Water Quality Significance of Chromium III

G. Fred Lee & Associates
________________________________________
27298 E. El Macero Dr.
El Macero, California 95618-1005
Tel. (530) 753-9630 Fax (530) 753-9956
e-mail gfredlee@aol.com
http://www.gfredlee.com
Please note the new area code for telephone and fax has been changed to 530

February 14,1997

Dr. Val Connor
Environmental Specialist
CVRWQCB
3443 Routier Road, Suite A
Sacramento, CA 95827

Dear Val:

In connection with the Sacramento River Watershed Toxics Control Program, I have raised the chromium toxicity issues at our subcommittee meetings where I have indicated that chromium has to be more appropriately monitored than is typically being done today because of its potential toxicity to aquatic life (zooplankton) at concentrations above about 0.5 ug/L. At this time, the monitoring for chromium VI and total chromium is sometimes done with a detection limit of 10 ug/L, i.e. the current US EPA NTR chronic criterion. In developing that criterion, the EPA did not incorporate the work of Dr. Donald Mount that showed that chromium VI was toxic to aquatic life at less than 2 ug/L since Dr. Mount did not determine a specific level of toxicity. Chris Foe has brought to my attention that in 1995, Environment Canada published a report which showed that chromium VI could be toxic to aquatic life at 0.5 ug/L.

At the recent San Francisco Bay Regional Monitoring Program annual meeting there were discussions of chromium issues related to the bioaccumulation of chromium under elevated flow conditions from the Yolo Bypass where chromium in Bypass waters increased significantly after the seven-year drought which resulted in increased chromium in San Francisco Bay waters and in mussels as part of the Mussel Watch Program in San Francisco Bay. The elevated chromium that occurred during and following YoIo Bypass high flows could be converted to chromium VI and, therefore, be toxic to aquatic life. While most potentially toxic constituents tend to sorb and, thereby, are detoxified during high flow conditions due to the elevated suspended solids present during high flows, chromium VI has low sorption tendencies and could readily cause aquatic life toxicity. It will, therefore, be important to sample the Sacramento River system during high flow events for aquatic life toxicity and, if found, determine whether it is due to chromium VI.

This raises yet another issue that has to be considered in the Sacramento River Watershed Toxics Control Program about the potential of toxic levels of chromium in the form of chromium III which will accumulate under low-flow conditions in Sacramento River tributaries and in the Yolo Bypass, where under elevated flow conditions this chromium is scoured into the water columns and is, at least in part, available for bioaccumulation in downstream shellfish and possibly other organisms. While I do not propose this be part of the Sacramento River Phase I monitoring, subsequent phases should include specific examination of chromium fluxes during rising hydrograph situations as well as monitoring freshwater clams and estuarine organisms in order to determine whether the chromium that accumulates under low-flow conditions from natural as well as wastewater sources cause downstream water quality use impairments. The Central Valley Regional Water Quality Control Board orders allow POTW's and others to discharge total chromium at concentrations of up to 50 ug/L. This could readily lead to an accumulation of chromium III in the receiving water sediments which are scoured into the water column and transported downstream during elevated flow conditions.

This is a situation that is similar to the mercury problem that Chris Foe and others are addressing on Cache Creek as well as some of the Sierra streams where mercury is present due to former gold mining activities where increased flows can make available significant increases in concentrations of constituents that accumulate in sediments or are present in particulates, such as mine tailings, that can and, certainly under some conditions do, lead to excessive concentrations in downstream waters that are adverse to the beneficial uses of these waters.

As you may recall, last fall I filed a Petition with the State Water Resources Control Board on the 50 ug/L discharge limit for chromium, asking the State Board to review the technical validity of the Central Valley Regional Water Quality Control Board's approach to allowing a total chromium discharge of 50 ug/L of which 40 ug/L could be chromium III and 10 ug/L could be chromium VI. Enclosed is a Supplement to that Petition which discusses the new information that has become available on the elevated flow bioaccumulation of chromium in San Francisco Bay mussels which is coincident with the increased flows following a low-flow period that cause an increased concentration of chromium in San Francisco Bay waters. This Petition provides additional background information on these issues.

If there are questions on this matter, please contact me.

Sincerely yours,

Fred

G. Fred Lee, PhD, DEE

Copy to: Chris Foe

Supplement/Addendum to Petition of Order No. 96-227
Issued by
the Central Valley Regional Water Quality Control Board
on August 9, 1996
to the University of California at Davis
for the UCD Campus Landfill Ground Water Cleanup System

To address the New Information Provided by
The University of California at Davis and the CVRWQCB Staff
at the CVRWQCB September 20, 1996 Hearing
Devoted to Chromium Technical Issues

Submitted by

G. Fred Lee, PhD, DEE
G. Fred Lee & Associates
27298 East El Macero Drive
El Macero, CA 95618

October 17, 1996

This Supplemental/Addendum to the September 9, 1996 Petition on Order No. 96-227 specifically addresses new issues that were raised by the CVRWQCB staff and/or the University of California, Davis through their presentations at the September 20, 1996 chromium technical issues hearing. This Supplement/Addendum is necessary since both the CVRWQCB staff and the UCD L. Vanderhoef administration provided new unreliable information to the CVRWQCB at this hearing on technical issues pertinent to regulating UCD's proposed discharge of west landfill leachate polluted groundwaters with a total chromium content of 50 g/L and protecting Putah Creek water quality from the potential adverse impacts of this discharge. CVRWQCB staff and UCD introduced for the first time new information that had not been previously made available to the public which they assert demonstrates that my position that Order No. 96-227 is not necessarily protective of Putah Creek water quality in accord with CVRWQCB Basin Plan objectives for the control of toxicity. If the UCD L. Vanderhoef administration and the CVRWQCB staff had followed appropriate, professional ethics and had brought the new material to the public's attention several days in advance of the September 20, 1996 hearing, I would have been able to provide the CVRWQCB with a discussion of the new issues at that hearing with appropriate documentation from the peer-reviewed literature. However, since both the CVRWQCB staff and the UCD L. Vanderhoef administration introduced the new and unreliable materials into the record for review of Order No. 96-227 without providing the public with the opportunity to comment on the technical appropriateness, it is appropriate to allow the incorporation into the record of the attached October 17, 1996 letter to J. Caffrey on these issues as well as this Supplemental/Addendum to the September 9, 1996 Petition.

