Efficient technology to remove BPA and similar chemicals from water

A multidisciplinary investigation of the technical and environmental performances of TAML/peroxide elimination of Bisphenol A compounds from water

As water treatment plants struggle to keep up with the chemical cocktail heading into our pipes, researchers say they’ve come up with a solution to remove one of the most ubiquitous contaminants—BPA.

There now exists economically viable, efficient technology to remove bisphenol A (BPA) and a host of similar chemicals from water.

2017 Study Conclusion

In developing Green Chemistry, it is important that chemists come to understand the scope of the challenges posed by everyday-everywhere endocrine disruptors (EDs) to the sustainability of both the chemical enterprise and our complex global civilization. The most troubling such EDs, like BPA, invariably hold their protected positions in the economy because of seductive technical and cost performances that enable large, diverse, profitable markets. For sustainable chemicals, the health, environmental and fairness performances also have to be integral components of the value proposition. Understanding the negative performances of unsustainable chemicals helps in mapping the properties sustainable chemicals should not have. Key aspects of this understanding include the knowledge of which chemicals are and are not EDs and are and are not capable of eliciting low dose adverse effects by non-endocrine processes, the extent and routes by which the environment and people are exposed to commercial EDs, the environmental and human health consequences of ED exposures, the methods of assessment of endocrine activity including the TiPED, the mechanisms of the low dose adverse effects, the design approaches to attaining new and replacement chemicals free of such effects, and the stewardship methodologies that are currently deployed or might be deployed to better protect health and the environment from commercial EDs. This BPA case study traverses the appropriate multidisciplinary landscape with emphasis on the integration of chemistry and environmental health science in the development of endocrine disruption-free processes to aid the chemical enterprise and society in reducing BPA exposures. Importantly, the litany of unfortunate facts presented about BPA exposures and health and environmental performances is relieved to some extent by the possibility of reduced releases arising from the TAML/H2O2 technology mapped out in the empirical section.

This experimental component demonstrates that TAML/H2O2 provides simple, effective water treatment methodologies, which depending on the pH, either decompose BPA or isolate it in low solubility oligomers. Both processes require only very low concentrations of TAML activator and H2O2 in further reflection of the remarkable efficiencies of the peroxidase enzymes that are faithfully mimicked by TAML activator and in marked contrast with the much higher relative iron- and peroxide-requiring Fenton processes. It remains to be established whether the current laboratory studies project to real world scenarios. These may include treatment of BPA-contaminated landfill leachates and paper plant processing solutions where the concentrations are similar to those employed in this study. In such scenarios, TAML/H2O2 would present an enzyme-mimicking method which in the case of TAML activator is comprised exclusively of biochemically common elements and has passed multiple TiPED assays that, in contrast with existing real world processes, avoids generation of BPA-contaminated sludges and associated subsequent releases to soil, that does not generate a contaminated adsorbent which must be replaced or regenerated at elevated temperature, that does not generate chlorinated forms of BPA, that does not generate a concentrated retentate, and that is remarkably simple to deploy using very low and cheap chemical inputs with all the positive potential consequences thereof for capital and operating expenses.

Finally, in order to avoid the habit or perception of greenwashing, a realistic perspective is essential to the integrity of green chemistry. We view the sustainability challenges posed by BPA as enormous—the experimental work presented could evolve into a solution for some of these problems but is, by no means, a general quick fix. BPA markets large and small are expanding rapidly, especially as the industry has learned how to produce even more effective replacements for glass and metal products. Huge new markets are developing such as those of plastic glass houses, and even houses, and automobile body parts that are comprised primarily of BPA. In this build-up, BPA’s unfortunate health and environmental performances continue to be given short shrift. Continuation of the present BPA expansion trends without limits, technical corrections and more aggressive stewardship advances of multiple kinds will menace society with an ever increasing oestrogenization of the entire ecosphere.

Sources and More Information
  • BPA breakthrough: New treatment takes controversial chemical out of water, EHN, August 2, 2017.
  • Science: Pay attention to two other messages in the breakthrough BPA water treatment paper, EHN, August 8, 2017.
  • A multidisciplinary investigation of the technical and environmental performances of TAML/peroxide elimination of Bisphenol A compounds from water, pubs, 19th July 2017.
  • Feature image credit Leland Francisco.

Multiple generations of chemical exposure may lead to absolute infertility in males

Science : Are we in a male fertility death spiral ?

Written by Pete Myers, Environmental Health Sciences, July 26, 2017.

Margaret Atwood’s 1985 book, The Handmaid’s Tale, played out in a world with declining human births because pollution and sexually transmitted disease were causing sterility.

Does fiction anticipate reality? Two new research papers add scientific weight to the possibility that pollution, especially endocrine disrupting chemicals (EDCs), are undermining male fertility.

