Iron reduction is an important redox reaction in anaerobic environments for both biological and chemical cycling of elements such as carbon. However, the controls on the rate and extent of iron reduction are poorly understood and unlike other major terminal electron accepting processes, iron reduction has the added complexity that its oxidized form (ferric iron) exists primarily as one of several solid phases in environments with pH greater than 3. Thus, the distribution and form of ferric iron minerals are important controls on iron reduction in natural systems. For the first phase of this research a series of sequential chemical extractions was performed on a core taken from a landfill-leachate-contaminated wetland-aquifer system at the Norman Landfill, Norman, OK. The phases targeted by the sequential extractions consist of easily water soluble salts and ions present in the soil solution; weakly acid soluble iron (such as siderite and ankerite); easily reducible iron (such as ferrihydrite and lepidocrocite); moderately reducible iron (such as goethite, akageneite, and hematite); organically bound iron; magnetite; and pyrite. The second phase of this research involved creating in situ microcosm experiments that exposed native microbial communities to a test solution amended with 2-line ferrihydrite (Fe5HO8∙4H2O), electron donor (lactate and acetate), and a conservative tracer for a period of eleven days. The kinetics of iron reduction were then evaluated over time and the resulting changes in microbial community structure documented through DNA and RNA analysis. Results document the spatial distribution of iron phases at the contaminated wetland-aquifer interface. Results of the sequential extractions indicate that ferrihydrite was present throughout the core. Accordingly, ferrihydrite was used in subsequent experiments on in situ microcosms to evaluate the kinetic controls on the microbial reduction of ferrihydrite. The results of these experiments show that microbial communities actively responded to the introduction of the amended ferrihydrite solution by increasing their community size and reducing ferrihydrite to an iron (II) phase in increasing amounts over an eleven day period.

Shooting ranges concentrate significant quantities of heavy metals, especially lead as spent shot and bullets, on very small parcels of land. Samples taken from a shooting range near Blacksburg, VA, USA provide information about the reservoirs and pathways of lead at shooting ranges in an upland setting and humid environment. Metallic lead corrodes rapidly and develops a coating of corrosion products. The type and amount of corrosion products found on lead shot and bullets are best understood through examination of Eh-pH relationships. X-ray diffraction analysis identified hydrocerussite (Pb₃(CO₃)₂(OH)₂) as the corrosion phase present on lead shot recovered from the range. Hydrocerussite dissolution can produce soluble lead concentrations ranging from 2 ppb to 2 ppm for the soil pH values at this site. This soluble lead is captured by the soil. Sequential chemical extractions revealed that vertical lead migration beyond the A-horizon was minimal. The bound-to-Fe & Mn oxides and bound-to-carbonates soil fractions were identified as significant reservoirs for sequestration of lead in the soil. The highest concentration of extractable lead contained in the soil was directly correlated with the highest concentration of lead shot and bullets measured on the shotgun range surface. The geochemical framework for understanding the corrosion process, identifying the corrosion product(s) that control lead solubility, and identifying the geochemical barriers to lead migration that were employed at the Blacksburg, VA shotgun range, provides a basis for selecting best management practices for this and other shooting ranges. / Master of Science

