Hair-biomonitoring assessment of rare-earth-element exposure in residents of the largest rare-earth mining and smelting area of China.

The long-term and large-scale mining of rare earth minerals may lead to an accumulation of rare earth elements (REEs) in the environment, posing potential health risks to residents. We collected scalp hair (n = 254) from residents of a smelting area, a mining area, and a reference area to clarify human exposure to REEs. The contents of 15 REEs investigated in human hair samples were notably higher in the mining and smelting areas than in the reference area. Significant differences between some REEs were observed between the mining and smelting areas, for instance, cerium (Ce), dysprosium, and praseodymium. In the study areas, exposure to different sources of REEs may be one of the factors that contributed to the variations of REE correlations and clusters in human hair. Furthermore, in the smelting area, Ce contents in hair decreased with increasing age of children. However, Ce contents in the hair of adults increased with age. In contrast, Ce accumulation continuously increased in the reference area residents' hair with age. Regression results indicated that age and location were more important than sex when considering the influence on REE accumulation in residents' hair. The results of this study may help policymakers to implement guidelines to alleviate residents' exposure to REE in mining and smelting areas.

Source-specific risk judgement and environmental impact of potentially toxic elements in fine road dust from an integrated industrial city, North China.

The contamination of potentially toxic elements (PTEs) in road dust of large industrial cities is extremely serious. Determining the priority risk control factors of PTE contamination in road dust is critical to enhance the environmental quality of such cities and mitigate the risk of PTE pollution. The Monte Carlo simulation (MCS) method and geographical models were employed to assess the probabilistic pollution levels and eco-health risks of PTEs originating from different sources in fine road dust (FRD) of large industrial cities, and to identify key factors affecting the spatial variability of priority control sources and target PTEs. It was observed that in FRD of Shijiazhuang, a typical large industrial city in China, more than 97% of the samples had an INI > 1 (INImean = 1.8), indicating moderately contaminated with PTEs. The eco-risk was at least considerable (NCRI >160) with more than 98% of the samples, mainly caused by Hg (Ei (mean) = 367.3). The coal-related industrial source (NCRI(mean) = 235.1) contributed 70.9% to the overall eco-risk (NCRI(mean) = 295.5) of source-oriented risks. The non-carcinogenic risk of children and adults are of less importance, but the carcinogenic risk deserves attention. The coal-related industry is a priority control pollution source for human health protection, with As corresponding to the target PTE. The major factors affecting the spatial changes of target PTEs (Hg and As) and coal-related industrial sources were plant distribution, population density, and gross domestic product. The hot spots of coal-related industrial sources in different regions were strongly interfered by various human activities. Our results illustrate spatial changes and key-influencing factors of priority source and target PTEs in Shijiazhuang FRD, which are helpful for environmental protection and control of environmental risks by PTEs.

Distribution of Al, Fe, Si, and DOC between size fractions mobilised from topsoil horizons with progressing degree of podzolisation.

Aluminium, Fe, Si, and dissolved organic C (DOC) accumulate in the subsoil of Podzols after mobilisation in the topsoil. We conducted laboratory experiments with topsoil horizons with progressing degree of podzolisation by irrigation with artificial rainwater at varying intensity and permanence. We monitored the concentrations and distribution of mobilised Al, Fe, Si, and DOC between size fractions (< 1000 Dalton, 1 kDa- < 0.45 µm, and > 0.45 µm). Total eluate concentrations were increased at the onset of the experiments and after the first irrigation interruption, indicating non-equilibrium release. There was no statistical effect of the degree of podzolisation on element concentrations. Release of Al, Fe, and DOC was mostly dominant in the fraction 1 kDa- < 0.45 µm, indicating metals complexed by larger organic molecules and colloids. Silicon released was dominantly monomeric silicic acid < 1 kDa. Particularly with the least podzolised soils, Al and Si concentrations < 1 kDa might have been controlled by short-range ordered aluminosilicates, while their transport in colloidal form was unlikely. Our study pointed to both quantitative and qualitative seasonality of element release during podzolisation, to decoupling of Al and Si release regarding size, and to different minerals that control element release as a function of the degree of podzolisation.

