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- Rodríguez, Nathalie Pérez
(author)
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Fractionation of Cu and Fe isotopes in metal-rich mine sites : biotic and abiotic processes
- 2012
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Licentiate thesis (other academic/artistic)abstract
- After mineral exploitation the residual grinded and milled material, rich in sulphide minerals and heavy metals, is often left exposed to the atmospheric variables. This weathered mine waste material can lead to the formation of acid mine drainage (AMD) which has negative effects to the environment. The fractionation of stable isotope of metals such as Cu and Fe can be measured using innovative analytical techniques developed recently and could offer a detailed hindsight of the geochemical processes occurring in mine contaminated sites. Tailings profiles from Northern Sweden with high content of Cu and Fe sulphides and in different stages of weathering and/or remediation, along with plant and soil samples from a phytoremediation test site in Ronneburg, Germany were analysed using MC-ICP-MS to measure the isotope ratios of 65Cu/63Cu and 56Fe/54Fe. The analytical method used requires anion exchange chromatography to extract Cu and Fe from a complex matrix prior to the proper isotope ratio measurement. The samples from the tailings profile were useful to interpret the geochemical processes that can lead to a fractionation of Cu and Fe in the field, since redox-driven reactions such as rock oxidation and mineral precipitation are present in such environment. This study shows that precipitation of covellite in a redox-boundary zone in a mine tailings can cause a clear fractionation of Cu (Δ65Curock-covellite= -5.66±0.05‰) and a depletion of the lighter Cu isotope in the oxidised areas of the tailings due to dissolution of the remaining Cu-sulphides. Precipitation of Fe(oxy)hydroxides as a result of the oxidation process of sulphide-bearing rocks can also fractionate Fe, being the precipitated mineral slightly enriched in 56Fe.The influence of soil bacteria and plant uptake in the fractionation of Cu and Fe was investigated in pot and field experiments at the Ronneburg site, where organic amendments were used. The results showed that the plant material was enriched in the lighter Fe isotope compared to the substrate used in the pot and field experiments, in spite of the application of a bacterial consortium. Cu isotope fractionation is more susceptible to the changes in the amendments used, being those bacterial consortium, mychorriza or compost than Fe isotope fractionation. There are differences in the fractionation values in pot and field trials, regardless of the type of organic amendment applied. As an overall view, leaves are enriched in the heavier Cu isotope compared to the soils, regardless of the amendment usedThe application of the results obtained in this work would help not only to offer a view in the cycle of Fe and Cu in the surface environment, and the understanding of the (bio)geochemical processes occurring in sulphide soil surfaces. But also in the way that current remediation techniques of metal contaminated sites could be evaluated, having in mind that simplified systems show a different Cu and Fe fractionation compared to natural systems where more variables are needed to take into account.
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| 2. |
- Land, Magnus, et al.
(author)
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Solid speciation and fractionation of rare earth elements in a Spodosol profile from northern Sweden as revealed by sequential extraction
- 1999
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In: Chemical Geology. - 0009-2541 .- 1872-6836. ; 160:1-2, s. 121-138
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Journal article (peer-reviewed)abstract
- A sequential extraction has been carried out on seven soil samples from a spodosol profile in till with granitic composition. The soil profile was sampled in northern Sweden. Five fractions were selected for extraction: (A) CH3COONa-extractable (exchangeable/adsorbed/carbonate); (B) Na4P2O7-extractable (labile organics); (C) 0.25 M NH2OH⋅HCl-extractable (amorphous Fe-oxyhydroxides/Mn-oxides); (D) 1 M NH2OH⋅HCl-extractable (crystalline Fe-oxides); and (E) KClO3/HCl-extractable (organics and sulphides). Extracted rare earth elements (REE) were determined with High Resolution ICP-MS. In addition to the soil, stream water suspended particulate matter was also analysed for REE. Total concentrations in the soil samples show that the REE have been fractionated during weathering. In the acidic (pH 4.28) E-horizon all REE are depleted relative to the unweathered till. The depletion decreases with increasing atomic number. Also in the B-horizon (pH 5.86) the REE are depleted, although to a lesser extent compared to the E-horizon. Secondary phases in the B-horizon fractionate the REE in different ways. Rare earth elements extracted in extractions A and C were enriched in the intermediate REE relative to heavy and light REE if normalized to local till. In extractions B and D, the heavy REE were enriched relative to the light REE, and in extraction E a large enrichment of light REE relative to heavy REE was found. Stream water suspended particulate matter is enriched in all REE relative to local till. The light REE are more enriched than the heavy REE. Normalized La/Lu ratios in the suspended matter ranged from 1.5 to 2.4, and were negatively correlated with stream water discharge as well as with content of detrital inorganic matter in the suspended load. The only extracted phase that potentially can explain the high normalized La/Lu ratio in the suspended matter is the phase extracted in extraction E, which has a ratio of 2.0–4.2. The normalized La/Lu ratio for the rest of the extractions ranged from 0.5 to 1.2. It is concluded that organic matter seems to be important for the particulate transport of REE in northern coniferous areas.