Testimony of R. Yaedon

At the September 20, 1996 hearing, Mr. Yaedon, Senior Engineer with the CVRWQCB, presented testimony on his views on technical issues pertinent to regulating chromium in the University of California, Davis west landfill leachate polluted groundwater discharge to Putah Creek. As in the past with CVRWQCB staff (Mr. McHenry who works for Mr. Yaedon), the staff have great difficulties presenting the facts and typically distort them in an attempt to support their ill-conceived position. As an example, Mr. Yaedon stated at the September 20, 1996 hearing:

"With regards to chromium conversion, both the petitioner and regional board staff have stated that conversion of chromium from chrome III and the more toxic chrome VI can go in both directions. The petitioner wants to assume the worst-case in that all or a significant portion of the total chrome will convert to chrome VI. Staff believes that it will be dependent on the conditions specific to the environment in Putah Creek and maintains that instream monitoring is the appropriate and reasonable approach to address this issue."

Mr. Yaedon's statement that the petitioner (Dr. G. Fred Lee) wants the CVRWQCB to "assume" that all or a significant part of chrome III will convert to chrome VI is a deliberate distortion of the facts. I have never stated that, and it is obvious to anyone who reviews the issue, that is not the issue of concern. The issue that I have raised is not whether all or substantially all of the Cr III that UCD could discharge under Order No. 96-227 at 50 g/L could convert to Cr VI to be toxic to aquatic life in Putah Creek. As I have pointed out, Putah Creek at times has substantial background chromium and since the US EPA's water quality criterion for Cr VI is 10 g/L, only a small part of the 50 g/L allowed in the discharge has to convert to Cr VI to exceed the US EPA ambient water criterion.

I am pleased the staff finally is beginning to acknowledge what I informed them of over a year ago, that the chemistry of chromium in Putah Creek is dependent on Putah Creek conditions. Further, as has now been documented by several sources, the chemically stable species of chromium in Putah Creek waters is Cr VI. While ordinarily the conversion of Cr III to Cr VI is slow, there are conditions, as I discussed at the September 20, 1996 hearing, which are documented in the literature where this conversion can be rapid, taking place in a few hours to a day or so.

Mr. Yaedon stated:

"With regards to the chromium limits in the permit, the petitioner requests that the effluent limits be set at 10 g/L for total chrome, assuming that all chrome will convert to chrome VI. Staff recommended the limits at 50 g/L total chrome based on the drinking water maximum contaminant level. Staff recommended limits of 10 g/L and 15 g/L for chromium VI based on the four-day average and the one-hour average US EPA national ambient water quality criteria, respectively. We do not believe that we have the regulatory justification to set more restrictive limits without actual data showing that chromium VI is causing an exceedance in the receiving stream."

It is not clear if this is an off-the-cuff statement that Mr. Yaedon made in an attempt to defend an ill-conceived Order or whether this represents a ruling by the Board's attorney on this issue. It would seem appropriate that the Board's staff would confer with the attorney before the staff makes such statements. As discussed below, when I questioned Mr. Yaedon on this matter following his testimony on whether the Board had the regulatory authority to enforce its Basin Plan requirements for control of toxicity, Mr. Yaedon stated:

"Yes we can, but the total chrome limit was actually based on the drinking water standard, the MCL of 50 parts per billion."

There is no doubt that the CVRWQCB has the authority to limit the chromium discharges to Putah Creek to comply with Basin Plan requirements of no toxicity in the creek waters.

As I discussed in my written and verbal submissions to the Board at the September 20, 1996 hearing, the basic issue I am trying to get this Board to address in regulating waste discharges from the University of California, Davis is compliance with the Basin Plan objectives, i.e. the control of toxicity. Thus far, this Board and its staff refuse to establish reasonable protection of the aquatic life beneficial uses of Putah Creek from the UCD L. Vanderhoef administration's waste management practices.

Mr. Yaedon in his September 20, 1996 testimony continued to distort the information regarding US EPA Region IX's (Phil Wood's) communication prior to the August 9, 1996 hearing. As I indicated in my Petition, following the August 9, 1996 hearing, I contacted Mr. Wood, who informed me that he did not discuss this matter with any CVRWQCB staff member. He also informed me that he left a telephone message for Mr. Yaedon which indicated that Cr III and Cr VI are interconvertable. Further, in my discussions with him, he indicated that Mr. McHenry's statement that he, Mr. Wood, said that Cr III would be the stable form of chromium in Putah Creek is not accurate.

Mr. Yaedon stated at the September 20, 1996 hearing in response to my question,

Lee: "This Board cannot set the limit to protect aquatic life from toxicity where there is a reasonable expectation that some forms of constituents while not toxic in the discharge could be converted to toxic forms in the receiving waters. This Board cannot do that."

Yaedon: "I believe we could, but I don't believe we have any evidence that it is going to convert into something that will actually be toxic to fish and that is why staff is asking that we have instream monitoring to see if there is any change in conversion, because we haven't seen evidence and I don't think anybody can actually state exactly what is going to happen. As far as I know, and I am no expert at chromium, but in reading the literature it is a very complicated issue. I can state that, and I don't think we are going to know until we actually get that."

As noted in my Petition, the State Board staff in an attempt to address the comments I made on the inadequacies of the August 9, 1996 Order, introduced at the last minute a stop gap monitoring for Cr VI in Putah Creek. A review of the record will show that I have been trying for over a year and a half to get proper monitoring of Putah Creek for assessing the individual as well as cumulative impacts of the UCD L. Vanderhoef administration's waste discharges to the Creek. Until August 9, 1996, the staff claimed there was no need for monitoring for potential toxics in Creek water such as chromium. However, as I discussed in my September 20, 1996 presentation (see enclosed) as well as at the hearing, the stop gap, last minute monitoring the staff introduced at the August 9, 1996 hearing is obviously non-credible for detecting the conversion of Cr III to Cr VI. This monitoring program involved only one station 100 feet downstream from the discharge. Such monitoring could represent a travel time of a couple minutes to a few hours to possibly a day or so, dependent on Creek flow. As I discussed, for a reaction that is well known to be slow, a single monitoring point of this type is obviously inadequate. Mr Yaedon indirectly acknowledged this when he stated,

"The Board can maintain the permit as it is or include an additional downstream monitoring point, perhaps upstream from the wastewater treatment plant to coincide with existing monitoring points."

