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Changes in seabed mining

Chapter 23 of the First World Ocean Assessment (WOA I) focused on marine mining, and particularly on established extractive industries, which are predominantly confined to near-shore areas, where shallow-water, near-shore aggregate and placer deposits, and somewhat deeper water phosphate deposits are found (United Nations, 2017a). At the time of publication, there were no commercially developed deep-water seabed mining (DSM) deposits but an assessment of mining leases and exploration activity was included. Since WOA I, the number of deep-water (depths greater than 200 m below the ocean surface) seabed exploration licenses has increased both within national jurisdictions of coastal, island and archipelagic States, and beyond in the Area (the seabed, ocean floor and subsoil thereof beyond the limits of national jurisdiction) under the administration of the International Seabed Authority (ISA). For the first time, in 2017 deep-water seabed test-mining was carried out by Japan at a water depth of 1,600 m within its exclusive economic zone (EEZ) (METI, 2017). The update in the present Chapter will focus on the nascent deep-water seabed mining industry and mineral deposits. Hereafter, we use seabed for deep-water seabed. Environmental issues focused on impacts from dredging activities and a list of references for some mining operations were provided. However, WOA I could not provide an environmental baseline for DSM and considered that environmental, social and economic aspects were often not adequately understood with available data. Data on potential environmental impacts are still scarce and can differ greatly between mineral extraction from near-shore and seabed mining sites. Information on economic benefits, and to some extent social impacts, of mining is becoming progressively more accessible due to several initiatives promoting an increase in transparency of extractive industries. In 2015, the 2030 Agenda for Sustainable Development was adopted by all United Nations Member States. It includes 17 Sustainable Development Goals (SDGs) to be addressed on the basis of a global partnership. DSM activities may have implications for the achievement of SDGs 1, 5, 7–10, 12–14, and 17.

Book chapter

MARINE MINERAL RESOURCES - AN UPDATE AND INTRODUCTION.

This article briefly traces the status of marine minerals development, and it describes papers presented in this special issue on the subject. Subjects covered include types of deposits, marine mining in Canada, Manganese nodules, metalliferous sulfides as seabed minerals, metallurgical processes for reducing sulfide minerals, U. S. phosphate industry, construction materials and placers, and industry problems.

Marine Technology Society Journal

A preliminary survey of marine contamination from mining-related activities on Marinduque Island, Philippines: porewater toxicity and chemistry results from a field trip, October 14-19, 2000

As a follow-up of an initial overview of environmental problems caused by mining activities on Marinduque Island, Philippines, USGS and TAMU-CC scientists went to Marinduque in October 2000 to do a preliminary assessment of potential impacts of mining-related activities on the marine environment. Like the previous visit in May 2000, the marine assessment was conducted at the invitation of Philippine Congressman Edmund O. Reyes. In this report we present the results of sediment porewater toxicity tests and chemical analyses. Toxicity tests consist of laboratory analyses for the assessment of adverse effects caused by environmental contaminants to animals or plants. Sediments (sand or mud) are known to accumulate contaminants (e.g., copper and other heavy metals). Therefore, it is common to perform toxicity tests using different phases of the sedimentary environment in order to analyze adverse effects of contaminants accumulated in the sediment. Sediment pore water (or interstitial water, i.e., the water distributed among the sediment grains) is a sedimentary phase which controls the bioavailability of contaminants to bottom dwelling aquatic organisms (both plants and animals). There are several different kinds of organisms with which toxicity tests can be performed. Among those, tests with sea urchin early life stages (gametes and embryos) are very common due to their high sensitivity to contaminants, ease of maintenance under laboratory conditions, and ecological importance, particularly in coral reefs. The basis of these tests is the exposure of gametes or embryos to the pore water to be analyzed for toxicity. If the pore water contains contaminants in levels that can adversely affect a number of marine species, fertilization and/or embryological development of sea urchins is inhibited. Chemical analyses provide additional information and aid in the interpretation of the toxicity test results. For the current study, chemical analyses were performed for the measurement of porewater concentrations of several heavy metals associated with copper mining activities. Pore waters for toxicological and chemical analyses were collected at several stations on the coast of Marinduque, near the mouths of the Boac and Mogpog rivers, and near the causeways formed by mine tailings disposal. Porewater samples were also collected at the Tres Reyes Marine Reserve, so that these non-contaminated samples could serve as a reference for test performance. Sea urchin embryological development and fertilization were only significantly impaired by two porewater samples, suggesting the presence of contaminants in toxic amounts at those stations. The toxic samples were collected near the up current side of the Calancan (Marcopper) mine tailings causeway (stations 2 and 3 – see figure 10). The pore water from station 2 also had the highest levels of heavy metals, particularly cadmium, cobalt, copper, nickel, lead and zinc (Table 5). The concentrations of cobalt, nickel and zinc were also elevated 2 at station 3. Copper concentrations were also elevated at the two river mouth stations (8 and 9) and near the CMI tailings causeway (station 7). Visual observations also indicated biological degradation due to heavy siltation and smothered coral at a gradient off the Calancan causeway, suggesting that siltation might also be causing a physical impact. This preliminary survey suggests that effects related to past mining activities are still evident and warrant a more comprehensive study to assess their severity and areal extent.

