Arsenic redox transformation by humic substances and Fe minerals

The toxicity and mobility of the redox-active metalloid As strongly depends on its oxidation state, with As(III) (arsenite) being more toxic and mobile than As(V) (arsenate). It is, therefore, necessary to know the biogeochemical processes potentially influencing As redox state to understand and predict its environmental behavior. The first part of this presentation will discuss the quantification of As redox changes by pH-neutral mineral suspensions of goethite [α-Fe^IIIOOH] amended with Fe(II) using wet-chemical and synchrotron X-ray absorption (XANES) analysis (Amstaetter et al., 2010). First, it was found that goethite itself did not oxidize As(III). Second, in contrast to thermodynamic predictions, Fe(II)–goethite systems did not reduce As(V). However, surprisingly, rapid oxidation of As(III) to As(V) was observed in Fe(II)–goethite systems. Iron speciation and mineral analysis by Mössbauer spectroscopy showed rapid formation of ⁵⁷Fe–goethite after ⁵⁷Fe(II) addition and the formation of a so far unidentified additional Fe(II) phase. No other Fe(III) phase could be detected by Mössbauer spectroscopy, EXAFS, scanning electron microscopy, X-ray diffraction or high-resolution transmission electron microscopy. This suggests that reactive Fe(III) species form as an intermediate Fe(III) phase upon Fe(II) addition and electron transfer into bulk goethite but before crystallization of the newly formed Fe(III) as goethite.The second part of the presentation will show that semiquinone radicals produced during microbial or chemical reduction of a humic substance model quinone (AQDS, 9,10-anthraquinone-2,6-disulfonic acid) can react with As and change its redox state (Jiang et al., 2009). The results of these experiments showed that these semiquinone radicals are strong oxidants and oxidize arsenite to arsenate, thus decreasing As toxicity and mobility. The oxidation of As(III) depended strongly on pH. More arsenite (up to 67.3%) was oxidized at pH 11 compared to pH 7 (12.6% oxidation) and pH 3 (0.5% oxidation). In addition to As(III) oxidation by semiquinone radicals, hydroquinones that were also produced during quinone reduction, reduced As(V) to As(III) at neutral and acidic pH values (less than 12%) but not at alkaline pH. In an attempt to understand the observed redox reactions between As and reduced/oxidized quinones present in humic substances, the radical content in reduced AQDS solutions was quantified and Eh-pH diagrams were constructed. Both the radical quantification and the Eh-pH diagram allowed explaining the observed redox reactions between the reduced AQDS solutions and the As.In summary these studies indicate that in the simultaneous presence of Fe(III) oxyhydroxides, Fe(II), and humic substances as commonly observed in environments inhabited by Fe-reducing microorganisms, As(III) oxidation can occur. This potentially explains the presence of As(V) in reduced groundwater aquifers.     

蒲阳河流域地下水水化学及同位素特征

保定西部山前地区位于太行山及华北平原交界带,为缓解极端气候灾害对生产生活的影响,维持地下水资源的可持续开发利用,开展相关的地下水水化学及同位素特征研究。研究区地下水化学类型以HCO3—Ca·Mg、HCO3·SO4—Ca·Mg及SO4·HCO3—Ca·Mg为主,区内地下水主要来源于大气降水,流域内地表水补给地下水;地下水中化学成分为Ca2＋、Mg2＋、HCO-3、SO2-4,主要来源于岩石风化作用,同时受到人类活动的影响,地下水中硝酸盐含量明显升高;由于受到褶皱构造的控制,流域的上游及平原区均出现年龄大于60年的地下水,多数岩溶水年龄较复杂,从现代水到大于60年的水均有分布。研究成果为流域内水资源的合理开发利用提供建议,区内岩溶地下水的开发将在一定程度上缓解极端天气的影响。     