As I pointed out in my testimony on September 20, 1996, the public is making slow but definite progress in getting the Regional Board and its staff to properly address protecting the public's interests from UCD's wastewater discharges to Putah Creek. In a year and a half, the public has, through repeated hearings, gotten the staff to admit there might be a need for two monitoring points to detect the Cr III to Cr VI conversion. Actually, as I have testified, there is need for a series of testing points along Putah Creek to monitor both Cr III and Cr VI as well as aquatic life toxicity to properly detect the potential adverse impacts of chromium that UCD proposes to discharge to the Creek under Order No. 96-227. It is important to note, however, that while the staff is showing a more enlightened approach toward monitoring, the Board, at the September 20, 1996 hearing, rejected the staff's recommendation of adding additional monitoring. At this time Order No. 96-227, as adopted on August 9, 1996, is fundamentally flawed in addressing the Putah Creek monitoring issue.

Mr. Yaedon stated:

"We are unsure of the more stable form [of chromium] in Putah Creek. Our statements are based on a number of sources, but one in particular was actually sent to us by the US EPA and that document was entitled 'Water Related Environmental Fate of the 129 Priority Pollutants.'"

A review of Chapter 10 of the December 1979 US EPA publication, "Water-Related Environmental Fate of 129 Priority Pollutants," which is devoted to chromium, section 10.3.2 "Chemical Speciation" shows that the US EPA considers the work of Schroeder and Lee (1975) as a definitive source of information on Cr III to Cr VI conversions. On page 10-3 Mr. Yaedon's cited source states:

"Schroeder and Lee (1975), in a laboratory study on the transformation of chromium in natural waters, found that Cr(III) and Cr(VI) are readily interconvertible under natural conditions. Their results indicated that Cr(VI) can be reduced by Fe(II), dissolved sulfides, and certain organic compounds with sulfhydryl groups, while Cr(III) can be oxidized by a large excess of Mn02 and at a slower rate by O2 under natural water conditions. Moreover, if aquatic conditions favor Cr(VI), then chromium will accumulate as soluble forms in waters; if, however, Cr(III) is favored, then the accumulation will occur in the sediments."

A review of section 10.3.2 on "Chemical Speciation" shows that the Schroeder and Lee work is featured as a definitive source of information on Cr III - Cr VI conversions. There is no information presented in this section or elsewhere in this publication which in any way changes the information that was developed by Schroeder and Lee.

The reference to Schroeder and Lee (1975) is: Schroeder, D.C. and G. F. Lee. 1975. Potential transformations of chromium in natural waters. Water Air Soil Pollut. 4:355-365. D. Schroeder did this work as a graduate student working under my supervision for a master's degree in water chemistry at the University of Wisconsin, Madison. It appears that not only did the US EPA (1979) consider Schroeder and Lee a definitive source of information on this topic, but also those within the US EPA who recently sent this material to Mr. Yaedon still consider the work that my graduate student and I did in the 1970s a definitive source of information on this topic.

Mr. Yaedon again provided distorted information in his September 20, 1996 testimony regarding the August 5, 1996 and August 8,1996 correspondence. He stated,

"The petitioner's August 8 letter continued discussion on a number of subjects, not all related to the hearing matter, and no new information on chromium was provided in that submittal."

Mr. Yaedon's characterization of my August 8, 1996 letter is more of the distorted information he provided to the Board on September 20, 1996. There were a number of key issues addressed in my letter which were in direct response to distorted information that Mr. Pinkos had provided to the Board in his August 5,1996 letter, which was not made available to me until a couple of days before the August 9, 1996 hearing. It was certainly appropriate for me, on behalf of the public, to provide for the record a discussion of the facts concerning the distorted information Mr. Pinkos had provided in his August 5, 1996 letter.

A review of the record will show that it was Mr. Pinkos in his August 5, 1996 letter that demonstrated as discussed in my August 8, 1996 letter that Board Chairman Longley ruled was inappropriate to be incorporated into the record at the August 9, 1996 hearing that he (Mr. Pinkos), and evidently Mr. Yaedon and Mr. McHenry, who almost certainly worked with Mr. Pinkos in developing his August 5, 1996 letter, do not have sufficient understanding of elementary water quality issues to recognize that the data on UCD's wastewater discharges from its campus wastewater treatment plant that Mr. Pinkos had included in his letter to support the position that UCD's wastewater discharges were non-toxic, in fact, demonstrated that they would be toxic based on the unionized ammonia content. If the CVRWQCB's staff and the administrative officers do not have sufficient understanding of water quality issues to recognize excessive concentrations of ammonia in a wastewater discharge when they use these data to try to show the discharge complies with regulatory requirements, then there is little hope that this staff can develop a credible permit covering wastewater discharges for a more complex constituent such as chromium.

Mr. Yaedon stated, in response to my August 8, 1996 letter,

"...the petitioner's response to our [comments] should have been more properly submitted through the mail."

If Mr. Yaedon had properly reviewed and reported on the facts, he would have found that Mr. Pinkos did not respond to my May 19, 1996 letter until his letter dated August 5, 1996, which I received a couple of days before the August 9, 1996 hearing. Upon receipt of Mr. Pinkos' letter, and finding that it provided large amounts of distorted information on issues which I had previously raised concerning UCD's proposed discharge of west landfill leachate polluted groundwaters to Putah Creek, I spent the next day preparing detailed documentation (my August 8, 1996 letter) of these distortions. While Mr. Yaedon suggested I should have mailed my response, if I had followed his approach, my response would not have been available in time to be included in the administrative record since the mailing would not have reached the Board until August 12, 1996, i.e. three days after the Board considered the matter.

In summary, Mr. Yaedon did not present any new, credible information at the September 20, 1996 hearing that in any way provides justification for the staff's recommendation at the August 9, 1996 hearing as well as the September 20, 1996 hearing that UCD should be allowed to discharge total chromium at concentrations up to 50 g/L to Putah Creek. If anything, Mr. Yaedon's testimony through bringing out that the US EPA in 1979 and in 1996 considers the Schroeder and Lee work of the early 1970s as a definitive source of information on Cr III - Cr VI conversions has provided strong additional support for the position that discharging Cr III concentrations of up to 50 g/L could result in sufficient Cr III to Cr VI conversion so that the total Cr VI in Putah Creek would be toxic to aquatic life in violation of the CVRWQCB's Basin Plan objectives for the control of toxicity.

