of time between sample collection and the count
that matters. Inspection of Figure 2 shows that, in contrast to 226Ra, the sooner the sample is
counted, the higher the result will be. The ingrowth of progeny from 224Ra detectable by the gross
alpha test takes place on the order of minutes, hence the very sharp increase in gross alpha
immediately after sample collection.
If 224Ra is of regulatory concern, such as is the case in New Jersey, the sample must be counted
as quickly following collection as possible, but not longer than 72 hours. In NJ, on the basis of the
prevalence of 224Ra in major aquifers, gross alpha is used as a conservative test to capture
elevated levels of 224Ra that are considered to be of regulatory concern. If 224Ra is not of regulatory
concern, however, the presence of this short-lived radionuclide will be detected by the gross alpha
measurement and increase the risk of non-compliance. In such cases, delaying the count of the
sample will minimize the likelihood that the gross alpha MCL will be exceeded.
Another limitation of all approved gross alpha evaporation methods2 relates to interference from
sample solids. High sample solids is a recognized interference to evaporation methods. Most
methods require that laboratories limit the size of sample that can be measured to that which will
produce less than one-hundred milligrams of dried solids. As sample solids concentrations
increase, the size of the sample that can be counted decreases and the uncertainty of results
increases. If solids concentrations are too high, it may not be possible for a laboratory to meet the
SDWA Required Detection Limits (RDL) for gross alpha of 3 pCi/L. While there is no formally
enforced limit, Standard Methods and EPA methods recommend using a co-precipitation method
instead of the evaporation method for samples containing more than 500 mg/L of total dissolved
solids.3
Although laboratories must adhere to the 100 mg limit on solids, and some laboratories extend
counting times to meet Required Detection Limits, these measures may not always produce
results that are compliant with SDWA requirements for sensitivity. It may be difficult or impossible
for data users (or even laboratories) to identify non-compliant data unless the laboratory
2
All methods except SM 7110C and EPA 00-02 rely on evaporation of the sample to prepare the test source.
3
SDWA-approved methods, SM 7110C and EPA 00-02, use the principle of co-precipitation to chemically isolate
alpha emitters from sample solids which can usually produce SDWA compliant results for samples containing
elevated solids above 500 mg/L.
calculates and reports the actual (a posteriori) SDWA Detection Limit achieved for each sample
result using information specifically associated with that sample. This sample-specific information
allows utilities to more readily identify non-compliant results that are not of sufficient quality to be
used to make compliance decisions.4
Another source of interlaboratory variability for the evaporation methods results from counting
sample planchets with unevenly distributed solids residues. While this is in part an intrinsic
weakness of a method that requires evaporation of a wide variety of types of waters, weak
laboratory technique can exacerbate the issue. Finally, an EPA Method 900.0 requirement
specifies that laboratories calibrate the instrument using solid residues obtained by evaporating
their tap water. This may result in calibration standards that are both poorly intercomparable with
other laboratories and poorly representative of samples being analyzed5, and thus introduce
varying degrees of bias into gross alpha measurements. The impact of these two issues on the
utilities’ results are best controlled by ensuring that results for internal quality control (QC) data
(laboratory control samples (LCS) and matrix spikes (MS)), and for proficiency testing (PT) show
results that are consistent with minimum requirements presented later in this document (i.e., Table
4).
These approaches all combine chemical complexation with co-precipitation to produce a test
source of purified radium in a barium sulfate precipitate. Alpha emissions from the test source are
analyzed using low-background gas flow proportional counting 8 with corrections applied for
detection efficiency, ingrowth, and in the case of SM 7110 B (but not EPA 903.0), chemical yield.
The turn-around time for this method can be as quick as 24 hours, although, as will be discussed
below, higher quality results can be obtained by delaying the counting of the sample after
preparation for up to three weeks.
These methods measure alpha-emitting isotopes of radium and are commonly given the
misleading name of “Total Radium” or “Total Alpha-Emitting Radium Isotopes”. Since isotopes of
a given element cannot be chemically separated from one another, the test source will contain
any radium isotopes present in the sample, including 228Ra, 226Ra, 224Ra, and 223Ra. While 228Ra
4
See the Generic SDWA Detection Limit Calculation in Appendix B.
5
since the chemical composition of dissolved solids in the calibration matrix differ from than that of samples being
analyzed
6
Alpha scintillation of the evaporated test source is permissible but is only infrequently performed. Alpha spectral
methods are available but not approved.
7
SM 7500-Ra D may optionally incorporate the precipitation approach used in SM 7500-Ra B.
8
Other alpha detection methods may be used but this is rare. The alpha spectral method is more sensitive but
requires more detailed wet chemistry preparation.
is of regulatory concern, it is a low-energy beta emitter and will not be detected using these
methods that are sensitive only to alpha emitters9. The other three radium isotopes are all alpha
emitters that will be detected if they are present in the test source at the time of the count. 226Ra
is the analyte of concern. 224Ra is an interference to the determination of the methods meant to
screen for 226Ra.10 While 224Ra is often present in freshly collected samples at levels similar to
228
Ra, it decays away in the first 2-3 weeks after sample collection (see discussion and Figure 2
above). 223Ra is a member of the naturally-occurring 235U decay chain that may be present in
samples at the time of collection at approximately five percent the concentration of 226Ra so it
does not contribute very significantly to the overall activity.
This precipitation / GPC method is generally described as a screening technique for 226Ra. The
largest weakness of this method regards interference from 224Ra. Similar to the approach
discussed for gross alpha above, delaying the sample count until at least 2-3 weeks after
collection allows time for 224Ra to decay away (see Figure 2). During this time, 222Rn and its
progeny continue to ingrow (see Figure 1) and effectively amplify the signal from 226Ra. This
further overwhelms any interference remaining from 224Ra to the point where its impact is
equivalent to less than about 2% of its original activity.
