This dissertation combines laboratory experiments and analysis of field samples to examine tungsten (W) geochemistry. Data from low ionic strength experimental solutions at room temperature containing between 0.01 M to 0.0002 M total sulfide and 0.0027 M - 0.0001 M tungstate were analyzed using UV/VIS spectrophotometry. Stability constants have been determined for the formation of mono-thiotungstate log K01= 3.43 ± 0.61, di-thiotungstate log K12 = 3.02 ± 0.61, tri-thiotungstate log K23 = 2.82 ± 0.02, and we estimated the tetra-thiotungstate log K34 ~ 2.34. Analysis of W, Mo, Mn, and Fe concentrations in estuarine surface and pore waters and sediments captured environmental samples from oxic and sulfidic conditions. Both surface waters and sediments demonstrated a positive correlation between W and Fe. Unlike Mo, which was depleted in sulfidic salt marsh pore waters, W was enriched in all pore waters in comparison to overlying waters. Thermodynamic modeling of W and Mo thioanion species in sulfidic pore water samples predicts ≤ 50% of tungstate (WO42-) forms thiotungstate species and complete conversion of molybdate (MoO42-) to tetrathiomolybdate (MoS42-). Unlike tetrathiomolydate that is known to be more particle reactive than molybdate, increases in dissolved W coincide with increases in dissolved sulfide in pore waters, suggesting thiotungstates are less particle reactive than thiomolybdates at circum-neutral pH. Finally, sediment analysis suggests sequestration of W is dependent on surface water salinity in the intermediate marsh sediments, and long-term W entrapment occurs in sulfidic salt marsh sediments. / acase@tulane.edu

The Atlantis II Deep is a location of modern submarine hydrothermal activity along the slowly spreading Red Sea rift axis. Venting of high-temperature hydrothermal fluids, similar to those associated with black smokers, takes place in a brine pool and has led to the accumulation of 90 Mt (dry, salt free) of stratiform, metalliferous sediment. The conditions of mineralization are unique in the modern oceans, but have been widely suggested as a possible analog of some important ancient stratiform base metal ore deposits. This study shows that many of the proposed genetic models for these ancient deposits may be highly simplified and do not take into account rapid diagenetic transformations, widespread non-equilibrium processes, and many other aspects of metal deposition. Sediment cores of the Atlantis II muds were last studied more than 30 years ago. High-resolution sampling and careful re-examination of the mineralogy and geochemistry of the sediments, using modern analytical techniques has significantly improved the understanding of the different processes responsible for the formation of the finely layered metallifeous sediments. The geochemistry of the individual layers is controlled by highly variable detrital, hydrogenic and hydrothermal input. Primary depositional pathways from the brine pool are the main control on basin-wide metal distribution (e.g., increasing Cu/Zn away from the vents) including variable enrichment in trace metals via scavenging from the brine pool and from the enriched pore waters. Cu and Zn have been deposited not only as sulfides but also with poorly crystalline Si-Fe-(oxy)hydroxides. A significant proportion of the original non-sulfide Cu and Zn are diagenetically transformed into sulfides, but also carbonates and clays, in large part reflecting sulfide deficient pore waters. Negative δ34S values, previously unrecognized in the sulfide- and metal-rich units, indicate a source of bacteriogenic sulfide. Syn-diagenetic processes also appear to have been responsible for the sharp laminations in the sediments, as well as distinctive zoning of carbonate and clay minerals around the vent source. The early diagenetic transformations observed in the Atlantis II Deep may not be preserved in the ancient rock record but nevertheless have important implications for metal deposition in some of the world’s largest and richest base metal ore deposits.