“The study is a wakeup that we are in a death spiral of infertility in men”

Frederick vom Saal, Curators’ Distinguished Professor Emeritus of Biological Sciences at the University of Missouri and expert on endocrine disruption.

The first, published Tuesday, is the strongest confirmation yet obtained that human sperm concentration and count are in a long-term decline: more than 50 percent from 1973 to 2013, with no sign that the decline is slowing.

“The study provides a mechanistic explanation for a progressive decrease in sperm count over generations.”

Frederick vom Saal.

The second, published last week by different authors, offers a possible explanation. It found that early life exposure of male mouse pups to a model environmental estrogen, ethinyl estradiol, causes mistakes in development in the reproductive tract that will lead to lower sperm counts.

But there is much more to this study, led by Washington State University doctoral student Tegan Horan and published in the journal PLoS Genet. The senior author on the paper, Washington State University’s Distinguished Professor of Molecular Biosciences, Patricia Hunt, is one of the world’s leading authorities on how endocrine disrupting chemicals harm the development of sperm and eggs.

What makes this study unique is that it examined what happened when three successive generations of males were exposed—instead of just looking only at the first. Hunt, in an email, said

“we asked a simple question with real-world relevance that had simply never been addressed.”

Successive, constant exposure

More than a dozen papers have now been published on “trans-generational epigenetic inheritance,” where exposure in a great-grandmother causes adverse effects in great-grandson—without further exposures and without changes in DNA sequence.

But crucially these experiments typically only expose one generation—the first—rather induce ongoing exposures across generations, which is the reality of human experience.

In the real world, since World War II, successive generations of people have been exposed to a growing number and quantity of environmental estrogens—chemicals that behave like the human hormone estrogen. Thousands of papers published in the scientific literature (reviewed here) tie these to a wide array of adverse consequences, including infertility and sperm count decline.

This phenomenon—exposure of multiple generations of mammals to endocrine disrupting compounds—had never been studied experimentally, even though that’s how humans have experienced EDC exposures for at least the last 70 years. That’s almost three generations of human males. Men moving into the age of fatherhood are ground zero for this serial exposure.

So Horan, Hunt and their colleagues at WSU set out to mimic, for the first time, this real-world reality. They discovered that the effects are amplified in successive generations.

They observed adverse effects starting in the first generation of mouse lineages where each generation was exposed for a brief period shortly after birth. The impacts worsened in the second generation compared to the first, and by the third generation the scientists were finding animals that could not produce sperm at all. This latter condition was not seen in the first two generations exposed. Details of the experimental results actually suggested that multiple generations of exposure may have increased male sensitivity to the chemical.

Laura Vandenberg, an expert on endocrine disruption effects at the University of Massachusetts, Amherst and who did not participate in either study called Horan and Hunt’s work

“an elegantly designed study that looks at several really important issues in environmental health.” “As the authors rightly point out, over the past several decades, exposures to environmental chemicals—and estrogens in particular—have continued to rise.” Exposure today, is life-long, not episodic. “Remarkably, the damage that is seen in any one generation gets worse and worse as more generations are exposed,” “I have never seen a study examine these different generations so beautifully – this is a tremendous amount of work!”

Vandenberg said.

Long-term decline

The first paper, published Tuesday in the journal Human Reproduction, analyzes data from all studies on the topic researchers could find published in the scientific literature between 1981 and 2013.  Researchers, including Hagai Levine of the Hebrew University of Jerusalem and Shanna Swan of the Icahn School of Medicine in New York found 185 studies that sampled a total of 42,000 men across four  decades beginning in 1973.

“20 percent of Danish men do not father children.”

Niels Skakkebæk, University of Copenhagen

Declines in sperm concentration and total sperm count were “highly significant” for samples from North America, Europe, Australia and New Zealand. Those from South America, Asia and Africa were not significant, possibly a result of a much smaller sample size.

Hunt sees considerable linkage between the two studies.

“Our data are showing that things get progressively worse as subsequent generations are exposed,” “These large changes in human sperm count and concentration reveal that we are already well down the road.”

she said.

Niels Skakkebæk, a Danish pediatrician and researcher whose 1992 paper with Elisabeth Carlsen reporting large long-term declines in human sperm count kicked off over 20 years of debate, added:

“These two new papers add significantly to existing literature on adverse trends in male reproductive health problems. Importantly, the data are in line with data on testicular cancer which is increasing worldwide.” “Here in Denmark, there is an epidemic of infertility,” “More than 20 percent of Danish men do not father children.” “Most worryingly [in Denmark] is that semen quality is in general so poor that an average young Danish man has much fewer sperm than men had a couple of generations ago, and more than 90 percent of their sperm are abnormal.”