In addition, Mr. Yaedon in his September 20, 1996 hearing testimony further demonstrates his lack of elementary understanding of reliable monitoring of Putah Creek waters to evaluate whether Cr III discharged by UCD as part of its groundwater remediation project for its west landfill could cause aquatic life toxicity in Putah Creek downstream of this discharge. Anyone with even the most elementary knowledge of water quality monitoring would acknowledge that a single station located 100 feet downstream of the discharge would not represent adequate sampling of Putah Creek to detect aquatic life toxicity due to the discharge.

University of California, Davis

Mr. D. Phillips, of the University of California, Davis presented testimony on behalf of UCD, where he initiated his testimony by name-dropping a number of UCD professors to whom he claimed he submitted my comments. He states,

"I don't think I need to elaborate any on the qualifications of these individuals. Dr. Longley knows most of them quite well I think and can attest to their technical expertise. Based on our analysis, our technical experts simply don't believe that the conversion of chrome III to chrome VI is a significant concern for Putah Creek."

While Mr. Phillips attempted to portray the image with the statement that "our experts simply don't believe" that Cr III will not convert to Cr VI in Putah Creek, the facts are, as were brought out in my questioning him, that his so-called name-dropped experts were not asked to review and support the UCD L. Vanderhoef administration's September 13, 1996 letter on this issue. As I pointed out, it is unfortunate that these individuals were not there to testify, since I believe they would have enlightened the Board with their knowledge/expertise on the topic and would likely have provided strong support for my position on a number of the issues I have raised such as the gross inadequacies of the Putah Creek monitoring program contained within Order No. 96-227.

Mr. Phillips attempted to discredit my testimony by claiming that my suggested approach is more restrictive than the US EPA's position on regulating chromium. The US EPA's position, as discussed in my statements and testimony in the past year, is that there is need to protect aquatic life from Cr VI chronic toxicity. The US EPA established a 10 g/L chronic toxicity criterion. As I testified, the Agency acknowledged, however, that that criterion may not be protective of some key forms of aquatic life. This issue is discussed further below.

While Mr. Phillips attempted to distort my position on issues, if he would critically review my testimony, he would find that the focus of my testimony was not achieving US EPA criteria but was on the credible implementation of the CVRWQCB's Basin Plan objectives of protecting aquatic life from toxicity. The CVRWQCB has an obligation to the public to implement its Basin Plan objectives with a high degree of certainty so that any NPDES permitted discharge will comply with these objectives in situations such as with a discharge of Cr III at 50 g/L. Where it is known from the literature that Cr III does convert to Cr VI and that Cr VI is highly toxic to aquatic life, it is mandatory that a highly credible monitoring program be developed to be certain that the Basin Plan objectives are, in fact, met by UCD's waste discharges. It is irresponsible to establish discharge requirements which allow a discharge of a potentially hazardous chemical in hazardous amounts and not require that the discharger properly monitor the receiving waters for the discharge. This is exactly what the CVRWQCB is doing now with Order No. 96-227. Basically, this Board is telling the public they are protecting water quality. However, the public has no reason to believe, and, in fact, has substantial reason to question, the reliability of this statement since this Board does not require adequate monitoring to detect potential problems.

Mr. Phillips states,

"If the University ever does elect to discharge groundwater to Putah Creek, we will monitor the chromium concentrations in our discharge and in Putah Creek as required to ensure that no instream exceedances of the permit will occur."

This is more of the recalcitrant polluter approach that the UCD L. Vanderhoef administration has been following of doing the least possible to just get by current, often inadequate, interpretation of the regulations by the Regional Board staff. Why did Mr. Phillips not state that UCD would establish a credible program to determine whether Cr III converts to Cr VI in Putah Creek waters and thereby cause aquatic life toxicity in Putah Creek? By stating that UCD will only do the monitoring "required" in the permit is more of the type of situation that causes the public to conclude that the UCD L. Vanderhoef administration has no interest in protecting the public's interests in protecting water quality in Putah Creek.

In questioning Mr. Phillips, I asked,

Lee: "With respect to the September 13 letter, were copies of that letter made available to the public?"

Phillips: "We directed our letter to Mr. Crooks at the Board. We did not provide copies to all members of the public, or, in fact, I think we limited our distribution to the Board itself."

Lee: "You don't feel it would be appropriate for the public to have a copy of a letter that introduces new material into these discussions that has not been brought forth previously for the public to review prior to this hearing?"

Phillips: "We leave that to the Board's discretion. Not knowing specifically who might be interested in all of these issues, we provide this information to the Board for their dissemination to the public."

It is preposterous for Mr. Phillips to claim that the UCD L. Vanderhoef administration did not know that I have an interest in this topic. I personally sent L. Vanderhoef a copy of my petition. I also provided him with copies of all correspondence on this matter. Clearly, this is another of the behind-the-scenes activities where there is an attempt to prevent the public from advising the Board of the technically invalid information the Board's staff, UCD, and some Board members, such as Chairman Longley, have been providing to the Board on these issues.

I have repeatedly called for a full, public, independent, expert peer review of these issues. It is clear the UCD L. Vanderhoef administration, W. Crooks, Chairman Longley, and, for that matter, the other members of the Board operate in a controlled information environment where they can manipulate the information that is used to formulate public policy on water quality protection of Putah Creek. It is also clear that UCD and the Board are afraid to have a full, public, independent peer review of these issues. They know, or should know, if they did this, they would find that their position on these issues is incorrect. I am fully prepared, and would welcome, the opportunity to have my views on these issues peer-reviewed by experts in the field. I am highly confident that if such a review would take place, my suggested approaches of requiring that UCD/the Board limit the total chromium in Putah Creek to 10 g/L, unless it is demonstrated through a credible monitoring program that higher concentrations of chromium can be present in Putah Creek waters without aquatic life toxicity, is appropriate. I am also confident a proper peer review of the issues would find that the CVRWQCB is not implementing its Basin Plan objectives of protecting Putah Creek aquatic life from toxicants discharged by the University of California, Davis in its wastewater discharges and stormwater runoff.