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| 3. |
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| 5. |
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| 6. |
- Ingri, Johan, et al.
(author)
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Temporal variations in the fractionation of the rare earth elements in a boreal river; the role of colloidal particles.
- 2000
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In: Chemical Geology. - 0009-2541 .- 1872-6836. ; 166:1-2, s. 23-45
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Journal article (peer-reviewed)abstract
- Rare earth element (REE) data from weekly sampling of the filtered (<0.45 μm) and suspended particulate phase during 18 months in the Kalix River, Northern Sweden, are presented together with data on colloidal particles and the solution fraction (<3 kDa). The filtered REE concentration show large seasonal and temporal variations in the river. Lanthanum varied between approximately 300 and 2100 pM. High REE concentration in the filter-passing fraction is related to increased water discharge and there is a strong correlation between the REE concentration, organic carbon, Al and Fe. Physical erosion of detrital particles plays a minor role for the yearly transport of particulate REE in this boreal river system. The suspended particulate fraction, which is dominated by non-detrital fractions, accounted for only 35% of the yearly total transport of La in the river. Approximately 10% of the REE were transported in detrital particles during winter. At spring-flood in May, about 30% of the LREE and up to 60% of the HREE where hosted in detrital particles. Ultrafiltration of river water during spring-flood shows that colloidal particles dominate the transport of filter-passing REE. Less than 5% of the filtered REE are found in the fraction smaller than 3 kDa. The colloidal fraction shows a flat to slightly LREE enriched pattern whereas the solution fraction (<3 kDa) show an HREE enriched pattern, compared with till in the catchment. Suspended particles show a LREE enriched pattern. Data indicate that the REE are associated with two phases in the colloidal (and particulate) fraction, an organic-rich phase (with associated Al-Fe) and an Fe-rich (Fe-oxyhydroxide) inorganic phase. The Ce-anomaly in the suspended particulate fraction in the river shows systematic variations, and can be used to interpret fractionation processes of the REE during weathering and transport. There was no anomaly at maximum spring-flood but during the ice-covered period the anomaly became more and more negative. The temporal and seasonal variations of the Ce-anomaly in the suspended particulate phase reflect transport of REE-C-Al-Fe-enriched colloids from the upper section of the till (and/or from mires) to the river at storm events.
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| 8. |
- Land, Magnus, et al.
(author)
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Ba/Sr, Ca/Sr and 87Sr/86Sr ratios in soil water and groundwater: implications for relative contributions to stream water discharge
- 2000
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In: Applied Geochemistry. - 0883-2927 .- 1872-9134. ; 15:3, s. 311-325
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Journal article (peer-reviewed)abstract
- Barium/Sr and Ca/Sr ratios have been used to model the relative importance of different sources of stream water. Major and trace element concentrations together with 87Sr/86Sr ratios were measured in precipitation, soil water, groundwater and stream water in a small (9.4 km2) catchment in northern Sweden. The study catchment is drained by a first order stream and mainly covered with podzolized Quaternary till of granitic composition. It is underlain by a 1.8 Ga granite. A model with mixing equations used in an iterative mode was developed in order to separate the stream water into 3 subsurface components: soil water, shallow groundwater, and deep groundwater. Contributions from precipitation are thus not included in the model. This source may be significant for the stream water generation, but it does not interfere with the calculations of the relative contributions from the subsurface components. The results show that the deep groundwater constitutes between 5 and 20% of the subsurface water discharge into the stream water. The highest values of the deep groundwater fraction occur during base flow. Soil water dominates during snowmelt seasons, whereas during base flow it is the least important fraction. Soil water accounts for 10–100% of the subsurface water discharge into the stream water. Shallow groundwater accounts for up to 80% of the subsurface water discharge with the lowest values at peak discharge during snowmelt seasons and the highest values during base flow. The validity of the model was tested by comparing the measured 87Sr/86Sr ratios in the stream water with the 87Sr/86Sr ratios predicted by the model. There was a systematic difference between the measured and modelled 87Sr/86Sr ratios which suggests that the fraction of soil water is overestimated by the model, especially during spring flood. As a consequence of this overestimation of soil water the amount of shallow groundwater is probably underestimated during this period. However, it is concluded that the differences between measured and predicted values are relatively small, and that element ratios are potentially effective tracers for different subsurface water flowpaths in catchments.