Open-File Report

Ocean floor manganese deposits

Much of the dissolved Mn delivered to the oceans is slowly oxidized and precipitated alongside varying amounts of Fe into Mn and ferromanganese (FeMn) mineral deposits that occur extensively in the deep ocean wherever sediment accumulation is low and substrate is available. FeMn crusts grow as pavements on rock outcrops throughout the global ocean whereas nodules form as individual FeMn-encrusted particles on the sediment-covered abyssal plains. Both crusts and nodules are composed predominantly of Fe and Mn oxide minerals that precipitate from seawater and for some nodules also from porewaters of deep-sea sediment. In contrast, hydrothermal oxide deposits consist predominantly of Mn or Fe oxide. FeMn crusts and nodules exhibit very high specific surface areas that allow them to scavenge abundant metals and other elements, recording the history of the source waters. Crusts especially serve as an important record of paleoceanographic conditions over the past 70 + million years. Critical metals essential to many computer, military, and green technologies are enriched in crust and nodule deposits to concentrations high enough to compare with, or exceed, typical terrestrial deposits, and they can be considered as potential resources for mining in the near future. Twenty-three contracts pertaining to exploration for nodules and crusts have been signed with the International Seabed Authority, and resource/reserve, baseline, and environmental impact assessments are underway. Many challenges remain to be addressed before full-scale mining of marine FeMn deposits will occur. However, their unique genesis and the growing worldwide need for rare and critical metals keep these deep-ocean deposits relevant to industry, scientists, and governments.

Book chapter

Nature and distribution of potential heavy-mineral resources offshore of the Atlantic Coast of the United States.

The US is dependent on foreign imports of placer heavy minerals for a majority of its ilmenite and rutile, and virtually all of its monazite requirements. Although sand deposits in the SE US are important domestic sources of these heavy minerals (HM) and a number of other less well-known heavy-mineral species, global onshore reserves of placer minerals may fall short of demand in as few as 20 years. Insofar as they are important commodities for the future, offshore HM placers will become more important, but much research on them remains to be done. Results of recent offshore studies, based on surficial grab samples, indicate an average of about 2 weight percent HM in surficial Atlantic Continental Shelf (ACS) sediments, in strong contrast with previous estimates of an average of 0.16% HM. Although provocative, the information from these grab samples does not include the thickness of the HM deposits and thus their volume and tonnage cannot be estimated.-from Author

Marine Mining

Insular and submarine ferromanganese mineralization of the Tonga-Lau region

Ferromanganese oxides in the Tonga-Lau region are divided into crusts and stratabound deposits. Crusts were collected from the Tonga and Lau Ridges and have Fe/Mn ratios greater than 1, and an average Co content of 0.25%. The crusts average less than 10 mm thick with a maximum of 50 mm, and growth rates of tens of millimeters per million years. The thickest crust is probably less than a million years old. Crusts formed by both hydrogenetic and hydrothermal precipitation, with the hydrothermal input averaging 76%. Stratabound deposits are divided into three types. The source rocks through which the circulating fluids passed controlled the dominant minor element compositions of the stratabound deposits from each area: Valu Fa Ridge, Mo; Tonga Ridge Ti; Tonumea, Sr and Eua, V. -from Authors

Marine Mining

Sphalerite oxidation in seawater with covellite: Implications for seafloor massive sulfide deposits and mine waste

