New Technology for Chromium Cleanup

The Environmental Security Technology Certification Program is trying to promote a new in-situ technology to eliminate hexavalent chromium from groundwater sources. Current technologies use plume containment methods, which do not target the source of contamination. The in-situ technology seems to be a fast and efficient way to remove hexavalent chromium from groundwater.

The in-situ technology, which allows water to be treated without first being extracted, uses chemical reduction and ferrous iron precipitation. Chemical reduction involves transferring electrons between ions, which creates a lower valence state for the “reduced” element. The purpose of chemical reduction is to lower the valence state of an element since different valence states react differently. Ferrous iron (Fe2+) can chemically reduce hexavalent chromium ions (Cr6+) in groundwater to form trivalent chromium ions (Cr3+) and Fe3+. After the chemical reduction, the ferrous iron precipitation takes place. Dilute hydrogen peroxide and sulfuric acid can be added to the groundwater to adjust the pH and to disrupt soluble chromium compounds. The Fe3+ then reacts with the hydrogen peroxide to form a highly insoluble iron oxyhydroxide precipitate, while the Cr3+ also precipitates. This removes hexavalent chromium from the groundwater and contains it in the subsurface of the water. A preliminary trial of the in-situ technology in its early stages showed promising results. At Anniston Army Depot in Alabama, in-situ technology removed between 67 and 100 percent of chromium from five groundwater samples, four of which had chromium concentrations below the water-drinking limit.

There are several advantages to in-situ technology over traditional methods. In-situ technology quickly removes chromium from groundwater without interfering with facilities or corporations and without having to operate for extended periods of time. This technology is also more economical; savings are expected to range from thirty to eighty percent compared to costs of groundwater extraction. Most importantly, in-situ technology “is a source reduction process rather than a plume containment process and thus eliminates the long-term source of groundwater contamination.” Thus, not only is in-situ technology thorough in removing chromium from groundwater, it is also fast and economical.

Combined Techniques Results in Lower Detection Levels

Recently, a new method for detecting hexavalent chromium in water was developed. This new method involves ion chromatography and inductively coupled plasma mass spectrometry (ICP-MS). This provides a significantly lower detection limit and eliminates false results caused by current methods of detection.

This lower detection method was developed for several reasons. Publicity and concern about hexavalent chromium has increased over the years, and has therefore caused the public to expect immediate action in the detection and removal of hexavalent chromium from water. The limit for hexavalent chromium in freshwater set by the U.S. National Water Quality is currently 11 micrograms per liter. However, this limit is expected to be lowered in the future. Also, more accurate and sensitive detection methods are needed to improve treatment systems and remediation studies.

As stated before, the method consists of ICP-MS and ion chromatography. ICP-MS uses plasma or a gas to ionize the elements in a compound. The ions pass into a mass analyzer, and the isotopes of the elements in the compound are identified by their mass to charge ratio. The amount of an element in the compound can then be determined by looking at the mass spectrum, where the intensity of a peak is proportional to the amount of the element in the compound. Ion chromatography is a technique that separates ions by relying on differences in absorbency of the ions. Separately, these two techniques both have restrictions and flaws. For example, if chloride, carbonate, or sulfate ions are present in a sample, ICP-MS will show a false positive for hexavalent chromium. Combining the two techniques eliminates false positives and negatives.

The new ion chromatography and ICP-MS method can detect concentrations of hexavalent chromium as low as nine nanograms per liter, which is thirty to forty times lower than the concentrations detected by the Environmental Protection Agency’s method (EPA Method 7199). The new method can be used to test drinking water, groundwater and sea water for hexavalent chromium. This accurate detection method can prevent mistakes in analyses and decisions, which can save corporations and facilities a significant amount of money.

