Titanium in Virginia

titanium has eroded from the Blue Ridge, including the Tye River region, and accumulated in Coastal Plain sediments (yellow)
titanium has eroded from the Blue Ridge, including the Tye River region, and accumulated in Coastal Plain sediments (yellow)
Source: US Gelogical Survey (USGS), Heavy-Mineral Sand Resources in the Southeastern U.S. Titaniun, in cmmercially-valuable deposits, has been found in Virginia in the Blue Ridge on the Piney River, in Hanover County, and near Emporia in the Old Hickory Heavy Mineral Sand Deposit.

The Vanadium Corporation of America began mining titanium at Piney River in Nelson County in 1931. It was processed into titanium dioxide, for use as a pigment in paint and in other products. Between 1957-1968, M and T Chemicals mined and processed primarily rutile (TiO2) in Hanover County for ceramics, including floor tiles. In both places, open pits exposed saprolite (weathered bedrock) derived from titanium-rich pegmatite dikes as well as the intrusive dikes.

At Piney River, the top 100' of saprolite were excavated. The primary mineral in the ore was ilmenite (FeTiO3). Along the Piney and Tye rivers, titanium was also present as rutile (TiO2). Rutile Lane is still located near Roseland in Nelson County.

Rutile Lane is a reminder of the titanium ore in Nelson County
Rutile Lane is a reminder of the titanium ore in Nelson County
Source: ESRI, ArcGIS Online

The ore was crushed, concentrated, and processed at a plant four miles from the mine to create titanium-dioxide pigment. The material was shipped via the Blue Ridge Railway, constructed originally in 1915 to transport chestnut trees to mills. The disappearance of the chestnut and the Great Depression could have caused the railroad to close, but the titanium mining/processing and nearby quarries kept the railroad in business.

Riverton Lime & Stone Company opened a quarry in 1939 that extracted aplite, another intrusive igneous rock rich in feldspars and quartz. Carolina Minerals opened a second aplite quarry in 1941.

The fine-grained aplite was found near coarse-grained pegmatite dikes. Both formed as magma derived from continental crust that crystallized into granite that metamorphosed into gneiss in the Blue Ridge. The aplite is rich is calcium phosphate, making it particularly useful for agricultural fertilizer.1

Nelsonite, designated the official state rock of Virginia in 2016, is composed primarily of ilmenite (FeTiO3) and apatite (Ca3(F,Cl)(PO4)3). The titanium and calcium phosphate minerals separated from the magma as it cooled and crystallized into nelsonite rock a billion years ago.2

In 1944, American Cyanamid Company bought the Piney River operation, expanded operations, and became a major employer in the area.

American Cyanamid Company mined and processed titanium ore on the Piney River from 1931-1971
American Cyanamid Company mined and processed titanium ore on the Piney River from 1931-1971
Source: US Gelogical Survey (USGS), Piney River 1:24,000 quadrangle map (1963)

The process for converting the titanium ore into the final product involved sulfuric acid, which the company dumped into the Piney River. In 1946, the Commission of Game Inland Fisheries (now the Department of Game and Inland Fisheries) issued a citation to American Cyanamid Company for "casting noxious substances into Piney river." A second citation was issued in 1947.

A lawsuit contesting the two $25 fines followed. The final appeal reached the Virginia Supreme Court in 1948, and it noted:3

The ore from which the ultimate product is obtained is found in combination with clay and other material. It is first crushed at a mill in Amherst county, then separated by a process which includes washing and the washings are released into Piney river. The concentrated ore is then carried to the chemical plant in Nelson county, just across Piney river, and there chemically created to extract the titanium.

In the course of these operations the defendant discharged into Piney river two kinds of waste, one being solid materials in suspension and the other sulphuric acid in liquid form. The solid material discolors the water, but the defendant claims it is harmless to fish life. Moreover, the defendant has begun the construction of a settling basin, which is expected to settle out most of the solid material.

The defendant admits that the other type of material - dilute sulphuric acid - which it wastes into the stream, constitutes pollution and destroys aquatic life; and so it admits that on the days charged in the warrants, and prior thereto, it did cast noxious substances into Piney river, by which fish or fish spawn would be destroyed if there were any then in the river.

