Kinetics of redox cycling of iron coupled with fulvic acid

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.     

武汉东湖沉积物中酸挥发性硫化物(AVS)的深度分布及其影响因素

提要沉积物中酸挥发性硫化物(AVS)是硫化物的生成、氧化和扩散等综合作用的反映,有机物的供给、硫酸盐的还原等因素都能影响其分布特征。本文对武汉东湖三个污染程度不同站点的AVS深度分布特征进行了研究,结果表明,AVS含量在一定深度沉积物中具有最大值,东湖沉积物中AVS的深度分布具有两种不同的模式,Ⅰ站和Ⅱ站AVS浓度峰在5cm左右的表层沉积物中,且AVS还原层深度较狭窄,而Ⅲ站AVS浓度峰处于10-20cm深度范围,沉积物中有机质负荷的差异是导致这种分布特征的重要原因。沉积物中有机质含量对AVS的深度分布具有重要影响,高有机质负荷导致AVS浓度峰向表层迁移,且AVS还原层分布于较狭窄的深度范围,对方涛等对流-扩散模型的应用表明,该模型在高有机质负荷沉积物中(Ⅰ、Ⅱ站)AVS深度分布的应用较为理想,然而低有机质负荷沉积物中(Ⅲ站)不能准确反映AVS的深度分布特征,说明其应用范围具有一定的局限性。     

The role of sediments in the phosphorus cycle in Lake Lugano. II. Seasonal and spatial variability of microbiological processes at the sediment-water interface

P, Fe, Mn, and S species were analyzed in water samples from the sediment-water interface collected at four seasonally different times during the course of a year at two sampling sites in the southern basin of Lake Lugano (Lago di Lugano). The results reveal the strong influence of the biogeochemical processes in the sediment on the chemical composition of the lake water above. Consumption of oxygen and nitrate under oxic to microoxic conditions in the water column as well as sequential release of reduced manganese and iron under anoxic conditions was observed as a direct or indirect consequence of microbially mediated degradation of organic matter. The seasonal pattern observed for the release and the retainment of dissolved reduced iron and manganese correlates well with the one for dissolved phosphate. Iron, manganese and phosphorus cycling are coupled tightly in these sediments. Both sediment types act as sinks for hydrogen sulfide and sulfate. An inner-sedimentary sulfur cycle is proposed to couple iron, manganese and phosphorus cycling with the degradation of organic matter. Nutrient cycling at the sediment-water interface might thus be driven by a microbially regulated electron pumping mechanism. The results contribute to a better understanding of the role of sediment processes in the lake's internal phosphorus cycle and its seasonal dynamics.     

Bildungsbedingungen von Zinkferriten im Hinblick auf die Entfernung von Schwermetallen aus Abwässern durch Magnetseparation

Conditions of the Formation of Zinc-bearing Ferrites in Regard of Heavy Metal Removal from Wastewater by Magnetic Separation Magnetic separation techniques can be applied for heavy metal removal from wastewater if it is reached to link together the heavy metals with a substance which is sufficiently influenced by a magnetic field. Such a substance is the ferrimagnetic magnetite which can be prepared under special conditions – by oxidation of ferrous hydroxide – in wastewater. In this paper, zinc was chosen as an example for technically relevant, diamagnetic heavy metals. The investigations deal with the influence of zinc onto the structure and the magnetic properties of the reaction products produced by oxidation of zink-bearing ferrous hydroxide in aqueous solutions at room temperature. The oxidation was caused by synthetic air passing through the suspension. During the reaction, the parameters pH value, redox potential, and concentration of dissolved oxygen were observed continuously. The plots of these parameters versus time yield typical courses which can be used as measurement for the progress of the reaction. The results show that magnet ite can only be prepared if the molar ferrous concentration at the beginning is four times higher than the concentration of the dissolved oxygen. Furthermore, the oxidation rate must be slow, a condition which could be achieved by mass transfer controlled kinetics. The products of the oxidation of zinc-bearing ferrous hydroxide show a colour between black and brown. They consist of magnetite, zinc-bearing ferrite and amorphous iron hydroxide. It can be observed that with increasing initial zinc concentrations, increasing amounts of zinc-bearing ferrite but also of amorphous iron hydroxide are produced. Therefore, it seems that the impact of zinc on the reaction is in such a way that more amorphous compounds instead of the thermodynamically stabile ferrite are formed; The magnetic properties show also a dependence on the initial zinc concentration: The saturation magnetization decreases with an increase of the zinc concentration. The reaction product which results from the experiment with an initial mole ratio of Zn:Fe = 1:1 points out only paramagnetic behaviour.     

