UCMR4: What Are We Seeing and What are the Issues? · There are 4 unique methods for chemicals. ......
Transcript of UCMR4: What Are We Seeing and What are the Issues? · There are 4 unique methods for chemicals. ......
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UCMR4: What Are We Seeing and
What are the Issues?
Andy Eaton, PhD, BCES, TDE*
* Technical Director Emeritus
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UCMR 4 – Where Are the
Gotchas?
Data, Data, and More Data
Sample Inventories
Methods and Analytes-the Devil’s in the details
Sample collection – more details
Data uploads
Speculation, based on a VERY limited data set
so far, because I will be retired before anyone
can prove me completely wrong….
Data, Data, Data…
UCMR 4 will ultimately generate more than
1 million sample data points
Plus a lot of batch QC data
And information on “matrix” impacts on
methods, to really know how rugged the
methods are
If the data are not good it leads ultimately to
poor decisions
And we have already discovered some
challenges with the data.
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There are Some Cases Where Sample
Inventories are Still not in SDWARS
There should be ~25,000 sample points (EP and
DS) plus 10,000-15,000 SR sites in the inventory.
As of July, 2018 there are still some that are not
complete (but a lot better than last fall…)
VA has 73 impacted utilities, and it appears that
ALL have set up inventories and schedules. It
represents about 700 unique sample points,
which will result in ~3200 samples over the life of
the UCMR 4 program.
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The Start of UCMR 4 Has Been a Bit
Rocky Compared to UCMR 3
Everything requires much more
vetting before it is released
compared to UCMR 3.
EDD formats have changed
several times since the start of
UCMR 4.
The Lab Approval Manual is on
it’s 3rd revision, and it’s only July.
There are definitely some method
ruggedness issues.
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ANALYTICAL METHODS
CHALLENGES
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A Lot of Methods Means Lots of
Opportunities for Analytical Issues
There are 3 unique methods for cyanotoxins.
544, 545, 546
There are 4 unique methods for chemicals.
525.3, 530, 541, 200.8
There is 1 method for HAA9
552.3 (or 557)
There are 2 methods to do Br and TOC.
300.0 (or 300.1) and SM5310C (or SM5310B) plus others
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Methods and Analytes: Assessment
Monitoring (17) –All Systems and LOW MRLs
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But it’s not necessarily the low MRLs that
create the challenges for labs. It’s also a
function of how rugged the method itself is.
Methods and Analytes: Cyanotoxin
Monitoring (10) – SW and GWUDI Systems
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In some cases, like the ELISA method for
total microcystins, it is indeed the MRL that
can be a challenge.
EPA 200.8 – Germanium and
Manganese
Germanium – previously
used as internal standard
Naturally occurring
Used in Electroplating
Manganese
Naturally occurring
Used in Steel production
Found in food
Both were included in UCMR3 small system sampling.
UCMR4 Method changes include no Field Blanks.
EPA 200.8 – Germanium and
Manganese
No real technical
issues; method is
tried and true.
One of the few
analytes where we
are highly likely to
have a lot of
detections (Mn).
See later slide.
Mn distribution in UCMR 3 small systems
EPA 525.3 – Pesticides by
SPE/SIM
Nine Pesticides – The Method lists 131 compounds.
alpha-Hexachlorocyclohexane Oxyfluorfen
Chlorpyrifos Profenofos
Dimethipin Tebuconazole
Ethoprop Tribufos
Total permethrin (cis & trans)
EPA 525.3 – Pesticides by
SPE/SIM
Surrogates are prone to low recovery.
Makes it almost impossible to automate
the extraction step, which leads to higher
processing costs.
Method is tricky enough that it requires a
dedicated analyst/extraction chemist (s)
Seeing occasional issues with
surrogate recoveries on some REAL
samples.
Potential for re-samples. More on this later.
EPA 530 – GCMS Semivolatiles
SPE/SIM
3 Compounds only – Butylated hydroxyanisole, o-
Toluidine, and Quinoline
Special preservatives
Buffering reagent – Trizma
Antimicrobial – Diazolidinyl Urea
Dechlorinating reagent – Ascorbic Acid
Metals inhibitor – EDTA
SPME/SIM procedure
Low reporting limits
pH acceptance limit issues – More on this later.
Both of our labs have seen occasional issues with low
surrogates.