The Virginia Supreme Court ruled the first citation was valid, but the second in 1947 had occurred after the State Water Control Board had issued a water pollution permit to the company. The General Assembly created the State Water Control Board in 1946, two years before the US Congress passed the Federal Water Pollution Control Act to address unrestricted pollution discharges at the Federal level. That law evolved into the 1977 Clean Water Act enforced by the Environmental Protection Agency, but in 1946 the regulation of water pollution was in its infancy.

The State Water Control Board permit authorized American Cyanamid Company to discharge sulfuric acid into the Piney River. The permit was issued after the company claimed it was still developing the first industrial process to recapture the acid and, without a discharge permit, the titanium facility would close and put all employees out of work.

The Virginia Supreme Court ruled that, though the sulfuric acid pollution killed fish in the river, the discharge was legal under the state permit. The second violation was voided, after the court recognized the balancing act required of the members appointed to the State Water Control Board before issuing the first permits that authorized harmful pollution:4

Some waters should be kept pure. A measure of pollution in others is necessary. Not all pollution can be abruptly stopped.

On the agreed facts here, for example, this industry would have to shut down if immediately required to cease discharging its acid waste into the river. The aesthetic and recreational features involved in the pollution problem are important, but the opportunity to make a living may be even more so.

Mining and titanium processing operations ceased in 1971. American Cyanamid Company relocated to Savannah, Georgia, where it had operated a plant since the mid-1950's.5

S. Vance Wilkins Jr. bought it in 1973. He sold it to a New Jersey corporation in 1976, one year before getting elected to the Virginia General Assembly and becoming the first Republican Majority Leader of the House of Delegates in 2000.

During his ownership, no titanum ore was mined or processed. Wilkins ensured the corporation who bought the property from him assumed all responsibility for any environmental remediation of the mining wastes, and he never had to pay any cleanup costs.

After the New Jersey corporation purchased the site, a swindler used it to obtain a fraudulent loan and bribe US Senator Harrison Williams. The swindler claimed he had obtained political influence sufficient to get the Department of Defense to order titanium and justify reopening the mine.

After an agent posed as an Arab sheik, the Federal Bureau of Investigation (FBI) obtained convictions of six members of the US House of Representatives and the New Jersey senator in the "Abscam" scandal. Both the supposed demand for titanium and the economic viability of reopening the Virginia mine were hoaxes.6

During the 40 years of processing the ore until the mill closed in 1971, waste material known as copperas was piled up next to the Piney River. The waste included iron and sulfur compounds that produced sulfuric acid in the runoff and the groundwater. During heavy rainfalls, fish kills were common.

In 1979, water flowing off the mining waste triggered another fish kill in the Piney River. Virginia officials forced the New Jersey corporation, US Titanum, to bury the mining waste in a landfill in Nelson County in 1980.

The cap on that initial landfill did not seal off the material adequately. Acidic groundwater flowed downhill from the pit, steadily killing vegetation and wildlife. The pH of seepage water was as low as 2.66. Iron precipitated out of the acidic leachate onto the bottom of the Piney River as ferric hydroxide sediment, disroupting the benthic community for over three miles.

a 2018 image shows reclamation of the American Cyanamid Company operations, downstream of an aplite quarry
a 2018 image shows reclamation of the American Cyanamid Company operations, downstream of an aplite quarry
Source: ESRI, ArcGIS Online

After further study, in 1983 the Environmental Protection Agency (EPA) added the US Titanium site to the National Priorities List established by the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA). That law is known most commonly as the Superfund Act.

An essential step in getting Federal funds for cleanup is to be added to the National Priorities List. About 50 acres of the 175 acres used by the titanium dioxide manufacturing facility ended up classified as a Superfund site.

Simply replacing the clay cap to block water effectively from entering the landfill would not correct the problem. The buried copperas was saturated with water and slowly dissolving via oxidation and hydrolysis. As the copperas slumped, a new clay cap would sink and crack - and the copperas creating the risk would still be in place.

The adopted solution was to pump chemicals into the copperas and dissolve it within the landfill (in-situ). The next step would be to extract the leachate and chemically treat it to oxidize the iron and sulfur, then neutralize the solution and precipitate solids that would not be harmful. Finally, the treated water would be discharged into the Piney River and the precipitated material would be buried in a sealed landfill.