Oxidation of sulfidic mine waste is of significant environmental concern due to the consequent formation of acid rock drainage (ARD), deteriorating the water quality of natural water systems. Iron (Fe) and sulfur (S) are two major redox elements involved in these reactions and typically the major redox-sensitive elements (whose solubility, speciation, and mobility are affected by pH and Eh) in water affected by ARD. Measurements of Fe and S species concentrations may reveal valuable information about geochemical processes in mine waste but are typically included when analyzing the chemical composition of ARD. In this study, robust and portable methods for the determination of Fe and S species concentrations in leachate water affected by sulfidic mine waste were tested and evaluated. The leachate water resulting from interaction with high-  and low-sulfide waste rock was collected from three leaching columns, each reflecting different geochemical environments that could occur during mine waste management: (1) fully oxidized conditions (reference column), (2) gradual oxygen depletion from atmospheric level to <1% (anoxic column), (3) treatment with alkaline industrial residual material (alkaline column). The leachate water was analyzed for its pH, Eh, electric conductivity (EC), and major and trace elements. UV-Vis spectrophotometric ferrozine method was tested and applied for Fe speciation and concentration analysis, allowing determination of Fe(II) and Fetot and further calculation of Fe(III) as a difference. The method was found to achieve accurate and reliable results. Turbidimetry was tested and evaluated for dissolved sulfate analysis, and even though the analytical precision was poorer, ca. ±20%, the method provides useful semi-quantitative estimations of dissolved sulfate concentrations. Both spectrophotometry and turbidimetry are easy to perform and utilizes robust, cheap and portable instrumentation. Leachate water from the high and low sulfide experiments had pH and Eh in the range of pH 2.6 – 12 and Eh 200 – 720 mV and pH 3.5 – 4 and Eh 550 – 700 mV, respectively. Measurements of iron species and sulfate concentrations revealed that sulfate was the dominating S species and during the background leachate Fe(II) was the predominant Fe oxidation state. Upon decreasing oxygen saturation and pH in the anoxic column, Fe speciation in the reference and anoxic column differed, with the relative importance of Fe(III) increasing in the anoxic column. Total Fe, pH and Eh potential measured in the leachate water did not respond to decreasing oxygen saturation, but changes in the Fe redox speciation coincided with this decrease. Under alkaline conditions, total Fe and sulfate concentrations decreased in the alkaline environment, indicating their immobilization in the solid phase. Geochemical calculations were carried out to gain further understanding of the dominant reactions in the columns. Theoretical values of Fe(II) and Fe(III) concentrations were calculated from the measured redox potential, and these were found to deviate from the measured concentrations. Therefore, estimation of Fe species distribution from redox measurements using a Pt-electrode is not considered sufficient in these systems. Mineral saturation indices of common secondary minerals associated with ARD indicated dissolution of ferrihydrite, jarosite and schwertmannite in the leachate water from the anoxic column. This suggests that these minerals are the probable source of the Fe and sulfate, as well as As and Cu released to the leachate water.

Abstract Millions of tons of mine tailings are generated worldwide annually. Since many valuable metals such as Ag, Cu, Pb, Zn, Au and Ni are usually incorporated into sulphidic minerals, a large proportion of the tailings generated contain high amounts of sulphates and heavy metals. Some of these tailings are used as paste backfill material at mining sites, but large amounts are still being deposited into the tailings dams under water coverage. Sulphidic minerals are stable underground but after mining of the ore and several processing steps these minerals can be oxidized when they come into contact with water and air. This oxidation generates acid and thus reduces the pH of the surrounding environment. Furthermore, the heavy metals present in the mine tailings can be leached into the environment. This phenomenon, called Acid Mine Drainage (AMD), is one of the most critical environmental issues related to the management of sulphidic-rich tailings. Since AMD generation can still occur hundreds of years after closure of the mine, the mine tailings need stable, sustainable and economically