高砷含水层沉积物含铁矿物特性及其对砷的水文地球化学作用

含水层沉积物中含铁矿物的特征与活性会影响砷的迁移转化行为。通过内蒙古含水层沉积物含铁矿物的溶解、还原动力学实验,研究了沉积物含铁矿物特征和活性及其与砷运移的关系。结果表明,沉积物中具还原活性的铁氧化物总量(m0)与岩性有关,细砂为52 μmol/g,黏土为45 μmol/g。初始还原速率k′均在10-5 s-1的数量级。表征活性均匀度的参数γ值介于合成铁氧化物矿物和表层沉积物之间。沉积物中Fe(Ⅲ)氧化物的还原活性主要介于人造纤铁矿与针铁矿的活性水平范围内。沉积物中可能存在两类活性水平不同的Fe(Ⅲ)氧化物。As更倾向于吸附在活性较强的Fe(Ⅲ)氧化物上。还原环境中,活性较强的Fe(Ⅲ)氧化物的还原性溶解,促进了沉积物中砷的释放。     

Rapid biotic molecular transformation of fulvic acids in a karst aquifer

The study of molecular transformation processes of dissolved organic carbon (DOC) in the environment significantly contributes to a better understanding of the global biogeochemical organic matter cycle. In an oxic karst groundwater system, in which the most powerful abiotic DOC degradative reactions, photodegradation and metal-mediated redox chemistry, are at best marginal contributors, a near complete turnover of fulvic acids (FAs) has been observed within decades (∼60 years). Depletion of oxygen for a very extensive range of aliphatic and aromatic carbon chemical environments has been confirmed as well as the formation of novel classes of compounds, suggesting a major contribution from biotic processes. From these results we infer that FAs must be perceived as a rather active participant in the global carbon cycle. Molecular-level alterations of such magnitude and rapidity on such short-time scales ought to be considered as widespread in the processing of “refractory” DOC in the environment.     

The effect of silica and natural organic matter on the Fe(II)-catalysed transformation and reactivity of Fe(III) minerals

The Fe(II)-catalysed transformation of synthetic schwertmannite, ferrihydrite, jarosite and lepidocrocite to more stable, crystalline Fe(III) oxyhydroxides is prevented by high, natural concentrations of Si and natural organic matter (NOM). Adsorption isotherms demonstrate that Si adsorbs to the iron minerals investigated and that increasing amounts of adsorbed Si results in a decrease in isotope exchange between aqueous Fe(II) and the Fe(III) mineral. This suggests that the adsorption of Si inhibits the direct adsorption of Fe(II) onto the mineral surface, providing an explanation for the inhibitory effect of Si on the Fe(II)-catalysed transformation of Fe(III) minerals. During the synthesis of lepidocrocite and ferrihydrite, the presence of equimolar concentrations of Si and Fe resulted in the formation of 2-line ferrihydrite containing co-precipitated Si in both cases. Isotope exchange experiments conducted with this freeze-dried Si co-precipitated ferrihydrite species (Si-ferrihydrite) demonstrated that the rate and extent of isotope exchange between aqueous Fe(II) and solid ⁵⁵Fe(III) was very similar to that of 2-line ferrihydrite formed in the absence of Si and which had not been allowed to dry. In contrast to un-dried ferrihydrite formed in the absence of Si, Si-ferrihydrite did not transform into a more crystalline Fe(III) mineral phase over the 7-day period of investigation. Reductive dissolution studies using ascorbic acid demonstrated that both dried Si-ferrihydrite and un-dried 2-line ferrihydrite were very reactive, suggesting these species may be major contributors to the rapid release of dissolved iron following flooding and the onset of conditions conducive to reductive dissolution in acid sulphate soil environments.     

Migration and transformation of manganese during the artificial recharging of a deep confined aquifer

Field tests and laboratory experiments were performed, using an artificial groundwater recharging site in Southeast China as an example, to investigate the migration and transformation of manganese during the artificial recharging of a deep confined aquifer. The migration and transformation of total manganese and divalent manganese (Mn(II)) were influenced by mixing, oxidation reactions, and the dissolution of minerals containing manganese, and increasing the dissolved oxygen (DO) concentration was found to promote the dissolution of minerals containing manganese. The laboratory experiments showed that the retardation factors were higher upstream than downstream of the recharging hole. The amount of dissolution that occurred decreased, and the amount of mixing that occurred increased as the distance from the recharging hole increased. The DO concentration decreased as the amount of dissolution of minerals containing manganese that occurred decreased. A high temperature, a high DO concentration, and the presence of microorganisms were found to promote the dissolution of minerals containing manganese, which caused the total manganese and Mn(II) concentrations to increase.     

