Yet another study: Fracking plays active role in generating toxic metal wastewater

Refer also to this new study:

New Study Confirms Fracking Wastewater Is Cancer-Causing. “Barium and Strontium were elevated in frac flowback water exposed cells.” Encana and Alberta government testing showed barium & strontium doubled in Ernst’s water after Encana’s illegal aquifer fracing

Fracking plays active role in generating toxic metal wastewater, study finds by Science Daily, December 15, 2015

Source: Dartmouth College

The production of hazardous wastewater in hydraulic fracturing is assumed to be partly due to chemicals introduced into injected freshwater when it mixes with highly saline brine naturally present in the rock. But a new study investigating the toxic metal barium in fracking wastewater finds that chemical reactions between injected freshwater and the fractured shale itself could play a major role.

The findings, which are published in the journal Applied Geochemistry, show that transformation of freshwater used for fracking to a highly saline liquid with abundant toxic metals is a natural consequence of water-rock reactions occurring at depth during or following fracking. Fracking wastewater poses a hazard to drinking water supplies if improperly disposed. A PDF is available on request.

The researchers examined samples from three drill cores from the Marcellus Shale in Pennsylvania and New York to determine the possible water-rock reactions that release barium and other toxic metals during hydraulic fracturing. The Marcellus Shale in the eastern United States contains large natural gas reserves, which have been extensively exploited in recent years using hydraulic fracturing. A mile below the earth’s surface where fracturing takes place, occur between water and fractured rock at elevated pressure and temperature and in the absence of oxygen.

…produced wastewater, or water that is produced along with shale gas and petroleum following fracking, is extremely saline and contains extraordinarily high concentrations of barium. It has been assumed that the peculiar composition of the produced wastewater results from mixing of freshwater used for fracking with high salinity water already underground that also contains barium. But the Dartmouth team found that a large amount of barium in the shale is tied to clay minerals, and this barium is readily released into the injected water as the water becomes more saline over time.

“Based on barium yields determined from laboratory leaching experiments of the Marcellus Shale and a reasonable estimate of the water/rock mass ratio during , we suggest that all of the barium in produced water can be reconciled with leaching directly from the fractured rock,” says senior author Mukul Sharma, a professor of Earth Sciences. “Importantly, behavior allows us to understand the behavior of radium, which is very abundant in produced water and is a very real environmental concern. There has been much discussion about injection of water with lots of toxic compounds during fracking. What is less known is that produced water is hazardous waste and chemical reactions between and the rock are likely playing a role in its formation, not simply a mixing of freshwater with natural brines in the rock.”

Journal Reference: Devon Renock, Joshua D. Landis, Mukul Sharma. Reductive weathering of black shale and release of barium during hydraulic fracturing. Applied Geochemistry, 2016; 65: 73 DOI: 10.1016/j.apgeochem.2015.11.001

UK shale has lots of poisonous selenium scientists warn by Marie Singer, December 23, 2015, Market Business News
UK shale has lots of poisonous selenium, an element our body uses in tiny amounts, but is toxic to humans when levels are high – and levels of selenium in rock samples taken by an international team led by the University of Aberdeen from an area targeted for shale gas extraction in the UK are very high.

Symptoms of selenosis (selenium poisoning) include garlic-smelling breath, hair loss, fatigue, irritability, sloughing of nails, gastrointestinal disorders, and neurological damage. In extreme cases the patient can develop cirrhosis of the liver, pulmonary edema, and may die.

The researchers, from the Aberdeen University’s School of Geosciences, Australia’s National Science Agency, and the Commonwealth Scientific and Industrial Research Organisation (CSIRO) in Australia, wrote about their study and its findings in the academic journal Applied Geochemistry. Toxic levels of selenium were found in rock samples taken from the Bowland Shale, a geological formation that is rich in shale gas in the north of England.