Chromium Contamination

The widespread concern about chromium-6 is due to the extent of contamination in the environment. Chromium-6 can be emitted into the air, into the water, and into the soil by any number of different industries. However, chromium-6 is not and cannot be regulated in the air. Levels between .01 and .03 micrograms of chromium-6 per cubic meter have been found in urban areas. Even drinking water has trace amounts of this carcinogen. Regular tap water has between .4 and 8.0 micrograms per liter and large bodies of water have higher concentrations of up to 10 micrograms per liter. Soil contains about 400 parts per million total chromium, but chromium in soil poses less of a threat. The organisms in the soil often turn chromium-6 into harmless chromium-3.

Chromium-6 is a common component in many industries including leather tanning, the production of textiles, dyes, and pigments, chrome plating, oil and coal combustion, stainless steel welding, steel production, cement plants, industrial paint and coating manufacture, and cooling towers. Concentrations of chromium-6 are the highest in chrome plating workshops. While workers are welding, concentrations can get as high as 1,500 micrograms per cubic meter of air. As little as two micrograms of chromium-6 per cubic meter of air can cause irritation and sneezing. Exposure to chromium-6 in the hundreds of micrograms is one of the main reasons workers often have higher levels of lung and nasal cancers. However, not only the workers are in danger. Their families, who come in contact with them or their clothes, pick up the powdered chromium and can get sick as well.

Yet, the chromium-6 contamination in the air, water and soil is not as dangerous as one might think. Trace amounts of chromium-6 in drinking water does not seriously harm humans, and, as stated before, chromium-6 in the soil is often converted to chromium-3. Still, people working around chromium must always be careful.

Brockovich's Crusades: Part 3 - A Struggle Closer to Home

Most know Erin Brockovich for her research and organization of a suit against PG&E for leaching Chromium-6 into the water supply of Hinkley, California. The media, including Hollywood, followed that story, as well as her crusade against PG&E in Kettleman Hills, California, with great interest. However, the celebrity’s least publicized crusade strikes closest to home, in the literal sense. Erin Brockovich was invited to speak to the Senate Committee on Health and Human Services on the topic of mold.

The committee, led by California’s Senator Deborah Ortiz of the Democratic National Party, asked Brockovich to speak at a panel discussing the Toxic Mold Protection Act. The potential bill would establish an exposure limit for mold, which Senator Ortiz equates with asbestos and lead. However, Erin Brockovich was not merely invited to speak on account of being an environmental activist and celebrity – she encountered numerous problems with mold in her own home in Agoura Hills. When she began asking questions as to why her family began ailing, she connected it to the mold inside her household.

Brockovich told the panel:
“I began to put two and two together. I have floors coming up. Why? The house smelled musty. Why? Could there be a water problem? And then I started thinking – water, mold, what’s going on? I’m sick.”
She claimed that “such legislation might have prevented her from buying the sprawling Agoura Hills home she and her family moved into in 1997.”

However, although Brockovich appears to be an environmental crusader being attacked by the very issue she fights against, she may, as usual, have an ulterior motive. Repairs to her house in Agora Hills have cost her more than $600,000. Although money is undoubtedly not a concern for her, the cost of repairs is still a large sum of money. No doubt annoyed, Erin Brockovich takes advantage once more of her deceit and celebrity-status to achieve her goals. Corporate America had best watch out.

The Business Aspect of Chromium

A report titled “The Economics of Chromium,” which was published on February 28, 2005, announced that prices of ferro-chrome (a major component in the production of stainless steel) have reached the highest levels in ten years as a result of high demand, restricted supply, and drastic increases in the costs of freight, energy, and raw materials for chromite. Because of the growth in the stainless steel industry, forecasts predict that chromium still has more growth and development to come. This promising forecast promotes plans for capacity expansion that would impact the ferro-chrome market to such an extent that there would be a surplus of ferro-chrome, which would also decrease costs. Surprisingly, in 2002, the market experienced the lowest prices of ferro-chrome in thirty years. Thus, the price of ferro-chrome seems to follow a cycle from low to high prices, which continually repeats over a period of years. This has led to an assimilation of chromite mining and ferro-chrome production as well as expansions due to improved processes.