Metal sulfide minerals exist in several marine environments and are in thermodynamic disequilibrium with oxygenated seawater from the time of their formation. Oxidation is both ubiquitous and heterogeneous, as observational and experimental evidence demonstrates that sulfide minerals may oxidize completely on decadal timescales (hydrothermal plumes) or incompletely in billions of years (mineral deposits); however, the processes, rates, and interactions among minerals as oxidative dissolution occurs are not well understood. Added impetus to understanding these processes exists due to the potential for mining of seafloor massive sulfide deposits and potential environmental impacts of that activity. Here, we present a laboratory-based experimental study on the galvanic oxidation of sphalerite and synthesized zinc sulfide and coupled to covellite. We find that, in contrast to single-mineral reactions, coupled mineral reactions are at least 2 orders of magnitude more rapid, light independent, and have a lower apparent activation energy for oxidation. These results begin to provide insight into observed differences between laboratory and environmentally observed oxidation rates and are a step in the direction of more accurately predicting environmental rates as well as any changes to those rates from anthropogenic disturbances.

ACS Earth and Space Chemistry

Chapter 11 The phosphoria formation: A model for forecasting global selenium sources to the environment

Mining of the Permian Phosphoria Formation — a marine, oil-generating, phosphatic shale — provided the selenium (Se) source implicated in the recent deaths of livestock in southeast Idaho. Field studies and the geohydrologic balance of Se in southeast Idaho confirm risk to animals from exposure to Se through leaching of mined waste shale into streams, discharge of regional drainage, and impoundment of drainage in wetland areas. Forage grown to stabilize waste rock contoured into hills or used as cross-valley fill provides an additional mechanism of Se exposure for the environment (Mackowiak et al., Chapter 19). The average Se concentration of the Meade Peak Member of the Phosphoria Formation is an order of magnitude higher than those of other exploited marine shales that have been linked to incidences of Se toxicosis via oil refining and irrigation in the western United States. The Phosphoria Formation accumulated in an environment that preserved organic matter and contributed to the formation of economic-grade phosphate and oil deposits. The addition of this phosphate-mining case study enables a comprehensive approach to the identification of marine sedimentary Se sources and a more complete range of ecotoxic field studies on which to establish the conditions and anthropogenic connections that determine uptake, release, and recycling of Se in food webs. A constructed conceptual model of Se pollution indicates that ancient organic-rich depositional marine basins, unre- stricted by age, are linked to the contemporary global distribution of Se source rocks. A global plot shows (a) the areal association of major basins hosting phosphate deposits and petroleum source rocks and (b) the importance of paleo-latitudinal setting in influencing the composition of the deposits. Given the geographic patterns, Se emerges as a contami- nant within specific regions of the globe that may limit phosphate mining, oil refining, and drainage of agricultural lands because of potential ecological risks to vulnerable food webs. Selenium also may serve as a geochemical exploration tool that signals an ancient productive biological environment.

Handbook of Exploration and Environmental Geochemi

Paleontological interpretations of crater processes and infilling of synimpact sediments from the Chesapeake Bay impact structure

Biostratigraphic analysis of sedimentary breccias and diamictons in the Chesapeake Bay impact structure provides information regarding the timing and processes of late-stage gravitational crater collapse and ocean resurge. Studies of calcareous nannofossil and palynomorph assemblages in the International Continental Scientific Drilling Program (ICDP)-U.S. Geological Survey (USGS) Eyreville A and B cores show the mixed-age, mixed-preservation microfossil assemblages that are typical of deposits from the upper part of the Chesapeake Bay impact structure. Sparse, poorly preserved, possibly thermally altered pollen is present within a gravelly sand interval below the granite slab at 1392 m in Eyreville core B, an interval that is otherwise barren of calcareous nannofossils and dinocysts. Gravitational collapse of watersaturated sediments from the transient crater wall resulted in the deposition of sediment clasts primarily derived from the nonmarine Cretaceous Potomac Formation. Collapse occurred before the arrival of resurge. Low pollen Thermal Alteration Index (TAI) values suggest that these sediments were not thermally altered by contact with the melt sheet. The arrival of resurge sedimentation is identified based on the presence of diamicton zones and stringers rich in glauconite and marine microfossils at 866.7 m. This horizon can be traced across the crater and can be used to identify gravitational collapse versus ocean-resurge sedimentation. Glauconitic quartz sand diamicton dominates the sediments above 618.2 m. Calcareous nannofossil and dinoflagellate data from this interval suggest that the earliest arriving resurge from the west contained little or no Cretaceous marine input, but later resurge pulses mined Cretaceous sediments east of the Watkins core in the annular trough. Additionally, the increased distance traveled by resurge to the central crater in turbulent flow conditions resulted in the disaggregation of Paleogene unconsolidated sediments. As a result, intact Paleogene clasts in Eyreville cores are rare, but clasts of semilithified Potomac Formation silts and clays are common.

