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Geology and mining history of the Southeast Missouri Barite District and the Valles Mines, Washington, Jefferson, and St. Francois Counties, Missouri

The Southeast Missouri Barite District and the Valles Mines are located in Washington, Jefferson, and St. Francois Counties, Missouri, where barite and lead ore are present together in surficial and near-surface deposits. Lead mining in the area began in the early 1700’s and extended into the early 1900’s. Hand mining of lead in the residuum resulted in widespread pits (also called shafts or diggings), and there was some underground mining of lead in bedrock. By the 1860’s barite was recovered from the residuum by hand mining, also resulting in widespread diggings, but generally not underground mines in bedrock. Mechanized open-pit mining of the residuum for barite began in the 1920’s. Barite production slowed by the 1980’s, and there has not been any barite mining since 1998. Mechanized barite mining resulted in large mined areas and tailings ponds containing waste from barite mills. The U.S. Environmental Protection Agency (EPA) has determined that lead is present in surface soils in Washington and Jefferson Counties at concentrations exceeding health-based screening levels. Also, elevated concentrations of barium, arsenic, and cadmium have been identified in surface soils, and lead concentrations exceeding the Federal drinking-water standard of 15 micrograms per liter have been identified in private drinking-water wells. Potential sources of these contaminants are wastes associated with barite mining, wastes associated with lead mining, or unmined natural deposits of barium, lead, and other metals. As a first step in helping EPA determine the source of soil and groundwater contamination, the U.S. Geological Survey (USGS), in cooperation with the EPA, investigated the geology and mining history of the Southeast Missouri Barite District and the Valles Mines. Ore minerals are barite (barium sulfate), galena (lead sulfide), cerussite (lead carbonate), anglesite (lead sulfate), sphalerite (zinc sulfide), smithsonite (zinc carbonate), and chalcopyrite (copper-iron sulfide). The Cambrian Potosi Dolomite is the most important formation for the ore deposits, followed by the Eminence Dolomite. Because galena, sphalerite, and barite are less soluble than dolomite, chemical weathering of the ore-bearing dolomite bedrock resulted in the concentration of ore minerals in the residuum. Most of the barite and lead mining was in the residuum, which averages 10 to 15 feet thick. Lead mining by French explorers may have begun in 1719 along Old Mines Creek at Cabanage de Renaudiere, which was followed shortly by the discovery of lead and the development of lead mines at Mine Renault (also called Forche a Renault Mine), Old Mines, and at other places along the Big River, Mineral Fork, and Forche a Renault Creek. Lead mining began sometime between 1775 and 1780 at Mine a Breton, the name of which was later changed to Potosi. Other mining areas were developed in the early part of the 19th century, including Fourche a Courtois (Palmer Mines), the French Diggings, and the Richwoods Mines. Zinc became a valuable resource after the Civil War, and the Valles Mines was an important supplier of zinc as well as lead, with at least some production up until the 1920’s. Lead mining declined in the early part of the 20th century as mining in the Old Lead Belt, Mine La Motte, and the Tri-State District expanded. The earliest lead mines were diggings in the residuum and were round holes (shafts) about 4 feet in diameter dug with pick and shovel about 15–20 feet deep, with drifts dug a short distance laterally from the bottom of the shafts. This mining process was repeated a short distance away until a large area was covered with pits. Some mining in bedrock began by about 1800, with shafts as deep as 170 feet and as much as several hundred feet of lateral drifts. Smelting of the lead ore to elemental lead was first done using a log furnace, which was inefficient; estimates have been made that only about 50 percent of the lead was recovered, and the remainder was lost to the ashes (slags) and to volatilization. Starting in 1798, ash furnaces were used to smelt the ashes from the log furnaces. These two furnaces were worked in tandem for many years but were gradually replaced by other furnaces, including the Scotch hearth. Estimates of lead recovery as high as 80–90 percent have been made for the Scotch hearth. By the mid-1870’s the air furnace was being used, also with estimated lead recovery as high as 80–90 percent. Zinc furnaces were built when zinc became a valuable commodity, but much of the zinc ore was shipped out of the area, either to a smelter in St. Louis, Missouri, or to other smelters. The total lead and zinc production from the Southeast Missouri Barite District and the Valles Mines is estimated at 180,000 tons of lead and 60,000 tons of zinc. An estimated 97,000 tons of lead and an estimated 120,000 tons of zinc were lost during smelting. The estimated losses do not include losses at the mine site during mining and preparation for smelting, such as the loss of fine-grained galena during hand cleaning or the discarding of zinc ore before its value was known, for which no estimates are available. Hand mining for barite in the residuum was active by at least the 1860’s and peaked from 1905 to the 1930’s when several thousand people were engaged in barite mining. Hand mining (diggings) and cleaning of the ore was done in much the same way as earlier lead mining, with the additional use of a rattle box to further clean the barite. Mechanized open-pit mining of old barite diggings began in 1924 to recover barite left behind by hand mining, and washing plants were used to clean the clay from the barite. Hand mining, however, continued to thrive, and washer plants began to close temporarily in 1931; nearly all of the barite produced before 1937 was by hand mining. By the 1940’s, however, all barite mining was mechanized. Mechanized mining used shovels powered by steam, gasoline, or electricity (and by the 1950’s draglines and front-end loaders) to mine the residuum. The ore was loaded onto rail cars (and by the 1940’s, trucks) for shipment to washer plants. Clay was removed from the barite using a log washer, and a jig was used to concentrate the barite. Overflow from the log washers was waste and went to a mud (tailings) pond. The coarse jig tailings went to tailings piles or were used as railroad ballast and, later, to create roads within the mine pit. Some barite was ground, depending on its final use, and some ground barite was bleached using a hot solution of sulfuric acid to remove impurities such as iron minerals and lead sulfide (galena). An earlier bleaching process used lead-lined tanks. Large quantities of water were required for milling the barite; some was recirculated water and the remainder came from dammed streams or was pumped from wells. Tailings and wastewater were impounded behind dikes that were built across small valleys and were increased in height as necessary using washer waste and any overburden that had been stripped. In some cases, dikes were built across valleys that had already been mined for barite. The total production of barite from the Southeast Missouri Barite District and the Valles Mines is estimated to have been about 13.1 million tons. Most of the barite production was from Washington County. Hand mining and processing of barite was inefficient. Estimates of barite recovery range from less than one-fourth to about one-half because pillars between the shafts in the residuum needed to be left unmined for stability. With mechanized mining, large amounts of barite were lost during the milling process. It has been estimated that about 30 percent of the barite was lost and that about two-thirds of the lost barite was fine-grained and was discharged to the tailings ponds. Some galena was lost to the tailings ponds. A 1972 inventory of tailings ponds by the Missouri Geological Survey identified 67 ponds in the Southeast Missouri Barite District (there are more than this currently documented). Results from samples from four ponds that were drilled were used to estimate that the 67 ponds contained almost 39 million tons (or cubic yards) of tailings averaging about 5 percent barite, for a potential reserve of 1.935 million tons of barite. It is not known how much lead was removed during barite mining, either by hand or mechanized mining and processing, how much lead was recovered, or how much lead went as fines to the tailing ponds or as coarse material to mine roads or was otherwise lost.