In 2004, Xstrata Alloys and SA Chrome joined together to become the world’s largest ferro-chrome producer:
“The Xstrata-SA Chrome Venture, Samancor Chrome of South Africa, and Kazkrom of Kazakhstan are the leading producers of chromite and ferro-chrome, accounting for nearly 55% of world output of both products.”
South Africa and Kazakhstan both have the potential to further increase production of ferro-chrome, which could greatly increase the “concentration” of the ferro-chrome supply in those countries.

There is certainly much promise for the chromium metal market. In 2004, it was estimated that the use of chromium metal increased by 15%, and there is a high probability that chromium use will increase at least 25% later this decade. Growth in the chromium metal market is expected over the next five years as a result of development in the aerospace and industrial gas turbine markets.

However, this optimism is not seen in the chromium chemical market. In 2003, the demand for chromium chemicals declined by approximately 3% and this trend appears to be continuing over the next few years. The limits on the use of chromium chemicals in wood preservation, pigments, leather tanning and metal surface treatments due to environmental and health concerns about exposure to hexavalent chromium has contributed to the decline in demand. Although the chromium chemical market is suffering now, it will hopefully recover soon in accordance with the cycle of chromium prices.

Chromium's Not So Humble Beginnings

Today, chromium is an indispensable element in industries ranging from metal plating to dyes. Its uses date back to the 1700s before this valuable metallic element was even discovered.

In 1761, chromium was unknowingly encountered found by Johann Gottlob Lehmann in the Beresof Mines in the Ural Mountains. There, Lehmann collected an orange-red mineral, which he named Siberian red lead. This Siberian red lead was actually a lead chromate called crocoite (PbCrO4). In 1770, Peter Simon Pallas collected Siberian red lead from the Beresof Mines. He noticed that the mineral became a yellow guhr (a loose, water-laid earthy deposit of a mixture of clay or ocher) when crushed. This led to the use of Siberian red lead in paints. The red lead was used as a pigment, as was the vibrant yellow guhr, which became a popular color for the nobility’s carriages in England and France. Siberian red lead was so fashionable that it even became a collector’s item.

However, it was not until 1797 that the element chromium was discovered. Nicolas-Louis Vauquelin, a chemistry professor at the School of Mines in Paris, analyzed samples of Siberian red lead that he had received. His analysis led to his discovery of a new element, which he named chromium from the Greek word for color. He also found chromium in valuable gems such as rubies and emeralds.

One year later, the pharmacist and chemist Johann Tobias Lowitz and German chemist Martin Heinrich Klaproth each found chromium in a heavy black rock near the Beresof Mines. In 1799, a German chemist named Tassaert also found chromium in the same heavy black rock, but in the south-eastern region of France. Tassaert identified the mineral as chromium-iron spinel, which is now known as chromite (FeOCr2O3). Tassaert’s discovery of chromite increased the use of chromium in the paint industry. As a result, chemical factories were built in Manchester, England in 1808. Chromium became a defining element of success in the paint industry. When Isaac Tyson from the Tyson mining family discovered chromite on the Maryland-Pennsylvania border in 1827, America held a monopoly on the supply of chromium in the paint industry. Turkey later controlled the supply of chromium after chromite was discovered near Bursa, Turkey in 1848. In 1906, chromium mining started in India and South Africa.

The discovery and use of chromium in the paint industry opened a gateway to numerous other industries. In 1820, Kochlin became the first to use potassium dichromate as a mordant in the dyes. Chromium salts were used in leather tanning starting in 1884. A patent for chromium in steel was granted in 1865. However, the use of chromium in steel did not become widely accepted until the 1900s when furnaces melted chromite into an alloy called ferrochromium.

Thanks to these discoveries and the progress of science, chromium is still widely used in industries. Although the risk of exposure to hexavalent chromium exists in industrial settings, appropriate precautions can be taken so as not to diminish the true value of chromium.