Mobilisation of Al, Fe, and DOM from topsoil during simulated early Podzol development and subsequent DOM adsorption on model minerals.

Podzols are characterised by mobilisation of metals, particularly Al and Fe, and dissolved organic matter (DOM) in topsoil horizons, and by immobilisation in subsoil horizons. We mimicked element mobilisation during early podzolisation by irrigating the AE horizon of a Dystric Arenosol with acetic acid at different flow velocities and applying flow interruptions to study rate-limited release in experiments with soil cylinders. We used eluates in batch experiments with goethite and Al-saturated montmorillonite to investigate DOM reactivity towards minerals. Both the flow velocity and flow interruptions affected element release, pointing to chemical non-equilibrium of release and to particles, containing Fe and OM mobilised at larger flow velocity, characteristic of heavy rain or snowmelt. Based on chemical extractions, the source of mobilised Al and Fe, the vast majority of which was complexed by DOM, was no oxide phase, but rather organic. Rate limitation also affected the composition of DOM released. Carboxyl and phenolic species were the most important species adsorbed by both minerals. However, DOM composition affected the extent of DOM adsorption on goethite more distinctly than that on montmorillonite. Our findings evidence that the intensity of soil percolation affects quantitative and qualitative element release during early podzolisation and adsorptive DOM retention in subsoil horizons.

Does silica addition affect translocation and leaching of cadmium and copper in soil?

Soil and groundwater contamination with potentially toxic elements (PTEs) including cadmium (Cd) and copper (Cu) has become a serious problem for ecosystem functioning. Silicon (Si) may precipitate these metals as silicates, and may also form, at undersaturation of silicates, 'Si-contaminant compounds', i.e. particles of polymerized silica with PTEs incorporated or adsorbed by inner-sphere complexes. While the formation of these compounds in aqueous solution has been proven, their formation in soil remains unclear yet. Therefore, we conducted column experiments with a topsoil horizon artificially contaminated with Cd or Cu solutions (10 mM) in the presence (10 mM) and absence of monomeric Si, and monitored the elemental composition of the eluates during 12 irrigation steps with artificial rainwater by microwave-plasma atomic emission spectrometry, the size and charge of the particles eluted by dynamic light scattering and phase analysis light scattering, and determined the spatial distribution of total and exchangeable Cd and Cu in soil after the experiments. When Si was previously applied to soil, significantly larger particles (up to > 200 nm) in the eluates indicated Si polymerization and formation of Si-contaminant compounds. However, Cd and Cu concentrations were very low (<0.4 µM), pointing to efficient retardation in soil. In any variant, the particles formed were slightly negatively charged (-11 mV). The molar metal:Si ratios in the eluates and significant correlations between the amounts of Si and metals in soil extracted by NH4NO3 pointed to the formation of Si-contaminant compounds, too. More Cu than Cd was retained in soil, and significantly more in the presence of Si, but less Cu than Cd was in exchangeable form. While particularly Cu formed Si-contaminant compounds, which reduced the concentration of Cu ions, the Si-contaminant-compound particles in the eluates remained very small, thus potentially susceptible to particulate export from soil into the groundwater.

Synthesis of short-range ordered aluminosilicates at ambient conditions.