Missouri↗

Sources and characteristics of organic matter in the Clackamas River, Oregon, related to the formation of disinfection by-products in treated drinking water

This study characterized the amount and quality of organic matter in the Clackamas River, Oregon, to gain an understanding of sources that contribute to the formation of chlorinated and brominated disinfection by-products (DBPs), focusing on regulated DBPs in treated drinking water from two direct-filtration treatment plants that together serve approximately 100,000 customers. The central hypothesis guiding this study was that natural organic matter leaching out of the forested watershed, in-stream growth of benthic algae, and phytoplankton blooms in the reservoirs contribute different and varying proportions of organic carbon to the river. Differences in the amount and composition of carbon derived from each source affects the types and concentrations of DBP precursors entering the treatment plants and, as a result, yield varying DBP concentrations and species in finished water. The two classes of DBPs analyzed in this study-trihalomethanes (THMs) and haloacetic acids (HAAs)-form from precursors within the dissolved and particulate pools of organic matter present in source water. The five principal objectives of the study were to (1) describe the seasonal quantity and character of organic matter in the Clackamas River; (2) relate the amount and composition of organic matter to the formation of DBPs; (3) evaluate sources of DBP precursors in the watershed; (4) assess the use of optical measurements, including in-situ fluorescence, for estimating dissolved organic carbon (DOC) concentrations and DBP formation; and (5) assess the removal of DBP precursors during treatment by conducting treatability "jar-test" experiments at one of the treatment plants. Data collection consisted of (1) monthly sampling of source and finished water at two drinking-water treatment plants; (2) event-based sampling in the mainstem, tributaries, and North Fork Reservoir; and (3) in-situ continuous monitoring of fluorescent dissolved organic matter (FDOM), turbidity, chlorophyll- a , and other constituents to continuously track source-water conditions in near real-time. Treatability tests were conducted during the four event-based surveys to determine the effectiveness of coagulant and powdered activated carbon (PAC) on the removal of DBP precursors. Sample analyses included DOC, total particulate carbon (TPC), total and dissolved nutrients, absorbance and fluorescence spectroscopy, and, for regulated DBPs, concentrations of THMs and HAAs in finished water and laboratory-based THM and HAA formation potentials (THMFP and HAAFP, respectively) for source water and selected locations throughout the watershed. The results of this study may not be typical given the record and near record amounts of precipitation that occurred during spring that produced streamflow much higher than average in 2010-11. Although there were algal blooms, lower concentrations of chlorophyll- a were observed in the water column during the study period compared to historical data. Concentrations of DBPs in finished (treated) water averaged 0.024 milligrams per liter (mg/L) for THMs and 0.022 mg/L for HAAs; maximum values were about 0.040 mg/L for both classes of DBPs. Although DBP concentrations were somewhat higher within the distribution system, none of the samples collected for this study or for the quarterly compliance monitoring by the water utilities exceeded levels permissible under existing U.S. Environmental Protection Agency (USEPA) regulations: 0.080 mg/L for THMs and 0.060 mg/L for HAAs. DOC concentrations were generally low in the Clackamas River, typically about 1.0-1.5 mg/L. Concentrations in the mainstem occasionally increased to nearly 2.5 mg/L during storms; DOC concentrations in tributaries were sometimes much higher (up to 7.8 mg/L). The continuous in-situ FDOM measurements indicated sharp rises in DOC concentrations in the mainstem following rainfall events; concentrations were relatively stable during summer base flow. Even though the first autumn storm mobilized appreciable quantities of carbon, higher concentrations of DBPs in finished water were observed 3-weeks later, after the ground was saturated from additional rainfall. The majority of the DOC in the lower Clackamas River appears to originate from the upper basin, suggesting terrestrial carbon was commonly the dominant source. Lower-basin tributaries typically contained the highest concentrations of DOC and DBP precursors and contributed substantially to the overall loads in the mainstem during storms. During low-flow periods, tributaries were not major sources of DOC or DBP precursors to the Clackamas River. Although the dissolved fraction of organic carbon contributed the majority of DBP precursors, at times the particulate fraction (inorganic sediment and organic particles including detritus and algal material) contributed a substantial fraction of DBP