Estimation of internal nutrient release in large shallow Lake Taihu, China

Based on field investigation of wave, sediment suspension and the changes in nutrient concentration of the water column in Lake Taihu, China, we proposed two release models to quantify nutrient release under static and dynamic conditions, respectively. Under static conditions, nutrient release from sediments to the overlying water mainly depends on chemical diffusion induced by concentration gradient, in which the nutrient release is controlled by the temperature, dissolved oxygen concentration in the sediment-water interface, oxidation-reduction potential and the concentration difference between porewater and overlying water. Under dynamic condition (or disturbed condition), both dissolved and particulate nutrients in sediments are released into the water column because of wind-induced sediment suspension. The amount of nutrient release under dynamic conditions is larger than that under the static condition. The release of dissolved nutrients, however, does not increase because the wind induced turbulence made oxidation of metallic elements such as Fe (ferric iron), Mn which are capable of precipitating soluble reactive phosphate (SRP). Under dynamic conditions, therefore, the release of total phosphorus (TP) increases dramatically but the release of SRP is close to those under static conditions. In sediments of Lake Taihu, high Fe content leads to a high ratio of Fe to P contents in sediments (Fe:P ratio). Under dynamic conditions, therefore, nutrient release is controlled by the intensity of disturbance, sediment consolidation and nutrient content in sediments. As for dissolved nutrients, especially SRP, the release is also controlled by the intensity of dynamic re-oxidation, Fe content in sediments and nutrient concentration gradient between porewater and overlying water. Based on these two release modes, the release flux in Lake Taihu has been estimated. In the static condition (i.e. laboratory experimental condition), total release of NH4 -N for whole lake is ca. 10,000 ton/a, and PO43--P is ca. 900 ton/a. In the dynamic condition, nutrient release following sediment suspension was estimated according to three different intensities of wind forcing which were defined as "calm" (wind speed is less than 2 m/s), "gentle" (wind speed is greater than 2 m/s and less than 6 m/s) and "gust" (wind speed is greater than 6 m/s). The release rate in the condition of "calm" was estimated in terms of the nutrient release in the laboratory experimental static condition; whereas the release rate in conditions of "gentle" and "gust" was estimated in terms of measurement during sediment resuspension conducted in flume experiments. With the observation of wind velocity and frequency in 2001, each type of wind forcing took the frequency of 12%, 82% and 6% for "calm", "gentle" and "gust", respectively. The yearly release of nitrogen was 81,000 ton and phos- phorus was 21,000 ton, which is about 2-6 folds of annual external loading, respectively.     

Stability of arsenopyrite and As(III) in low-temperature acidic solutions

Arsenopyrite is one of the most important pri-mary arsenic mineral. In the Eh-pH diagram of the As-O2-S-H2O system, if the total arsenic concentration (TAs) is taken to be 0.75 mg/L, the total sulfur con-centration, 32 mg/L, the temperature, 25℃and the pressure, one atmosphere pressure for the discrimina-tion of arsenic species, it may be found that under hy-pergene conditions, arsenopyrite is a moderately stable mineral. Only in the strongly alkaline and reducing environment can arsenopy…     

Microbial iron reduction during passive in situ remediation of an acidic mine pit lake mesocosm