Federal Trade Commission Cracks Down on False Advertising

An earlier weblog entry titled “Chromium: The Weight Loss Aid” discussed the potential benefits of chromium as a weight loss supplement. While the claim that chromium is a weight loss aid has both support and criticism, claims made by some weight loss products today are completely unsubstantiated. Hundreds of weight loss products swarm the market, vying for overweight customers. With all of these different companies trying to make a profit, it is no surprise that some employ false advertising in order to increase their sales.

With so many products on the market, it would be impossible to check every one for accurate advertising. This was the Federal Trade Commission’s point when it created the Red Flag brochure, which notified all of the advertising agencies which weight loss products advertised false claims. Even though the FTC created this list, it is no where near finding all of the false products advertised in magazines, infomercials and newspapers.

However, when the FTC does catch people who falsely advertise products, they are prosecuted to the full extent of the law. On June 30, 2003, the FTC filed two settlements and one complaint in U.S. district court against the false claims of weight loss supplements containing ephedra. The FTC challenged the claims that the supplements caused “rapid, substantial, and permanent weight-loss without diet or exercise, and that 'clinical studies' or 'medical research' prove these claims.” The FTC also challenged claims that the supplements were “100% safe” or had “no side effects.” Michael S. Levey was charged with false advertising on three of his products: Zymax, MillinexES, and Serotril. Not only did Levey promise quick and permanent weight loss, but he also claimed that CartazyneDS, a dietary supplement, would cure arthritis within days.

Obviously, people like Levey will try to make a profit even at the expense of their customers. The best way for customers to make sure that these kinds of businessmen do not steal their money is to learn what to look for in a diet supplement. The FTC’s homepage provides important advice for exactly that:
“Products and programs that promise quick and easy weight loss are bogus. To lose weight, you have to lower your intake of calories and increase your physical activity. There are no miracle weight-loss products. Be skeptical of products and programs that claim they can keep weight off permanently. Be skeptical about exaggerated claims.”
Customers should always remember to do their homework before they spend money on health supplements. With simple research, they can save themselves a lot of money and maybe even make themselves healthier in the process.

Brockovich's Crusades: Part 2 - Trouble in Paradise

Erin Brockovich’s “environmental crusades” brought her to Hawaii, where she was married, one year ago, to her husband Eric Ellis. Apparently, the money and fame she received as a result of her movie and her numerous cases in California were not enough. Her desire to further her own causes has led her to create trouble in paradise, on the Hawaiian island of Oahu. In conjunction with a Hawaiian law firm, Tam & Stanford, Brockovich and her boss Edward Masry claim that local and national companies such as Delmont and Dole foods have applied pesticides to crops grown in Central Oahu, thereby contaminating the Oahu water supply with DBCP and EDB. As always, Brockovich immediately went to the media, using her Hollywood fame and powers of deceit to lead the Hawaiian press into believing that she only wished to fight for the list of several hundred plantiffs who were allegedly harmed as a result of the defendants’ “poor housekeeping practices.”

Brockovich explained to the Honolulu-Start Times her reasons for investigating the case:
“I see myself as a vehicle for a greater message about corporate deceit and what it does to us as a people," she said. "Corporate deceit and ground water contamination did not begin, nor does it end, in Hinkley, California.”

Brockovich filed the first complaint against Dole Foods Corporation in a Hawaiian Circuit Court on March 7th, 2000, coinciding with the release of the movie “Erin Brockovich.”

Brockovich's Crusades: Part 1 - PG&E’s Suffering, Continued

Erin Brockovich, who exposed high levels of chromium-6 in the water supply of Hinkley, California and who brought PG&E to a 333 million dollar settlement, has continued her “environmental crusades.” As discussed in an earlier weblog entry titled “Brockovich v. Fumento: Part 3 - Brockovich's Blunder,” Brockovich did not end her career after her overwhelmingly successful case against PG&E. In fact, even before her crusade against Beverly Hills, Brockovich continued her relentless, albeit false, accusations against PG&E.