As the environmental regulations and technical progress have forced the factories’ old “end of pipe” solutions to improve, the metal emissions from point sources have decreased. Instead, the diffuse consumption emissions from goods in use now are in focus. The increased awareness of traffic as a major diffuse metal emission source emphasizes the need for more detailed information on the various traffic related sources. The main scope of this thesis is to study specific parts of metal emissions from some road traffic related sub sources such as brake lining and tyres. The metals in focus are antimony (Sb), cadmium (Cd), copper (Cu), chromium (Cr), lead (Pb), nickel(Ni) and zinc (Zn), and the research quantifies emissions from the different sub sources, trace changes over time as well as dispersal patterns and metal mobility in the roadside environment. The results show that even if the road traffic associated metal stocks are small compared to total in use stocks, their emissions are of major importance. The updated figures show that despite material developments during the last 10 years, tyres still are one of the main sources of Zn and Cd, while it can be excluded as a source of concern for the other metals studied. Brake linings are shown to be an especially pronounced source for Cu and Sb. The Pb and Cd emissions from brake linings and tyres have decreased as a result of decreasing material concentrations in these sources, most likely a result of EU regulations. Further the results reveals galvanized goods to be a major road traffic related source for Zn. The results show that the total metal concentrations in roadside soils have increased 3-16 times compared to regional background during the last decades. Each metal has a limited dispersal distance from the roads as well as down in the soil profile. Most metals are found within 10 m from the road in the uppermost 10 cm of the topsoil. However, the sequential extractions show that a large part of the metals found in the soil are rather easily mobilized and can be redistributed if the roadside soils become disturbed. Metals emitted due to decelerating activities are not correlated to elevated concentrations near road junctions. Instead the metals appear to be more evenly spread along the whole driven distance. The study points out Sb as an element that might be problematic to analyse. For Sb, which is sparsely studied as a roadside contaminant, there is a need of more general knowledge as it has a high accumulation rate in roadside soils. / I takt med ökade regleringar inom miljöområdet och en snabb teknikutveckling har fabrikerna allt mer spelat ut sin roll som emissionskällor till miljön. Istället har den diffusa emissionen som kommer från produktanvändning fått en större betydelse. En ökad medvetenhet om transporter och trafikens betydelse för samhällets konsumtionsemissioner understryker det ökade kunskapsbehovet för de trafikrelaterade emissionskällorna. Avhandlingens huvudsyfte är att studera specifika delar av metallemissionen från vissa trafikrelaterade källor så som bromsbelägg och däck. Metallerna som är i fokus är antimon (Sb), bly (Pb), kadmium (Cd), koppar (Cu), krom (Cr), nickel (Ni) och zink (Zn) och forskningen strävar efter att kvantifiera emissionerna från de olika källorna, spåra förändringar i emissioner över tid, kartlägga utsläppsmönster och metallrörlighet i vägnära jord. Resultaten pekar på att även om de trafikrelaterade källorna kvantitativt är små i jämförelse med de totala källorna så är deras emissioner av stor betydelse. De nya siffrorna visar att trots en materialutveckling inom området under det senaste årtiondet så är fortfarande däck en av de största källorna för Cd och Zn i stadsmiljö, medan de kan avfärdas som källa för de övriga studerade metallerna. Studien visar att bromsbelägg fortfarande är en viktig källa för Cu och Sb. Bly- och Cd-emissionerna från däck och bromsbelägg har däremot minskat drastiskt under samma period. Denna minskning beror troligen på en reglering på EU-nivå. Dessutom visar resultaten att galvaniserade ytor är den viktigaste källan till Zn i stadsmiljö. Metallkoncentrationerna i vägnära jord har ökat med 3 – 16 ggr jämfört med bakgrundshalterna i de undersökta områdena. Metallerna uppvisar endast en begränsad spridning från vägen och ner i jordprofilen. Den största metallpåverkan återfinns inom 10 m från vägen och i de översta 10 cm av jorden. Trots den begränsade spridningen så uppvisar de flesta metallerna en förhållandevis hög rörlighet, vilket innebär att de kan bli mobila vid störning av jorden. De bromsrelaterade metallerna uppvisar ingen korrelation till förhöjda halter nära korsningar utan är mer jämnt spridda över hela körsträckan. Studien pekar ut Sb som ett element som kan vara problematiskt att analysera på grund av dess flyktighet. Trots att Sb för närvarande har en snabb ackumulationstakt i trafikmiljö så är den endast sparsamt studerad. Mer generell kunskap om Sb är därför önskvärd.