One difference between the two most commonly used approaches is that EPA 903.0 does not
apply a chemical yield correction, whereas SM 7110 B does. Radiochemical methods routinely
correct results for losses occurring during chemical separation based on the recovery of
carriers/tracers that are added to the sample prior to processing. Failure to account for such
losses could result in significantly low results and failure to properly identify water as being out of
compliance with SDWA requirements.
Interlaboratory proficiency testing data for 226Ra precipitation / gas flow proportional counting
methods (Appendix A) show positive bias and high relative uncertainties. The skew toward high
results may be evidence that at least some laboratories are counting ERA Proficiency Testing
samples (PTs) that contain ingrown 224Ra promptly after separation. EPA 903.0 shows a mean
recovery of 107% and a relative standard deviation (%RSD) of 44% with the average recovery
and %RSD rising to 120% and 70%, respectively, at concentrations in the 3-10 pCi/L range where
compliance decisions are made. A high %RSD for proficiency testing results, especially when
there are data from large numbers of laboratories, usually indicates that a method is inherently
variable. SM 7500-Ra B shows a mean recovery of 100% with a %RSD of 16%. Although there
is no change in average recovery, the %RSD rises to 20% at concentrations in the 3 -10 pCi/L
range where compliance decisions are made. While the reason for the difference in performance
of the two similar methods cannot be determined with certainty, the extended discussion in
Method SM 7500-Ra B of the impact of 224Ra on measurements may prompt laboratories to delay
counting of sample to address the interference.
Radon-Emanation Methods
In contrast to the precipitation methods above, which are often described as screening methods,
radon emanation methods are generally considered to be definitive or confirmatory methods
capable of very accurate and precise measurements. The cost for these methods tends to be
higher than the precipitation GPC approach.
Radium in the sample is first chemically separated using the complexation approach common to
the precipitation methods above. The precipitate is dissolved and the liquid transferred to a
bubbler apparatus, purged of radon, and sealed and stored for a period of time to allow 222Rn to
9
See below for further discussion of 228Ra methods.
10
Except in New Jersey.
ingrow (see Figure 1). The radon gas is then carefully flushed into an alpha scintillation cell for
counting on a photomultiplier tube device.
This is an old, but tried -and-true method. When run reliably, it can deliver accurate and precise
measurements. In practice, however, it is very time intensive and technique dependent. It requires
complex glassware and a skilled analyst. The most commonly run method, EPA Method 903.1,
does not correct results for losses during processing (chemical yield). Unknown losses of radon
can also occur during the transfer of radon gas. While in the hands of a capable analyst, these
losses are generally, on average, minimal, but more significant issues may occur with individual
samples and the problem will never be detected. Frequent analysis of standards can help identify
recurring leakage and weak technique, but the additional quality control is time consuming and
costly. Turn-around times for this method vary from 1 - 4 weeks depending on the length of the
ingrowth period used by the laboratory, with 3-4 weeks being typical to achieve the best sensitivity
levels.
Interlaboratory proficiency testing data for EPA Method 903.1 (Appendix A) show an average
recovery of 97% with a %RSD of 18%.
This is a newer option for drinking water analysis. High Purity Germanium (HPGe) gamma-ray
spectrometry, however, has been used for at least two decades to produce highly accurate and
precise determinations of 226Ra and 228Ra in water samples. While the sensitivity of this approach
may not quite match that of the precipitation or de-emanation approaches, this is more than
compensated for by the reliability and specificity possible using gamma-ray spectrometry, and the
relative ease and robustness of sample preparation and analysis. While the cost of this method
tends to be somewhat higher than for the precipitation and de-emanation methods (due to the
high cost of the detection system), it does allow both 226Ra and 228Ra to be determined in a single
measurement. To increase the sensitivity at low levels, however, large sample sizes (e.g., 3-4
liters) and / or a considerable increase in counting time is needed.
Given that this is a method has only been more recently approved for use with SDWA, the
interlaboratory proficiency testing data (Appendix A) are sparse; however results are generally
tighter than for the other types of methods. The most frequently performed method is the Georgia
Tech (GA Tech) method. Average recovery for 226Ra is 99% with a %RSD of 12%.
Interlaboratory proficiency testing data (Appendix A) for approved 228Ra methods that employ gas
flow proportional counting show average recoveries ranging from 97-108% (overall average
100%), with %RSDs ranging from 20-26% (overall 24%). It is noted that the acceptance range
for PT samples containing 228Ra at the 5 pCi/L MCL is 41% to 153% and for PT samples
containing 228Ra at 15 pCi/L where counting uncertainty is lower, would be 53% - 135%. EPA’s
Drinking Water Certification Manual specifies that recoveries for control samples (LCS/LFB) which
can be spiked at the higher activity, should fall in the range of 100 ± 20% (1σ = 8.3%).
At present, there are insufficient criteria in the existing methods to ensure that utilities will
consistently get reliable results from multiple labs, even while the labs are following approved
methods. The purpose of this section is to provide a framework for utilities to use in contracting
with laboratories that, if followed, will allow them to improve the precision and accuracy of
measurements. Ultimately, EPA needs to update the SDWA radionuclide methods, but that is
not a short term solution. In the meantime utilities need to know that before they invest significant
capital on treatment systems, that they truly have verified a compliance problem.
At the low end of the PT acceptance range, counting uncertainty is by far the largest contributor
to overall uncertainty of the result. This error-source identification is positive since counting
uncertainty is generally the most predictable and easily managed component of uncertainty. The
effect on the results can be minimized by processing larger amounts of sample and by extending
sample count times. Neither of these measures requires that methods be modified so they can
be done within the bounds of approved methods. As larger sample sizes are processed and count
times are extended and measurement uncertainties approach a minimum, the uncertainty is
controlled by uncertainties associated with the core efficacy/reliability of the analytical approach
itself, factors such as the uncertainty associated with yield determinations and detector
calibrations.