We report here on structure-related aggregation effects of short-range ordered aluminosilicates (SROAS) that have to be considered in the development of synthesis protocols and may be relevant for the properties of SROAS in the environment. We synthesized SROAS of variable composition by neutralizing aqueous aluminium chloride with sodium orthosilicate at ambient temperature and pressure. We determined elemental composition, visualized morphology by microscopic techniques, and resolved mineral structure by solid-state 29Si and 27Al nuclear magnetic resonance and Fourier-transform infrared spectroscopy. Nitrogen sorption revealed substantial surface loss of Al-rich SROAS that resembled proto-imogolite formed in soils and sediments due to aggregation upon freezing. The effect was less pronounced in Si-rich SROAS, indicating a structure-dependent effect on spatial arrangement of mass at the submicron scale. Cryomilling efficiently fractured aggregates but did not change the magnitude of specific surface area. Since accessibility of surface functional groups is a prerequisite for sequestration of substances, elucidating physical and chemical processes of aggregation as a function of composition and crystallinity may improve our understanding of the reactivity of SROAS in the environment.

Formation and properties of inorganic Si-contaminant compounds.

Soil contamination with inorganic contaminants such as lead (Pb), copper (Cu) and cadmium (Cd) is a major environmental issue. Silicon (Si) may reduce the mobility of the contaminants in the environment so that we studied the extent and the mechanisms of the interactions between Pb2+, Cd2+ and Cu2+ and silicic acid during its polymerization. We used tetraethyl orthosilicate as Si source and separately Pb(NO3)2, Cd(NO3)2 or Cu(NO3)2. Selectivity of Si towards the metals was tested in an equimolar solution of all three salts and the polymerizing Si source. Time-dependency of particle growth was examined using dynamic light scattering. Transmission electron microscopy was used for visualizing the particles. We characterized the solid phases by Fourier transform infrared (FTIR) and 29Si nuclear magnetic resonance (NMR) spectroscopy. Polymerized silica bound relative to the initial concentrations (10 mmol L-1) up to 2.1‰ Cd2+, 2‰ Cu2+ and 1.4‰ Pb2+. The FTIR spectra indicated an incorporation of the metals in the polymeric network. 29Si-NMR relaxation experiments showed an accelerating effect of Cu2+ on the 29Si longitudinal relaxation time. It appears that the proportion of the rapidly relaxing components decreases with increasing distance to the surface. This points to a predominant location of Cu centers close to the surface of the Si matrix. Thus, polymerizing silica may contribute to reduced metal mobility in the environment.

Bacterial colonization of minerals in grassland soils is selective and highly dynamic.

Bacteria colonize reactive minerals in soils where they contribute to mineral weathering and transformation. So far, the specificity, patterns and dynamics of mineral colonization have rarely been assessed under natural conditions. High throughput Illumina sequencing was employed to investigate the bacterial communities assembling on illite and goethite during exposure to natural grassland soils. Two different types of organic carbon sources, simple carbon compounds representing root exudates and detritus of two dominant grassland plant species were applied, and their effects on the temporal dynamics of bacterial communities were investigated. The observed temporal patterns suggest that the surfaces of de novo exposed minerals in soils drive the establishment of bacterial communities and override the effect of the type of carbon sources and of other environmental properties. Mineral colonization was selective and specific bacterial sequence variants exhibited distinct colonization patterns, among which early, intermittent, and late colonizers could be distinguished. Based on our results, soil minerals are not only colonized by specific bacterial communities but enable a succession of different bacterial communities. Our results thereby expand the concept of the mineralosphere and provide novel insights into mechanisms of community assembly in the soil ecosystem.

Sulfur-modified organoclay promotes plant uptake and affects geochemical fractionation of mercury in a polluted floodplain soil.

We investigated effects of the application of a sulfur-modified organoclay (SMOC) at doses of 1%, 3% and 5% (w/w) on the geochemical fractionation of mercury (Hg) and its accumulation by pea and corn in a polluted floodplain soil. Soil Hg was fractionated sequentially to five operationally defined fractions as follows: F1: water soluble Hg; F2: "human stomach acid" soluble Hg; F3: organo-chelated Hg; F4: elemental Hg; and F5: Hg-sulfur-compounds/residual Hg. The high dosage of SMOC caused a decrease of Hg in F3 (18%) and F5 (36-63%), and 6.7 fold increase of Hg in the mobile fraction (MF = F1+F2) as compared to control soil. The transformation of Hg from F5 to the MF in SMOC-treated soil might be due to the associated decrease of soil pH. Pea accumulated more Hg than corn. Mercury contents were larger in roots than in shoots of both plants and increased significantly by a factor of up to 11 by SMOC addition. The potential transformation of Hg from the hardly soluble to the MF by SMOC addition and the associated increase of Hg accumulation by plants imply a great potential of the SMOC for enhancing Hg phytoremediation.