EPA 541 – Alcohols GCMS
SPE/SIM
3 Alcohols
1-Butanol: used as solvent
2-Methoxyethanol : used in cosmetics
2-Propen-1-ol : used in chemical manufacture
Preservatives added prior to shipment
Sodium sulfite
Sodium bisulfate
Relatively small sample volume
Chromatography challenges
This method is relatively straightforward. The only issue
we had was pH of receipt; and EPA changed the specs.
Note: Method can also be used for
1,4-dioxane; and EPA has noted
that combined preservatives are
now an option for method 522
EPA 552.3 – Haloacetic Acids
9 Haloacetic Acids – only 5 currently regulated
Preservative
Ammonium Chloride
Acidic Methanol for derivatization
Gas Chromatography with EC Detector
Smaller batch sizes due to needed vortexing
Stability issues with TBAA in particular
Again, occasional surrogate issues, but
relatively straightforward.
EPA 552.3 – Haloacetic Acids
TAME is a better solvent for extraction and
derivatization, etc., but costs have jumped to
almost $1K for 500 ml, and the method uses a
lot of it.
Very laborious method so prone to potential
failures due to human error and standards.
TBAA tends to be unstable, so lots of
standard prep required.
EPA 546 – ELISA for Total
Microcystins by ADDA
Specific instrument required
Can do manual or automated
Lysing challenges
Accuracy concerns- response varies by
congener.
How do results
compare to LC/MS/MS?
EPA 546 – ELISA for Total
Microcystins by ADDA
Poor precision, even with automated system, so
potential for batch failure or rework
It took several efforts to meet the DOC/PIR,
because it is tight compared to the method
itself.
Unless you have a large number of samples in a
batch, consumable and supply costs are major.
We have not seen as many “false positives” as
expected, but we have seen positive blanks.
EPA 544 – Microcystins and Nodularin
SPE/LC/MS/MS
6 Microcystins – LA, LF, LR, LY, RR, YR
Special preservatives Buffering reagent – Trizma
Antimicrobial – 2-Chloroacetamide
Dechlorinating reagent – Ascorbic Acid
Metals inhibitor - EDTA
Surrogate added to 500 ml sample before cell lysing
Lysing challenges
SPE used with concentration step
Analysis by LC/MS/MS
Some issues with pH of receipt.
Method is NOT a good
choice for source
waters. Risk of filter
clogging if there is a
bloom.
EPA 544 – Microcystins and Nodularin
SPE/LC/MS/MS
Purity and consistency of standards
(particularly for RR and YR) is a challenge.
Batch sizes are extremely small (triggered
monitoring) so cost of running the method
becomes very high.
Filter clogging, even on relatively “clean”
samples can “kill” the analysis.
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EPA 545 – Anatoxin-a and
Cylindrospermopsin
Preservatives Acidic microbial inhibitor – Sodium Bisulfate
Dechlorinating agent – Ascorbic Acid
Internal Standards added prior to direct injection
LC/MS/MS with Electrospray Ionization
Still requires lysing
Chromatography issues with
internal standard - Uracil
OTHER BE-DEVILING DETAILS
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“Non-Analytical Issues”
Having mechanisms in place for chlorine/pH checks (and documentation).
And watching for false positives on chlorine with DPD
We definitely saw this during the first few months
The first 3 months of UCMR 4 were “hell” because the methods had not been thoroughly validated by EPA and others and rules for acceptance limits changed.
Being sure that LIMS captures ALL of the appropriate metadata.
The UCMR 4 EDD requires lots of batch details
The UCMR 4 EDD format has changed since the start.
Both of our labs are facing challenges with uploads.
SAMPLE COLLECTION
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Sampling for Everything Requires a
Lot of Bottles
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Chemistry - 8 bottles
Cyanotoxins – 5 bottles
HAA – 1 bottle
TOC/Br – 1 to 4 bottles
Why So Many Bottles and So Much
Volume?
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Each lab
may be
unique in
their bottle
choices.
Batch QC
requirements
Preservation
checks on
receipt.