For this reason, EPA’s Drinking Water Certification Manual specifies that the recovery for control
samples (LCS/LFB), which can be spiked at higher activities, should fall within the range of 100
± 20%. This ensures that relative uncertainties be maintained at approximately 8.3% (1σ) and
forces laboratories to ensure that they have control of core analytical process (as opposed to
relying on counting uncertainty to explain anomalous results).
Once laboratories have control over the core integrity of their analytical method, they and the
utility are in a position to obtain data optimized to make reliable decisions. By using performance
data such as QC and PT sample results, water utilities can identify reliable and well qualified
laboratories to perform analysis. They can make ongoing decisions that balance the need for
high precision, accuracy and reliability against cost based on what they do (or do not) know about
water samples. For example, if they expect results to be close to key decision points (e.g., MCLs
or levels that impact the frequency of required testing) or if they just do not know what levels of
contaminant may be in a sample, they can instruct the laboratory to minimize result uncertainty
by implementing more costly measures. Such measures might include using the most reliable,
accurate and precise methods, processing larger samples, and/or extending count times. In
contrast, when results are expected to be well below key decision points and the need for
precision is lower, they can allow the laboratory to use less costly analytical approaches. This
requires extensive communication with the laboratory that should be considered as part of the
original contracting process between the lab and the utility.
The first flow chart addresses the process that can be used to identify laboratories that are
qualified and capable of meeting and exceeding minimum requirements specified in EPA’s
Manual for the Certification of Laboratories Analyzing Drinking Water Criteria and Procedures
Quality Assurance (5th Edition, 2005).
Seek another
Request qualifications lab for this
from each potential lab parameter
standing parameter?
(certification/
accreditation)
Yes
for all Send compliance samples for
parameters? analysis.
Review PT results and corrective
No
actions for each parameter
Consider whether lab can Write request for bid Including Evaluate bids and confirm
Yes requirements to implement
function as back-up for capabilities and award to
parameters for which they recommendations of this one or more of the best
report. qualified labs.
are certified. Review internal QC result
information
alpha
No combined > ½ MCL
Water Compliance Measurements for gross alpha.
radium (7.5 No
>2 pCi/L pCi/L)
Some of the recommendations go beyond literal requirements of the SDWA program – but
following these requirements will improve the accuracy and precision of results and can
minimize the rate of decision errors about compliance with SDWA requirements.
11
New Jersey regulates 224Ra. NJ’s required methods require initial and second counting of the sample within 48
hours of collection which will help ensure that samples containing significantly elevated levels of 224Ra will be
reliably identified. If the gross alpha at that point is elevated above 5 pCi/L, testing for 226Ra directly is indicated.
This approach conservatively presumes uniform strong association among the Ra radionuclide occurrences,
which is true for many (but not all) aquifers. The additional alpha count of the sample approximately three
weeks after preparation with amplifed signal from 226Ra, is not required although it is advisable. Exceeding the
15 pCi/L MCL for Combined Gross Alpha after the counts are completed within 48 hours necessitates action by
the utility on the basis of the prevalence of 224Ra in aquifers of the State of New Jersey.
12
For example, only 7% and 2%, respectively, of the amount of 224Ra initially present will remain 14 and 21 days
after sample collection (Figure 2).
o Ensure that the SDWA Required Detection Limit (RDL) of 3 pCi/L has been met for
each sample by optimizing the sample aliquot and count time.
Optimize the volume of sample taken for analysis – There are multiple
sources of uncertainty in the gross alpha analysis, but the dominant
source in low-activity samples is the counting uncertainty, which is
inversely proportional to the square root of the number of counts.
Processing larger sample aliquots will provide higher signal-to-noise and
decrease the counting uncertainty. Beyond practical limitations
(available equipment, bounds of validated methods), the maximum size
of sample that can be processed is limited by methods to that which will
produce ≤ 100 mg of solid residue in a 2” planchet.
If sample TDS concentration is known, process enough sample to
ensure that the RDL will be met in the count time planned for samples.
Gross alpha counting efficiency is highly impacted by the solids
present in the sample. Lower counting efficiencies result in lower
count rates and much greater uncertainty.
If solids concentrations in samples are unknown, estimate the TDS
(using conductivity of an unpreserved portion of multiplied by 0.6).
Alternatively a small portion of sample may be evaporated and used to
estimate the solids in the sample. Once an estimate of the solid content
is obtained, this can be used to calculate the amount of sample needed
to produce residues that approach but do not exceed 100 mg in a 2”
diameter planchet
If the TDS concentration is known to exceed 500 ppm, analyze the
sample using a coprecipitation method (e.g., SM 7110 C) rather than
an evaporation method (e.g., EPA 900.0 or 7110 B).
Clearly, there is a practical limit to how long a sample can be counted.
Count samples to meet a SDWA detection limit of 3 pCi/L, or to result
in a relative counting uncertainty of less than or equal to 16% (1.96σ)
assuming 15 pCi/L is present in each sample, whichever is longer.
The laboratory should calculate the actual SDWA DL13 achieved for
each sample and QC sample analyzed and verify that they have at least
met the RDL of 3 pCi/L for gross alpha. Require that the laboratory
report, for each result, the DL achieved in the laboratory report to the
utility and to regulators (see Appendix B for a generic calculation). If the
13
A generic calculation for the SDWA Detection limit is presented in Appendix B. Note that the SDWA DL is specific
to the SDWA and should not be confused with other detection concepts such as: LLD, MDA, MDC, RL, or Lc. The
SDWA DL should be calculated and reported for each sample result.
detection limit is not met, consider reprocessing the sample using more
optimal conditions to obtain the required sensitivity.
