03/21/2013 - Email to DEQ - troubling results ... and resulting thread
3/21/2013 email from Roger Rayle to Sybil Kolon, DEQ, et al:
Sybil--
The Feb sampling from Pall contains some really troubling results...
MW-120s-02-28-13-10:45-1 7 (ppb)
MW-121d-02-14-13-09:45-1 2
MW-123s-02-28-13-11:25-1 3
MW-124d-02-12-13-10:00-1 2
The first three show hits on previously non-detect locations near the expanded Prohibition Zone's north and northwest boundaries [image]
The last one shows a hit on another previously non-detect location far away from the supposedly leading edge of the plumes.
And two of these samples, like most of the samples Aug-Nov 2012, were held beyond the 14-day holding period for dioxane before being analyzed.
The MW-121d hit is especially troubling since it's screened in the middle of 50-foot-thick, contiguous, wet layers at about the same elevation as 465 Dupont and MW-77 and could indicate a northerly or northwesterly groundwater flow towards Scio Township properties with wells ... that have no access to municipal water... just outside the expanded Prohibition Zone.
It's strange that this many previously non-detect wells show hits at the same time. Maybe the sampling procedures were wrong. Maybe Pall screwed up trying to correct for their previously low readings as compared with the DEQ's during January's split sampling. Maybe these results are indeed accurate because of more rigorous sampling procedures and the prior non-detect results were understated. Maybe the plumes are moving faster than previously thought. It's really hard to know the reality of the situation without knowing how good the data are... or were.
Or ... because of the previous brouhaha created by Pall's data anomalies and its lack of QA/QC with with the Maynard House sampling and their subsequent whining to DEQ honchos Sygo and Marlof that led to the cutoff of DEQ's access to the Pall's sampling database of their dioxane in our Waters of the State, ... do we have to wait for another quarter's readings before bringing these results to the attention of the public?
I think not, since the results were surely "fully QA/QC'ed" by Pall before being released in the Feb 2013 report... as assured by Pall attorney Michael Caldwell in his 11/11/2011 letter. In any case, the public's "right-to-know' trump's the company's desire for secrecy... even if it was only another company sampling screw-up.
Nearly 30 years after the dioxane was first discovered in the Third Sister Lake, we still do not know enough about how much of the 850,000 lbs of dioxane is left or its environmental fate.
--Roger--
Roger Rayle
Chair, Scio Residents for Safe Water (SRSW); member, Coalition for Action on Remediation of Dioxane (CARD)
New Google Earth Mashups of the Pall/Gelman Site
SRSW & CARD will be at the 2013 Ann Arbor Earth Day Festival Sunday, April 21, 2013
3/22/2013 Response from Sybil Kolon, DEQ, et al:
Roger,
We also noted the issues you raise and share your concern. We have asked PLS to respond to these concerns and have asked them to resample the four monitoring wells mentioned at the beginning of your note if they have any question that they are not accurate. We also plan to collect split samples the next time they are sampled.
I have seen one individual response to your note from a homeowner near the Huron River. I am not able to access her email address. By copy of this note I am conveying the DEQ’s position that the recent results do not require any additional residential well sampling at this time.
We will keep you informed as we learn more about the status of the February data.
Thanks,
Sybil
Sybil Kolon
Senior Environmental Quality Analyst
Remediation and Redevelopment Division
Department of Environmental Quality
301 E. Louis Glick Hwy.
Jackson, MI 49201
phone: 517-780-7937
fax: 517-780-7855
e-mail: kolons@michigan.gov
Environmental emergencies: 1-800-292-4706
3/27/2013 email from Sybil Kolon, DEQ, et al:
Attached is the February data in Excel spread sheet format (in zip file) as well as a follow-up note from PLS lab staff with the QC. PLS clarified that: All QC is always reviewed prior to sample data being reported. The report that was sent yesterday is a summary of all the QC/QA data for the month with statistics.
PLS believes the unexpected detections on MWs that have previously been non-detect (MWs 120s, 121d, 123s, 124d) are a result of carry-over from prior samples and has agreed to resample. The DEQ will split samples on those MWs and send the samples to the DEQ lab for analysis.
PLS is also collecting samples in March for the samples that exceeded holding time, which occurred due to several factors besides the power outage.
DEQ staff continues to review other data concerns and hopes to resolve them in the near future.
Thanks,
Sybil
Sybil Kolon
Senior Environmental Quality Analyst
Remediation and Redevelopment Division
Department of Environmental Quality
301 E. Louis Glick Hwy.
Jackson, MI 49201
3/27/2013 email from Mike Gebhard, Washtenaw County, to Sybil Kolon, DEQ, et al:
Hi Sybil,
The explanation provided is the simple answer but what part of the sampling protocol was violated and how did this happen over several days and at different locations? The order of the sampling does not appear to strongly support this explanation of carry-over. The previous sample would need to be a positive result in excess of the subsequent result and not an ND. How would an ND carry-over to a 12 ppb?