precursors. Considering just the main-stem sites, on average, 10 percent of THMFP and 32 percent of HAAFP were attributed to particulate carbon. This finding suggests water-treatment methods that remove particles prior to chlorination would reduce finished-water DBP concentrations to some degree. Overall, concentrations of THM and HAA precursors were closely linked to DOC concentrations; laboratory DBP formation potentials (DBPFPs) clearly showed that THMFP and HAAFP were greatest in the downstream tributaries that contained elevated carbon concentrations. However, carbon-normalized "specific" formation potentials for THMs and HAAs (STHMFP and SHAAFP, respectively) revealed changes in carbon character over time that affected the two types of DBP classes differently. HAA precursors were elevated in waters containing aromatic-rich soil-derived material arising from forested areas. In contrast, THM precursors were associated with carbon having a lower aromatic content; highest STHMFP occurred in autumn 2011 in the mainstem from North Fork Reservoir downstream to LO DWTP. This pattern suggests the potential for a link between THM precursors and algal-derived carbon. The highest STHMFP value was measured within North Fork Reservoir, indicating reservoir derived carbon may be important for this class of DBPs. Weak correlations between STHMFP and SHAAFP emphasize that precursor sources for these types of DBPs may be different. This highlights not only that different locations within the watershed produce carbon with different reactivity (specific DBPFP), but also that different management approaches for each class of DBP precursors could be required for control. Treatability tests conducted on source water during four basin-wide surveys demonstrated that an average of about 40 percent of DOC can be removed by coagulation. While the decrease in THMFP following coagulation was similar to DOC, the decrease in HAAFP was much greater (approximately 70 percent), indicating coagulation is particularly effective at removing HAA precursors'likely because of the aromatic nature of the carbon associated with HAA precursors. Several findings from this study have direct implications for managing drinking-water resources and for providing useful information that may help improve treatment-plant operations. For example, the use of in-situ fluorometers that measure FDOM provided an excellent proxy for DOC concentration in this system and revealed short-term, rapid changes in DOC concentration during storm events. In addition, the strong correlation between FDOM values measured in-situ and HAA5 concentrations in finished water may permit estimation of continuous HAA concentrations, as was done here. As part of this study, multiple in-situ FDOM sensors were deployed continuously and in real-time to characterize the composition of dissolved organic matter. Although the initial results were promising, additional research and engineering developments will be needed to demonstrate the full utility of these sensors for this purpose. In conclusion, although DBPFPs were strongly correlated to DOC concentration, some DBPs formed from particulate carbon, including terrestrial leaf material and algal material such as planktonic species of blue-green algae and sloughed filaments, stalks, and cells of benthic algae. Different precursor sources in the watershed were evident from the data, suggesting specific actions may be available to address some of these sources. In-situ measurements of FDOM proved to be an excellent proxy for DOC concentration as well as HAA formation during treatment, which suggests further development and refinement of these sensors have the potential to provide real-time information about complex watershed processes to operators at the drinking-water treatment plants. Follow-up studies could examine the relative roles that terrestrial and algal sources have on the DBP precursor pool to better understand how watershed-management activities may be affecting the transport of these compounds to Clackamas River drinking-water intakes. Given the low concentrations of algae in the water column during this study, additional surveys during more typical river conditions could provide a more complete understanding of how algae contribute DBP precursors. Further development of FDOM-sensor technology can improve our understanding of carbon dynamics in the river and how concentrations may be trending over time. This study was conducted in collaboration with Clackamas River Water and the City of Lake Oswego water utilities. Other research partners included Oregon Health and Science University in Hillsboro, Oregon, Alexin Laboratory in Tigard, Oregon, U.S. Geological Survey National Research Program Laboratory in Denver, Colorado, and the U.S. Geological Survey Water Science Centers in Portland, Oregon, and Sacramento, California. This project was supported with funding from Clackamas River Water, City of Lake Oswego, the U.S. Geological Survey, and the Water Research Foundation.

Oregon↗