Richard Burau, Professor Emeritus of Environmental Toxicology in Soil Science, testified at the September 20, 1996 hearing on the Cr III to Cr VI conversion issues. His testimony was initiated by his lecturing the Board on basic chemistry issues where he stated,

"In oxygenated water go to the issue of thermodynamic stability, in oxygenated water, without the presence of other oxidizing or reducing substances, chromium VI is the thermodynamically stable species."

Further, he stated,

"Therefore, the first point I want to make is that, with respect to the argument of thermodynamic stability, chromium VI is the stablest species; there is no question about that and is confirmed by a great many theoretical studies."

This is exactly what I have been telling the Board for over a year and a half.

Mr. Burau then lectured the Board on the role of kinetics (rates of reaction) in achieving thermodynamic equilibrium. To illustrate his point, he attempted to discuss the reaction between ferrous iron and oxygen. He states,

"In fact, another reaction that I would bring up is the oxidation of ferrous iron to ferric by oxidation by oxygen, again an abiotic consideration. This, too is a fairly slow reaction, but it is much, much faster than the hydrogen oxidation reaction. In swampy areas and in some of the subsurface waters of this state, we do have water that contains ferrous iron. It is reduced so it's iron in the ferrous state. When this water is brought to the surface, oxygen enters it and almost immediately you will begin to see the precipitation of ferric hydroxide; oxidation of ferrous to ferric. But it doesn't go really rapid. It is one of those cases where if you take a glass of such water, set it on a table, over a period of days you will see visible increase in turbidity from this reaction. So this is a reaction wich instead of taking billions of years will go in a few hours to a few days."

As was brought out in my questioning of R. Burau, I spent one year as a post-doctoral fellow at Harvard University studying the reaction between ferrous iron and oxygen. I asked Dr. Burau if he was familiar with the expression

d Fe(II) = - k(FeII)(O2)(OH-)2
d t

He recognized this is a rate expression for the reaction between ferrous iron and dissolved oxygen. He did not, however, discuss the fact that the rate of this reaction is highly pH dependent where small changes in pH greatly influence the rate. If R. Burau had been familiar with this expression, he would have known that his example of kinetic control of a reaction is exactly the point I have been making with the Board. While Burau characterizes this reaction as "slow," if he had properly investigated this issue, he would have found that at the Putah Creek water pH values this reaction is virtually instantaneous. While the reaction can be slow in a low pH groundwater or swamp water, in the areas of concern, with respect to most environmental conditions of pH values greater than 7.5, this reaction is quite rapid. While a swamp water groundwater could have a pH between 6.0 and 6.5 where the reaction would take hours to a day as Dr. Burau described, in Putah Creek waters with pHs of 8.0 to 9.0, the reaction is over 1,000 times more rapid than the conditions that he chose to describe to the Board. Further, if he had been familiar with the topic he was discussing, he would have known there are a wide variety of chemical constituents in natural waters which significantly accelerate (catalyze) this reaction. Basically, R. Burau provided unreliable information on this reaction to the Board and, in fact, provided information which strongly supports my position that site-specific conditions must be considered in evaluating whether sufficient chromium in UCD's proposed discharge of leachate polluted groundwaters to Putah Creek at a concentration of up 50 g/L could be converted to Cr VI to cause aquatic life toxicity in the Creek downstream of the discharge.

R. Burau also lectured the Board on Cr III solubility issues. Again, he provided unreliable information to the Board as it relates to Putah Creek. If he had become familiar with Cr III chemistry, and had reliably reported on it to the Board in his testimony, he would have pointed out, as I did in questioning him, that far more Cr III can be present in the water in Putah Creek than would be predicted based on his approach, which only considers chromium precipitation as a hydroxide. When I questioned him on this issue, I brought out that he did not report on the complexation of Cr III with organics. He did admit under questioning, however, that this could be an important reaction that would change the solubility of Cr III in Putah Creek waters.

While R. Burau stated,

"OK. In conclusion, I believe it is a reasonable probability that chromium III transferring to chromium VI will be slow. I further believe that the rate of precipitation as chromium hydroxide will exceed that of the oxidation, and thus I expect the majority of the chromium to go in the direction of precipitation, not oxidation. Thank you."

He relied on the statement by R. Zasoski for the information on Cr III to Cr VI conversion, which as I discussed during the September 20, 1996 hearing and as is summarized below and in the attachment to this Supplemental/Addendum Petition, is based on an unreliable, biased review of the literature that ignores manganese dioxide catalysis/reaction of the Cr III to Cr VI conversion. Further, with respect to his solubility reactions, R. Burau has ignored complexation Cr III with organics that are present in Putah Creek water. Overall, an independent peer review of the credibility of R. Burau's testimony would show that he has provided unreliable testimony to the Board on several key issues that need to be addressed by the Board on determining the appropriateness of allowing the UCD L. Vanderhoef administration to discharge Cr III to Putah Creek at 50 g/L.

Dr. R. Zasoski cited the work of Saleh et al. (1989) as justification for support for his conclusion that Cr III would not be expected to be converted to Cr VI in Putah Creek waters. One of the authors of the Saleh et al. (1989) article was Dr. Ken Dickson. Dr. Dickson is Director of the Aquatic Toxicology program at the University of North Texas. He is an internationally recognized authority on aquatic toxicology/water quality issues. Dr. Saleh, who co-authored the paper with Dr. Dickson, obtained her Ph.D. degree working under my supervision at the University of Texas at Dallas where I helped establish and then directed for a period of five years the Center for Environmental Studies. Subsequent to the September 20, 1996 hearing, I had an opportunity to discuss with Dr. Dickson his views on regulating chromium with reference to the possibility of Cr III converting to Cr VI leading to aquatic life toxicity. Dr. Dickson informed me that it is his finding that since this conversion does take place in some waters, especially as influenced by manganese, the total chromium should be regulated to prevent toxicity conditions from developing in the receiving waters due to the conversion of Cr III to Cr VI. Therefore, it is inappropriate for R. Zasoski to assert that Cr III would not be converted to Cr VI to lead to toxic conditions in Putah Creek based on the Saleh - Dickson work that he cited as a reference. Dr. Dickson does not support that view. If there is interest, I can provide Dr. Dickson's telephone number so that he may be contacted in order to discuss these issues directly with him.

