Chromium Contamination Associated with Chromite Ore Processing Residue (COPR) in the Area of Kanpur, Uttar Pradesh, India

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Chromium Contamination Associated with Chromite Ore Processing Residue (COPR) in the Area of Kanpur, Uttar Pradesh, India Chromium contamination associated with Chromite Ore Processing Residue (COPR) in the area of Kanpur, Uttar Pradesh, India I n a u g u r a l - D i s s e r t a t i o n zur Erlangung des Doktorgrades der Mathematisch-Naturwissenschaftlichen Fakultät der Universität zu Köln vorgelegt von Katrin Matern aus Bonn Köln 2017 Berichterstatter: Prof. Dr. Tim Mansfeldt Prof. Dr. Georg Bareth Tag der mündlichen Prüfung: 13. April 2016 Summary I Summary Chromite ore processing residue (COPR) is a hazardous waste derived from the chromate 2– (CrO4 ) extraction roasting process. It is a major source of environmental contamination as it contains high amounts of chromium (Cr) in both the trivalent [Cr(III)] and the hexavalent [Cr(VI)] valence states. While Cr(III) is known to be an essential micronutrient for mammals, Cr(VI) is considered to be carcinogenic and causes allergic contact dermatitis. Despite its (eco)toxico- logical potential, COPR has been dumped in uncontrolled surface landfills in several countries. The leaching of Cr(VI), resulting in the contamination of groundwater, is a key environmental risk arising from these CORR dumps. Since the contamination pathways of Cr(VI) are not fully understood, the objective of this dissertation was to evaluate the Cr contamination associated with COPR in the area of Kanpur (Uttar Pradesh, India). To investigate these issues, COPR samples were taken from two landfill sites in the area of Kanpur and characterized in terms of their chemical and mineralogical nature. The total Cr content in the studied COPR samples amounted to 81 and 74 g kg–1, 20 and 13% of which was Cr(VI) respectively. In addition to the common mineral phases present in COPR, previ- ously reported in other studies, a further Cr host mineral, grimaldiite [CrO(OH)], was identified by X-ray powder diffraction and scanning electron microscopy. Further, the COPR contained easily soluble phases such as sodium chromate (Na2CrO4). To determine the Cr(VI) leaching behavior of COPR, column experiments under water-saturated conditions were conducted. The results indicated that Cr(VI) concentrations in the leachates were dominated by the disso- lution of Na2CrO4, as well as mineral solubility control of the Cr(VI) hosting minerals CAC-14 (Ca4Al2O6(CrO4)·14H2O) and Katoite ((CaO)3Al2O3(H2O)6). During leaching, Cr(VI) concentra- tions decreased from 1800 to 300 and 1200 to 163 mg L–1 during 12 pore volumes, which conforms to two years of monsoon precipitation. Furthermore, the release of Cr(VI) was par- 2– tially rate-limited, which was identified by flow interruptions. Batch studies showed that CrO4 adsorption from COPR eluates was inhibited due to the high pH of the eluates and the inves- 2– tigated soils. Furthermore, the chemical composition of the COPR eluates diminished CrO4 adsorption due to their high ionic strength and carbonate concentration as a competitive anion. The Cr(VI) release from a COPR-contaminated soil at varying water content and redox condi- tions was studied using column experiments. Since Cr(VI) was present in high concentrations 2− at the beginning of the experiment, the redox potential was controlled by CrO4 /Cr2O3(s) or 2− CrO4 /(Fe,Cr)OOH redox couples. The results indicated that Cr(VI) was highly mobile under oxidizing conditions and Cr was gradually immobilized and irreversibly sequestered via reduc- tive precipitation under moderately reducing conditions. To evaluate the role of monsoon pre- cipitation on Cr(VI) contamination of groundwater in the vicinity of COPR dumps, samples were taken both in the pre-monsoon season (n = 57) and during the monsoon season (n = 70). The Summary II Cr(VI) concentrations of groundwater ranged from <0.005 to 115 mg L–1, with the maximum values found close to the COPR dumpsites. Additionally, the results showed that most samples exhibited multiple non-COPR contaminates including fluoride, nitrate, arsenic, molybdenum, and uranium. Overall, the water from 95% of the wells was not drinkable. However, monsoon precipitation was not found to have a significant effect on Cr(VI) concentration and spatial dis- tribution. This study has shown that the area of Kanpur is highly affected by COPR dumps that continu- ously leach Cr(VI) in high concentrations. Hexavalent Cr is not adsorbed by the soils in the surroundings, which is reflected in the elevated Cr(VI) concentrations in the groundwater around the dumpsites. This is particularly alarming since the local population uses the ground- water not only to water livestock and for irrigation but also as drinking water. The use of per- meable reactive barriers (either as a stand-alone remediation process or