Small-scale distribution of copper in a Technosol horizon studied by nano-scale secondary ion mass spectrometry.

RATIONALE: In contaminated soil, copper (Cu) is commonly distributed among various very small particles. To enlighten the qualitative distribution of Cu in a contaminated Technosol (a soil developed from deposited technogenic material) on the sub-micron scale, we used nano-scale secondary ion mass spectrometry (NanoSIMS). METHODS: We studied seven areas (up to 40 µm × 40 µm) on a thin section of a soil horizon by NanoSIMS, measuring 12 C- , 18 O- , 32 S- , 63 Cu- and 56 Fe16 O- . We evaluated the NanoSIMS measurements with a novel digital image processing tool to enlighten the composition of measured areas and thus the distribution of Cu at the sub-micron scale. Image processing comprised spatial and spectral smoothing, normalization, endmember extraction and supervised classification. RESULTS: Copper was present in all areas studied on the thin section in hotspots. 63 Cu- was never the ion with the highest number of mean-normalized counts (MNCs). In classes indicating Cu accumulation, Fe or S had the highest MNCs with mostly small values for O, pointing to the presence of Cu in sulfides. Copper adsorbed on Fe oxides was also indicated. Direct interaction of Cu with organic matter was less important. Copper-containing minerals were rather adjacent to or surrounded by an organic matrix. CONCLUSIONS: The combination of NanoSIMS analyses with digital image processing gave us new insights into the distribution of Cu in contaminated soil. We suggest this combination as a new powerful tool for the identification of ionic contaminants in soil and other solid phases in the environment.

Modelling the potential mobility of Cd, Cu, Ni, Pb and Zn in Mollic Fluvisols.

European floodplain soils are frequently contaminated with potentially toxic inorganic substances. We used a multi-surface model to estimate the aqueous concentrations of Cd, Cu, Ni, Pb and Zn in three Mollic Fluvisols from the Central Elbe River (Germany). The model considered complexation in solution and interactions with soil organic matter (SOM), a clay mineral and hydrous Al, Fe and Mn oxides. The amounts of reactive metals were derived from extraction with 0.43 M HNO3. Modelling was carried out as a function of pH (soil pH ± 1.4) because it varies in floodplain soils owing to redox processes that consume or release protons. The fraction of reactive metals, which were dissolved according to the modelling, was predominantly <1%. Depending on soil properties, especially pH and contents of SOM and minerals of the clay fraction, the modelled concentrations partially exceeded the trigger values for the soil-groundwater pathway of the German soil legislation. This differentiation by soil properties was given for Ni, Pb and Zn. On the other hand, Cd was more mobile, i.e., the trigger values were mostly exceeded. Copper represented the opposite, as the modelling did not predict exceeding the trigger values in any horizon. Except for Pb and partially Zn (where oxides were more important), SOM was the most important adsorbent for metals. However, given the special composition and dynamics of SOM in mollic horizons, we suggest further quantitative and qualitative investigations on SOM and on its interaction with metals to improve the prediction of contaminant dynamics.

Modelling the concentrations of dissolved contaminants (Cd, Cu, Ni, Pb, Zn) in floodplain soils.