1. MW-120s/d 02/28/2013:
a. MW-120s was sampled first @10:35 AM and returned a ND result, then MW-120d was sampled @ 10:45 AM returning 7 ppb. If carry over is the explanation, then why is the previous sample ND.
b. Only 10 minutes between collections times. Tough to decon. the equipment, pull three well volumes, and collect the sample in only 10 minutes. For example, MW-105 s/d had over an hour between the shallow and deep samples. The total well volume and ability to provide water play into the picture but only to a point.
2. MW-121s/d 02/14/2013:
a. Again the first sample collected was ND.
b. Time interval between samples was 35 minutes.
3. MW-123s/d 02/28/2013:
a. Previous sampling event prior to MW-123s was the positive result at MW-120s.
4. MW-124 d 02/12/2013:
a. First sample of the day other than HC/HR & Outfall.
i. A question to ask might be: Do they use the sample pumps for the Outfall & Honey Creek
ii. On that day the outfall had 2 ppb not no time and HC/HR were bromate samples.
The other variable in direct contact is the water level meter but the same logic applies as in MW-120s/d, the well that was ND was sampled first.
Another question that arises which samples had carry-over? The locations in question were expected to be ND so any variation from ND raised a flag.
If you have any questions please feel free to contact me at your earliest convenience.
Cheers,
Mike
Michael R. Gebhard, CPG | Application Specialist
gebhardm@eWashtenaw.org
Washtenaw County Information Technology
110 North Fourth Ave. P.O. Box 8645, Ann Arbor Michigan 48107-8645
4/1/2013 email from Sybil Kolon, DEQ to Michael Gebhard, et al:
Mike and others,
We raised several questions about the February data and have gotten feedback from PLS. I will repeat a few earlier comments so hopefully all of this will be in one place.
1. The two notes that transmitted the data in different formats (one PDF and two Excel spreadsheets) had a note that appeared to indicate that it had been done “without QC”. PLS has acknowledged that wording was easy to mis-interpret. In fact, the QA/QC had been done. This is what PLS said: “All QC is always reviewed prior to sample data being reported. The report that was sent yesterday is a summary of all the QC/QA data for the month with statistics.”
2. PLS believes the unexpected detections on MWs that have previously been non-detect (MWs 120s, 121d, 123s, 124d) are a result of carry-over from prior samples (during laboratory analysis, not during sample collection) and has agreed to resample. During the time period that those samples were analyzed, PLS was also doing a seven-day pilot study (not related to the Gelman site) which could have resulted in the carry over. The DEQ will split samples on those MWs on Wed, April 3, and send the samples to the DEQ lab for analysis.
3. 8 samples with a result of non-detect were run using a reporting limit of 5 ppb, meaning they could have had detections up to 4 ppb and be reported as ND. When these samples were initially run, PLS provided the following explanation: “Lab had to repeat the samples due to normal laboratory variations (e.g. internal standards being too high or too low, LFB not passing ). The samples are being re-sampled for March and are being analyzed this week.”
4. We questioned why holding times were exceeded on 49 samples, due to “power problems from snow storm”, when the 14-day hold time was exceeded by a week or so in many cases. PLS response: “On February 14, 2013, the lab ran out of purge gas due to a faulty regulator. Since then, the regulator has been repaired. Proper amount of gas was ordered immediately but delivered on February 26, 2013. The samples were then loaded at once. On February 27, 2013, a sever power surge damaged the auto-samplers which caused the GC/MS to shut down. Since the auto-sampler could not be fixed, it was switched out with another sampler and a new sampler/concentrator was ordered. At this time, all the samples in question are being re-sampled and analyzed this week.“
Other concerns and questions about data are still under review and additional information will be provided in the future.
Thanks,
Sybil
Sybil Kolon
Senior Environmental Quality Analyst
Remediation and Redevelopment Division
Department of Environmental Quality
301 E. Louis Glick Hwy.
Jackson, MI 49201
phone: 517-780-7937
fax: 517-780-7855
e-mail: kolons@michigan.gov
Environmental emergencies: 1-800-292-4706
4/1/2013 email from Roger Rayle to Sybil Kolon, DEQ, et al:
Sybil--
Pall's responses to 1 & 2 show that Pall's QA/QC is inadequate. Let the record show that it was Pall's lack of adequate QA/QC that might have led to another Maynard House incident.
It seems that without someone else catching their errors, faulty data would continue to be propagated ... like has happened over and over again for this site. More justification for full, up-to-date access to Pall's sampling database. It shouldn't take 30+ days to re-sample.
The supposed carry-over from "a seven-day pilot study (not related to the Gelman site)" seems fishy. I hope whomever the pilot study was for was informed that the carry-over might have worked both ways!
Response 3... if the past data is to be believed, non-detects with dioxane reporting limits > 1ppb happened only twice...