Chesapeake Bay

Comparison of the Eastern and Western Kentucky coal fields (Pennsylvanian), USA-why are coal distribution patterns and sulfur contents so different in these coal fields?

More than 130 Mt of Pennsylvanian coal is produced annually from two coal fields in Kentucky. The Western Kentucky Coal Field occurs in part of the Illinois Basin, an intercratonic basin, and the Eastern Kentucky Coal Field occurs in the Central Appalachian Basin, a foreland basin. The basins are only separated by 140 km, but mined western Kentucky coal beds exhibit significantly higher sulfur values than eastern Kentucky coals. Higher-sulfur coal beds in western Kentucky have generally been inferred to be caused by more marine influences than for eastern Kentucky coals. Comparison of strata in the two coal fields shows that more strata and more coal beds accumulated in the Eastern than Western Kentucky Coal Field in the Early and Middle Pennsylvanian, inferred to represent greater generation of tectonic accommodation in the foreland basin. Eastern Kentucky coal beds exhibit a greater tendency toward splitting and occurring in zones than time-equivalent western Kentucky coal beds, which is also inferred to represent foreland accommodation influences, overprinted by autogenic sedimentation effects. Western Kentucky coal beds exhibit higher sulfur values than their eastern counterparts, but western Kentucky coals occurring in Langsettian through Bolsovian strata can be low in sulfur content. Eastern Kentucky coal beds may increase in sulfur content beneath marine zones, but generally are still lower in sulfur than mined Western Kentucky coal beds, indicating that controls other than purely marine influences must have influenced coal quality. The bulk of production in the Eastern Kentucky Coal Field is from Duckmantian and Bolsovian coal beds, whereas production in the Western Kentucky Coal Field is from Westphalian D coals. Langsettian through Bolsovian paleoclimates in eastern Kentucky were favorable for peat doming, so numerous low-sulfur coals accumulated. These coals tend to occur in zones and are prone to lateral splitting because of foreland tectonic and sedimentation influences. In contrast, Westphalian D coal beds of western Kentucky accumulated during low differential tectonic accommodation, and therefore tend to be widespread and uniform in characteristics, but exhibit higher sulfur values because they accumulated in seasonally drier paleoclimates that were unfavorable for peat doming. Hence, basin analyses indicate that many differences between the mined coals of Kentucky's two coal fields are related to temporal changes in paleoclimate and tectonic accommodation, rather than solely being a function of marine influences. ?? 2002 Elsevier Science B.V. All rights reserved.

International Journal of Coal Geology

Manganese

Manganese is an essential element for modern industrial societies. Its principal use is in steelmaking, where it serves as a purifying agent in iron-ore refining and as an alloy that converts iron into steel. Although the amount of manganese consumed to make a ton of steel is small, ranging from 6 to 9 kilograms, it is an irreplaceable component in the production of this fundamental material. The United States has been totally reliant on imports of manganese for many decades and will continue to be so for at least the near future. There are no domestic reserves, and although some large low-grade resources are known, they are far inferior to manganese ores readily available on the international market. World reserves of manganese are about 630 million metric tons, and annual global consumption is about 16 million metric tons. Current reserves are adequate to meet global demand for several decades. Global resources in traditional land-based deposits, including both reserves and rocks sufficiently enriched in manganese to be ores in the future, are much larger, at about 17 billion metric tons. Manganese resources in seabed deposits of ferromanganese nodules and crusts are larger than those on land and have not been fully quantified. No production from seabed deposits has yet been done, but current research and development activities are substantial and may bring parts of these seabed resources into production in the future. The advent of economically successful seabed mining could substantially alter the current scenario of manganese supply by providing a large new source of manganese in addition to traditional land-based deposits. From a purely geologic perspective, there is no global shortage of proven ores and potential new ores that could be developed from the vast tonnage of identified resources. Reserves and resources are very unevenly distributed, however. The Kalahari manganese district in South Africa contains 70 percent of the world’s identified resources and about 25 percent of its reserves. South Africa, Brazil, and Ukraine together accounted for nearly 65 percent of reserves in 2013. The combination of total import reliance for manganese, the mineral commodity’s essential uses in our industrialized society, and the potential for supply disruptions because of the limited sources of the ore makes manganese among the most critical minerals for the United States. Manganese is the 12th most abundant element in Earth’s crust. Its concentration varies among common types of rocks, mostly in the range of from 0.1 to 0.2 percent. The highest quality manganese ores contain from 40 to 45 percent manganese. The formation of these ores requires specialized geologic conditions that concentrate manganese at several hundred times its average crustal abundance. The dominant processes in forming the world’s principal deposits take place in the oceans. As a result, most important manganese deposits occur in ancient marine sedimentary rocks that are now exposed on continents as a result of subsequent tectonic uplift and erosion. In many cases, other processes have further enriched these manganiferous sedimentary rocks to form some of today’s highest grade ores. Modern seabed resources of ferromanganese nodules cover vast areas of the present ocean floor and are still forming by complex interactions of marine microorganisms, manganese dissolved in seawater, and chemical processes on the seabed. Manganese is ubiquitous in soil, water, and air. It occurs most often in solid form but can become soluble under acidic conditions. Manganese mining, like any activity that disturbs large areas of Earth’s surface, has the potential to produce increases in manganese concentrations that could be harmful to humans or the environment if not properly controlled. Although manganese is an essential nutrient for humans and most other organisms, overexposure can lead to neurotoxicity in humans. Workers at manganese mining and processing facilities have the greatest potential to inhale manganese-rich dust. Without proper protective equipment, these workers may develop a permanent neurological disorder known as manganism. Each manganese mine is unique and presents its own suite of potential hazards and preventative measures. Likewise, various nations have their own sets of standards to ensure safe mining, isolation of mine waste, treatment of mine waters, and mine closure and restoration. Interest in mining trace metals contained in ferromanganese nodules and crusts on the seabed has increased rapidly in the past decade. Prime areas for future research include overcoming the technological challenges presented by mining as deep as 6,500 meters below sea level and understanding and mitigating the potential impacts of seabed mining on marine ecosystems.