Ferric iron reduction was studied in a pilot-scale enclosure experiment for passive biological remediation of an acidic mine pit lake in Lusatia, Germany. The metabolic properties of prokaryotes involved in Fe(III) reduction may be important for the outcome of biological remediation, as chemolithotrophic Fe(III) reduction can counteract the desired pH increase, but heterotrophic Fe(III) reduction will provide the necessary Fe(II) for precipitation of sulfide minerals following sulfate reduction. Therefore, vertical profiles of sediment parameters related to iron and sulfur cycling were determined in conjunction with viable counts of different ferric iron-reducing micro-organisms using selective media. Findings were compared to an untreated reference site. The addition of organic matter stimulated ferric iron reduction and sulfate reduction in the enclosure and led to elevated pH and accumulations of ferrous iron and reduced sulfur compounds. Numbers of neutrophilic heterotrophic Fe(III) reducers increased during treatment, those of acidophilic heterotrophic Fe(III) reducers remained similar, and those of acidophilic chemolithotrophic Fe(III) reducers decreased. Zones of ferric iron-reducing activity corresponded well with microbial depth profiles; however, viable counts of neutrophilic or acid-tolerant Fe(III) reducers must have been underestimated based on the corresponding observed activity levels. Ferric iron reduction by chemolithotrophic acidophiles seemed to be of minor importance, so a lowering of pH values due to Fe(III) reducing activity is unlikely.     

Flood effects on phosphorus immobilisation in a river water filled pit lake—Case study Lake Goitsche (Germany)

Between 1999 and 2002, a former open-cast mine was filled with river water forming the recent Lake Goitsche. During filling initially acid water was neutralised. Phosphorus (P) imported from Mulde River was nearly completely removed from the water column by co-precipitation with iron (Fe) and aluminium (Al) and deposited in the sediment.During extremely high waters of the Mulde River in 2002, a dike breach facilitated a second high import of P into Lake Goitsche with suspended and dissolved matter. The analysis of total phosphorus (TP), however, showed that P again had been eliminated from the water body a few months after the flood event. Sediment investigations before filling with river water, during filling, and after the flood event were used to analyse the process of P immobilisation in a lake with acid mine drainage history.The ratios of Fe to soluble reactive P (SRP) of sediment pore water were up to three orders of magnitudes higher than in natural lakes and can serve as an indicator for potential internal P loading from sediments. The SRP concentrations at the oxic/anoxic boundary were near or below the limit of quantification (< 0.2 μmol/L). Fe and manganese (Mn) redox cycling were responsible for hindering P dissolution from sediment to lake water.Finally it can be stated, that the risk of eutrophication for such a lake seems to be low.     

Diel changes in metal concentrations in a geogenically acidic river: Rio Agrio,Argentina

Rio Agrio in Patagonia, Argentina is a geogenically acidic stream that derives its low-pH waters from condensation of acidic gases near its headwaters on the flanks of the active Copahue Volcano. This study reports the results of three diel (24-h) water samplings in three different pH regimes (3.2, 4.4 and 6.3) along the river. Changes in the concentration and speciation of Fe dominated the diel chemical changes at all three sites, although the timing and intensity of these cycles were different in each reach. At the two acidic sampling sites, total dissolved Fe and dissolved Fe(III) concentrations decreased during the day and increased at night, whereas dissolved Fe(II) showed the reverse pattern. These cycles are explained by Fe(III) photoreduction, as well as enhanced rates of precipitation of hydrous ferric oxide (HFO) during the warm afternoon hours. A strong correlation was observed between Fe(III) and As at the furthest upstream (pH 3.2) site, most likely due to co-precipitation of As with HFO. At the downstream (pH 6.3) location, Fe(II) concentrations increased at night, as did concentrations of rare earth elements and dissolved Al. Photoreduction does not appear to be an important process at pH 6.3, although it may be indirectly responsible for the observed diel cycle of Fe(II) due to advection of photochemically produced Fe(II) from acidic upstream waters.     