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| 9. |
- Land, Magnus, et al.
(author)
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Chemical weathering rates, erosion rates and mobility of major and trace elements in a boreal granitic till
- 2000
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In: Aquatic geochemistry. - 1380-6165 .- 1573-1421. ; 6:4, s. 435-460
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Journal article (peer-reviewed)abstract
- Chemical weathering rates and erosionrates of granitic till in northern Sweden have beenestimated. The present-day chemical weathering rate iscompared with the long-term average weathering ratesince the last deglaciation approximately 8,700 yearsago. Also, the present-day release rates of major andtrace elements due to chemical weathering are comparedwith the mobility of these elements in a spodosolprofile as shown by soil water samples from the vadozezone. The estimation of the past weathering rate isbased on elemental depletion trends in a soil profile(typic haplocryod), whereas the present weatheringrate is based on elemental input/output budgets in asmall catchment ...
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| 10. |
- Land, Magnus, et al.
(author)
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Past and present weathering rates in northern Sweden
- 1999
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In: Applied Geochemistry. - 0883-2927 .- 1872-9134. ; 14:6, s. 761-774
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Journal article (peer-reviewed)abstract
- Past and present chemical weathering rates in granitic till have been estimated. The Kalix River watershed in northern Sweden was used as a study area in which 17 evenly distributed soil profiles were investigated. The two estimations are based on elemental depletion trends in soil profiles and input/output budgets for the elements in the watershed, respectively. In the calculations of the past weathering rate it was assumed that zircon is resistant, and thus Zr was considered to be immobile during weathering. The long-term average chemical erosion rate since the area was deglaciated 8700 a ago, expressed as the sum of major element oxides (SiO2, Al2O3, CaO, Fe2O3, K2O, MgO, MnO, Na2O), was estimated to be 5.8 g·m−2·a−1. In terms of base cation (Ca2+, Mg2+, Na+, K+) depletion this corresponds to 0.36 keq·ha−2·a−1. All elements analysed have been depleted from the E-horizon, and the most affected elements are P with an average mass loss of 86% (as P2O5), La 81%, Co 78%, Cu 77% and Ni 76%. The present-day weathering rate was calculated as the difference between outputs and inputs in the Kalix River watershed. The input was considered as the contribution from precipitation, while the output was calculated as the sum of (1) the river-transported dissolved fraction, (2) the river-transported suspended non-detrital fraction (chemically precipitated Fe- and Mn-oxy-hydroxides and matter sorbed on these particles), and (3) the biotic nutrient net uptake. River-transported outputs were measured for an annual cycle starting in September 1991 and ending in August 1992. The present-day chemical erosion rate of the till was estimated to be 6.3 g·m−2·a−1 (sum of major element oxides), or a base cation flux of 1.42 keq·ha−2·a−1. Part of this present-day rate is related to carbonate weathering in the Caledonian mountain range which makes it difficult to compare the present weathering rate with the historical weathering rate. After correction for carbonate weathering the resulting present-day weathering rate of granitic till in terms of base cation flux was estimated to be 0.65–0.75 keq·ha−2·a−1. This result indicates that the present cation flux has increased by a factor of 1.8–2.1 compared to the long-term average. However, given the uncertainties introduced by the carbonates in the Caledonian mountain range it is not possible to prove any significant difference between the mean post-glacial and the present-day weathering rate with the methods used in this study.
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