Central European floodplain soils are often contaminated with potentially toxic metals. The prediction of their aqueous concentrations is a prerequisite for an assessment of environmental concerns. We tested the aqueous concentrations of cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn) derived from multi-surface adsorption modelling (on hydrous iron, aluminum and manganese oxides, clay and soil organic matter) against those analyzed in situ in the soil solution of four horizons of floodplain soils at the Elbe River, Germany. The input data for the reactive metals were derived from a seven-step sequential extraction scheme or from extraction with 0.43 M nitric acid (HNO3) and evaluated in four modelling scenarios. In all scenarios, measured and modelled concentrations were positively related, except partially for Pb. Close reproduction of the measured data was obtained using measured data of accompanying cations and anions together with amounts of reactive metals from both the sequential extraction or from 0.43 M HNO3 extraction, except for Cu, which was often strongly overestimated, and partially Cd. We recommend extraction with 0.43 M HNO3 to quantify reactive metals in soil because the modelling results were metal-specific with better or equal results using the single extractant, the application of which is also less laborious. Approximations of ion concentrations and water contents yielded similar results. Modelled solid-phase speciation of metals varied with pH and differed from that from sequential extraction. Multi-surface modelling may be an effective tool to predict both aqueous concentrations and solid-phase speciation of metals in soil.

Exploiting biogeochemical and spectroscopic techniques to assess the geochemical distribution and release dynamics of chromium and lead in a contaminated floodplain soil.

Scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDX) combined with a seven steps sequential extraction technique were used to assess the geochemical distribution of chromium (Cr) and lead (Pb) in a contaminated floodplain soil. Total contents of Cr and Pb were 490.3 and 402.1 mg kg(-1), respectively. The residual fraction was 59.5 and 56.3% of total Cr and Pb. The crystalline iron (Fe) oxide was the dominant non-residual fraction of Cr (35.9% of total Cr). Considerable amounts of Pb were found in the organic fraction (35.4%). Using (13)C nuclear magnetic resonance spectroscopy, the soil organic matter was identified as 48.9% aromatic carbon, which indicated that a certain portion of Pb and Cr might be associated with aromatic compounds. The SEM-EDX images demonstrate a concomitant occurrence of Pb, manganese (Mn), Fe, and aluminum (Al) as well as a coexistence of Cr and Fe. The release dynamics of dissolved Cr and Pb as affected by redox potential (EH), pH, Fe, Mn, dissolved organic carbon, and sulfate was quantified using an automated biogeochemical microcosm apparatus. Soil pH decreased under oxic conditions. The release of Cr, Pb, Fe, and Mn increased under acidic oxic (pH = 3.7, EH = 521 mV) conditions due to the associated decrease of pH (7.1-3.7). The mobilization of Cr and Pb was affected by the Fe and Mn. In conclusion, our multi-technique approach identified the geochemical distribution of Cr and Pb and verified major factors that explain mobilization of Cr and Pb in floodplain soils.

Novel Sample Preparation Technique To Improve Spectromicroscopic Analyses of Micrometer-Sized Particles.

Microscale processes occurring at biogeochemical interfaces in soils and sediments have fundamental impacts on phenomena at larger scales. To obtain the organo-mineral associations necessary for the study of biogeochemical interfaces, bulk samples are usually fractionated into microaggregates or micrometer-sized single particles. Such fine-grained mineral particles are often prepared for nanoscale secondary ion mass spectroscopy (NanoSIMS) investigations by depositing them on a carrier. This introduces topographic differences, which can strongly affect local sputtering efficiencies. Embedding in resin causes undesired C impurities. We present a novel method for preparing polished cross-sections of micrometer-sized primary soil particles that overcomes the problems of topography and C contamination. The particles are coated with a marker layer, embedded, and well-polished. The interpretation of NanoSIMS data is assisted by energy-dispersive X-ray spectroscopy on cross-sections prepared by a focused ion beam. In the cross-sections, organic assemblages on the primary soil particles become visible. This novel method significantly improves the quality of NanoSIMS measurements on grainy mineral samples, enabling better characterization of soil biogeochemical interfaces. In addition, this sample preparation technique may also improve results from other (spectro-) microscopic techniques.