If sample gross alpha concentrations are unknown, may be variable, or are known or are
expected to be within 5 pCi/L of the 15 pCi/L MCL, proceed as follows, and as price permits:
o Use the most reliable method for analysis. Based on PT data analyzed in this paper,
we would recommend that SM 7110 C be used (regardless of solids content) since it
allows use of a significantly larger aliquot while producing a much more reproducible
test source;
o Follow recommendations from above regarding delay of processing samples until 2-3
weeks after collection;
o Minimize the time between the preparation and counting;
o Maximize the sample aliquot. If possible process up to 1 L of sample to minimize
uncertainty;
o Increase the counting time to target 1σ counting uncertainties of 5-8% (or better);
o Ensure that requirements for batch QC samples summarized in Table 4 are met or
exceeded.
o Review all results to ensure that only results that are compliant with SDWA
requirements are used to make compliance decisions.
228
Ra analysis
Ensure that the laboratory meets all requirements defined in 40 CFR 141 and that the
laboratory uses a validated method that satisfies the batch quality control requirements
summarized in Table 6 below.
o Preferably specify the use of the GA-Tech method in lieu of EPA Method 904.0.
The specificity of the spectrometric method and the ability to more easily
process much larger samples produces more precise and accurate results.
Interlaboratory study results indicate that the GA Tech method yields results
with a relative standard deviation of 16% (1σ), as compared to 26% for EPA
Method 904.0 (see discussion above and data in Appendix A)
o If using Methods 904.0 or 7500 Ra-D which require determination of yield using
gravimetric methods, the laboratory’s LCS and MS recoveries should be inspected.
These methods have numerous chemical separation steps and
measurement of the barium and yttrium yield can be inaccurate. This can be
exacerbated if samples contain more than a few mg of barium to begin with.
(In theory elevated levels of barium should not occur in finished drinking
waters, as the barium MCL is 2 mg/L but some source waters may contain
high levels.)
If mean/median values significantly less than 100% are observed, we
recommend that yield measurements be confirmed by monitoring barium
with either ICP-AES or ICP-MS analysis or by using 133Ba as a tracer. If
gravimetric yield and confirmation method differ by more than 10%
absolute, repeat sample preparation with a fresh aliquot as the non-
gravimetric techniques are not currently allowed for compliance
measurements until new versions of the methods are approved (Consider
whether re-precipitation (i.e., repeating BaSO4, or Y2(C2O4)3 precipitation
steps) may be used to purify precipitates)14. Alternatively, use a more
reliable method (e.g., GA Tech).
14
This may require involving the regulator to obtain concurrence on the approach to be used.
Optimize the sample aliquot and count samples to meet a SDWA detection limit of 1 pCi/L,
or to result in a relative counting uncertainty of 16% (1.96σ) assuming 5 pCi/L is present
in each sample, whichever is more restrictive.
o The laboratory should calculate the actual SDWA DL achieved for each sample
and QC sample analyzed (see Appendix B for a generic DL calculation) and verify
that they have at least met the RDL of 1 pCi/L for 228Ra. Require that the laboratory
report, for each result, the DL achieved in the laboratory report to the utility and to
regulators (if the regulatory reporting system allows that). If the detection limit is
not met, consider whether reprocessing the sample using more optimal conditions
will result in meeting the required sensitivity.
Appendix A contains a detailed summary and analysis of proficiency testing results by analyte
and method that indicate performance for different methods for all drinking water laboratories.
The data also show differences between methods as shown in the following proficiency testing
data review.
Interlaboratory proficiency testing samples contained activities ranging from 7 pCi/L to 70 pCi/L.
The NELAC FOPT table acceptance ranges for Gross Alpha (230Th) PT samples at 7 pCi/L, 15
pCi/L (the MCL for Corrected Gross Alpha), and 25 pCi/L are 10%-204%, 25%-167%, and 38%-
154%, respectively.
The result that ranges for recovery converge towards 100% with increasing activity is consistent
with findings of other such tabulations. Although the distribution of results is largely normal, long
tails reflect intermittent extreme results. It is not clear whether this reflects method performance
or the fact that data contain results from more and less reliable laboratories.
PT results for gross alpha evaporation methods showed an average recovery of 95% and a %RSD
of 23% (1σ). At concentrations close to the MCL of 15 pCi/L where compliance decisions are
made, the %RSD for Method 900.0 was somewhat higher at 29% (1σ) with SM 7110 B largely
15
See Appendix A for detailed analysis of drinking water laboratory proficiency testing results.
unchanged at 22% (1σ). PT results for Gross Alpha co-precipitation methods showed an average
recovery of 92% with an %RSD of 18% (1σ). For method SM 7110 C, at concentrations close to
the MCL of 15 pCi/L, where compliance decisions are made, the average recovery was 91% with
a %RSD of 15% (1σ). At concentrations around the MCL, EPA co-precipitation Method 00-02
showed average recovery of 96% and %RSD of 26% (1σ).
For the four approved methods for which there were a significant number of results provided,
there were notable differences in the quality of results. While the range of average recoveries
among the methods was relatively small (91%-97%), the most commonly used method, EPA
900.0, showed the poorest precision with a standard deviation of 24% (1σ). In contrast, co-
precipitation method SM 7110 C, showed a relative standard deviation of 16% (1σ) which is 20-
33% lower than the other methods, likely a result of the nearly uniform planchet matrix and mass
generated by the technique. For 7110 C, 95% of reported results fell between 62% and 124%, a
range that, although slightly skewed low, is close to the ideal range targeted for internal quality
control sample results (LCS/LFB) in the Drinking Water Certification Manual. As such, SM 7110 C
would appear to be the best method available for samples with unknown activities, or samples
with true activities close to a trigger point.
It is important to note that the alpha emitter in gross alpha PT samples is 230Th, which does not
exhibit the time-sensitive changes in activity discussed for 226Ra and 224Ra. Thus, PT statistics
provide a false sense of security about the quality of results that will be obtained when
analyzing real samples. As described above, and depending on individual laboratory practices,
time-sensitive effects may introduce additional bias and uncertainty into actual test results in
excess of 400% of the activity of radium isotopes present. Especially as the sample activity
approaches the MCLs, the uncertainty apparent in the PT results will combine with uncertainty
associated with the timing of the count and significantly increase the risk that measurement
conditions may result in arbitrary compliance decisions.