Rate and extent of cobalt sorption to representative aquifer minerals in the presence of a moderately strong organic ligand

There is an increasing awareness that rate-limited sorption reactions can play an important role in the transport of solutes in groundwater. The rate and extent of reactions between aqueous metals and mineral surfaces are affected by many factors, including the temperature, the presence of organic chelating agents, and adsorbent mineralogy. Cobalt sorption was investigated in terms of temperature, citrate concentration, and silica sand surface coating. The kinetic sorption data were described well by two simultaneous second-order reactions. The results suggested that decreasing temperature or the presence of citrate resulted in a slower approach to equilibrium for Co sorption to the uncoated silica sand that contained small amounts of secondary minerals. Using the same sand coated with an amorphous Fe(III) oxide, increasing temperature or the presence of citrate resulted in a faster approach to equilibrium for Co sorption. The equilibrium adsorption isotherms were described well by a generalized two-layer surface complexation model. Citrate decreased the extent of Co sorption to the uncoated silica; the effect was most pronounced at low temperature. Conversely, citrate increased the extent of Co sorption to the Fe-coated silica. These results suggest that citrate decreased the rate and extent of adsorption to the uncoated silica through the formation of a stable anionic aqueous complex that has a lower affinity for the surface than Co²⁺. Conversely, the higher anion sorption capacity of the Fe-coated silica increased the rate and extent of Co sorption with citrate present, presumably through the formation of an organo-metallic ternary surface complex.     

Arsenic solubilization and redistribution under anoxic conditions in three aquifer sediments from a basin-fill aquifer in Northern Utah: The role of natural organic carbon and carbonate minerals

The basin-fill aquifers of the Western U.S. contain elevated concentrations of arsenic in the groundwater due to ancient volcanic deposits that host arsenic minerals. Microcosms were constructed using two oxidized sediments and, by contrast, a reduced sediment collected from a shallow basin-fill aquifer in the Cache Valley Basin, Northern Utah to evaluate the fate of geologic arsenic under anoxic conditions. Sequential extractions indicated the primary arsenic host mineral was amorphous iron oxides, but 13%–17% of the total arsenic was associated with carbonate minerals. Arsenic was solubilized from the sediments when incubated with groundwater in the presence of native organic carbon. Arsenic solubilization occurred prior to iron reduction rather than the commonly observed co-reactivity. Arsenic(V) associated with carbonate minerals was the main source of arsenic released to solution and redistributed onto less soluble minerals, including FeS and siderite as defined by chemical extraction. Arsenic reduction occurred only in the site-oxidized sediments. The addition of a carbon and energy source, glucose, resulted in enhanced arsenic solubilization, which was coupled with iron reduction from the site-oxidized sediments. Adding glucose promoted iron reduction that masked the role of carbonate minerals in arsenic solubilization and retention as observed with incubation with groundwater only.     