Synthesis of cryptomelane- and birnessite-type manganese oxides at ambient pressure and temperature.

Cryptomelane-type octahedral molecular sieves (K-OMS-2) were successfully synthesized at ambient pressure and temperature by a simple one-step reaction pathway. We designed three synthesis mixes based on redox reactions of either MnSO4 or MnCl2 together with KMnO4 in aqueous solution. The synthesis products were characterized structurally (XRD, FTIR spectroscopy), morphologically (SEM, BET surface area), and chemically (SEM-EDX, ICP-OES). For all mixes, a precursor octahedral layered K-birnessite (K-OL-1) was formed after 1d that subsequently transformed into K-OMS-2. This transformation process depends on the pH of the reaction solution, the respective Mn(II) salt and time. We obtained K-OMS-2 materials with BET surface areas between 50.4 and 104.5 m(2) g(-1) and different crystallinities. The described method is reliable, reproducible, easy to handle and may be the basis to produce well defined Mn oxides that could be used for remediation and catalysis purposes.

Kinetic control of contaminant release from NAPLs--experimental evidence.

Mass transfer processes of pollutants from non-aqueous phase liquids (NAPL) may control groundwater pollution at abandoned industrial sites. We studied release kinetics of polycyclic aromatic hydrocarbons (PAHs) from fresh and aged tar phases using a dialysis tubing technique. Time for equilibration ranged from several days to more than three years. For fresh tar materials the release seems to be limited by retarded pore diffusion, while for two of three aged tars diffusion limited release influenced by dissolved organic matter (DOM) was assumed. The equilibration process was driven by solubilization thermodynamics expressed by Raoult's law. Yet, solubility enhancement was observed potentially due to the presence of organic mobile sorbents. The results show that the release of PAHs from tar phases is generally rate limited and partitioning according to Raoult's law is the driving mechanism of the exchanges process.

Arsenic strongly associates with ferrihydrite colloids formed in a soil effluent.

Arsenic mobility may increase in liquid phase due to association with colloidal Fe oxides. We studied the association of As with Fe oxide colloids in the effluent from water-saturated soil columns run under anoxic conditions. Upon exfiltration, the solutions, which contained Fe2+, were re-aerated and ferrihydrite colloids precipitated. The entire amount of effluent As was associated with the ferrihydrite colloids, although PO4(3-), SiO4(4-), CO3(2-) and dissolved organic matter were present in the effluent during ferrihydrite colloid formation. Furthermore, no subsequent release of As from the ferrihydrite colloids was observed despite the presence of these (in)organic species known to compete with As for adsorption on Fe oxides. Arsenic was bound via inner-sphere complexation on the ferrihydrite surface. FTIR spectroscopy also revealed adsorption of PO4(3-) and polymerized silica. However, these species could not impede the quantitative association of As with colloidal ferrihydrite in the soil effluents.

Fractionation of organic matter due to reaction with ferrihydrite: coprecipitation versus adsorption.

In soil and water, ferrihydrite frequently forms in the presence of dissolved organic matter. This disturbs crystal growth and gives rise to coprecipitation of ferrihydrite and organic matter. To compare the chemical fractionation of organic matter during coprecipitation with the fractionation involved in adsorption onto pristine ferrihydrite surfaces we prepared ferrihydrite-organic matter associations by adsorption and coprecipitation using (i) a forest-floor extract or (ii) a sulfonated lignin. The reaction products were studied by (13)C CPMAS NMR, FTIR, and analysis of hydrolyzable neutral polysaccharides. Relative to the original forest-floor extract, the ferrihydrite-associated organic matter was enriched in polysaccharides, especially when adsorption took place. Moreover, mannose and glucose were bound preferentially to ferrihydrite, while fucose, arabinose, xylose, and galactose accumulated in the supernatant. This fractionation of sugar monomers was more pronounced during coprecipitation and led to an enhanced ratio of (galactose + mannose)/(arabinose + xylose). Experiments with lignin revealed that the ferrihydrite-associated material was enriched in its aromatic components but had a lower ratio of phenolic C to aromatic C than the original lignin. A compositional difference between the adsorbed and coprecipitated lignin is obvious from a higher contribution of methoxy C in the coprecipitated material. Coprecipitated organic matter may thus differ in amount and composition from adsorbed organic matter.