Professional Paper

Chemical data for rock, sediment, biological, precipitate, and water samples from abandoned copper mines in Prince William Sound, Alaska

Introduction In the early 20th century, approximately 6 million metric tons of copper ore were mined from numerous deposits located along the shorelines of fjords and islands in Prince William Sound, Alaska. At the Beatson, Ellamar, and Threeman mine sites (fig. 1), rocks containing Fe, Cu, Zn, and Pb sulfide minerals are exposed to chemical weathering in abandoned mine workings and remnant waste piles that extend into the littoral zone. Field investigations in 2003 and 2005 as well as analytical data for rock, sediment, precipitate, water, and biological samples reveal that the oxidation of sulfides at these sites is resulting in the generation of acid mine drainage and the transport of metals into the marine environment (Koski and others, 2008; Stillings and others, 2008). At the Ellamar and Threeman sites, plumes of acidic and metal-enriched water are flowing through beach gravels into the shallow offshore environment. Interstitial water samples collected from beach sediment at Ellamar have low pH levels (to ~3) and high concentrations of metals including iron, copper, zinc, cobalt, lead, and mercury. The abundant precipitation of the iron sulfate mineral jarosite in the Ellamar gravels also signifies a low-pH environment. At the Beatson mine site (the largest copper mine in the region) seeps containing iron-rich microbial precipitates drain into the intertidal zone below mine dumps (Foster and others, 2008). A stream flowing down to the shoreline from underground mine workings at Beatson has near-neutral pH, but elevated levels of zinc, copper, and lead (Stillings and others, 2008). Offshore sediment samples at Beatson are enriched in these metals. Preliminary chemical data for tissue from marine mussels collected near the Ellamar, Threeman, and Beatson sites reveal elevated levels of copper, zinc, and lead compared to tissue in mussels from other locations in Prince William Sound (Koski and others, 2008). Three papers presenting results of this ongoing investigation of sulfide oxidation in Prince William Sound are in press. Koski and others (2008) provide an overview of rock alteration, surface water chemistry, and the distribution of metals at the Ellamar, Threeman, and Beatson mine sites. Based on a 60-day, stream-discharge experiment at Beatson in 2005, Stillings and others (2008) analyze changes in water chemistry during storm events and the flux of metals to the shoreline. Foster and others (2008) investigate the biomass and diversity of microbial communities present in surface waters (streams, seeps, pore waters) using fatty acid methyl ester (FAMES) data and principal component analysis. The publications cited above contain a subset of the total chemical data for rock, sediment, biological, precipitate, and water samples collected from the three mine sites in 2003 and 2005. The purpose of this report is the presentation of complete chemical data sets for all samples collected during the two field periods of fieldwork. Data for a small number of samples collected at two other mines (Schlosser and Fidalgo, fig. 1), visited in 2003, are also included in the tables.