57Fe Mössbauer study of pumpellyiteokhotskite-julgoldite series minerals

Summary Fe and Mn distribution in the pumpellyite group minerals (W ₈ X ₄ Y ₈ Z ₁₂0_56-n (OH) _n ) has been studied by using⁵⁷Fe Mössbauer spectroscopy. The studied Fe-pumpellyites, belonging to the pumpellyite-julgoldite series, were collected from two localities; metabasites in the Tokoro belt, Hokkaido, and gabbroic sills in the Shimane Peninsula, Japan. Okhotskite, an Mn³⁺-dominant pumpellyite group mineral, was separated from the ores of metamorphosed manganiferous iron ore deposits in the Tokoro belt.⁵⁷Fe Mössbauer spectrum of Tokoro Fe-pumpellyite is composed of two Fe²⁺- and two Fe³⁺-doublets. On the basis of the single crystal structure refinements of Al-pumpellyites published so far, doublets were assigned to Fe _W ²⁺ (IS= 1.01 andQS = 2.73 mm/s), Fe _X ²⁺ (IS = 0.97 andQS = 3.18 mm/s), Fe _X ³⁺ (IS = 0.29 andQS =1.37 mm/s) and Fe _Y ³⁺ (IS = 0.36 andQS = 2.09 mm/s), whereIS is isomer shift relative to a metallic iron absorber andQS is quadrupole splitting. The Mössbauer spectrum of the Mitsu Fepumpellyite is composed of three doublets assigned to Fe _X ²⁺ (IS= 1.14 andQS = 3.20 mm/s), Fe _X ³⁺ (IS = 0.36 andQS =1.13 mm/s) and Fe _Y ³⁺ (IS = 0.37 andQS= 1.93 mm/s). These assignments show strong preference of Fe³⁺ in the X-site. The Mössbauer spectrum of the okhotskite is composed of two doublets by Fe _X ³⁺ (IS= 0.37 andQS = 1.13 mm/s) and Fe _Y ³⁺ (IS = 0.42 andQS = 2.18 mm/s). The area ratio shows that Fe _X ³⁺ :Fe _Y ³⁺ ratio is 94:6. On the basis of chemical and Mössbauer analyses, Mn _X ³⁺ :Mn _Y ³⁺ ratio is given as 19:81, indicating stronger Y-site preference of Mn³⁺ than Fe³⁺, what is consistent with Jahn-Teller theory. Al, Mn³⁺ and Fe³⁺ prefer the Y-site in this order.

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Eine⁵⁷Fe Mössbauer-Studie von Mineralen der Pumpellyit-Okhotskit-Julgoldit-Serie

Zusammenfassung Die Fe- und Mn-Verteilung in Mineralen der Pumpellyit-Gruppe (W ₈ X ₄ Y ₈ Z ₁₂O_56-n (OH)n) wurde mittels Mössbauer-Spektroskopie studiert. Die untersuchten Fe-Pumpellyite der Pumpellyit-Julgoldit-Serie stammen von zwei verschiedenen japanischen Lokalitäten: von Metabasiten des Tokoro-Gürtels, Hokkaido, und von Gabbro-Sills der Shimane Halbinsel. Okhotskit, ein Mn³⁺-dominiertes Mineral der Pumpellyit-Gruppe, wurde aus Erzen einer Mn-führenden Eisenerzlagerstätte des Tokoro-Gürtels separiert. Das⁵⁷Fe Mössbauer-Spektrum der Tokoro Fe-Pumpellyite zeigt zwei Fe²⁺- und zwei Fe³⁺-Doubletten. Auf Grund bisher publizierter verfeinerter Einkristall-Strukturuntersuchungen von Al-Pumpellyiten werden diese Doubletten folgendermaßen zugeordnet: Fe _W ²⁺ (IS = 1.01 undQS = 2.73 mm/s), Fe _X ²⁺ (IS = 0.97 undQS = 3.18 mm/s), Fe _X ³⁺ (IS = 0.29 undQS =1.37 mm/s) und Fe _Y ³⁺ (IS = 0.36 undQS = 2.09 mm/s).IS bezeichnet dabei die Isomer-Shift relativ zu einem metallischen Eisenabsorbenten,QS das Quadrupole-Splitting. Diese Zuordnungen belegen den bevorzugten Einbau von Fe³⁺ in die X-Position. Das Mössbauer-Spektrum von Okhotskit zeigt zwei Doubletten bei Fe _X ³⁺ (IS = 0.37 undQS = 1.13 mm/s) und Fe _Y ³⁺ (IS = 0.42 undQS = 2.18 mm/s). Das Flächenverhältnis zeigt, daß das Verhältnis Fe _X ³⁺ :Fe _Y ³⁺ 94:6 ist. Auf Grund der chemischen und der Mössbauer-Analysen wird das Mn _X ³⁺ :Mn _Y ³⁺ Verhältnis mit 19:81 angegeben. Mn³⁺ zeigt somit eine stärkere Präferenz für die Y-Position als Fe³⁺, ein Resultat, das mit der Jahn-Teller-Theorie konsistent ist. Der bevorzugte Einbau in die Y-Position ist, in dieser Reihenfolge, Al>Mn³⁺>Fe³⁺.