The UCD L. Vanderhoef administration indicates in its September 13, 1996 letter that Dr. R. Burau and Dr. R. Zasoski are "experts in the field of water chemistry." As I indicated in my statement on this issue, based on the curriculum vitae provided for these individuals by UCD, I concluded that neither of these individuals would be considered experts in the field of water chemistry by the water chemistry profession. As I discussed, they are both soil scientists. Those knowledgeable in the field know there is a significant difference between the education background and qualifications of individuals with expertise in the soil sciences and those with true expertise in water chemistry. Subsequent to the September 20, 1996 hearing, I have been provided with a UCD Contracts and Grants Office autobiographical statements prepared by Zasoski and Burau in the UC Davis Experts File. Neither of these individuals list themselves in the UCD Contracts and Grants Office records as having expertise in water chemistry. They both list "soil sciences" as their area of funding for research. It appears that my characterization of their qualifications and their own, based on UCD Contracts and Grants Office records, are in a good agreement and the UCD L. Vanderhoef administration's September 13, 1996 statement, which indicates that these individuals are "experts in water chemistry," is more of the distorted information that the UCD L. Vanderhoef administration continues to provide to this Board in an attempt to influence its waste discharge requirements. If there is interest, I can provide the WRCB with a copy of the UCD Contracts and Grants Office records pertinent to this matter.

Mr. J. Stagner, UCD dump-tender, presented the closing arguments on behalf of UCD, where he introduced new information in an attempt to discredit my testimony. This information was presented in the form of some redox potential measurements that were made by Dames & Moore of Putah Creek water. While I am not sure if the UCD L. Vanderhoef administration would claim that Mr. Stagner is a world expert on aquatic chemistry, those who have an elementary understanding of this topic know that it is not possible to reliably measure redox potentials in Putah Creek water. While I do not know who within Dames & Moore was responsible for these measurements and whether they claimed that these measurements provide a reliable measure of the thermodynamic characteristics of Putah Creek water at the time of measurement, I do know from my review of Dames & Moore's work associated with UCD waste management activities, that this group had made, and continues to make, significant errors in site investigation and reliably reporting on the information obtained. If there is interest, I can readily document unreliable information that has been provided by Dames & Moore to UCD and the Department of Energy.

The reliable evaluation of the redox conditions that exist in an aquatic system is of considerable interest to water chemists. I have personally done considerable work on this topic as part of my teaching and research on the aqueous environmental chemistry of a variety of chemical constituents in aquatic systems. Further, I am highly familiar with the literature on it. While there are some individuals who are not knowledgeable in the topic area who will stick a noble metal electrode and a reference electrode in a creek water and claim that they can use this to "measure" the redox potential of that water, as Mr. Stagner testified was done by Dames & Moore staff, those knowledgeable in the topic know that such an approach is, at best, naive and highly unreliable. Stumm and Morgan in their classical introductory text, Aquatic Chemistry, Third Edition (1996), which was first published in the early 1970s, discuss on pages 491-498 why the kind of information that Mr. Stagner presented to the Board at the September 20, 1996 hearing demonstrates his complete lack of knowledge of the topic that he discussed, i.e. measurement of redox potentials in aquatic systems. Stumm and Morgan discuss a variety of factors that are well-known to water chemists about why such measurements should not be used to determine the stable pH potential field for Cr III and Cr VI in oxygenated Putah Creek water.

If Mr. Stagner was knowledgeable and had reliably reported on this knowledge on the topic of measuring redox potentials in aquatic systems, he would have reported that while these potentials can be used to provide general indications of the redox state, such as oxidizing or reducing, they are not reliable for measuring the subtle changes of the type Mr. Stagner reported on in his closing statement. Redox measurements of this type are known to those familiar with the topic to represent mixed potentials and do not properly represent true thermodynamic characteristics of the water. A particular redox pair can significantly influence the potential measured, yet have no influence on whether Cr III or Cr VI is a thermodynamically stable species in Putah Creek water. It should be noted that Dr. Burau spent considerable time during his testimony discussing the pH potential (stability field ) diagram for chromium. Most of his testimony was devoted to an elementary discussion of the nature of this diagram and was appropriate. However, he stated,

"One of the last things that I would like to point out to you is that Mr. Phillips has provided me with some measurements on the water of Putah Creek. These measurements are plotted in this graph as the points or spots on the graph. These were apparently done by a consulting agency or a laboratory. If you notice that they do fall around pH 8, some below, some above, but as you also notice, the Eh is below the value of 0.8, therefore, according to these measurements, chromium III is actually the stable species under those conditions. Chromium III is the stable."

Dr. Burau's statement on the pH potential measurements clearly demonstrates that he is not a qualified aquatic chemist. No qualified aquatic chemist would ever provide that type of information to a regulatory board or, for that matter, anyone else since it is well-known in the aquatic chemistry field to be unreliable for a variety of reasons discussed in elementary aquatic chemistry texts such as the Stumm and Morgan text.

Mr. Stagner commented,

"We have brought several people we feel are experts. They are professors at a renowned institution throughout the country and if not the world, and Dr. Lee has attempted to discredit them. He has dismissed the experts appointed by our Board to oversee the EIR cumulative impacts, so apparently nobody in the world knows anything about this issue except Dr. Lee. The point is that these standards of 10 and 50 were set at state and national levels with lots of discussion. We can bring tons of information to bear as can Dr. Lee and enter into a very lengthy technical discussion about this, but the point is that he is asking you to overturn basic restrictions or requirements that have been set through much more technical discussions than we can proffer here."

The credibility of Mr. Stagner's statement can be judged by the unwillingness of the UCD L. Vanderhoef administration to participate in a full public peer review of issues by knowledgeable experts for which I have been calling for almost two years. As I have repeatedly pointed out, I am willing to have my findings on these issues subjected to a full public peer review by experts. Why will L. Vanderhoef and other members of his administration, Chairman Longley, Executive Officer Crooks, and others not support conducing such a review or participate in it? Why must they conduct behind-the-scenes deals with their hand-picked "experts" which exclude the public from being participants in Putah Creek water quality decisions affecting the public's interests?