Risk of selenium getting into groundwater

The authors said there is a serious risk that high levels of selenium could be released into groundwater during ‘fracking’ (drilling) operations. Fracking companies need to be extremely careful during extraction to make sure that levels are kept to a minimum.

Study leader, Professor John Parnell, said:

“A major factor to be considered during shale gas drilling is the accompanying water, which may contain chemicals that require careful treatment.”

Recently, there was widespread concern in the US when water wells near a shale drilling site were found to contain selenium at levels that exceeded the maximum amount considered safe to drink, and this was assumed to have been released from the shale during drilling.”

“The samples we have analysed from the Bowland Shale are some of the most selenium-rich in the British Isles, and far in excess of the levels of selenium found in the US example. Indeed, a number of the samples we tested exceeded the far stricter European Union limits, so it is clear that any drilling to extract shale gas in the Bowland Shale area must be carefully managed.”

Same problem in Ireland

The study also found high selenium levels in equivalent rocks in the Republic of Ireland. Scientists know that shales in Ireland have caused selenium toxicity in farm animals “further underlying the importance of the issue.”

However, in spite of these concerns, high levels of selenium in the Bowland Shale offer opportunities, the scientists added. Selenium is a rare element in high demand – this demand is likely to grow.

Professor Parnell said:

“While this is first and foremost an environmental issue, the concentration of selenium and other trace elements in extraction waters could be regarded as an opportunity.”

“Selenium is a rare element for which demand is likely to increase, so there is a commercial incentive here which companies will no doubt be mindful of.”

“This study emphasises the importance of research when looking at areas to explore, in order to be fully aware of the potential impacts.” [Emphasis added]

Citation: “Selenium enrichment in Carboniferous Shales, Britain and Ireland: Problem or opportunity for shale gas extraction?” John Parnell, Connor Brolly, Sam Spinks, Stephen Bowden. Applied Geochemistry. December 2015. DOI: 10.1016/j.apgeochem.2015.12.008.

Scientists seek more data on existing water in shale formations by Kathiann M. Kowalski, December 21, 2015, Midwest Energy News

In hydraulic fracturing, what goes down isn’t always the same as what comes back up.

… Along the way, drilling and production also bring up brine from the ground – super-salty liquid with elevated levels of heavy metals, radium and other chemicals.

If scientists can learn more about that naturally-occurring water in the shale formations, drilling companies and well operators might figure out better ways to protect equipment and well integrity. More complete information could also lead to safer disposal options and other actions to protect public health and the environment. [Why say “safer?” Why not say “safe” disposal options?].

… What comes up

Fracking and horizontal drilling have led to a boom in oil and natural gas production. Yet just as the process uses large quantities of water to crack rock, it also produces huge amounts of liquid waste as flowback and produced fluids.

“Flowback usually is what we get out when we clean the well up after a hydraulic fracking job,” usually within the first week or two, explained Taras Bryndzia, a geologist with Shell International Exploration and Production, Inc. Flowback typically produces huge quantities of water in a short time period.

Produced fluid comes up afterward and as the well continues in operation. The quantities are much less than flowback on a daily basis.

“The composition in the flowback period is not the same as what comes back later,” said Blondes, who presented her research on produced fluid from the Utica shale at the GSA meeting.

In addition to radium, produced fluid from the Marcellus and Utica shale usually has higher levels of salt and heavy metals than fracking fluid does.

As a result, produced fluid could “be worse for the environment than what’s being injected in there,” Blondes continued. “That could affect disposal.”

Produced fluid is also “more of a problem” for well operators, Bryndzia noted, particularly when it comes to “salt in our production facilities.” Among other things, chemicals could crystalize inside pipes and reduce the rate of production.

“If I know where this stuff is coming from, I can actually mitigate against having salting out in production,” Bryndzia said.

Going deeper

“It seems very clear that what we’re looking at is actually natural formation water,” Blondes said.

Yet knowing that the produced fluid is “stuff that’s naturally there” doesn’t solve the mystery of how it got there in the first place, she said.

