Oxidation mechanisms and chemical bioavailability of chromium in agricultural soil – pH as the master variable     

《Applied Geochemistry》2016

Chromium (Cr) is a heavy metal that exists in soils in two stable oxidation states, +III and +VI. The trivalent species is an essential nutrient, whereas the hexavalent species is highly toxic. This study investigated the environmental impact of Cr^III potentially released into soil from wastes and various materials by determining the risk of oxidation of initially soluble inorganic Cr^III into hazardous Cr^VI. The principal aim was to describe the pH-dependent mechanisms that regulate 1) the formation of Cr^VI from the easily soluble Cr^III and 2) the potential bioavailability of Cr^III and that of Cr^VI species produced in the oxidation of Cr^III in agricultural soil (fine sand, organic carbon 3.2%). The amount of Cr^VI formed in oxic soil conditions was regulated by two counteracting reactions: 1) oxidation of Cr^III into Cr^VI by manganese oxide (Mn^IVO₂) and 2) the subsequent reduction of Cr^VI by organic matter back to Cr^III. The effect of pH on this net-oxidation of Cr^III and on the chemical availability of both Cr^III and Cr^VI species was investigated in soil samples incubated with or without excessive amounts of synthetic MnO₂, over the chemically adjusted pH range of 3.9–6.3 (+22 °C, 47 d). In soil subsamples without added MnO₂, the net-oxidation of Cr^III into Cr^VI (1 mM CrCl₃ in soil suspensions, 1:10 w/V) was negligible. As for the MnO₂-treated soils, at maximum only 4.7% of added Cr^III was oxidized – regardless of the high oxidation potential of these subsamples. The lowest production of Cr^VI was observed under acidic soil conditions at pH ∼4. At low pH, the net-oxidation diminished as result of enhanced reduction of Cr^VI back to Cr^III. At higher pHs, the oxidation was limited by enhanced precipitation (or adsorption) of Cr^III, which lowered the overall amount of Cr^III susceptible for oxidation. Moreover, the oxidation reactions by MnO₂ were inhibited by formation of Cr(OH)₃ coverage on its surface. The pH-dependent chemical bioavailability of added Cr^III differed from that of the Cr^VI formed. At elevated pHs the chemical availability of Cr^III decreased, whereas that of Cr^VI produced increased. However, the risk of Cr^VI formation through oxidation of the easily soluble inorganic Cr^III was considered to be low in agricultural soils high in organic matter and low in innate MnO₂.  相似文献   

Processes of water–rock interaction in the Turonian aquifer of Oum Er-Rabia Basin, Morocco     

Said Ettazarini 《Environmental Geology》2005,49(2):293-299

Possible water–rock interaction processes, in the Moroccan basin of Oum Er-Rabia, were discussed by a geochemical study of groundwater from the Turonian limestone aquifer, the most important water resource in the region. Different types of water according to the classification of Piper were defined. Waters have shown an evolution from dominant CHO₃–Ca–Mg type through mixed to SO₄–Cl–Ca–Mg type. The use of geochemical diagrams and chemical speciation modeling method has shown that water–rock interaction is mainly controlled by carbonate and anhydrite dissolution, ion exchange and reverse ion exchange processes. Water–rock equilibrium conditions are favorable for the precipitation of calcite, dolomite, kaolinite and magnesian smectite.  相似文献   

Bindungsverhalten ausgewählter Elemente in Sedimenten eines sauren Tagebaurestsees/FNR>     

Jürgen W. Einax  Wolf v. Tümpling  Katharina Zehl 《洁净——土壤、空气、水》2004,32(1):7-15

Binding Character of Selected Elements in Acidic Mining Lake Sediments To investigate the vertical element distribution in an acidic mining lake the concentrations of selected elements were measured by ICP‐MS and ICP‐OES. By knowing the metal concentrations in different depths it is possible to divide these metals into three groups. While the concentrations of iron, manganese, and zinc decline with decreasing depth, those of aluminium, copper, and nickel rise up. For lead and cobalt no distinct tendency could be determined. The limit value for all measured elements was not exceeded in any sampling location. The binding character of the metals is, besides the seasonal conditions of the lake (circulation in spring and stagnation in summer), influenced by the sediment depth. The addition of Carbokalk® for lake water neutralization had no significant effect on binding character of the analyzed metals. The application of a sequential extraction procedure enabled a classification of the available metal binding forms. All analyzed metals occurred mainly in compounds which are difficult to mobilize and for environment only slightly available.  相似文献   