Mr. Stagner's statement represents a desperate attempt by him to regain some credibility with the UCD administration for his informing the public that the UCD L. Vanderhoef administration's proposed construction of a new "west" campus landfill would eventually pollute groundwaters and that the L. Vanderhoef economic analysis justifying the construction of this new landfill was fundamentally flawed since it did not include the long-term costs of the inevitable groundwater pollution that would occur as a result of constructing this landfill.

With respect to the so-called "experts" review issue that he has raised, this is the blue ribbon panel issue where the public in the spring of 1995 called for a full, public, independent, peer review of cumulative impacts of UCD's wastewater discharges and stormwater runoff on Putah Creek water quality. The UCD L. Vanderhoef administration rejected that approach. Instead, according to a UCD L. Vanderhoef administration member, a behind-the-scenes deal was cut between the UCD administration and Board Chairman Longley which enabled UCD to hire hand-picked consultants without public review to address the public's concerns. As it turned out, neither of the consultants they hired have the expertise needed to address the issues of concern. Further, the public will obviously not accept a blue ribbon panel picked by the Board Chairman, who has shown an obvious bias against the public's interests, and UCD to act on behalf of the public's interests. The public has substantial justification for rejecting such an approach based on Board Chairman Longley's approach for addressing issues and the UCD L. Vanderhoef administration's recalcitrant polluter approach, where they deliberately manage information in an attempt to control the public's review of issues.

Mr. Crooks, in his closing arguments by the staff, stated,

"I feel that the permit that you adopted last month was based on good science. You did the right thing. It is protective and the monitoring program is protective."

Mr. Crooks went on to state in response to a question asked by a Board member,

"I would like to ask the executive officer, what is his reaction to Dr. Lee's judgement of using the daphnids or Ceriodaphnia as an additional set.

"I don't concur.

"Yeah, but on what basis, sir?

"On the basis that it is not necessary and on the basis that the permit that you have adopted is protective and it is based upon the creek and the size of the discharge and we are not doing to anybody else, including the County of Sacramento. We do use it in our chronic testing periodically to look at stream safety and toxic conditions. We do it on a limited basis. I take that back. We do have a limited amount of chronic toxicity testing by our very large dischargers. The County of Sacramento does, in fact, do at times that test. It is expensive, it is time consuming, and in our judgement, it is not at all required in a situation like this and I disagree, I feel that it is very precedent setting."

Basically, Mr. Crooks is saying that the people concerned with Putah Creek water quality are not entitled to the same protection as those who are interested in Sacramento River quality. Mr. Crooks needs to review his region's Basin Plan. This Basin Plan does not allow this Board the option of deciding which water bodies in the basin are to be protected from aquatic life toxicity. According to the Basin Plan toxicity objective, toxics are to be controlled in all waters in the region, not just those he and the Board decide are important to someone. If Mr. Crooks would become familiar with the topic area, he would find that quite possibly UCD's wastewater discharges could do far more damage to Putah Creek's designated beneficial uses than Sacramento County's wastewater discharges to the Sacramento River.

Basically, Mr. Crooks is operating with a 1960s level of water quality protection. It was not until his statement at the September 20, 1996 meeting that it was clear he does not understand and/or support the control of toxics. He basically is a BOD, suspended solids executive officer who is resisting adopting a 1990s level of understanding of aquatic chemistry, aquatic toxicology, and water quality management. Mr. Crooks, in his 1960s level approach, is highly concerned that adopting a 1990s level would be "precedent setting" for the Central Valley and possibly the state. It is time the CVRWQCB start to issue waste discharge permits that reflect a 1990s level of understanding of toxics impacts and their control. If Mr. Crooks does not start to adopt a more enlightened approach toward control of all toxics in the region, then it is time for the public to call for an executive officer who will support the CVRWQCB's Basin Plan requirements.

In a discussion following the testimony, Mr. Schnabel asked some questions of the staff concerning water quality standards issues. It was clear from the responses by the staff, that the staff do not understand these issues. Mr. Crooks in response to a question raised by Mr. Schnabel stated,

"Drinking water standards for chrome III, but for chrome VI we took the water quality standard that is currently on the book and of course, Dr. Lee does not agree that those standards are correct, but he doesn't agree that a lot of things are correct."

This is another cheap shot by Mr. Crooks to attempt to discredit me by providing unreliable information to the Board. First of all, I was a member of the US EPA peer review panel that established the current US EPA water quality criteria development approach. I was also a member of a US EPA panel that recommended several of the current criteria. I am highly familiar with, and contrary to the cheap shot statement made by Mr. Crooks, I am strongly supportive of the approach used by the US EPA in developing water quality criteria. I have repeatedly pointed out this situation in my previous statements to the Board. Those knowledgeable in the topic area know that meeting US EPA water quality criteria for potentially toxic chemicals such as Cr VI does not mean that there will be no aquatic life toxicity in the receiving waters due to Cr VI. In fact, the US EPA in developing the criteria acknowledged that the US EPA water quality criteria are not protecting all aquatic life from toxicity. They acknowledge there will be some small percentage of certain organisms killed or adversely impacted by waters that meet the current criteria.

The basic issue, however, that has to be properly addressed by the CVRWQCB which is the issue I raised, is that this Board adopted Basin Plan objectives that require the control of all toxicity. Therefore, this Board cannot adopt the approach of stating that since we meet the criteria, we are protecting aquatic life from toxicity and fulfill their mandated requirements of implementing their Basin Plan objectives of protecting aquatic life from toxicity. These objectives are explicit in requiring,

"...waters shall be maintained free of toxic substances in concentration that produce detrimental physiological responses in human, plant, animal, or aquatic life."

They apply to all waters within the Central Valley Region that have a aquatic life designated beneficial use, such as Putah Creek, independent of the value that Mr. Crooks or the Board members may place on them. This means that the Basin Plan objectives which Mr. Crooks and the Board are choosing to largely ignore in developing and implementing waste discharge requirements for the University of California, Davis require the protection of all aquatic life, not just those that would be protected by US EPA criteria.

