On the mechanistic modeling of As(III) adsorption on gibbsite

Arsenite adsorption on gibbsite was examined as a function of pH, ionic strength (I) and contact time (t(C)). As(III) showed a weak affinity for gibbsite surface. The trends of pH=f(Gamma(ads)) curves have showed a marked deviation from a typical anion adsorption edge showing a maximum Gamma(ads) around pH approximately 8.2. The experimentally derived proton exchange ratio has always converged to zero when 0.26< summation operator [As(III)]<7 microM and 6.2相似文献   

Macroscopic and vibration spectroscopic evidence for specific bonding of arsenate on gibbsite

The As(V) adsorption onto gibbsite under different experimental conditions was examined. Macroscopic data suggests strong As(V) bonding on gibbsite possibly via a bidendate binuclear complexation mechanism. The As(V) adsorption was quantified with the charge distribution multi-site ions complexation (CD-MUSIC) model distributing the anion charge over 0- and 1-planes according to the modified Pauling's bond valence theory. In the dual-adsorbates system of As(III) and As(V), the As(III) adsorption was predicted up to pH 8 utilizing the binding constants derived for single-adsorbate data. However, with pH > 8, the modeled As(III) adsorption data is overestimating the experimental values.     

Parameterization and evaluation of sulfate adsorption in a dynamic soil chemistry model

Sulfate adsorption was implemented in the dynamic, multi-layer soil chemistry model SAFE. The process is modeled by an isotherm in which sulfate adsorption is considered to be fully reversible and dependent on sulfate concentration as well as pH in soil solution. The isotherm was parameterized by a site-specific series of simple batch experiments at different pH (3.8-5.0) and sulfate concentration (10-260 micromol 1(-1)) levels. Application of the model to the Lake Gardsj6n roof covered site shows that including sulfate adsorption improves the dynamic behavior of the model and sulfate adsorption and desorption delay acidification and recovery of the soil. The modeled adsorbed pool of sulfate at the site reached a maximum level of 700 mmol/m(2) in the late 1980s, well in line with experimental data.     

Insights into the mercury(II) adsorption and binding mechanism onto several typical soils in China

To better understand the Hg(II) adsorption by some typical soils and explore the insights about the binding between Hg(II) and soils, a batch of adsorption and characteristic experiments was conducted. Results showed that Hg(II) adsorption was well fitted by the Langmuir and Freundlich. The maximum adsorption amount of cinnamon soil (2094.73 mg kg^?1) was nearly tenfold as much as that of saline soil (229.49 mg kg^?1). The specific adsorption of Hg(II) on four soil surface was confirmed by X-ray photoelectron spectroscopy (XPS) owing to the change of elemental bonding energy after adsorption. However, the specific adsorption is mainly derived from some substances in the soil. Fourier transform infrared spectroscopy (FTIR) demonstrated that multiple oxygen-containing functional groups (O–H, C=O, and C–O) were involved in the Hg(II) adsorption, and the content of oxygen functional groups determined the adsorption capacity of the soil. Meanwhile, scanning electron microscopy combined with X-ray energy dispersive spectrometer (SEM–EDS) more intuitive revealed the binding of mercury to organic matter, metal oxides, and clay minerals in the soil and fundamentally confirmed the results of XPS and FTIR to further elucidate adsorptive phenomena. The complexation with oxygen-containing functional groups and the precipitation with minerals were likely the primary mechanisms for Hg(II) adsorption on several typical soils. This study is critical in understanding the transportation of Hg(II) in different soils and discovering potential preventative measures.     

pH及Zn2+对土壤和铁、铝氧化物吸附苄嘧磺隆的影响

用平衡吸附法研究了3种供试样品(广州赤红壤、铝氧化物、针铁矿)对苄嘧磺隆的等温吸附,同时研究了pH及Zn2 对供试样品吸附苄嘧磺隆的影响.结果表明,在实验所用的苄嘧磺隆的浓度范围内,供试样品对苄嘧磺隆的吸附量各不相同;供试样品吸附苄嘧磺隆的量随溶液pH及Zn2 浓度的改变而变化,且影响不尽相同,这主要与供试样品的组成有关.     