Coinciding with the release of the movie Erin Brockovich, Brockovich and her boss, Ed Masry, drove out to Kettleman Hills, California to inspect another PG&E plant. Although Masry surveyed the cooling towers and abandoned buildings and found no sign of contamination, Brockovich did her own investigation:
“[Brockovich] noticed a white powder on the needles of the tamarisk trees, an abnormality she remembered from Hinkley. And soon, she was at it again, mining records and tracking down anyone who lived or worked at Kettleman. Among the boxloads of documents she copied was a 1964 letter from the U.S. Interior Department notifying PG&E about unhealthy levels of Chromium-6 in Kettleman's water well.”

As in the Hinkley case, the plantiffs claimed that exposure to the chromium-6 in their water supply caused anything from nosebleeds to Crohn’s disease. However, unlike before, PG&E refused to settle, learning from their mistakes. Hopefully, the truth will prevail and PG&E will win the case, despite Brockovich’s crusade against them. Furthermore, although PG&E’s recent filing for bankruptcy may affect the case, Masry and Brockovich will no doubt turn it to their advantage.

Chromium and Diabetes

Although chromium cannot cure diabetes, there is evidence that suggests chromium could help aid the living conditions for those who have it. R.H. Logan, a Chemistry instructor at North Lake College, summarized what numerous scientific studies have shown:
“Chromium Picolinate which is the biologically active form of Chromium helps insulin do its job. It does its job by the cofactor equation with insulin. The cofactor equation is the theory that our body has receptor sites for each hormone, mineral, or vitamin that is necessary for the body. Research have shown that Chromium levels determine the number of cell receptors for insulin, therefore if there are adequate insulin levels this will prevent the onset of Noninsulin Dependent Diabetes. In theory Chromium may help insulin deliver glucose to your cells more efficiently.”
Because chromium plays an active role in the body with insulin, many people have conducted research on the effects of chromium on diabetes. This site discussed one study done in china, which showed promising results for chromium treatments. After four months, those who took chromium supplements showed lower levels of blood sugar and their hemoglobin A had dropped to a normal level. Obviously, many people wanted to find out more about chromium after the results of this study were published. However, another site declared that this study was flawed because the chromium levels of the patients were not measured before the start of the study and that it would not be applicable to the United States because the Chinese are less likely to be obese than Americans. Even with this negative view on these findings, the United States Department of Agriculture started backing chromium research in 1996, which still continues today.

Hexavalent Chromium at the Source

On its website, the Awwa Research Foundation posted the results of a study it had conducted on the efficiency of water treatment systems. The research team took samples from 407 different drinking-water sources. These source waters came from 189 utilities in 41 different states that agreed to participate in the study. 273 of the samples were taken from groundwater sources, while the remaining 134 were taken from surface water sources.

These source water samples were analyzed and the concentration of chromium as well as boron was measured in each. Awwa found that the average concentration of chromium (trivalent and hexavalent chromium) was 2.0 micrograms per liter. The average concentration of hexavalent chromium alone in the samples was 1.1 micrograms per liter. The research team also discovered that hexavalent chromium was more prevalent in groundwater sources than in surface water sources. While the chromium detected in the surface water samples was mainly trivalent chromium, the chromium discovered in the groundwater sources was almost entirely hexavalent chromium. Because the samples came from utilities across the United States, the research team also analyzed “regional occurrence trends.” The team noted that the concentration of both trivalent and hexavalent chromium was the largest in EPA Region 9, which encompasses California, Nevada, Arizona, Hawaii, Guam, the Trust Territories, American Samoa, and the Northern Mariana Islands. Although source water samples were not taken from all of these states or territories, the trend showed that the chromium concentration tended to be higher in these regions.

Based on its findings, the Awwa Research Foundation stated that conventional treatment systems only removed trivalent chromium; no other treatment systems could remove hexavalent chromium. The research team concluded:

“This research provides a new baseline of national boron and chromium—total and hexavalent—occurrence in drinking water sources. It also indicates that existing treatment technologies do not effectively remove boron or hexavalent chromium. If chromium or boron are to be further regulated in drinking water, this research offers meaningful national occurrence information necessary for the regulatory development process.”