If gross alpha were used only as a screening technique for radium, and if exceedances were
always followed by confirmation using more reliable testing methods (such as is the case for 226Ra
or beta emitters), elevated uncertainties might be tolerable. This is not the case for adjusted gross
alpha, however, where the result obtained is compared directly to the gross alpha MCL to make
a final compliance decision. Thus, uncontrolled uncertainty (and bias) in the gross alpha
measurement can have quite a large and arbitrary effect on compliance decisions. Further
discussion of the impact of measurement uncertainty and measures that might be taken to
minimize its negative impact on compliance decisions follows below.
Table 2: Summary of 226Ra Proficiency Testing Results from ERA PT Studies 55-99
Interlaboratory proficiency testing samples contained with activities ranging from 3 pCi/L to 20
pCi/L. PT acceptance ranges for samples containing 226Ra at 5 pCi/L (Ra MCL) and 15 pCi/L are
65%-133% and 64% - 125%, respectively. Convergence in the ranges of recovery is not as
noticeable with increasing concentration as it is for increasing gross alpha activity because the
specific isotope analyses for 226Ra uses more elaborate preparation techniques and
instrumentation that produce results considerably more accurate and precise than the gross alpha
measurement (the exception being use of GPC for Method 903.0).
Among the four approved methods for which there were a significant number of results provided,
there were notable differences in the quality of results. While the difference in average recoveries
among the methods was relatively small (99-107%), the most commonly used method, EPA
903.0, demonstrably showed the poorest precision with a standard deviation of 44% (1σ). In
contrast, the least commonly used method, the gamma spectrometry method from Georgia Tech,
showed a standard deviation of 12% (1σ) which was 25-73% better than the other methods.
Consistent with this observation, 95% of reported results for the Georgia Tech method fell
between 85% and 125%, a range that is very close to the ideal range 80%-120% targeted in the
Drinking Water Certification Manual for internal quality control sample results (LCS/LFB). As
such, the Georgia Tech gamma spectrometry method would appear to be the best method
available for samples with unknown activities, or samples with true activities close to a trigger
point.17
16
See Appendix A for detailed analysis of drinking water laboratory proficiency testing results.
17
It is noted that the number of data points available for the GA Tech method was small, but the statistics are
consistent with method performance that would be expected using much more modern spectrometric
instrumentation. There is a possibility of inadvertent sample compilation bias with regards to this method – if
only experienced labs offering high level of sample care from expert analytical staff use it. Investigation may be
warranted to further characterize the performance of this method as more data become available. The authors
do note gradual movement at laboratories away from de-emanation while gamma spectrometry appears to be
Table 3: Summary of 228Ra Proficiency Testing Results from ERA PT Studies 55-99
The PT samples contained activities that range from 3 pCi/L to 20 pCi/L. PT acceptance ranges
for samples containing 228Ra at 5 pCi/L (Ra MCL) and 15 pCi/L are 41% - 153% and 53% - 135%,
respectively.
Among the five approved methods for which there were a significant number of results provided,
there were notable differences in the quality of results. While the difference in average recoveries
among the methods was relatively small, the most commonly used method, EPA 904.0, showed
the poorest precision with a standard deviation of 26% (1σ). In contrast, the least commonly used
method, the gamma spectrometry method from Georgia Tech, showed a standard deviation of
16% (1σ) which was 20-40% lower than the other methods. Consistent with this observation, 95%
of reported results for the Georgia Tech method fell between 72% and 137%, a range that is close
to the ideal range targeted in the Drinking Water Certification Manual for internal quality control
sample results (LCS/LFB). As such, the Georgia Tech gamma spectrometry method would
appear to be the best method available for samples with unknown activities, or samples with true
activities close to a trigger point.19 There are no comparable approaches that provide better
sensitivity of even comparable accuracy and precision as was the case for the de-emanation
method for 226Ra.
Listed here are some lab performance characteristics that should help in evaluation of a lab’s
ability to meet requirements.
gaining in popularity. While the de-emanation method offers similar (and better performance at the lowest
detection levels (i.e., <<0.5 pCi/L where detection capability of the gamma spectral method diminishes). As far as
228
Ra is concerned, the absolute sensitivity of the gamma measurement is not as good as for 226Ra, but in relative
terms, it is at least comparable to that provided by GPC with significantly better performance as far as bias,
precision, specificity, and robustness and reliability are concerned.
18
See Appendix A for detailed analysis of drinking water laboratory proficiency testing results.
19
It is noted that the number of data points available for the GA Tech method was small, but the statistics are very
consistent with method performance that would be expected using much more modern spectrometric
instrumentation. See footnote 15.
Gross alpha/beta
Method selection
o Commitment and ability to use a method that does not delay the count of samples
for 72-hours after preparation as documented by an SOP that states that samples
shall be counted as quickly as possible but which establishes a holding time
between sample preparation and counting of 48 hours (and preferably sooner). At
present this would eliminate Method 900.0 as an option, but it is expected that
EPA’s newer version of 900.0 will eliminate the 72-hour delay (in upcoming
revisions).
o Commitment and ability to use co-precipitation for any samples with TDS >500
ppm, and for samples that are deemed to require higher precision results (i.e.,
results that are very close to decision or trigger points).
LCS spikes are high enough to minimize counting uncertainty. Current LCS control charts
are provided to demonstrate that the QC limits for LCS fall within the range of 100 ± 20%
(3σ), and that the laboratory is consistently able to meet these requirements.
Matrix spikes (MS) are at approximately 10 times the lab’s default detection limit (or 10
times the expected sample activity, whichever is higher), which under the SDWA must be
at or below 3 pCi/L for alpha, so ~30 pCi/L. Current MS control charts are provided to
demonstrate that the QC limits for MS fall within the range of 100 ± 30% (3σ), and that the
laboratory is consistently able to meet these requirements.