In addition, some overly-acidic soils in the area near the landfill would be neutralized. A groundwater treatment system would include an oxidation/settling pond, a constructed wetland, and a limestone neutralization bed to reduce pH before flowing int the Piney River. Total cost of the In-Situ Dissolution and Treatment alternative was estimated at $5,895,000.

the Environmental Protection Agency identified spots at the US Titanium site that might generate heavy metal and sulfuric acid contamination
the Environmental Protection Agency identified spots at the US Titanium site that might generate heavy metal and sulfuric acid contamination
Source: Environmental Protection Agency, Superfund Record of Decision: U.S. Titanium, VA

The dissolution-and-treatment approach of the buried copperas removed the risk of future contamination by acidic goundwater discharge. It was not as dramatic or as expensive a "fix" as the only other alternative that would provide a permanent solution - excavate the landfill (Area 1) and chemically treat the copperas on the surface. In 1989, the Environmental Protection Agency estimated that full excavation and treatment to neutralize the copperas would cost $12,567,000.

the 50-acre US Titanium Superfund site is in Nelson County, including Site 1 where mining waste (copperas) was buried in a landfill in 1980
the 50-acre US Titanium Superfund site is in Nelson County, including Site 1 where mining waste (copperas) was buried in a landfill in 1980
Source: Environmental Protection Agency, Fourth Five-Year Review Report for the US Titanium Superfund Site (Figure 2)

The adopted alternative did meet the objectives of local residents. They had reacted strongly to a comment by a contractor for American Cyanamid Company, which was a "potentially responsible party" that would be required to pay for most of the remediation. The contractor and American Cyanamid Company proposed initially just adding more clay to the cap on the landfill, rather than treating the copperas directly. Just adding more clay would cost only $533,000.

There were no materials at the titanium processing site, such as polychlorinated biphenyls (PCB's), which would be classified as "hazardous waste" under Subtitle C of the Resource Conservation and Recovery Act (RCRA). The contractor had stated:7

...there are no hazardous wastes on the site. Ferrous Sulfate is not hazardous waste. The pH of the material, all the water coming off the site, is no higher than that of lemon juice... We're not dealing with something that if you jump into it, you are going to dissolve, it's just not going to foam away, it is no more acidic than lemon juice.

One response summed up the local reaction:8

Folks around here on the Piney and Tye Rivers don't want the Piney River turning into lemonade.

The Environmental Protection Agency's Record of Decision for treatment of pollution at the site was signed in 1989. The Federal agency, American Cyanamid Company, and the state of Virginia accepted a Consent Decree for the cleanup plan in 1991. In a 1993 corporate reorganization, American Cyanamid Company transferred responsibility for the site remediation to Cytec Industries Inc.

In 1995, the treatment process was modified. Soil and copperas from the landfill (Area 1) was excavated and neutralized on the surface, rather than through the in-situ dissolution that the Environmental Protection Agency had approved. In addition, a tank was constructed to treat ground water and the iron-rich sludge was then precipitated in a pond. Groundwater treatment has reduced iron concentrations in some areas in some areas, but as of 2015 some locations were still unacceptably low in pH (i.e., too acidic) and high in iron.9

starting in 1996, acidic groundwater was neutralized in a tank before it was discharged into the Piney River
starting in 1996, acidic groundwater was neutralized in a tank before it was discharged into the Piney River
Source: Environmental Protection Agency, U.S. Titanium Superfund Site Community Update (Spring 2017)

Titanium minerals also eroded from the deposits in the Blue Ridge, and washed downstream to the Atlantic Ocean shoreline in what is now Dinwiddie, Greensville, and Sussex counties. Heavy grains of ilmenite, rutile, and zircon were concentrated in beach deposits, and have been mined commercially by RGC Mineral Sands and its successor corporation Iluka Resources.10

Titanium in the Old Hickory Heavy Mineral Sand Deposit

Virginia Blue Ridge Railway

old beach sands which concentrated titanium-rich minerals have been mined near Emporia
old beach sands which concentrated titanium-rich minerals have been mined near Emporia
Source: ESRI, ArcGIS Online