Alaska

Chemical data for rock, sediment, biological, precipitate, and water samples from abandoned copper mines in Prince William Sound, Alaska

In the early 20th century, approximately 6 million metric tons of copper ore were mined from numerous deposits located along the shorelines of fjords and islands in Prince William Sound, Alaska. At the Beatson, Ellamar, and Threeman mine sites (fig. 1), rocks containing Fe, Cu, Zn, and Pb sulfide minerals are exposed to chemical weathering in abandoned mine workings and remnant waste piles that extend into the littoral zone. Field investigations in 2003 and 2005 as well as analytical data for rock, sediment, precipitate, water, and biological samples reveal that the oxidation of sulfides at these sites is resulting in the generation of acid mine drainage and the transport of metals into the marine environment (Koski and others, 2008; Stillings and others, 2008). At the Ellamar and Threeman sites, plumes of acidic and metal-enriched water are flowing through beach gravels into the shallow offshore environment. Interstitial water samples collected from beach sediment at Ellamar have low pH levels (to ~3) and high concentrations of metals including iron, copper, zinc, cobalt, lead, and mercury. The abundant precipitation of the iron sulfate mineral jarosite in the Ellamar gravels also signifies a low-pH environment. At the Beatson mine site (the largest copper mine in the region) seeps containing iron-rich microbial precipitates drain into the intertidal zone below mine dumps (Foster and others, 2008). A stream flowing down to the shoreline from underground mine workings at Beatson has near-neutral pH, but elevated levels of zinc, copper, and lead (Stillings and others, 2008). Offshore sediment samples at Beatson are enriched in these metals. Preliminary chemical data for tissue from marine mussels collected near the Ellamar, Threeman, and Beatson sites reveal elevated levels of copper, zinc, and lead compared to tissue in mussels from other locations in Prince William Sound (Koski and others, 2008). Three papers presenting results of this ongoing investigation of sulfide oxidation in Prince William Sound are in press. Koski and others (2008) provide an overview of rock alteration, surface water chemistry, and the distribution of metals at the Ellamar, Threeman, and Beatson mine sites. Based on a 60-day, stream-discharge experiment at Beatson in 2005, Stillings and others (2008) analyze changes in water chemistry during storm events and the flux of metals to the shoreline. Foster and others (2008) investigate the biomass and diversity of microbial communities present in surface waters (streams, seeps, pore waters) using fatty acid methyl ester (FAMES) data and principal component analysis. The publications cited above contain a subset of the total chemical data for rock, sediment, biological, precipitate, and water samples collected from the three mine sites in 2003 and 2005. The purpose of this report is the presentation of complete chemical data sets for all samples collected during the two field periods of fieldwork. Data for a small number of samples collected at two other mines (Schlosser and Fidalgo, fig. 1), visited in 2003, are also included in the tables.

Alaska

Formation and distribution of coal balls in the Herrin Coal (Pennsylvanian), Franklin County, Illinois Basin, USA

Large areas of concentrated coal balls (permineralized peat) up to 4 m thick obstructed longwall mining in the Herrin Coal at the Old Ben No. 24 mine. The largest coal‐ball area mapped contained >1500 m 3 ; several areas contained >400 m 3 of coal balls. In‐mine mapping established that there were two types of roof (freshwater and marine), and that the coal balls were spatially correlated with the marine roof units. Regional studies and local data revealed that the younger, freshwater Energy Shale (mud) originally covered all of the peat deposited at the mine, but the mud was locally removed during a period of erosion. The great majority of coal balls are found within the coal seam, where they were permineralized in situ by carbonates. Some coal balls are found exposed on the eroded coal surface and others are within the channel fill associated with the erosion, which predates any marine sedimentation. Thus, the mineralization of the coal balls was synchronous with the erosion of the Energy Shale mud. Data from C‐and O‐isotope, geochemical, and mineralogical analyses of coal balls and associated materials were used to refine a depositional model of coal‐ball formation. The concentrated coal‐ball areas were created by the triggered degassing of CO 2 from partially decomposed peat in the presence of cations from fresh waters; 13 C/ 12 C ratios in these coal balls average −23.9‰. 13 C/ 12 C ratios as low as −34‰ occurring in the most concentrated coal balls are consistent with CO 2 produced by anaerobic oxidation of methane. Top‐of‐seam coal balls were formed later and show slight to strong marine influence; their 13 C/ 12 C ratios average −10.8‰.

Illinois