Estimation of internal nutrient release in large shallow Lake Taihu,China

Based on field investigation of wave, sediment suspension and the changes in nutrient concentration of the water column in Lake Taihu, China, we proposed two release models to quantify nutrient release under static and dynamic conditions, respectively. Under static conditions, nutrient release from sediments to the overlying water mainly depends on chemical diffusion induced by concentration gradient, in which the nutrient release is controlled by the temperature, dissolved oxygen concentration in the sediment-water interface, oxidation-reduction potential and the concentration difference between porewater and overlying water. Under dynamic condition (or disturbed condition), both dissolved and particulate nutrients in sediments are released into the water column because of wind-induced sediment suspension. The amount of nutrient release under dynamic conditions is larger than that under the static condition. The release of dissolved nutrients, however, does not increase because the wind induced turbulence made oxidation of metallic elements such as Fe (ferric iron), Mn which are capable of precipitating soluble reactive phosphate (SRP). Under dynamic conditions, therefore, the release of total phosphorus (TP) increases dramatically but the release of SRP is close to those under static conditions. In sediments of Lake Taihu, high Fe content leads to a high ratio of Fe to P contents in sediments (Fe:P ratio). Under dynamic conditions, therefore, nutrient release is controlled by the intensity of disturbance, sediment consolidation and nutrient content in sediments. As for dissolved nutrients, especially SRP, the release is also controlled by the intensity of dynamic re-oxidation, Fe content in sediments and nutrient concentration gradient between porewater and overlying water. Based on these two release modes, the release flux in Lake Taihu has been estimated. In the static condition (i.e. laboratory experimental condition), total release of NH₄ ⁺-N for whole lake is ca. 10,000 ton/a, and PO₄ ^3?-P is ca. 900 ton/a. In the dynamic condition, nutrient release following sediment suspension was estimated according to three different intensities of wind forcing which were defined as “calm” (wind speed is less than 2 m/s), “gentle” (wind speed is greater than 2 m/s and less than 6 m/s) and “gust” (wind speed is greater than 6 m/s). The release rate in the condition of “calm” was estimated in terms of the nutrient release in the laboratory experimental static condition; whereas the release rate in conditions of “gentle” and “gust” was estimated in terms of measurement during sediment resuspension conducted in flume experiments. With the observation of wind velocity and frequency in 2001, each type of wind forcing took the frequency of 12%, 82% and 6% for “calm”, “gentle” and “gust”, respectively. The yearly release of nitrogen was 81,000 ton and phosphorus was 21,000 ton, which is about 2–6 folds of annual external loading, respectively.     

From surface acidity to surface reactivity; inhibition of oxide dissolution

Paul Schindler's early work on the acid-base chemistry of oxides was instrumental for the development of the concept of surface complexation. This approach has not only been important in establishing a theory on the adsorption of metal ions and ligands as a function of pH and solution variables, but has become essential in establishing surface speciation (coordinative structural and electronic arrangement at the solidwater interface) which in turn determines surface reactivity. The factors that affect dissolution of Fe(III) (hydr)oxides and inhibition of dissolution are discussed. A few examples for the inhibition of reductive and ligand-promoted dissolution by binuclear complexes of oxoanions (phosphate, borate) and of protonpromoted dissolution by Cr(III) are given.     