Skakkebæk did not participate in either study.

Skakkebæk’s concerns about younger men are reinforced by some of the details of the new sperm study because it reports that men in a subgroup of the total sample whose partners are not yet pregnant nor do they have children (i.e., they are not confirmed fertile men) have experienced a drop in average sperm count of almost 50 percent over four decades, to 47 million sperm per milliliter. That puts counts close to what the World Health Organization considers impairment in ability fertilize an egg—40 million sperm per milliliter.

Indicator of male health?

Poor sperm count is associated with overall morbidity and mortality.

That’s the average reduction. Every average has a distribution: Some with more reduction, some less. And those who fall in the “more” category may wind up below the level where WHO considers fertilization unlikely—15 million sperm per milliliter. The new study specifically notes that a high proportion of men from Western countries have concentrations below 40 million per milliliter.

The sperm count study raises a larger issue, beyond reductions in the ability to fertilize an egg.

“Poor sperm count is associated with overall morbidity and mortality,” “A decline in sperm count might be considered as a ‘canary in the coal mine’ for male health across the lifespan. Our report of a continuing and robust decline should, therefore, trigger research into its causes, aiming for prevention.”

the authors wrote.

Are we, as suggested by Dr. vom Saal, in a “death spiral” of male infertility? And if so, what are the larger implications? Perhaps the most far-reaching, if this is true, would be what this means there will be changes in age distributions in populations in nations suffering from this spiral.

A core assumption driving economic policies around the world is that growth is essential. Populations that are declining because of infertility face big problems because economic activity depends upon have a large number of working people compared to those that are retired. Expectations for economic growth diminish.

Would further declines in male fertility undermine the assumptions that fuel faith in economic growth, as the age distribution shifts to one with more retired people and fewer working? These are vital questions that traditional demographers have largely chosen to ignore.

Pete Myers,
Founder and chief science officer of Environmental Health News, publisher of EHN.org and DailyClimate.org.

Featured image credit womenshealth.gov.

The fundamental roles of hormones and the effect of endocrine disrupting chemicals

Pete Myers, CE100 Annual Summit 2016

Video published on 3 August 2016 by Ellen MacArthur Foundation.

Professor Pete Myers is founder, CEO and Chief Scientist of Environmental Health Sciences.

In this video he talks through some of the health, chemical and material challenges facing the future of the economy.

More Information

Endocrine disrupting chemicals and children’s health

Forget about global warming : this is the real threat…

Video published on 23 Feb 2012 by piscesgutt sin kanal channel.

From a Swedish documentary about the chemical cocktail that enters our body from food, drink and pollution.

More information

BPA linked to Errors in Human Egg Development and Infertility

Bisphenol-A and human oocyte maturation in vitro

BPA linked to errors in human egg development
More evidence linking BPA to infertility and birth defects

A recent study (Bisphenol-A and human oocyte maturation in vitro) – funded by the NIEHS Center Grant Pilot Project and first study to investigate Bisphenol-A effects on human egg development – showed that BPA causes errors that can prevent human eggs from developing fully and may contribute to infertility. The findings are consistent with numerous animal studies. Additional studies with a larger number of oocytes are required to confirm the present results.

Abstract

STUDY QUESTION
Does exposure to bisphenol-A (BPA) affect the maturation of human oocytes in vitro?

SUMMARY ANSWER
There was a dose-response association of BPA exposure with altered human oocyte maturation in vitro.

WHAT IS KNOWN ALREADY
There is widespread exposure of the general population to BPA. BPA has been detected in the human follicular fluid. Animal studies have shown that BPA exposure is associated with maturation arrest and spindle abnormalities in maturing oocytes.

STUDY DESIGN, SIZE, DURATION
A randomized trial, using 352 clinically discarded oocytes from 121 patients.

PARTICIPANTS/MATERIALS, SETTING, METHODS
The study population was drawn from patients undergoing IVF/ICSI cycles in our program at Brigham and Women’s Hospital from March 2011 to April 2012. Oocytes from only one cycle for each patient were included in the study. Cycles with at least two germinal vesicle stage oocytes were included with random allocation of one oocyte to culture for 30 h without BPA and remaining sibling oocytes to medium-containing BPA (20, 200 ng/ml or 20 µg/ml). Oocytes were fixed and labeled for tubulin, actin and chromatin and examined with immunofluorescence and confocal microscopy. Oocytes were assessed for meiotic stage (n = 292), and those at metaphase II (MII, n = 175) were further classified according to their spindle configurations and patterns of chromosome alignment. McNemar’s test was used to compare dichotomized maturation status. Generalized estimating equations were used to account for the correlation between oocytes from the same woman and for the spindle analysis.