Agreement to follow the requirements of the Lab Certification Manual for radiochemistry
and the batch QC requirements presented in Table 4.
Ability to report elapsed time between prep and counting and the SDWA detection limit
achieved for each sample.
Maximum DL of 1 pCi/L
o The laboratory determines compliance with SDWA on a sample-by-sample basis
and reprepares any samples for which sensitivity requirements are not met..
LCS spikes are high enough to minimize counting uncertainty (e.g., 15 pCi/L)
o Current LCS control charts are provided to demonstrate that the QC limits for LCS
fall within the range of 100 ± 10% (3σ), and that the laboratory is consistently able
to meet these requirements.
Matrix spikes are at approximately 10 times the lab’s default detection limit (which must
be at or below 1 pCi/L under the SDWA), or 10 times the sample activity, whichever is
higher); so ~10 pCi/L, depending on sample activity.
o Current MS control charts are provided to demonstrate that the QC limits for MS
fall within the range of 100 ± 20% (3σ), and that the laboratory is consistently able
to meet these requirements.
Agreement to follow the requirements of the Lab Certification Manual for radiochemistry
and the batch QC requirements presented in Table 5.
Ability to report elapsed time between prep and counting and the SDWA achieved for each
sample.
Maximum DL of 1 pCi/L
o The laboratory determines compliance with SDWA on a sample-by-sample basis
and reprepares any samples for which sensitivity requirements are not met.
LCS spikes are high enough to minimize counting uncertainty (e.g., 15 pCi/L)
o Current LCS control charts are provided to demonstrate that the QC limits for LCS
fall within the range of 100 ± 20% (3σ), and that the laboratory is consistently able
to meet these requirements.
Matrix spikes are at approximately 10 times the lab’s default detection limit (which must
be at or below 1 pCi/L under the SDWA), or 10 times the sample activity, whichever is
higher); so ~10 pCi/L, depending on sample activity.
o Current MS control charts are provided to demonstrate that the QC limits for MS
fall within the range of 100 ± 30% (3σ), and that the laboratory is consistently able
to meet these requirements.
Agreement to follow the requirements of the Lab Certification Manual for radiochemistry
and the batch QC requirements presented in Table 6.
Ability to report elapsed time between prep and counting and the SDWA achieved for each
sample. Control chart of gravimetric barium yield available.
& Ten and twenty sample limits do not include quality control samples.
** Although extending the duration of a sample count can lower uncertainty, for methods that measure 222Rn following separation
from 226Ra, recounting must be conducted promptly to be a viable option due to the short half-life of the analyte. For methods
that measure gamma spectrometry methods, extending counts will help achieve lower uncertainty. Sample counts should not
be extended beyond the duration if the routine background subtraction count since the laboratory cannot demonstrate
statistical control over longer counts.
++ The LCS is also referred to as the Laboratory Fortified Blank (LFB).
Over 7,000 data points for gross alpha, Gross Beta, 226Ra and 228Ra from studies Rad-55 – Rad
99 were obtained from ERA, the sole provider of radiochemistry proficiency testing for drinking
water. The information in Excel spreadsheet format included: study ID; analyte; laboratory
reported method IDs; laboratory reported result; ERA assigned true value. All laboratory identifiers
had been removed by ERA, which prevented an assessment of single laboratory versus overall
performance. It is also noted that measurement uncertainty and detection limits are not captured
by the PT data reporting program, and that ERA does not report uncertainties for its assigned
values. This prevents rapid assessment of whether individual results had been run with sufficient
precision to meet EPA assigned measurement quality objectives for SDWA.
Since ERA allows laboratories to manually enter method identifiers, a large number of variants of
methods were present in the data. The data had to be manually reviewed to eliminate records
where the laboratory supplied method identifier could not unambiguously be correlated to EPA-
approved methods. The remaining data were then collated. Methods for which fewer than 30 data
points were reported were eliminated.
The percent recovery (the reported value divided by the true value times 100) was evaluated for
the three critical analytes (gross alpha, 226Ra, and 228Ra), and any method for which the minimum
of 30 data points was available. A normal probability plot was prepared for all methods and for
each of the methods to qualitatively assess the normality of results. The vast majority of results
appear to be normally distributed, and thus appear to be consistent with likely true output from
the method as opposed to spurious data points attributable to non-method-related occurrences in
the lab, such as data entry errors. Descriptive statistics were calculated on the remaining data
set, and again on smaller subsets of results close to the Maximum Contaminant Level.
For gross alpha methods, the distribution of recoveries generally conforms to a normal distribution
with a small number of apparent outlying data points. EPA Method 900.0 is the exception with a
positive skew and fat high tail. This implies that the standard deviation underestimates the number
of points in the high tail of the distribution.
For 226Ra, the analyte recovery distribution is largely normal. Methods EPA 903.0 and SM 7110
B show a heavier high-side tail than do the isotope specific methods. A high tail would be
consistent with results impacted by 224Ra present as an accumulated decay product of 228Ra in
the test samples20. While the distribution of results for the GA Tech method appears to conform
well to a normal distribution, the number of points available is too small to make firm conclusions.
Continued data collection is needed to develop a more robust characterization of the performance
of this method.
For 228Ra, methods EPA 904.0, and to a lesser extent EPA Ra-05, show a heavy high-side tail,
likely due to bias associated with yttrium yield correction. The distribution of analyte recovery for
methods SM 7500-Ra D and the Brooks and Blanchard Method appear to conform well to a
normal distribution. The distribution of results for the GA Tech method appears to conform to a
normal distribution, but the number of points available is too small to make any firm conclusions.
Similar to 226Ra, continued data collection is needed to develop a more robust characterization of
the performance of this method.