in conjunction with the capping of the COPR dumpsites) is a cost effective and practical solution to counteract the negative effects of Cr(VI) pollution. Furthermore, Cr-mitigation at the household level should be provided. Zusammenfassung III Zusammenfassung Chromerzverarbeitungsrückstände, die im Englischen als Chromite Ore Processing Residue (COPR) bezeichnet werden, sind umweltgefährliche Abfälle, die aus dem Röstungsprozess 2– zur Chromat (CrO4 ) Extraktion stammen. Sie sind eine bedeutende Quelle für Umweltver- schmutzungen, da sie große Mengen an Chrom (Cr), sowohl im drei- [Cr(III)] als auch im sech- wertigen [Cr(VI)] Valenzzustand enthalten. Obwohl Cr(III) bekanntlich ein Mikronährelement für Säugetiere darstellt, wird Cr(VI) als karzinogen eingestuft und verursacht allergische Kon- taktekzeme. In einigen Ländern wurden COPR aber trotz ihres (öko)toxikologischen Gefähr- dungspotentials in unkontrollierten Oberflächenhalden abgelagert. Eine große Gefahr, die von den COPR-Halden ausgeht, ist die Auswaschung von Cr(VI) und die damit verbundene Kon- tamination des Grundwassers. Da die Pfade der Cr(VI) Kontamination nicht vollständig geklärt sind, war das Ziel dieser Dissertation daher die Cr-Kontamination in Verbindung mit COPR in dem Gebiet um Kanpur (Uttar Pradesh, Indien) zu beurteilen. Um diesen Sachverhalt zu untersuchen, wurden COPR Proben von zwei Halden in der Region von Kanpur genommen und im Hinblick auf ihre chemische und mineralogische Zusammen- setzung hin untersucht. Der Gesamtchromgehalt betrug 81 und 74 g kg–1, wovon 20 bzw. 13% als Cr(VI) vorlagen. Abgesehen von den gängigen Mineralphasen, die in den COPR in anderen Studien benannt wurden, konnte ein weiteres Mineral, Grimaldiit [CrO(OH)], mittels Röntgen- beugung und Rasterelektronenmikroskopie identifiziert werden. Des Weiteren enthielten die COPR leicht lösliche Phasen wie Natriumchromat (Na2CrO4). Um das Auslaugverhalten von Cr(VI) in COPR zu untersuchen, wurden Säulenversuche bei gesättigtem Fluss durchgeführt. Die Ergebnisse lassen darauf schließen, dass die Auflösung von Na2CrO4, sowie die Löslich- keitskontrolle von den Cr(VI) enthaltenden Mineralphasen CAC-14 (Ca4Al2O6(CrO4)·14H2O) und Katoite ((CaO)3Al2O3(H2O)6) für die Cr(VI) Konzentration in dem Sickerwasser verantwort- lich waren. Während der Auslaugung, verringerten sich die Cr(VI) Konzentrationen von 1800 auf 300 mg L–1 und 1200 auf 163 mg L–1 innerhalb von 12 Porenvolumen, was zwei Jahren Monsunniederschlag entspricht. Flussunterbrechungen ergaben, dass die Freisetzung von Cr(VI) teilweise ratenlimitiert war. Schüttelexperimente zeigten, dass die Adsorption von 2– CrO4 in den COPR-Eluaten aufgrund der hohen pH-Werte von Böden und Eluaten gehemmt war. Außerdem führte die chemische Zusammensetzung der COPR-Eluate aufgrund ihrer ho- hen Leitfähigkeit und Anzahl an konkurrierenden Anionen (v.a. Carbonationen) zu einer ver- ringerten Adsorption. Die Freisetzung von Cr(VI) in einem COPR-kontaminierten Boden wurde in Abhängigkeit variierender Wassergehalte und Redoxpotenziale in Säulenexperimenten un- tersucht. Durch die hohe Cr(VI) Konzentration zu Beginn des Experimentes, wurde das Re- 2− 2− doxpotenzial durch die Redoxpaare CrO4 /Cr2O3(s) oder CrO4 /(Fe,Cr)OOH kontrolliert. Die Ergebnisse zeigten auch, dass Cr(VI) unter oxidierenden Bedingungen sehr mobil war, unter Zusammenfassung IV moderat reduzierenden Bedingungen schrittweise immobilisiert und irreversibel durch reduk- tive Fällung abgesondert wurde. Um die Abhängigkeit von Monsunniederschlägen auf die Cr(VI) Kontamination im Grundwasser in der Umgebung der COPR-Halden zu untersuchen, wurden Proben vor Monsunbeginn (n = 57) und während des Monsuns (n = 70) genommen. Die Cr(VI)-Konzentrationen reichten von <0.005 bis 115 mg L–1 und erreichten Maximalwerten in der Nähe der COPR-Halden. Zusätzlich ergaben die Ergebnisse, dass die meisten Proben mehrfach mit Fluorid, Nitrat, Arsen, Molybdän und Uran kontaminiert waren, was allerdings nicht in den Zusammenhang mit den COPR Halden gebracht werden konnte. Insgesamt war das Wasser von 95% der Brunnen nicht trinkbar. Allerdings konnte kein Zusammenhang zwi- schen Monsunniederschlägen und der räumlichen Verteilung der Cr(VI) Konzentration im Grundwasser festgestellt werden. Die Studie hat gezeigt, dass die Gegend um Kanpur durch die COPR-Halden, aus denen kon- tinuierlich Cr(VI) ausgewaschen wird, sehr beeinträchtigt ist. Das sechswertige Cr wird in den umgebenden Böden kaum gebunden, was sich in erhöhten Cr(VI) Grundwasserkonzentratio- nen widerspiegelt. Das ist besonders bedenklich, da die ansässige Bevölkerung das Grund- wasser nicht nur für die Tränkung der Tiere und für die Bewässerung der Ackerflächen benö- tigt, sondern auch als Trinkwasser nutzt. Die Verwendung einer permeablen reaktiven Barriere (entweder alleine oder in Kombination mit der Überdachung der COPR Halden) bietet eine kostengünstige
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