As I discussed during my September 20, 1996 presentation, the highly distorted information that the University of California, Davis presented in their September 13, 1996 letter to Wm. Crooks which neither L. Vanderhoef, members of his administration, Mr. Crooks, or Chairman Longley chose to make available to the public, caused me to review the US EPA criterion document for chromium. I have provided in the enclosed write-up a summary of key issues which arose from this review, including the fact that certain key important daphnids are adversely impacted by Cr VI at less than 2 g/L. I pointed out that this has highly significant implication on the adequacy of only meeting the 10 g/L Cr VI US EPA criterion. While that approach would be acceptable to the US EPA, it is not adequate to achieve the Basin Plan objectives since the waters that meet the US EPA criterion of 10 g/L could still be toxic to certain forms of aquatic life. Subsequent to the hearing, I have become aware of an Environment Canada 1995 review (Priority Substances List - Assessment Reports, Chromium and its Compounds, PSL-39) in which it is indicated that the safe concentration of Cr VI for certain key daphnids is around 0.5 g/L. This conclusion is a follow-up to the US EPA's 1984 Chromium Ambient Water Quality Criteria document where it was reported that the US EPA Duluth Laboratory had found that Cr VI was toxic to Daphnia magna at less than 2 g/L. This work was done by Dr. Donald Mount, former Director of that laboratory. In order to protect aquatic life in Putah Creek from chronic toxicity, the University of California, Davis may have to reduce chromium in the discharge to keep the Cr VI in Putah Creek at less than 1 g/L in order to achieve the Basin Plan objectives. The finding that Cr VI is toxic to some forms of aquatic life at less than 1 g/L places even greater emphasis on the need for using Ceriodaphnia chronic toxicity testing of Putah Creek waters as part of ensuring the Basin Plan objectives are, in fact, met.

The 1960s mentality that exists now within the Board's staff and the Board of assuming the Basin Plan objectives will be met if BOD and suspended solids are removed to some permitted discharge limit, as was done about a year ago by the CVRWQCB staff in judging whether UCD's discharge of "west" landfill leachate polluted groundwaters could be discharged to the campus wastewater treatment plant, should be immediately terminated. This Board urgently needs leadership in addressing these issues.

Summary

It can be concluded that neither the Central Valley Regional Water Quality Control Board staff (Mr. Yaedon and Mr. Crooks) nor the University of California, Davis staff (Mr. Phillips and Mr. Stagner) and UCD soil science faculty (R. Burau and R. Zasoski) have provided any new information in connection with the September 20, 1996 hearing that in any way supports the position that my Petition to the WRCB on the highly significant technical deficiencies in the CVRWQCB Order No. 96-227 is inappropriate. In fact, as a result of this hearing and the inappropriate approaches followed and unreliable information presented by Yaedon, Crooks, Phillips, Stagner and Burau, there is considerable additional justification for the WRCB to support my September 9, 1996 Petition on the technical deficiencies in Order No. 96-227. The basic issue that the WRCB must address is whether this Order provides a reasonable degree of protection of aquatic life in Putah Creek from potential Cr VI toxicity which could occur at less than 1 g/L and thereby be in accord with the CVRWQCB's Basin Plan objective of controlling aquatic life toxicity in the Central Valley Region.

As long as the UCD L. Vanderhoef administration refuses to voluntarily implement a meaningful, highly reliable aquatic life toxicity monitoring program for Putah Creek waters that would ensure that the Basin Plan toxicity objective is, in fact, being met and as long as the CVRWQCB refuses to require that the UCD L. Vanderhoef administration implement a reliable aquatic life toxicity monitoring program for Putah Creek waters that would ensure that the Basin Plan toxicity objective is, in fact, being met, then the total concentration of chromium in Putah Creek waters should be limited to less than 10 g/L Cr VI. In fact, it may be necessary, because of the new information that has become available as the result of the September 20, 1996 hearing on the toxicity of Cr VI to certain forms of aquatic life, to require that the total concentration of Cr VI in Putah Creek water be less than 1 g/L. Because of this information, it is now mandatory that a comprehensive Ceriodaphnia chronic toxicity testing program be conducted of Putah Creek waters as part of this Order.

The WRCB should require that the CVRWQCB properly and reliably implement its Basin Plan toxicity water quality objective. This implementation will require that all dischargers of potentially toxic constituents, including the University of California, Davis, conduct chronic toxicity testing of the ambient waters that could be impacted by the discharge in order to fulfill the Basin Plan requirements.

All other deficiencies, such as inadequate regulation of TDS, failure to reliably monitor for hazardous bioaccumulatable chemicals, etc., discussed in my September 9,1996 Petition are still applicable and should be addressed by the WRCB.

Interested Parties

The interested parties in connection with the September 20, 1996 hearing remain the same as those listed in my September 9, 1996 Petition, with the addition of William Jennings, DeltaKeeper.

Hearing

The petitioner requests that, if necessary, a hearing be held to discuss these issues. While the petitioner believes that adequate evidence has been presented in the original Petition as well as in this supplement/addendum to that Petition to enable the State Board to act on this matter in affirmation of the Petition, if the State Board concludes otherwise, then a hearing is requested for full public review of the issues.

Notice of Appeal

A copy of this supplement/addendum to the September 9, 1996 Petition has been provided to the Central Valley Regional Water Quality Control Board and Chancellor L. Vanderhoef of the University of California, Davis.

A copy of the request that was made by the petitioner to the Regional Board to prepare a supplemental administrative record covering the September 20, 1996 hearing is enclosed.

List of Appendices to Supplement/Addendum Petition

Letter to Karl Longley, Chair, regarding CVRWQCB summary agenda for the September 20, 1996 Board hearing, from G. Fred Lee, dated September 13, 1996.

"Technical Deficiencies in the CVRWQCB Order No. 96-227 Discharge of the UCD "West" Landfill Leachate-Polluted Groundwaters to Putah Creek Presented at CVRWQCB September 20, 1996 Hearing," by Dr. G. Fred Lee.

Letter to John Caffrey, Chairman, regarding supplemental/addendum to the September 9, 1996 petition arising from the September 20, 1996 CVRWQCB chromium technical issues hearing, from G. Fred Lee, dated October 17, 1996.

Reference as: "Lee, G. F., 'Water Quality Significance of Chromium III,' Letter to V. Connor Central Valley Regional Water Quality Control Board, Sacramento, CA, February (1997)"

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