20
While some labs delay counting of the test source until 2-3 weeks after preparation to allow for 224Ra to decay,
other labs do not which would result in high bias for results counted more promptly after preparation.
Summary of Method Performance Data for ERA Gross Alpha PT Studies 55-99 Results
Data Stnd. 2.5 97.5
Method Points Average Dev. Min. percentile Median percentile Max
EPA 900.0 1537 95% 24% 27% 52% 93% 148% 246%
Gross EPA 00-02 223 91% 20% 40% 49% 93% 130% 195%
Alpha SM 7110 C 198 92% 16% 7.5% 62% 92% 124% 133%
SM 7110 B 161 97% 22% 7.2% 54% 98% 137% 174%
All Methods 2119 94% 23% 7.2% 52% 93% 143% 246%
100
90 40 Alpha MCL
80 Alpha MCL
70
30
60 1:1 Line 1:1 Line
50
40 20
30
20 10
10
0 0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 0 5 10 15 20 25 30
Known Value (pCi/L) Known Value (pCi/L)
60
55 25
50
45 Alpha MCL 20
40
35 15
30
25 1:1 Line 1:1 Line
10
20
15
10 5
5
0 0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 0 5 10 15 20 25 30
Known Value (pCi/L) Known Value (pCi/L)
70 Alpha MCL
65
60 Alpha MCL 20
55
50
45 15
40
35
30 10 1:1 Line
1:1 Line
25
20
15 5
10
5
0 0
0 5 10 15 20 25 30 35 40 45 50 55 60 0 5 10 15 20 25 30
Known Value (pCi/L) Known Value (pCi/L)
SM Method 7110B
SM Method 7110B Gross Alpha Results < 25 pCi/L
All Gross Alpha Results 30 y = 0.9365x - 0.0211
90 y = 0.9316x + 1.46
85 25 Alpha MCL
80
Reported Value (pCi/L)
75
Reported Value (pCi/L)
70 20
65
60
55
50 Alpha MCL 15
45 1:1 Line
40
35 10
30 1:1 Line
25
20 5
15
10
5 0
0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 0 5 10 15 20 25 30
Known Value (pCi/L) Known Value (pCi/L)
Summary of Method Performance Data for ERA 226Ra PT Studies 55-99 Results
Data Stnd. 2.5 97.5
Method Points Average Dev. Min. percentile Median percentile Max
EPA 903.0 534 107% 44% 16% 80% 103% 321% 619%
EPA 903.1 312 97% 18% 23% 61% 97% 125% 223%
Radium
226 SM
150 100% 16% 55% 70% 99% 133% 171%
7500-Ra-B
Ga. Tech 33 99% 12% 77% 85% 99% 125% 143%
All Methods 1029 103% 34% 16% 68% 99% 146% 619%
35
30 5 pCi/L MCL 20
25 5 pCi/L MCL
1:1 Line 15
20
15 10 1:1 Line
10
5
5
0 0
0 5 10 15 20 0 1 2 3 4 5 6 7 8 9 10
Known Value (pCi/L) Known Value (pCi/L)
30 5 pCi/L MCL
20 5 pCi/L MCL
25
20 15 1:1 Line
15
1:1 Line 10
10
5
5
0 0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 0 1 2 3 4 5 6 7 8 9 10
Known Value (pCi/L) Known Value (pCi/L)
20
Reported Value (pCi/L)
0 0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 0 1 2 3 4 5 6 7 8 9 10
Known Value (pCi/L) Known Value (pCi/L)
5 pCi/L MCL
10
15
10
1:1 Line 5
5
1:1 Line
0 0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 0 1 2 3 4 5 6 7 8 9 10
Known Value (pCi/L) Known Value (pCi/L)
GA Tech Method
All Ra-226 Results
40
y = 0.912x + 1.0185
35
Reported Value (pCi/L)
30 5 pCi/L MCL
25
20
15
1:1 Line
10
5
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Known Value (pCi/L)
Summary of Method Performance Data for ERA 228Ra PT Studies 55-99 Results
5 pCi/L MCL
SM 7500-Ra D SM 7500-Ra D
Ra-228 Results Ra-228 Results from 3-10 pCi/L
40 15
y = 0.9196x + 0.4135 y = 0.9524x + 0.2732
35
Reported Value (pCi/L)
30 5 pCi/L MCL
25 10 5 pCi/L MCL
20 1:1 Line
15
1:1 Line 5
10
5
0 0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 0 1 2 3 4 5 6 7 8 9 10
Known Value (pCi/L) Known Value (pCi/L)
Ra-228 - GA Tech
Activity Stnd. 2.5 97.5
(pCi/L) number Average dev. minimum percentile median percentile Maximum
All results 40 102% 16% 70% 72% 101% 137% 155%
3-10 28 101% 16% 70% 71% 102% 136% 155%
10-20 12 104% 17% 85% 86% 97% 133% 136%
GA Tech
Ra-228 Results
40 y = 1.0039x + 0.1035
35
Reported Value (pCi/L)
30 5 pCi/L MCL
25
20
15
1:1 Line
10
5
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Known Value (pCi/L)
|A − B|
RER =
√sa2 + sb2
where;
A = Activity of the first measurement (in pCi/L)
B = Activity of the second measurement made from a different aliquot from the same
sample (in pCi/L)
sa = 1-sigma counting uncertainty of the first measurement (in pCi/L)
sb = 1-sigma counting uncertainty of the second measurement (in pCi/L)
Note that this formulation requires that the terms sa and sb be 1-sigma uncertainties. Inputting
1.96σ uncertainty, as has occurred at some laboratories, will result in the failure to properly identify
problematic precision for samples containing activity near the maximum contaminant level (MCL)
and can result in elevated rates of compliance decision errors for radium.