viable management methods in order to prevent AMD production in the long term. The aim of this PhD thesis was to study various solidification/stabilization (S/S) methods for the immobilization of sulphidic mine tailings. The main focus was to develop a suitable chemical environment for achieving effective heavy metal (mainly arsenic) and sulphate immobilization while simultaneously ensuring good mechanical properties. Three treatment methods were tested: alkali activation, stabilization using hydrated lime (Ca(OH)2) and blast furnace slag (GBFS), and calcium sulphoaluminate-belite (CSAB) cement stabilization. The mine tailings used in this study contained large amounts of sulphates and heavy metals such as Cr, Cu, Ni, Mn, Zn, V and As. The leaching of arsenic and sulphates from powdered tailings exceeded the legal limits for regular and inert waste. All treatment methods were found to generate a hardened matrix that was suitable for use as a backfilling or construction material, but the calcium-based binding system was the most suitable for effective immobilization of all the heavy metals (including arsenic) and the sulphates. Precipitation in the form of calcium sulphates/calcium arsenate and the formation of ettringite are the main stabilization methods employed in calcium-based stabilization/solidification (S/S) systems. Some evidence of physical encapsulation occurring simultaneously with chemical stabilization was noted. These results can be exploited further to develop more sustainable mine tailing management systems for use in the future. The tailings could be stored in a dry landfill area instead of in tailing dams, and in this way a long-term decrease in AMD generation could be achieved, together with a high potential for recycling. / Tiivistelmä Monet arvometallit kuten kulta, kupari ja nikkeli ovat sitoutuneena sulfidipitoisiin mineraaleihin. Louhittaessa ja rikastettaessa näitä sulfidimineraaleja syntyy miljoonia tonneja sulfidipitoisia rikastushiekkoja vuosittain. Rikastushiekat voivat sisältää myös runsaasti erilaisia raskasmetalleja. Osa rikastushiekoista hyödynnetään kaivostäytössä, mutta suurin osa rikastushiekoista läjitetään edelleen ympäristöön rikastushiekka-altaisiin veden alle. Kun sulfidipitoinen malmi kaivetaan ja käsitellään, sulfidiset mineraalit hapettuvat ollessaan kosketuksissa veden ja hapen kanssa. Hapettuessaan ne muodostavat rikkihappoa, laskien ympäristön pH:ta jolloin useimmat raskasmetallit liukenevat ympäristöön. Muodostuvia happamia kaivosvesiä voi syntyä vielä pitkään kaivoksen sulkemisen jälkeen ja ovat näin ollen yksi suurimmista kaivosteollisuuteen liittyvistä ympäristöongelmista. Lisäksi suuret rikastushiekka-altaat voivat aiheuttaa vaaraa myös ihmisille, mikäli altaan rakenteet pettävät. Rikastushiekkojen kestäviä ja ympäristöystävällisiä varastointimenetelmiä täytyy kehittää, jotta näitä ongelmia voidaan tulevaisuudessa ehkäistä. Tässä työssä tutkittiin menetelmiä, joilla kultakaivoksella syntyvät sulfidipitoiset vaaralliseksi jätteeksi luokitellut rikastushiekat saataisiin stabiloitua tehokkaasti. Työssä keskityttiin kolmeen erilaiseen menetelmään: alkali-aktivointiin, stabilointiin kalsiumhydroksidin ja masuunikuonan avulla ja stabilointiin CSAB sementin avulla. Valmistettujen materiaalien mekaanisia ja kemiallisia ominaisuuksia arvioitiin. Tavoitteena oli ymmärtää, miten eri menetelmät soveltuvat raskasmetallien (erityisesti arseenin) ja sulfaattien sitoutumiseen ja mikä on eri komponenttien rooli reaktioissa. Alkali-aktivoimalla rikastushiekkaa sopivan sidosaineen kanssa saavutettiin hyvät mekaaniset ominaisuudet ja useimmat haitta-aineet sitoutuivat materiaaliin. Ongelmia aiheuttivat edelleen sulfaatit ja arseeni. Kalsiumpohjaiset menetelmät sitoivat raskasmetallit (myös arseenin) ja sulfaatit tehokkaimmin. Sulfaatit ja arseeni saostuivat muodostaen niukkaliukoisia komponentteja kalsiumin kanssa. Samanaikaisesti rakenteeseen muodostui ettringiittiä, jolla on tutkitusti hyvä kyky sitoa erilaisia raskasmetalleja rakenteeseensa. Raskasmetallit myös kapseloituivat rakenteen sisään. Työn tuloksia voidaan hyödyntää, kehitettäessä rikastushiekkojen turvallista varastointia. Kun materiaalille saavutetaan riittävän hyvä lujuus ja kemiallinen stabiilius, rikastushiekat voitaisiin läjittää tulevaisuudessa kuivalle maalle altaan sijaan. Näin vältyttäisiin rikastushiekka-altaiden rakentamiselta ja voitaisiin vähentää happamien kaivosvesien muodostumista pitkällä ajanjaksolla. Saavutettujen tulosten perusteella rikastushiekkoja voidaan mahdollisesti tulevaisuudessa hyödyntää myös erilaisissa betonin tapaisissa rakennusmateriaaleissa.

No description available.