Speciation of Arsenic Using Chelation Solvent Extraction and High Performance Liquid Chromatography     

Shamil J. Cathum  Carl E. Brown  Alison Obenauf  Monique Punt 《洁净——土壤、空气、水》2007,35(1):71-80

Research interest in speciation of arsenic stems from its species dependent behavior in the environment and in living organisms. The complexity of the matrix to be analyzed and low concentrations of target arsenic species that may be labile or difficult to chromatogram, indicate that a suitable pre‐treatment methodology is required. This study investigated the usefulness of chelation solvent extraction – high performance liquid chromatography (CSE‐HPLC) for the speciation of arsenic in water. It involved reacting arsenic with the chelant known for its affinity towards arsenic, followed by extraction, separation, and identification of the arsenic‐chelant‐arsenic complex. Arsenic species having different physicochemical properties were investigated. Species, such as, As₂O₃, As₃O₅, KH₂AsO₄, Na₂HAsO₄, and NaAsO₂ were detected as a group of closely eluted peaks with different retention times and spectral properties, whereas, the organic arsenic species CH₃Na₂AsO₃, o‐arsanilic acid, roxarson and triphenyl arsine separated quite well on the EnviroseP‐CM HPLC column. Key method parameters, such as, type of HPLC column, composition of mobile phase and organic solvents affecting peak resolution and sensitivity were optimized. Real environmental matrices contaminated with arsenic were analyzed under varying wavelengths (λ_max = 190, 210, 220, 234, 244, and 282 nm), with good precision. Different arsenic species were detected in these samples with excellent background and signal‐to‐noise ratios demonstrating the robustness of the method. The detection limit, reproducibility, selectivity, accuracy, and dynamic range of the calibration curves were evaluated.  相似文献   

Arsenic remobilization from sediments contaminated with mine tailings near the Adak mine in Västerbotten district (northern Sweden)     

Joyanto Routh  Aparajita Bhattacharya  Ambujom Saraswathy  Gunnar Jacks  Prosun Bhattacharya 《Journal of Geochemical Exploration》2007

Weathering of mine tailings have resulted in high As concentrations in water (up to 2900 μg l^− 1) and sediment (up to 900 mg kg^− 1) samples around the Adak mine. Notably, As occurs as As(III) species (15–85%) in the oxic surface and ground water samples, which is not common. Time-series based sediment incubations were set up in the laboratory with contaminated sediments to study the microbial processes involved in transformation and remobilization of As across the sediment–water interface. The microcosm experiments indicate that microorganisms are capable of surviving in As-rich sediments and reduce As(V) to As(III). A decrease in total As concentration in sediments is coupled to an increase in As(III) concentration in the aqueous media. In contrast, the controls (treated with HgCl₂ and formaldehyde) did not show growth, and As(V) concentrations increased steadily in the sediments and aqueous medium. The results imply that active metabolism is necessary for As(V) reduction. These microorganisms possess reduction mechanisms that are not necessarily coupled to respiration, but most likely impart resistance to As toxicity.  相似文献   

Photochemistry of Cu complexed with chromophoric dissolved organic matter: implications for Cu speciation in rainwater     

Melanie Louise Inez Witt  Stephen Skrabal  Robert Kieber  Joan Willey 《Journal of Atmospheric Chemistry》2007,58(2):89-109

Significant quenching of fluorescence by Cu in rainwater samples from southeastern North Carolina demonstrates that chromophoric dissolved organic matter (CDOM) is an effective ligand for Cu in rainwater. A strong inverse correlation between the decrease in fluorescence upon Cu addition and CDOM abundance suggests the presence of excess binding sites for Cu in high CDOM samples. Electroanalytical studies indicate that CDOM extracted from C₁₈ cartridges formed Cu complexes with concentrations and conditional stability constants similar to ligands found in ambient rainwater. When authentic rainwater samples were photolyzed with simulated sunlight both photoproduction and photodestruction of ligands were observed, suggesting the photochemical response of Cu-complexing ligands in rainwater is the result of two competing reactions. The rate of CDOM photobleaching was directly related to changes in strong ligands (K_CuL ∼ 10¹⁵) whereas weaker ligands (K_CuL < 10¹³) were not correlated, suggesting the photolabile CDOM resides in the strong ligand class. A photolysis study comparing filtered and unfiltered rainwater samples indicated that Cu-complexing ligands adsorbed onto or otherwise associated with particles are photodegraded much more rapidly than dissolved ligands. Photolysis with UV radiation appears to be most effective at engendering changes in Cu ligands, however a significant photochemical response was also observed when samples were exposed to photosynthetically active radiation with wavelengths greater than 400 nm. Results from this study demonstrate that complexation of Cu by CDOM has important ramifications for controlling both the speciation of the metal and the reactivity of CDOM in rainwater.  相似文献   