In evaluating data for radionuclides, particularly if results are very close to compliance points (e.g.
gross alpha substitution near the trigger level for 226Ra monitoring, 226Ra or 228Ra near the MCL,
gross alpha near the MCL), it is important to understand how the uncertainty of the measurement
may affect results. Even though uncertainty is not considered in most states as part of the
compliance decision (California is an exception, where gross alpha substitution for combined
radium compliance and adjusted gross alpha compliance is based on adding the error to the
measured value to be more conservative), minimizing measurement uncertainty is critical in
maximizing the likelihood of correct compliance decisions. This appendix demonstrates how
uncertainty of radionuclide measurements may influence those decisions.
For any measurement there is a finite possibility that results will generate a false positive or a
false negative. Figure 5 demonstrates that phenomenon.
Figure 5: Distribution of Possible Results for Samples Containing No Activity and Activity
at the MCL
In this example, the average measured concentration of analyte in the sample is equal to the
analytical action level. For SDWA analysis, the AAL might be the MCL (even though
compliance is based on the running annual average of quarterly samples, a utility would want
to be assured that no single measurement could drive it out of compliance.
Half of our measurement results will fall above the average and half below.
If we compare the results of each measurement directly to the action level, we will:
Incorrectly decide that the sample is in compliance (i.e., true value is less than
the action level) approximately 50% of the time (red shaded area).
Correctly decide that our sample is out of compliance (i.e., true value is equal to
or greater than the action level) approximately 50% of the time.
The blue curve emphasizes why it is so important to ensure that we control the uncertainty /
sensitivity of our measurements.
The blue curve shows the distribution of measurements of a sample that contains
no analyte (i.e., a blank sample).
In this case, the measurement uncertainty is large enough that a certain portion
of our measurements will produce results that are greater than the action level
such that we will incorrectly decide that there is activity above the AAL when
lower levels of activity are present (blue shaded area).
The next figure (Figure 6) shows a generic power curve, which relates the likelihood of
decision errors to the analyte concentration and allows one to assess the impact of incorrect
decisions. So how much uncertainty can we accept and achieve acceptable decision error
rates?
Decision makers use power curves to graphically show the rate of decision errors
relative to analyte concentration in the sample.
While we can minimize measurement uncertainty, this costs time and money.
Decision makers try to balance the cost of making incorrect decisions against the
cost of minimizing measurement uncertainty that make their decisions more
reliable.
The gray region is the area on either side of the action level.
Its width is controlled by decision makers’ confidence about their tolerance to
making incorrect decisions.
The rate of decision errors outside of the gray region is controlled at low rates
that are deemed to be acceptable by decision makers.
Within the gray region, the concentration approaches the action limit and
measurement uncertainty will limit project planners’ ability to control decision
errors at the low rate possible outside the grey region.
Ideally, the gray region should kept be as small as possible, but higher precision
measurements cost time and money.
An example of how uncertainty impacts our gross alpha measurement is shown in Figure 7.
0 1
21
Figure 6 is from US EPA Office of Environmental Information, EPA-QA/G4 - Guidance on Systematic Planning
Using the Data Quality Objectives Process, EPA/240/B-06/001 February 2006, Washington, DC.
We want to determine whether a sample contains activity that is in compliance with the MCL
for gross alpha.
The laboratory successfully follows the approved method and obtains an SDWA
DL of 3 pCi/L.
The width of results distribution is a function of measurement uncertainty which
results when a measurement satisfies the SDWA required detection limit (RDL).
About 5% of our distribution of measurements falls to the right of the action level.
Compare the measured result to the MCL for adjusted gross alpha to determine compliance
Since 5% of our measurement results will fall above the MCL, one in twenty
measurements will incorrectly produce a result that indicates that the water is not
in compliance with SDWA regulations.
It is this guide’s goal to provide a relatively straightforward road map that will help water
utilities manage the analytical process and reasonably minimize the probability of making
incorrect compliance decisions by decreasing measurement uncertainty.
References
Georgia Tech (2004) The Determination of Radium-226 and Radium-228 in Drinking Water by
Gamma-ray Spectrometry Using HPGE or Ge(Li) Detectors, Revision 1.2. Georgia Institute of
Technology, Atlanta, GA.
Standard Methods (2012) Method 7110 B - Evaporation Method for Gross Alpha-Beta Standard
Methods for the Examination of Water and Wastewater, 22nd edition, 2012. American Public
Health Association, Washington, D.C.
Standard Methods (2012) Method 7110 C - Coprecipitation Method for Gross Alpha Radioactivity
in Drinking Water Standard Methods for the Examination of Water and Wastewater, 22nd edition,
2012. American Public Health Association, Washington, D.C.
Standard Methods (2012) Method 7500-Ra B - Precipitation Method Standard Methods for the
Examination of Water and Wastewater, 22nd edition, 2012. American Public Health Association,
Washington, D.C.
USEPA (1984) Method 00-02 – Radiochemical Determination of Gross Alpha Activity in Drinking
Water by Coprecipitation in: Radiochemistry Procedures Manual December 1984 EPA 520/5-84-
006 Washington, DC
USEPA (1980). Method 900.0 - Gross Alpha and Gross Beta Radioactivity in Drinking Water in:
Prescribed Procedures for Measurement of Radioactivity in Drinking Water, EPA 600/4- 80-032,
Cincinnati, OH
USEPA (1980) Method 903.0 - Alpha-Emitting Radium Isotopes in Drinking Water in: Prescribed
Procedures for Measurement of Radioactivity in Drinking Water, EPA 600/4-80-032 Cincinnati,
OH
USEPA (1980) Method 903.1 - Radium in Drinking Water, Radon Emanation Technique in:
Prescribed Procedures for Measurement of Radioactivity in Drinking Water, EPA 600/4-80-032
Cincinnati, OH
USEPA (1980) Method 904.0 - Radium-228 in Drinking Water in: Prescribed Procedures for
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USEPA (2005). Manual for the Certification of Laboratories Analyzing Drinking Water Criteria
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