www.EurofinsUS.com/Eaton

UCMR4: What Are We Seeing and

What are the Issues?

Andy Eaton, PhD, BCES, TDE*

* Technical Director Emeritus

2

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.

3

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.

4

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.

5

ANALYTICAL METHODS

CHALLENGES

6

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

7

Methods and Analytes: Assessment

Monitoring (17) –All Systems and LOW MRLs

8

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

9

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.

21

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

23

“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

25

Sampling for Everything Requires a

Lot of Bottles

26

Chemistry - 8 bottles

Cyanotoxins – 5 bottles

HAA – 1 bottle

TOC/Br – 1 to 4 bottles

Why So Many Bottles and So Much

Volume?

27

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

28

Keeping samples cold in transit is

CRITICAL

Lots of Things to Pay Attention to on

the COC for UCMR4

29

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

30

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..

31

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.

32

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

33

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

34

Detections by Analytes - HAAs

35

How Does HAA9 Compare with

HAA5 and What % of HAA is HAABr?

36

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.

37

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.

38

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

39

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

40

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.

41

Any Questions?

Andy Eaton, PhD, BCES

Technical Director Emeritus

andyeaton@eurofinsus.com

626.386.1125

Eurofins Eaton Analytical, LLC

www.eurofinsus.com/eaton