For both the Utica and Marcellus layers, brine in produced fluid likely started out in an ancient sea.

The salt content of that ancient sea water would have become more and more concentrated as water evaporated. Some liquid may still exist in either deep shale or adjacent rock layers. If the water evaporated completely, solids could have been left in the rock.

Pumping large quantities of fracking fluid down into the deep shale formations could dissolve some chemicals from the rock. Similarly, some amount of liquid could still remain in the tiny pores of that rock and then come up after fracking.

Bryndzia’s research on the Marcellus shale, also presented at the GSA meeting, suggested that lots of brine likely began in the shale layer in one of these ways. However, his data also showed that some brine could come from an adjacent layer.

Indeed, it would be unlikely for the Marcellus shale layer to be the source for all of the produced water, said Brian Stewart, a geologist at the University of Pittsburgh who also spoke at the GSA meeting. Stewart’s team analyzed drill cuttings from Marcellus shale operations in New York.

“There’s not enough salt or water in those pores to really explain the super salty water that comes back,” Stewart said.

Instead, the fluid could come from part of the formation “that’s maybe not really a shale, like a little lens of sand in there that might hold more water,” he suggested. “Or, it could come from rock formations above or below the shale.”

In order for that to happen, some interaction with that other layer would have to take place. One possibility is the fracking process itself.

“When you hydraulically fracture, you basically create cracks under those formations, and the water can leak back into your well,” Stewart said.

“It’s clear that the fractures extend outside of the target formation” in the fracking process, he added. “It’s not really possible to keep it within a relatively thin shale unit.” Other research presented at the GSA meeting supports this position.

In some cases, some upward migration of gas or fluids may be possible, which is why there’s some concern about areas with lots of older, abandoned oil and gas wells. However, groundwater contamination would be “extremely difficult” as a result of fracturing done in deep unconventional shale layers, Stewart said.

“You’re still not getting anywhere close to the surface,” Stewart noted. When groundwater contamination has occurred, the more likely reason is faulty drilling or well completion, he said.

Data wanted

Getting more exact answers gets tricky, especially because there’s a bit of a “chicken and egg” problem, Blondes noted. Fluids from deep shale layers generally don’t come up unless fracking is done, so it’s harder to figure out what would come up otherwise.

In the case of produced fluid from the Utica shale, “ it’s likely it’s from Utica itself,” Blondes suspects. “It seems somewhat different from the Marcellus.”

“We definitely cannot say for sure,” though, she said, “because we don’t necessarily have samples overlying and underlying the formation.” To get those samples, she and other researchers need more access to wells, particularly those in the Utica shale.

“We’re actually mostly interested in some of the older wells that have been in production for a while,” since those would have the highest proportion of natural formation water, Blondes said.

USGS is “not a regulatory agency,” she added, “and we take utmost care to not give away any proprietary data.”

“We only have a couple of data points from the Utica,” Blondes said. “Our goal is to be able to sample the Utica and above and below.” [Emphasis added]

[Refer also to:

2009 11 09: Pennsylvania lawsuit says drilling polluted water

A Pennsylvania landowner is suing an energy company for polluting his soil and water in an attempt to link a natural gas drilling technique with environmental contamination. George Zimmermann, the owner of 480 acres in Washington County, southwest Pennsylvania, says Atlas Energy Inc. ruined his land with toxic chemicals used in or released there by hydraulic fracturing. Water tests at three locations by gas wells on Zimmermann’s property — one is 1,500 feet from his home — found seven potentially carcinogenic chemicals above “screening levels” set by the U.S. Environmental Protection Agency as warranting further investigation.