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With 4 Figures     

Episodic Biogeochemical Variability in a Low-Flow Mediterranean Estuary

To investigate to what extent episodic physical processes regulate nutrient availability and phytoplankton assemblages of the Mahon estuary (Minorca Island), we carried out an intensive field study during 2010–2011. During the study period, environmental conditions spanned from intense stratification to a continuous mixing and from lack of riverine inflow to intense runoff. Our data reveals a sequence of biogeochemical states of the estuary that result from the interplay between runoff, other non-periodic forcings (winds, sea level oscillations), and variations in water renewal. Seasonal runoff was revealed as a major driver of winter circulation and of the influx of inorganic nutrients, in particular nitrate. However, because of the combination between runoff and flushing time, the effects of floodwater events on phytoplankton are short-lived (days). Conversely, during summer, when freshwater influx declines, water renewal relies on pulsed atmospheric forcing that may be of local or remote origin. As depicted from the low nitrate concentrations (<1 μM) and enhanced ammonium (>1 μM), this change in circulation and external loads carries nutrient assimilation within the estuary head and forces the use of remnant nutrients through regenerating pathways to sustain an enhanced phytoplankton biomass at the lower estuary. Episodic variability represented between 52 and 65% of the annual chlorophyll variance. Despite the fact that episodic pulses represented intense departures from base biogeochemical state of the estuary, at time scale larger than weeks, the phytoplankton community composition and dynamics was largely regulated by the integrated effect of these episodes and other environmental drivers associated with seasonality rather than by individual storm events only. Our results suggest that even though the system presents good recovery capacity to individual storm episodes, it may be more vulnerable to increased nutrient fluxes during summer, as well as to changes in episode timing and frequency.     

Precipitation of secondary Fe(III) minerals from acid mine drainage

Oxidation of FeS₂ in mine waste releases ${\mathrm{SO}}_4^{2-}$, Fe(II) and H⁺, resulting in acid mine drainage (AMD). Subsequent oxidation and precipitation of Fe produces different Fe(III) phases where the mineralogical composition depends on pH and the ambient concentrations of metal ions and complexing ligands. The oxidation and precipitation of Fe in AMD has been studied under various conditions with the intent of understanding the role these processes play in the natural attenuation of metal contaminants in the AMD. The combined process of Fe oxidation and precipitation in AMD from the Kristineberg mine, northern Sweden, has been investigated with pH-stat experiments at pH 5.5 and 7 at 10 and 25 °C. The precipitates formed have been characterised in terms of mineralogy and surface area. Similar phases formed at both temperatures, while the oxidation and precipitation occurred more readily at the higher temperature and higher pH. At pH 7, mainly lepidocrocite (γ-FeOOH) was precipitated while at a lower pH of 5.5, a mixture of schwertmannite, goethite, ferrihydrite and lepidocrocite formed. The ambient Zn(II) concentration was immediately reduced to acceptable levels (according to Swedish EPA) at pH 7 whereas a 2–3 weeks ageing period was necessary to achieve the same effect at pH 5.5. The presence of natural organic matter (NOM) reduced the attenuating effect at pH 5.5 after ageing but increased it slightly at pH 7. Addition of Zn(II) at pH 8 resulted in a mixed Fe(III)–Zn(II) precipitate of unknown composition with some Zn(II) adsorbed at the surface. The Fe(III) precipitates formed are potentially useful for the natural attenuation of metal contaminants in AMD although based on these investigations, the degree of success depends upon pH and NOM concentration.     

Processes controlling acid attenuation in the unsaturated zone of a Triassic sandstone aquifer (U.K.), in the absence of carbonate minerals