Competitive adsorption,release and speciation of heavy metals in the Yellow River sediments,China   总被引：2，自引：0，他引：2  

Qingyun Fan  Jiang He  Hongxi Xue  Changwei LÜ  Ying Liang  Saruli  Ying Sun  Lili Shen 《Environmental Geology》2007,53(2):239-251

The competitive adsorption and the release of selected heavy metals and their speciation distribution before and after adsorption in the Yellow River sediments are discussed. The adsorption of metals onto sediments increases with increasing pH value and decreases with increasing ionic strength. The competitive coefficient K _c and the distribution coefficient K _d are obtained to analyze the competitive abilities of selected heavy metals, which are ranked as Pb > Cu >> Zn > Cd. The competition among selected heavy metals becomes more impetuous with increasing ion concentration in water. Speciation analysis was done by an improved analytical procedure involving five steps of sequential extraction. Cu, Pb and Zn were mainly transformed into the carbonate-bound form (50.8–87.7%) in adsorption. Most of (60.7–77.3%) Cd was transformed into the exchangeable form, and the percentage of carbonate-bound Cd was 19.7–30.4%. The release reaction was so quick that the release capacity of selected heavy metals from sediments to aqueous solution reached half of the maximum value only in 30 s. As opposed to adsorption, the release capacities of selected heavy metals were ranked as Cd > Zn >> Cu > Pb. In this study, Cd produces the most severe environmental hazards, because its concentration in the release solution is 85.8 times more than the human health criteria of US EPA.  相似文献   

Speciation of polycyclic aromatic hydrocarbons (PAH) in aquatic sediments     

R. Püschel  W. Calmano 《洁净——土壤、空气、水》1995,23(5):226-232

A simple sequential extraction technique is presented for the examination of PAH speciation in aquatic sediments. This method is discussed with special emphasis on the sorption of PAH to humic substances and coal-like particles. Sorption experiments were carried out with sediments after treatment with H₂O₂ or after lipid removal by organic solvent extraction. The results show that lipids exert only a minor influence on PAH sorption. Furthermore, deviations from simple partition behaviour are discussed.  相似文献   

喀斯特地区代表性土壤中铜的形态研究   总被引：2，自引：0，他引：2  

王济  李阳兵  王文琼 《中国岩溶》2006,25(4):290-292

在贵州省贵阳市附近喀斯特区选择两种典型的土壤进行采样,并对土样中各种形态的铜进行测试。结果显示在喀斯特地区石灰土中铜的氧化锰结合态铜、无定形氧化铁结合态铜和紧结合有机态铜要比黄壤中相应形态的铜更为活跃,石灰土中可交换态铜为1. 520mg /kg; 而黄壤中铜的可交换态铜、碳酸盐结合态铜、松结合有机态铜和晶型氧化铁结合态铜比石灰土的活跃,可交换态铜可达5. 458mg /kg。   相似文献   

A study on zinc speciation of Tungabhadra River sediments,Kurnool, south India: A tool in metal pollution monitoring     

Madakka Mekapogu  Jayaraju Nadimikeri  Pramod Kumar Madri  Sowjanya Devi 《国际泥沙研究》2018,33(4):510-517

The Tungabhadra River is one of the sacred rivers in south India. Industrial and mining operations on its banks generate enormous amounts of effluent that have led to substantial metal and nutrient contamination of the aquatic system. In the present investigation an attempt has been made to assess variation in the physico-chemical characteristics and speciation of zinc in the water and sediment of the Tungabhadra River. Most of the metal ions in the collected samples were in high concentrations compared to the applicable standards. The Individual Contamination Factor (ICF) of Zn was found to be more at Site-B compared to sites A and C. Zinc-bearing particles were characterized by the different morphologies measuring from large colloidal to small particles which were associated with biological structures or may be present in amorphous nature which were observed by Transition electron microscopy (TEM) with X-EDS (Energy dispersive spectrometry). In conclusion, the level of Zn contamination in the Tungabhadra River is increasing at an alarming rate due to industrial activities.  相似文献