Baseline tests on Zimmermann’s water a year before drilling began were “perfect,” he said. In June, water tests found arsenic at 2,600 times acceptable levels, benzene at 44 times above limits and naphthalene five times the federal standard. Soil samples detected mercury and selenium above official limits, as well as ethylbenzene, a chemical used in drilling, and trichloroethene, a naturally occurring but toxic chemical that can be brought to the surface by gas drilling. The chemicals can cause many serious illnesses including damage to the immune, nervous and respiratory systems,…. [Emphasis added]

2013 06: FrackingCanada The Science is Deafening: Industry’s Gas Migration

“An Engineering and Materials Testing firm in Alberta recommends that dissolved methane, barium and strontium are added tests to the government standard because they are indicators of methane gas migration into water wells.”

Tests on the Ernst well water before (by Encana) and after Encana illegally fractured Rosebud’s drinking water aquifers (by Alberta Environment):

showed barium and strontium doubling and chromium increasing by a factor of 45.

2006 Toxic chemicals found by the regulator in Ernst drinking water

2006 Toxic chemicals found by the regulator in Rosebud Hamlet drinking water

After these damning results is when Encana began refusing metals testing in “baseline” water well testing.

Alberta Environment did not test for arsenic, mercury, and much more. What were they knowingly avoiding in their testing?

FOIP records released to Ernst by Alberta Environment after years of struggle and $1,500 personal funds:

Tests by Alberta Environment on their Rosebud “monitoring” water well installed 3 years after Encana illegally fractured the community’s drinking water aquifers and 6 years after Encana began frac experiments into area fresh water zones, show the carcinogen hexavalent chromium to be higher than in other Alberta Environment monitoring well data provided.

2013 08 02: New Peer Reviewed Study: Elevated levels of methanol and heavy metals may be from fracking in Texas, Water contamination highest near frack sites

A new study of 100 private water wells in and near the Barnett Shale showed elevated levels of potential contaminants such as arsenic and selenium closest to natural gas extraction sites…. The peer-reviewed paper focuses on the presence of metals such as arsenic, barium, selenium and strontium in water samples. Many of these heavy metals occur naturally at low levels in groundwater, but disturbances from natural gas extraction activities could cause them to occur at elevated levels.

… Ninety-one samples were drawn from what they termed “active extraction areas,” or areas that had one or more gas wells within a five kilometer radius. Another nine samples were taken from sites either inside the Barnett Shale and more than 14 kilometers from a natural gas drilling site, or from sites outside the Barnett Shale altogether. The locations of those sites were referred to as “non-active/reference areas” in the study. 

On average, researchers detected the highest levels of these contaminants within 3 kilometers of natural gas wells, including several samples that had arsenic and selenium above levels considered safe by the Environmental Protection Agency. For example, 29 wells that were within the study’s active natural gas drilling area exceeded the EPA’s Maximum Contaminant Limit of 10 micrograms per liter for arsenic, a potentially dangerous situation. The areas lying outside of active drilling areas or outside the Barnett Shale did not show the same elevated levels for most of the metals.

2015 04 09: California farmers rely on Chevron’s wastewater to irrigate. Some refuse: “I would rather let my trees die” than use Chevron’s water

Avner Vengosh, a Duke University geochemist, is serving on an expert panel for the U.S. Geological Survey while it begins to look into the quality of produced oil-field water from Kern County. His data are “only preliminary,” but he has found “high levels of vanadium, chromium and selenium” in the samples of wastewater he has tested…. Those levels are consistent with data from oil- and gas-produced water from other basins in the U.S., according to Vengosh.

Vanadium, a metal, is classified as “possibly carcinogenic” by the International Agency for Research on Cancer. Certain forms of chromium and selenium, both heavy metals, are associated with myriad health problems, including cancer, from chronic high exposure.None of these metals are required to be tested for by the Central Valley Water Board.

2015 05 19: Alberta Health Services Warning: Drinking water contamination in Kneehill County: Toxic Selenium and Uranium found in private water wells; Metals testing not mandatory before fracing, waste dumping and injection, not even when companies frac into drinking water aquifers

2015 11 15: Hydraulic Fracturing Stimulation contaminating drinking water, 25 per cent of water wells tested by Dr. Zack Hildenbrand show contamination with man-made chemicals used in fracking the Eagle Ford: “This practice is having an affect”

“What we found is the closer people’s water wells got to gas wells that had been stimulated by hydraulic fracturing, the concentrations of arsenic, selenium, strontium, and barium went up quite significantly,” Hildenbrand said.