Continuous core samples were taken through the unsaturated zone at three sites on the outcrop of Permo-Triassic sandstone in the British West Midlands. Sample sites were chosen for lack of recent, direct anthropogenic disturbance, and for differing vegetation: heathland, birch woodland and conifer forest. Interstitial water was extracted and analyzed for 32 major and trace elements. Solid phases were analyzed for exchangeable cations and mineralogy. The rate of recharge calculated using a Cl mass balance method was three times greater below heathland than below afforested sites owing to higher evapotranspiration rates in the woodlands.Carbonate minerals were absent from the unsaturated zone at each site. Soil solutions were acidic and soils at the woodland sites were more acidic (pH 4.0) than those at the heathland site (pH 4.5). Acidic interstitial water solutions were found to up to 5.0 m depth in the unsaturated zone and are partially neutralized by two aluminosilicate mineral reactions in the unsaturated zone: cation exchange and K-feldspar dissolution. The rate at which these acid neutralizing reactions act to neutralize acidity is revealed by the rate of depletion of base cations from the unsaturated zone in recharge solutions; K⁺ (dissolution), Ca⁺² + Mg⁺² (cation exchange). The total base cation depletion rate was greatest below heathland; this can be attributed mainly to the greater rate of SO₄ assimilation by the woodland biome.     

Biogeochemical studies of a Native American runoff agroecosystem

Research on soil fertility is presented in the context of runoff agriculture, a venerable farming system that has been used for millennia in arid to semiarid regions, where water is a major limiting resource for crop production. The agroecology of runoff farming was studied with the Zuni to evaluate nutrient and hydrologic processes, management, maize productivity, and soil quality in some of the oldest recognized fields in the United States. This ancient Southwest agriculture has functioned without conventional irrigation or fertilization by tapping into biogeochemical processes in natural watersheds connected to fields. Carefully placed fields are managed on alluvial fans and other valley margin landforms to intercept runoff and associated sediment and organic debris transported from adjoining forested uplands. We report on research to evaluate and link nitrogen and phosphorus, two key nutrients for crop production, in watershed, soil, and crop components of this agroecosystem. Nutrient data have been collected by observational and experimental methods for each component and the transport of nutrients from watershed to field to maize. The condition of Zuni agricultural soils suggests that their knowledge and management of soils contributed to effective conservation. This study and others indicate the need for further long‐term monitoring and experimental research on watersheds, runoff processes, field soils, and crops across a range of arid to semiarid ecosystems. © 2007 Wiley Periodicals, Inc.     

The influence of crystal field stabilization energy on Fe2+ partitioning in paragenetic minerals

In order to explore possible quantitative relations between crystal field stabilization energy, CFSE, and partitioning behaviour of the 3d ⁶-configured Fe²⁺ ion, a suite of 29 paragenetic rock-forming minerals from 12 high-grade metamorphic rock samples of the Ukrainian shield, including the parageneses garnet/orthopyroxene/clinopyroxene (2x), orthopyroxene/clinopyroxene, garnet/clinopyroxene, garnet/orthopyroxene/biotite, garnet/biotite, garnet/cordierite, garnet/cordierite/biotite, garnet/orthopyroxene/clinopyroxene/Ca-amphibole, Ca-amphibole/biotite (retrograde), was studied by electron microprobe analysis to obtain the respective K _D Fe^{2+ (Ph1/Ph2)} values and by polarized single crystal electronic absorption spectroscopy to evaluate the respective CFSE_Fe2+ values. Other than in the case of Cr³⁺, a clear quantitative relation between K _D ^(Ph1/Ph2) and the ΔCFSE^(Ph1/Ph2) was only observed when geometrical factors, mainly the volume of crystallographic sites and ionic radii of ions competing in the partitioning process, are similar in the respective two paragenetic phases to within 15–20%. In such cases, the ΔCFSE_Fe2+ contribution to K _D ^(Ph1/Ph2) amounts to 0.1 to 0.2 log K _D per 100 cm⁻¹ΔCFSE. The conclusion is that ΔCFSE_Fe2+ plays only a secondary role after geometrical factors, in the partitioning behaviour of Fe²⁺. The reason for this is seen in the facts that, compared to the 3d ³-configured Cr³⁺ ion, CFSE of the 3d ⁶-configured Fe²⁺ amounts only to 20–25%, and that the former ion enters only octahedral sites with similar geometrical properties in the paragenetic mineral phases. Received: 17 November 1998 / Accepted: 28 June 1999     

Note on the 57Fe mössbauer spectroscopy of oriented paramagnetic minerals

The theoretical variation law for the (saturation-free) intensity ratio of a paramagnetic doublet is written in a way which allows one to check easily whether or not experimental data which are intended to be fitted by a (saturation-free) theoretical spectrum or subspectrum follow actually this law. The expression of this law is still simplified by taking the absorber symmetries into account. This is illustrated by two examples: a sheet-silicate mosaic and an olivine single-crystal.     