Saginaw Forest Cabin #4 nd 08/09/12 09:05 09/13/12 2.0
MW-127s nd 08/08/12 11:05 09/13/12 2.0
But of course, for bromate sampling, it happens many times each month. Maybe the DEQ should do some unannounced split samples for bromate.
Response 4... bad luck (karma?) I guess, but why does it take 30+ days to re-sample?
--Roger--
Roger Rayle
Chair, Scio Residents for Safe Water (SRSW); member, Coalition for Action on Remediation of Dioxane (CARD)
4/10/2013 email from Michael Gebhard to Sybil Kolon, DEQ, et al:
Hi Sybil,
I received PALL’s monthly email of analytical results for the March sampling event yesterday which do not include the resampling results for the wells of concern from the February data with the exception of MW-121s (likely a component of the regular sampling schedule). Were the wells resampled PALL and were split samples collected by the MDEQ? If so when?
Considerable time has passed and PALL has completed another regular sampling round in the interim. For the standard residential well sampling we perform for the State our results from the State Laboratory are returned within 14 days. Obviously, PALL is in control of their own sampling priority as they typically us their in-house State certified analytical laboratory. Pall is able to turn around 1,4-1,4-dioxane samples during the vertical delineation phase of drilling in an very short timeframe in order to facilitate the selection of screen locations during drilling. Considering the potential public health implications do you have a time frame when we can expect to see the resampling results and split sampling results for the wells of concern?
Cheers,
Mike
4/11/2013 email from Sybil Kolon, DEQ to Michael Gebhard, et al:
Mike,
We received the results you mentioned on March 19. Within a few days we had scheduled the re-sampling, including DEQ split samples, for April 3. Those samples were collected and no results have been received from either the PLS or DEQ lab.
As you know, we normally get PLS’s monthly sampling results in about the middle of the following month. We would expect to see April’s results in mid-May. The DEQ lab should complete their analysis by April 17. It normally takes several days for the lab to complete their reporting process. When we receive DEQ’s results I will request PLS’s results and forward them to the group. I expect that will be toward the end of April.
The concentrations reported were unexpected, and there is a question as to whether those results reflected actual detections, or were a result of carryover from lab equipment. Based on the initially reported concentrations being considerably below the generic residential cleanup criterion, we believe this time frame for reporting of the resampling results to be adequate.
Thanks,
Sybil
4/11/2013 email from Roger Rayle to Sybil Kolon, DEQ, et al:
Sybil--
I repeat my March 28 comments...
Maybe the "bad" readings were the result of "carry-over" during the analysis process not during the sampling. In any case, it's an indication of the sloppiness that seems to have permeated Pall's sampling, data handling, and cleanup procedures over the past many months (years?).
So now after getting questionable data 3-7 weeks after sampling, we'll have to wait another 30-60 days for trustworthy data?
--Roger--
4/23/2013 email from Sybil Kolon, DEQ to Michael Gebhard, et al:
Attached are the DEQ lab results from the split samples collected on 4/3/2013 to determine if detections in the February results were accurate or were the result of carry-over from lab equipment. All four DEQ samples were non detect, as were PLS lab results from the same sampling event.
Sybil Kolon
DEQ lab split sample results from 4-3-2013.pdf
4/23/2013 email from Michael Gebhard to Sybil Kolon, DEQ, et al:
Hi Sybil,
Thanks for sending out the results. During this process did PALLs Laboratory present or have indicators from QA/QC data that this event was the result of laboratory error (carry-over) beyond simple statements that this was the case? I only say this because at the moment what we have is one sample collection event (February) with low-level detections and one follow-up sample collection with NDs (split samples being a laboratory cross-check not related to the groundwater results). The resampling adds weight to the case for carry-over being the cause but does not determine definitively if they were accurate, in the absence of detailed laboratory evidence. This can only begin to be accomplished through repeated sampling events. The proximity of high levels of 1,4-dioxane and the theorized migration pathways by PALL suggest that these compliance wells will likely record detectable concentrations (not necessarily above compliance triggers or cleanup standards).
PALLs presentations and analysis by Neven Kresic for the Evergreen Area did indicated some westward and northern migration, though the primary driving component of migration being to the east. If the migration pathways theorized by PALL are accurate we will see low levels at some point in some or all of these wells. A risk-adverse conservative approach may be to increase the frequency for a period of time so that we have consecutive groundwater sample results with no detectable concentrations before establishing the level of accuracy for the February results.
I realize the MDEQ has probably gone over this at considerable length, but since the entering into formal Dispute Resolution on various issues some years back and the apparent legal case tentative agreement, the MDEQ has been unable to discuss or provide feedback on many topics related to the PALL/Gelman project. As a result, those following the case/project are at times left with a “shotgun approach” to presenting concerns or ideas." Hoping we present an issue of concern to the community that is germane to either a dispute resolution issue or any tentative legal agreement. So please consider the above as a discussion topic not a criticism.
If you have any question or concerns please feel free to contact me at your earliest convenience.
Cheers,
Mike