In Reality You End up Having 3 (or 4)
Types of Sample Kits
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Keeping samples cold in transit is
CRITICAL
Lots of Things to Pay Attention to on
the COC for UCMR4
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Identify sample type (SR, EPTDS or DS) SR=
Source Water; EPTDS =Entry Point to the
Distribution System; DS= Distribution System
Sample
Identify Cyanotoxin Sample Event #: SEA1,
SEA2, SEA3, SEA4, SEA5, SEA6, SEA7, and
SEA8 or the Regular Sample Event # SE1, SE2,
SE3, SE4
If resampling, please reference the original
sample event on the COC
DATA AND SPECULATION
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Original Speculation: What Are We
Actually Going to See in UCMR 4?
HAA5… those data are readily available…
HAA6Br… the addition of BCAA. Expected in
higher bromide systems. EEA has a lot of
existing data so we know it will occur.
HAA9… Some BDCAA and CDBAA.. Not likely
to see much, if any TBAA
Manganese. Was included in small systems
for UCMR 3 and it was frequent even
sometimes at levels above the SMCL.
Germanium. Maybe some but not much..
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Did We Expect to See Anything
Else?
For the chemistry, I doubted we will see more than a
handful of hits (but we are looking pretty low, so I could
have been wrong).
Total microcystins: maybe, but we are monitoring
finished water at a “high” MRL (0.3 ug/L), so there won’t
be many hits.
Indvidual microcystins by 544: If there are positives for
total microcystins, we will see the individuals because
the 544 MRLs are VERY low.
Anatoxin-a and Cylindrospermopsin: Probably not,
because again we are measuring finished water
samples.
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What are We ACTUALLY Seeing:
Out of a Relatively Small Data Set
~ 200 PWS so far (Monrovia lab only; SB adds
about the same additional, but I can’t yet pull
those data).
~500 sample results for chemistry
~800 sample results for HAA9
~ 500 sample results for total microcystins
and anatoxin-a
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Detections by Analyte - Metals
Manganese: ~50% detects (>0.4 ppb)
Max of 62 ppb (above SMCL of 50 ppb)
95% are below 15 ppb
Median of 0.4 ppb
So Yes, speculation is correct, but much lower
concentrations than the UCMR3 small systems
Germanium: ~10% detects (>0.3 ppb)
Max of 3 ppb
98% are below 1 ppb (UCMR 3 MRL)
About the same detection frequency as UCMR 3
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Detections by Analytes - HAAs
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How Does HAA9 Compare with
HAA5 and What % of HAA is HAABr?
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As expected from literature,
HAA5 is generally 50-90% of
the total HAA9.
Brominated HAAs may
constitute a large percentage
of the total HAA9.
TBAA is a very small fraction of the Total HAAs, with a maximum value of 6 ppb.
Detections by Analytes – Br and
TOC in Source Waters
50% of samples tested so far have detectable
TOC (>0.3 mg/L)
TOC levels range as high as 12 mg/L
80% of samples tested so far have detectable
bromide (>5 ug/L).
25% of samples have >130 ug/L bromide, likely
why we see so many brominated HAAs
Bromide levels range as high as 900 ug/L.
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DBPs – Going Beyond UCMR 4
We have a project with WRF (4711) looking at
bromide and iodide in source waters across
the country.
Piggy backing on our UCMR 4 work.
If you are interested in having one of your
sources tested for iodide and iodate in
addition to bromide, let me know.
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Detection by Analyte –
SOCs/Pesticides
A few surprises here, but still a small data set
1-Butanol (Used as a solvent, food additive and in
production of other chemicals) showing up
sporadically (1%), at levels up to 10 ppb in a
few utilities (SW and GW). Way below HRL of 700
Quinoline (Used as a pharmaceutical (anti-malarial)
and flavoring agent; produced as a chemical
intermediate; component of coal ) also showing up
sporadically, at levels up to 0.07 ppb. Above the
HRL of 0.01
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Detection by Analyte – Cyanotoxins
No surprises, but still a small data set
Only 1 hit for total microcystins (barely over
the MRL)
0 hits for anatoxin
0 hits for cylindrospermopsin
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So How is My Speculation Doing?
Other than 1-Butanol and Quinoline, I’m on
track… and I think those will reduce in
frequency as more data are gathered.
We should have a much better sense of things
once we reach the end of 2018.
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Any Questions?
Andy Eaton, PhD, BCES
Technical Director Emeritus
626.386.1125
Eurofins Eaton Analytical, LLC
www.eurofinsus.com/eaton