X-ray K-edge absorption spectra of Fe minerals and model compounds: Near-edge structure

Synchrotron radiation has been used to collect high-resolution Fe K absorption near-edge spectra of a suite of Fe minerals and compounds having a range of Fe environments. These spectra, along with those of previous workers, indicate that the number, position, and intensity of near-edge features are characteristic of Fe valence and general site geometry. For example, the crest of the K-edge for Fe²⁺ in a six-coordinated site in the oxides studied is about 3 eV lower in energy than that for Fe³⁺ in a similar site. The K-edge crest for Fe³⁺ in a four-coordinated site is 1 to 2 eV lower than for Fe³⁺ in a regular site. The shape of the edge crest is sensitive to the details of first-neighbor bonding distances, tending to be broader in species with irregular Fe sites and varying in energy according to the average bond length. Comparison with Ca²⁺ and Zn²⁺ spectra from the literature is made and the applicability and utility of edge measurements discussed.     

Local relaxations around Fe3+ and Cr3+ in Al sites in minerals

Second-order zero-field splitting (ZFS) parameters from the literature for Fe³⁺ in twelve and for Cr³⁺ in seven minerals substituting for Al were evaluated by application of the superposition model. For Fe³⁺ in monoclinic site symmetries a fair agreement of the observed splitting patterns with those calculated from the crystal structure data was observed in most cases, but the distortions for Fe³⁺ appear to be usually larger than those of the unrelaxed Al sites. In cases of not too large local relaxation the unknown sign of the axialZFS parameterb ₀ ² could be predicted, in two cases a different sign than that reported was postulated. In cordierite and scolecite the reportedEPR spectra could thus be assigned to the sites with larger average bond distances. For Fe³⁺ in beryl the relaxation of the axial site can be deduced within narrow limits. For Cr³⁺ significantly larger differences between observed and calculatedZFS patterns are found suggesting additional relaxations due to the non-spherical electron distribution in the ground state of this ion.     

Hydrogeology of limited aquifer in a granitic terrain

 Detailed hydrogeological studies in a granitic micro-watershed have been carried out to determine the extent, behavior, and characteristics of the aquifer. The study includes analysis of lithologs, drill time log, pumping tests, and slug tests. Realistic field conditions have been taken into account for characterizing the aquifer system. Slug tests were carried out to estimate aquifer parameters at the wells which could not sustain pumping. Received: 20 November 1997 · Accepted: 23 February 1998     

X-ray K-edge absorption spectra of Fe minerals and model compounds: II. EXAFS

K-edge extended X-ray absorption fine structure (EXAFS) spectra of Fe in varying environments in a suite of well-characterized silicate and oxide minerals were collected using synchrotron radiation and analyzed using single scattering approximation theory to yield nearest neighbor Fe-O distances and coordination numbers. The partial inverse character of synthetic hercynite spinal was verified in this way. Comparison of the results from all samples with structural data from X-ray diffraction crystal structure refinements indicates that EXAFS-derived first neighbor distances are generally accurate to ±0.02 Å using only theoretically generated phase information, and may be improved over this if similar model compounds are used to determine EXAFS phase functions. Coordination numbers are accurate to ±20 percent and can be similarly improved using model compound EXAFS amplitude information. However, in particular cases the EXAFS-derived distances may be shortened, and the coordination number reduced, by the effects of static and thermal disorder or by partial overlap of the longer Fe-O first neighbor distances with second neighbor distances in the EXAFS structure function. In the former case the total information available in the EXAFS is limited by the disorder, while in the latter case more accurate results can in principle be obtained by multiple neighbor EXAFS analysis. The EXAFS and XANES spectra of Fe in Nain, Labrador osumulite and Lakeview, Oregon plagioclase are also analyzed as an example of the application of X-ray absorption spectroscopy to metal ion site occupation determination in minerals.