Plant roots are critical weathering agents in deep soils, yet the impact of resulting mineral transformations on the vast deep soil carbon (C) reservoir are largely unknown. Root-driven weathering of primary minerals may cause the formation of reactive secondary minerals, which protect mineral-organic associations (MOAs) for centuries or millennia. Conversely, root-driven weathering may also transform secondary minerals, potentially enhancing the bioavailability of C previously protected in MOAs. Here we examined the impact of root-driven weathering on MOAs and their capacity to store C over pedogenic time scales. I compared soil that experienced root-driven weathering, resulting in the formation of discrete rhizosphere zones in deep soil horizons (100-160 cm) of the Santa Cruz Marine Terrace chronosequence (65 ka-226 ka), with adjacent soil that experienced no root growth. Using a combination of radiocarbon, mass spectrometry, Mössbauer spectroscopy, and X-ray spectromicroscopy approaches, we characterized MOA transformations in relation to changes in C content, turnover and chemistry across four soils ranging in age (65 ka-226 ka). We found that the onset of root-driven weathering (65-90 ka) increased the amount of C associated with poorly crystalline iron (Fe) and aluminum (Al) phases, particularly highly-disordered nano-goethite. The increase in C coincided with greater overall C concentrations, longer C residence times, and a greater abundance of microbially-derived C. Continued root-driven weathering (137-226 ka) did not significantly change the amount of C associated with crystalline Fe and Al phases, but resulted in a decline in the amount of C associated with poorly crystalline metal phases. This decline in C associated to poorly crystalline phases coincided with a decrease in C concentrations and potential turnover rates, and a shift toward plant-derived C. In contrast, soil not affected by root-driven weathering showed low amounts of C bound to poorly crystalline Fe and Al phases regardless of soil age and, correspondingly, lower C concentrations and estimated residence times. My results demonstrate that root-driven formation and disruption of poorly crystalline Fe and Al phases directly controls both C accrual and loss in deep soil. Hence root impacts on soil C storage are dependent on soil weathering stage, a consideration critical for predictions of the vulnerability of deep soil C to global change.

Depuis au moins 2000 ans, le massif des Vosges a été le siège d’activités minières qui ont conduit (i) à l’émission de particules contaminées en éléments traces métalliques (ETMs), (ii) aux dépôts de déchets miniers et sidérurgiques et (iii) à des modifications du paysage. Les ressources présentes dans ce système de moyenne montagne, et utilisées par les populations, rendent nécessaire la mesure des impacts des activités anthropiques passées sur l’écosystème forestier.Ce travail de thèse propose une approche multi-proxy couplant géochimie, palynologie et écotoxicologie. Différentes phases de dépôts en ETMs ont été retracées sur les 2000 dernières années et regroupent celles connues à l’échelle de l’hémisphère Nord et des phases plus locales. L’impact paysager des activités minières semble quant à lui réduit par rapport à ce que laissaient penser les archives historiques qui présentaient des déserts forestiers dus aux activités minières. La biodisponibilité et le risque associés au transfert des ETMs ont été évalués dans un ancien district minier de production de plomb (Pb) et d’argent grâce à une campagne de bioindication active avec un indicateur de la qualité des sols, Cantareus aspersus. Sur huit stations, quatre présentent des excès de transfert induisant un risque toxicologique élevé et comprennent deux sites archéologiques miniers et un potager communal. Le fractionnement et la spéciation du Pb permettent de montrer une pratique à risque avec l’utilisation de scories comme amendements sur le potager. La contamination du milieu en ETMs par les activités minières est ici toujours transférable aux organismes du sol et donc potentiellement dans le réseau trophique / Since at least the last two millennia, mining and smelting activities have occurred in the Vosges Mountains and conducted to (i) the emission of trace metal (TM) contaminated particles in the atmosphere, (ii) the presence of mining and smelting wastes and (iii) landscape changes. Due to the use of resources from this mountainous area by local populations, it is necessary to measure impacts of these past activities on the forested ecosystem.This PhD thesis proposes a multi-proxy approach coupling geochemistry, palynology and ecotoxicology. Several phases of TM deposits have been recorded and correspond to major phases of TM contamination known in the northern hemisphere and also local periods of mining/smelting activities. The impact of mining activities on the landscape appears to be reduced contrary to historical data that described shortage of wood due to mining activities. The bioavailability and the risk associated to TMs from mining activities have been assessed in a former lead (Pb)-silver mining district by an active bioindication campaign using Cantareus aspersus, considered as indicator of soil quality. Among the eight stations, four of them present an excess of TM transfer conducting to a high ecological risk, particularly in two archaeological mining sites but also in a kitchen garden. Lead fractionation and speciation highlight the use of slags as amendments in the kitchen garden. Trace metal contamination of the soil due to mining activities is still bioavailable for soil organisms and so potentially transferred in food chain.