The solubility of iron sulphides in synthetic and natural waters at ambient temperature

A critical evaluation of literature values for the solubility products, K _sp ^NBS = [Fe²⁺][HS^–] Fe²⁺ HS^– (H _NBS ⁺ )^–1, of various iron sulphide phases results in consensus values for the pKs of 2.95 ± 0.1 for amorphous ferrous sulphide, 3.6 ± 0.2 for mackinawite, 4.4 ± 0.1 for greigite, 5.1 ± 0.1 for pyrrhotite, 5.25 ± 0.2 for troilite and 16.4 ± 1.2 for pyrite.Where the analogous ion activity products have been measured in anoxic freshwaters in which there is evidence for the presence of solid phase FeS, the values lie within the range of 2.6–3.22, indicating that amorphous iron sulphide is the controlling phase. The single value for a groundwater of 2.65 (2.98 considering carbonate complexation) agrees. In seawater four values range between 3.85 to 4.2, indicating that mackinawite or greigite may be the controlling phase. The single low value of 2.94 is in a situation where particularly high fluxes of Fe (II) and S (–II) may result in the preferential precipitation of amorphous iron sulphide. Formation of framboidal pyrite in these sulphidic environments may occur in micro-niches and does not appear to influence bulk concentrations. Calculations show that the formation of Fe₂S₂ species probably accounts for very little of the iron or sulphide in most natural waters. Previously reported stability constants for the formation of Fe (HS)₂ and (Fe (HS)₃)^– are shown to be suspect, and these species are also thought to be negligible in natural waters. In completely anoxic pore waters polysulphides also have a negligible effect on speciation, but in tidal sediments they may reach appreciable concentrations and lead to the direct formation of pyrite. Concentrations of iron and sulphide in pore waters can be controlled by the more soluble iron sulphide phase. The change in the IAP with depth within the sediment may reflect ageing of the solid phase or a greater flux of Fe (II) and S (–II) nearer the sediment surface. This possible kinetic influence on the value of IAPs has implications for their use in geochemical studies involving phase formation.     

Contributions of phosphatase and microbial activity to internal phosphorus loading and their relation to lake eutrophication

Phosphatase may accelerate the process of lake eutrophication through improving phosphorus bioavailability. This mechanism was studied in three Chinese eutrophic shallow lakes (Lake Taihu, Lake Longyang and Lake Lianhua). Phosphatase activity was related to the concentration of soluble reactive phosphorus (SRP) and chlorophyll a. Stability of dissolved phosphatase in reverse micelles may be attributed to molecular size, conformation and active residues of the enzyme. At the site with Microcystis bloomed in Lake Taihu, dissolved phosphatase activity was higher and more stable in micelles, SRP concentrations were lower in interstitial water, the contents of different forms of phosphorus and the amounts of aerobic bacteria were lower while respiration efficiency was higher in sediments. Phosphobacteria, both inorganic and organic and other microorganisms were abundant in surface water but rare in sediments. Therefore, internal phosphorus may substantially flux into water column by enzymatic hydrolysis and anaerobic release, together with mobility of bacteria, thereby initiating the bloom. In short, biological mechanism may act in concert with physical and chemical factors to drive the internal phosphorus release and accelerate lake eutrophication.     

Genesis of arsenic in groundwater of North Bengal Plain using PCA: A case study of English Bazar Block,Malda District,West Bengal,India