MAIN RESULTS AND THE ROLE OF CHANCE
As the BPA dose increased, there was a decrease in the percentage of oocytes that progressed to MII (P = 0.002) and increases in the percentage of oocytes that were degenerated (P = 0.01) or that had undergone spontaneous activation (P = 0.007). Among MII oocytes, as the BPA dose increased, there was a significant trend (by test for trend) for a decreased incidence of bipolar spindles (P < 0.0001) and aligned chromosomes (P = 0.02).

LIMITATIONS, REASONS FOR CAUTION
Although we used sibling oocytes to overcome potential confounders, such as infertility diagnosis and maternal age, additional studies with a larger number of oocytes are required to confirm the present results. Having access only to clinically discarded oocytes, we were limited to evaluating only those oocytes that failed to mature in vivo despite having been exposed to gonadotrophin stimulation and the ovulatory trigger of HCG.

WIDER IMPLICATIONS OF THE FINDINGS
To our knowledge, this is the first study investigating the effect of BPA on oocyte meiotic maturation, spindle morphology and chromosome alignment in human oocytes. Together with prior animal studies, the data support the negative influences of BPA on cell cycle progression, spindle architecture and chromosome organization during oocyte maturation. Furthermore, the increased rates of abnormal maturation in oocytes exposed to BPA may be relevant to our understanding of the decrease in fertility reported in the last decades.

Read BPA linked to errors in human egg development
by John Peterson Myers, Environmental Health News, 8 Aug 2013

Sources: Bisphenol-A and human oocyte maturation in vitro
NCBI, Jul 2013 – Full PDF

The BPA Safety deeply challenged by a new Discovery, will the FDA reconsider?

High Bioavailability of Bisphenol A from Sublingual Exposure

BPA is absorbed in the mouth; could explain high blood levels
Will the FDA reconsider about BPA ?

A new experiment with dogs finds that Bisphenol-A (BPA) can be absorbed in the mouth and pass directly into the bloodstream, just as nitroglycerin under the tongue. This way it bypasses detoxification in the liver after absorption in the gut. The result is that much more biologically active BPA is available to possibly cause health effects, with major implications for how much risk BPA may pose for human health.

2013 Study Abstract

Background
Bisphenol A (BPA) risk assessment is currently hindered by the rejection of reported higher than expected BPA plasma concentrations in humans after oral ingestion. These are deemed incompatible with the almost complete hepatic first-pass metabolism of BPA into its inactive glucurono-conjugated form, BPA glucuronide (BPAG).

Objectives
Using dogs as a valid model, plasma concentrations of BPA were compared over a 24-h period after intravenous, orogastric and sublingual administrations, in order to establish the absolute bioavailability of BPA administered sublingually and to compare it with oral bioavailability. Methods: Six dogs were sublingually administered with BPA at 0.05 mg/kg and 5mg/kg. The time course of plasma BPA concentrations was compared with that obtained in the same dogs after intravenous administration of the same BPA doses and after a 20mg/kg BPA dose administrated by orogastric gavage.

Results
The data indicated that the systemic bioavailability of BPA deposited sublingually was high (70-90%) and that BPA transmucosal absorption from the oral cavity led to much higher BPA internal exposure than obtained for BPA absorption from the gastro-intestinal tract. The concentration ratio of BPAG to BPA in plasma was approximately 100-fold lower following sublingual administration than after oral dosing enabling the two pathways of absorption to be easily distinguished.

Conclusions
These findings demonstrate that BPA can be efficiently and very rapidly absorbed through the oral mucosa by the sublingual route. This efficient systemic entry route of BPA may lead to far higher BPA internal exposures than known for BPA absorption from the gastrointestinal tract.

Our Stolen Future

A book by Dr. Theo Colborn, Dianne Dumanoski and Dr. John Peterson Myers

Our stolen Future, a Book on Flickr

DES was just one of many new synthetic chemicals that promised to give us control over the forces of nature…

A book by Dr. Theo Colborn, Dianne Dumanoski and Dr. John Peterson Myers

Read Our Stolen Future: Excerpts from Chapter 4, Hormone Havoc

DES books set on Flickr  DES Diethylstilbestrol's photostream on Flickr

More DES DiEthylStilbestrol Resources

Our stolen Future

The hardback edition, released March 1996

DES was just one of many new synthetic chemicals that promised to give us control over the forces of nature

Our Stolen Future
We should have known better!
You can’t mess with Mother Nature, and win …

A book by Dr. Theo Colborn, Dianne Dumanoski and Dr. John Peterson Myers

Read Our Stolen Future: Excerpts from Chapter 4, Hormone Havoc.

More DES DiEthylStilbestrol Resources