Links

References

1. Stanley S. Johnson, "Iron and Titanium Mineral Pigments in Virginia," Virginia Minierals, Volume 10, Number 3 (August 1964), p.1, p.3, p.6, https://www.dmme.virginia.gov/DGMR/pdf/vamin/VAMIN_VOL10_NO03.PDF; "History," Rockfish Valley Foundation, https://www.rockfishvalley.org/blog/tye-river-study/history/; "Virginia Blue Ridge Railway," Whippany Railway Museum, http://www.whippanyrailwaymuseum.net/visitor-info/virginia-blue-ridge-railway/43-museuminformation/visitor-information/157-virginia-blue-ridge-railway-page-3; "Industrial Rock and Mineral Resources in Virginia," Virginia Minerals, Volume 28, Number 1 (February 1982), p.8, https://www.dmme.virginia.gov/commercedocs/VAMIN_VOL28_NO01.PDF; "Superfund Site Nelson County VA: Blue Rock, Titanium, and Intrigue," Decoded={science}, November 26, 2017, https://www.decodedscience.org/superfund-site-nelson-county-va-blue-rock-titanium-intrigue/62385 (last checked November 4, 2018)
2. "Virginia's State Rock: Nelsonite," The Geology of Virginia blog, College of William and Mary, August 1, 2016, http://geology.blogs.wm.edu/2016/08/01/virginias-state-rock-nelsonite/ (last checked November 4, 2018)
3. American Cyanamid Co. v. Com, 187 Va. 831, 833-34 (Va. 1948), Casetext, https://casetext.com/case/american-cyanamid-co-v-com (last checked November 4, 2018)
4. American Cyanamid Co. v. Com, 187 Va. 831, 833-34 (Va. 1948), Casetext, https://casetext.com/case/american-cyanamid-co-v-com. "Understanding Wastewater Regulation In Virginia," Guide for Local Government Leaders, Virginia Municipal League, May, 2006, https://www.vml.org/wp-content/uploads/pdf/06WaterReg_Rpt_0.pdf (last checked November 4, 2018)
5. "The Great Acid Dump," Field and Stream, December 1972, p.14, https://books.google.com/books?id=Wet--YbqPcUC (last checked November 4, 2018)
6. "Piney River Hustle: Local site played role in scandal popularized by Hollywood film," Nelson County Times, January 15, 2014, https://www.newsadvance.com/nelson_county_times/news/piney-river-hustle-local-site-played-role-in-scandal-popularized/article_51fcf67e-7e06-11e3-bde0-001a4bcf6878.html (last checked November 4, 2018)
7. "A Second Big Fish Kill In 2 Years Discovered In Two Virginia Rivers," New York Times, August 28, 1979, https://www.nytimes.com/1979/08/28/archives/a-second-big-fish-kill-in-2-years-discovered-in-two-virginia-rivers.html; "Superfund Record of Decision: U.S. Titanium, VA," Environmental Protection Agency (EPA), November 29, 1989, p.8, p.12, p.15, p.26, p.44, p.49, p.58, https://nepis.epa.gov/Exe/ZyPURL.cgi?Dockey=91003C1D.TXT; "Fourth Five-Year Review Report for the US Titanium Superfund Site," Environmental Protection Agency (EPA), March 2015, p.4, http://go.usa.gov/xKYxB (last checked November 4, 2018)
8. "Superfund Record of Decision: U.S. Titanium, VA," Environmental Protection Agency (EPA), November 29, 1989, p.47, https://nepis.epa.gov/Exe/ZyPURL.cgi?Dockey=91003C1D.TXT (last checked November 4, 2018)
9. "Fourth Five-Year Review Report for the US Titanium Superfund Site," Environmental Protection Agency (EPA), March 2015, pp.8-10, p.21 http://go.usa.gov/xKYxB (last checked November 4, 2018)
10. "Iluka Resources Inc. Concord Mine Conditional Use Permit Support Document," Iluka Resources, October 2013, p.3, http://www.dinwiddieva.us/DocumentCenter/View/1816/C-13-4-Iluka-Support-Doc (last checked December 16, 2019)


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