The study area is located on the western part of the alluvium‐filled gap between the Rajmahal hills on the west and the Garo hills on the east. Groundwater occurs under unconfined condition in a thick zone of saturation within the Quaternary alluvial sediments. Three hydrochemical facies with distinct characteristics have been identified which are dominated in general by alkaline earths and weak acids. The major‐ion chemistry of the area is controlled by weathering of silicate minerals, rainfall recharge, ion‐exchange processes and anthropogenic activities such as irrigation return flow and the application of inorganic fertilizers and pesticides. A stoichiometric approach suggests that mineral dissolution and anthropogenic activities contribute 79% and 21% of the total cations dissolved in groundwater. Principal component analysis (PCA) of 42 groundwater samples using 13 chemical parameters indicates that the combined processes of recharge of groundwater from rainfall, sediment water interaction, groundwater flow, infiltration of irrigation return water (which is arsenic rich due to the use of arsenic‐bearing pesticides, wood preservatives, etc. and the pumping of arsenic‐rich groundwater for agriculture purpose), oxidation of natural or anthropogenic organic matter and the reductive dissolution of ferric iron and manganese oxides play a key role in the evolution of groundwater in the study area. Factor 2 scores, associated with the infiltration of irrigation return water and spatial distribution of arsenic concentration reveal that the groundwater of the municipal area will not be affected by arsenic in the future in spite of heavy groundwater abstraction. Another PCA with geologic, geomorphic, anthropogenic, geochemical and landuse factors indicates that arsenic concentration in groundwater increases with increasing area of mango orchards, sand lithofacies and nitrate and decreases with increasing distance of paleochannel from the monitored well and depth of bore wells. High loading on nitrate may be attributed to the use of fertilizer, pesticides, etc. in mango orchards and agricultural land. High loadings on log pCO₂, mango orchards (with negative sign) and phosphate (with positive sign) indicate that mango orchards provide the organic waste material which is decomposed to form organic carbon. The organic carbon undergoes oxidative carbon degeneration by different oxidants and increases the concentration of CO₂ in the aquifer. The reducing condition thus developed in the aquifer helps to dissolve the arsenic adsorbed on iron hydroxide or oxy‐hydroxide coated margins of sand, iron rich heavy mineral grain margins, clay minerals and Fe–Mn concretions present in the aquifer matrix. Copyright © 2007 John Wiley & Sons, Ltd.     

Estimation of internal nutrient release in large shallow Lake Taihu,China

Based on field investigation of wave, sediment suspension and the changes in nutrient concentration of the water column in Lake Taihu, China, we proposed two release models to quantify nutrient release under static and dynamic conditions, respectively. Under static conditions, nutrient release from sediments to the overlying water mainly depends on chemical diffusion induced by concentration gradient, in which the nutrient release is controlled by the temperature, dissolved oxygen concentration in the sediment-water interface, oxidation-reduction potential and the concentration difference between porewater and overlying water. Under dynamic condition (or disturbed condition), both dissolved and particulate nutrients in sediments are released into the water column because of wind-induced sediment suspension. The amount of nutrient release under dynamic conditions is larger than that under the static condition. The release of dissolved nutrients, however, does not increase because the wind induced turbulence made oxidation of metallic elements such as Fe (ferric iron), Mn which are capable of precipitating soluble reactive phosphate (SRP). Under dynamic conditions, therefore, the release of total phosphorus (TP) increases dramatically but the release of SRP is close to those under static conditions. In sediments of Lake Taihu, high Fe content leads to a high ratio of Fe to P contents in sediments (Fe:P ratio). Under dynamic conditions, therefore, nutrient release is controlled by the intensity of disturbance, sediment consolidation and nutrient content in sediments. As for dissolved nutrients, especially SRP, the release is also controlled by the intensity of dynamic re-oxidation, Fe content in sediments and nutrient concentration gradient between porewater and overlying water. Based on these two release modes, the release flux in Lake Taihu has been estimated. In the static condition (i.e. laboratory experimental condition), total release of NH₄ ⁺-N for whole lake is ca. 10,000 ton/a, and PO₄ ³⁻-P is ca. 900 ton/a. In the dynamic condition, nutrient release following sediment suspension was estimated according to three different intensities of wind forcing which were defined as “calm” (wind speed is less than 2 m/s), “gentle” (wind speed is greater than 2 m/s and less than 6 m/s) and “gust” (wind speed is greater than 6 m/s). The release rate in the condition of “calm” was estimated in terms of the nutrient release in the laboratory experimental static condition; whereas the release rate in conditions of “gentle” and “gust” was estimated in terms of measurement during sediment resuspension conducted in flume experiments. With the observation of wind velocity and frequency in 2001, each type of wind forcing took the frequency of 12%, 82% and 6% for “calm”, “gentle” and “gust”, respectively. The yearly release of nitrogen was 81,000 ton and phosphorus was 21,000 ton, which is about 2–6 folds of annual external loading, respectively.