Clearly, the Awwa Research Foundation reported significant information on the levels of chromium found in water sources across the country and on the ineffectiveness of water treatment systems. However, it is the job of the utilities and water-regulating agencies to use this information to improve water treatment systems and to reduce the level of potentially harmful hexavalent chromium in the nation’s water sources.

Fumento v. Brockovich: Part 4 - The Climactic Finish

When the show 60 Minutes arranged a segment on Erin Brockovich, they attempted to have a joint appearance with Michael Fumento and Erin Brockovich. Despite her refusal, the show was able to interview both separately and combine clips from the two interviews into one televised program. At last, after all of Fumento and Brockovich’s fighting, the two were able to debate one another, albeit not face to face.

The segment focused entirely on the two Erin Brockovich cases previously mentioned (see “Fumento v. Brockovich” parts 1-3.) The interview began with a discussion of the Hinkley case, and once more, Brockovich used deceit and revealed her own fraudulence. Although she tried to paint an image of children running through water laced with chromium-6, the interviewer, Mike Munro, noted that there was no cancer cluster in Hinkley, California. In response Brockovich stated that the case had nothing to do with cancer, rather it dealt with a corporation dealing irresponsibly with dangerous chemicals. Her tangential response belies her lack of a case.

In his own interview, Fumento also discussed the Hinkley cases, primarily in context with the movie Erin Brockovich. He stated:

“There were some true facts in the movie. For example, there is an Erin Brockovich, there is a state of California, there is a town in that state called Hinkley. But for the most part, the movie was fiction.”

The segment concluded by noting that in the Beverly Hills case, Erin Brockovich’s entire reputation and fame hangs by a thread. Munro noted ironically that her downfall may come as she attacks the very town that made her famous. Fumento merely hopes that they will indeed go to trial because he believes that Masry and Brockovich will lose in court.

The Colors of Chromium

Chromium comes from a Latin root word that means color. So it is no surprise that chromium has some very interesting color effects. Chromium is solely responsible for the emerald and the ruby, both very valuable gems. Without chromium a ruby would be the crystal corundum and an emerald would just be the crystal beryl. You can find pictures of these crystals here along with more information on rubies and emeralds. The chromium that makes emeralds and rubies is actually an impurity in the crystal structure. It replaces some of the atoms in the crystal, aluminum oxide molecules in ruby and beryllium aluminum silicate in emerald, by chemically bonding to the surrounding atoms in the crystal. The chromium absorbs the light differently in the two crystals. In corundum, chromium absorbs the green and violet, which makes the gem a reddish color with a tinge of blue. In beryl, chromium absorbs the yellow-red light and the blue light, which gives the gem its green color. Thanks to chromium, our world has these beautiful minerals that are adored the world over.

Chromium-6 in the Workplace

Hexavalent chromium is a commonly used compound in industries involving pigments, metal plating, stainless steel welding, and chemical synthesis as ingredients and catalysts. Studies have shown that workers who have been exposed to hexavalent chromium have an increased risk of lung cancer, asthma, nasal septum ulcerations, nasal cancer, skin ulcerations, and skin irritation. Because of these adverse health effects, the exposure limit for hexavalent chromium in the industrial workplace for an eight-hour time span is fifty-two micrograms per cubic meter of air. In October of 2004, the Occupational Safety and Health Administration (OSHA) proposed a new regulation to lower the exposure limit to one microgram per cubic meter of air. The proposed regulation also included standards for protective clothing and equipment, medical surveillance, exposure control, and recordkeeping to protect employees. In a news release titled “OSHA Schedules Public Hearings on Hexavalent Chromium,” OSHA announced that public hearings would be held in Washington, D.C. starting on February 1, 2005 to discuss OSHA’s proposed regulation. Although the proposed regulation was designed to protect workers from exposure to hexavalent chromium, many companies claim that the new regulation would hardly help workers and would be too expensive to uphold. However, the court will ultimately decide whether OSHA’s regulation is necessary.