Identification of iron-cyanide complexes in contaminated soils and wastes by Fourier transform infrared spectroscopy.

Persistent cyanide species in soil are mainly iron-cyanide (Fe-CN) complexes. They originate from anthropogenic inputs of compounds such as Fe4[Fe(II)(CN)6]3 in deposited gas-purifier wastes (GPW) or K2Zn3[Fe(II)(CN)6]2 in deposited blast-furnace sludge (BFSI). Fe-CN species in de-inking sludge (DIS) and sewage farm soils (SF) are still unknown. We investigated 35 soil and waste samples from 15 European sites and five synthesized Fe-CN-containing compounds by Fourier transform infrared spectroscopy. Furthermore, we determined the contents of total and adsorbed CN and pH. In all samples (pH 2.2-9.5), adsorbed Fe-CN complexes were negligible. In GPW and DIS samples, Fe4[Fe(II)(CN)6]3 and KFe[FeII(CN)6] were the only Fe-CN compounds (total CN contents 0.4-449 g kg(-1)). Several BFSI samples were free of CN. The spectra of other BFSI samples partially indicated dissolution of the characteristic compound K2Zn3[Fe(II)(CN)6]2, resulting in a loss of CN (contents < 12.3 g kg(-1)). Distinctive changes in BFSI with respect to CN speciation occurred within relatively short periods, <20 years. Dissolution of K2Zn3[Fe(II)(CN)6]2 was followed by dissociation of free CN from [Fe(CN)6](3-/4-) and adsorption of [Fe(II)(CN)6](4-) on organic surfaces. In DIS and SF samples, Fe4[Fe(11)(CN)6]3 and K2Zn3[Fe(II)(CN)6]2 (SF only) were identified.

Oxidation of ferrocyanide by birnessite.

The Fe-CN complexes ferrocyanide, [FeII(CN)6]4-, and ferricyanide, [FeIII(CN)6]3-, which are contaminants in soil and groundwater, form a redox couple, [FeII(CN)6]4- <==> [FeIII(CN)6]3- + e-, E(H) = 356 mV. We studied the oxidation of [FeII(CN)6]4- by birnessite, delta-MnIVO2, in batch experiments as influenced by [FeII(CN)6]4- concentration, pH, and reaction time. Additionally, stopped-flow experiments were carried out at five temperatures (10-30 degrees C) and four pH values (pH 4.1-5.3). In the batch experiments, [FeII(CN)6]4- was completely oxidized to [FeIII(CN)6]3-, and oxidation did neither depend on time for t > 2 min, nor on concentration (0.12-0.47 mM), nor on pH (pH 3.3-9.9). Lasting adsorption of Fe-CN complexes on the birnessite surface or precipitation of manganese ferricyanide were not detected. Manganous ions resulting from the reductive dissolution of birnessite did not precipitate as manganese oxide because an identical decrease of Mn solution concentrations was observed under air and under a N2 atmosphere. Two processes were detected by the stopped-flow experiments. The first rapid one with an activation energy of approximately 60 kJ mol(-1) was attributed to short-term adsorption and simultaneous oxidation of [FeII(CN)6]4- on the birnessite surface. The second slower process with an activation energy of approximately 20 kJ mol(-1) was attributed most probably to diffusion of the reaction product Mn2+ into the interior of the birnessite, which creates fresh reaction sites at the outer surface.