2014 08 04: Scientists Find ‘Alarming’ Amount Of Arsenic In Groundwater Near Texas Fracking Sites; New perspectives on the effects of natural gas extraction on groundwater quality

… That boom started about 10 years ago, and the University of Texas researchers compared their results with previous water tests conducted before that boom. What they found was what researcher Zacariah Hildenbrand called an “alarming” increase in the amount of arsenic and other heavy metals in 30 percent of the groundwater wells within 1.8 miles of gas drilling sites.

“This is indirect evidence that drilling does affect the water,” Hildenbrand said. [Emphasis added]

New perspectives on the effects of natural gas extraction on groundwater quality by Zacariah L. Hildenbrand, Brian E. Fontenot, Doug D. Carlton Jr and Kevin A. Schug, all at The University of Texas at Arlington, United States, May 24, 2014, in Global Water, Issues and Insights by R. Quentin Grafton, Paul Wyrwoll, Chris White and David Allendes, May 2014

ISBN 9781925021660 (Print version)
ISBN 9781925021677 (Online)

Elevated arsenic levels found in Leduc, Parkland and Sturgeon Counties, Province is asking residents who have private wells to get water tested by CBC News, December 14, 2014

“The levels that we’re seeing, we don’t have immediate cause for concern,” said Dr. Chris Sikora with AHS. [Is AHS trustworthy? Citizens at Rosebud impacted by Encana’s illegal aquifer frac’ing begged Alberta Health for help only to be shunned like lepers] “That being said, it’s best to protect your own health.”

Alberta Health Services wants residents in Leduc, Parkland and Sturgeon Counties to get their private water wells tested after higher-than-acceptable levels of arsenic and manganese were found during routine monitoring.

Some private wells on properties south of Township Road 544 and north of Township Road 502, between Range Roads 39 and 250, have shown elevated levels of the two elements.

In some cases, arsenic levels were found to be twice as high as recommended provincial guidelines for drinking water – and manganese levels were up to 50 times the recommended level.

Elevated arsenic, manganese levels measured

Acceptable arsenic levels: 0.01 mg/litre

Measured arsenic levels: 0.02 mg/litre

Acceptable manganese levels: 0.05 mg/litre

Measured manganese levels: 0.5-0.9 mg/litre

(Source: Dr. Chris Sikora, AHS)

The elevated levels were discovered during routine monitoring by Alberta Health Services.

Despite the alarming-sounding numbers, Dr. Chris Sikora with AHS says residents do not need to be scared.

“The levels that we’re seeing, we don’t have immediate cause for concern. The levels that we’re seeing might have a cause for an individual who drank water over the 75-year lifetime.”

“That being said, it’s best to protect your own health.”

AHS recommends that private well-users in the area send in water samples for one-time free testing by the province.

Once elevated levels are detected, filtration mechanisms can be added to help reduce the levels.

Water would taste, look different

Sikora said both arsenic and manganese are naturally occurring elements. [Why avoid the critical fact that the oil and gas industry is a significant cause of increasing “naturally occurring” arsenic, mercury, barium, strontium, manganese in drinking water in Alberta?]

“This naturally-occurring arsenic … has been seen in numerous other watersheds and basins [across Alberta].”

Sikora said the heightened levels of arsenic and manganese would taste and look different from normal drinking water.

“The water is actually discoloured and will stain clothes if used in a washing machine, so I’m quite confident that people wouldn’t be using that water for consumption purposes.”

Those who live in the area but get their water from regional or municipal water services, such as EPCOR, will not be affected.

The province will be mailing out additional information about water safety to those living in the affected area. [Emphasis added]

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