Influence of redox potential (Eh) on the availability of arsenic species in soils and soils amended with biosolid

A study was done on the influence of redox potential on the mobility and availability of the various arsenic chemical forms in a Mollisol soil from central Chile amended with biosolid. Arsenic availability was strongly dependent on the applied redox potential. As expected, under reducing conditions (-200 mV vs Hg/Hg(2)Cl(2)) arsenic availability increased significantly, and arsenic was found mainly as arsenite. On the contrary under oxidizing conditions (200 mV vs Hg/Hg(2)Cl(2)) arsenic solubility decreased markedly and was governed by the presence of arsenate. The greatest concentration of organic arsenic species was found under reducing conditions, which would indicate that methylated species may participate in the transformation of arsenate to arsenite. In biosolid-amended soils the concentrations of methylated species increased as a function of time under reducing conditions, which can be attributed to the greater microbial activity resulting from the organic matter supply from the biosolid to soil. In all the systems, a high concentration of As(V) was found under reducing conditions, indicating that the chemical kinetics for the conversion of arsenate to arsenite is slow. Along time, the content of As(V) increased in the control soils, which may be attributed to the possible dissolution of iron oxides and hydroxides under reducing conditions.     

A study of gas-phase mercury speciation using detailed chemical kinetics.

Mercury speciation in combustion-generated flue gas was modeled using a detailed chemical mechanism consisting of 60 reactions and 21 species. This speciation model accounts for the chlorination and oxidation of key flue-gas components, including elemental mercury (Hg0). Results indicated that the performance of the model is very sensitive to temperature. Starting with pure HCl, for lower reactor temperatures (less than approximately 630 degrees C), the model produced only trace amounts of atomic and molecular chlorine (Cl and Cl2), leading to a drastic underprediction of Hg chlorination compared with experimental data. For higher reactor temperatures, model predictions were in good accord with experimental data. For conditions that produce an excess of Cl and Cl2 relative to Hg, chlorination of Hg is determined by the competing influences of the initiation step, Hg + Cl = HgCl, and the Cl recombination reaction, 2Cl = Cl2. If the Cl recombination reaction is faster, Hg chlorination will eventually be dictated by the slower pathway Hg + Cl2 = HgCl2.     

Reduced mercury deposition in New Hampshire from 1996 to 2002 due to changes in local sources

Changes in deposition of gaseous divalent mercury (Hg(II)) and particulate mercury (Hg(p)) in New Hampshire due to changes in local sources from 1996 to 2002 were assessed using the Industrial Source Complex Short Term (ISCST3) model (regional and global sources and Hg atmospheric reactions were not considered). Mercury (Hg) emissions in New Hampshire and adjacent areas decreased significantly (from 1540 to 880 kg yr⁻¹) during this period, and the average annual modeled deposition of total Hg also declined from 17 to 7.0 μg m⁻² yr⁻¹ for the same period. In 2002, the maximum amount of Hg deposition was modeled to be in southern New Hampshire, while for 1996 the maximum deposition occurred farther north and east. The ISCST3 was also used to evaluate two future scenarios. The average percent difference in deposition across all cells was 5% for the 50% reduction scenario and 9% for the 90% reduction scenario.     

Mercury accumulation in grass and forb species as a function of atmospheric carbon dioxide concentrations and mercury exposures in air and soil

The goal of this study was to investigate the potential for atmospheric Hg degrees uptake by grassland species as a function of different air and soil Hg exposures, and to specifically test how increasing atmospheric CO(2) concentrations may influence foliar Hg concentrations. Four common tallgrass prairie species were germinated and grown for 7 months in environmentally controlled chambers using two different atmospheric elemental mercury (Hg major; 3.7+/-2.0 and 10.2+/-3.5 ng m(-3)), soil Hg (<0.01 and 0.15+/-0.08 micro g g(-1)), and atmospheric carbon dioxide (CO(2)) (390+/-18, 598+/-22 micro mol mol(-1)) exposures. Species used included two C4 grasses and two C3 forbs. Elevated CO(2) concentrations led to lower foliar Hg concentrations in plants exposed to low (i.e., ambient) air Hg degrees concentrations, but no CO(2) effect was apparent at higher air Hg degrees exposure. The observed CO(2) effect suggests that leaf Hg uptake might be controlled by leaf physiological processes such as stomatal conductance which is typically reduced under elevated CO(2). Foliar tissue exposed to elevated air Hg degrees concentrations had higher concentrations than those exposed to low air Hg degrees , but only when also exposed to elevated CO(2). The relationships for foliar Hg concentrations at different atmospheric CO(2) and Hg degrees exposures indicate that these species may have a limited capacity for Hg storage; at ambient CO(2) concentrations all Hg absorption sites in leaves may have been saturated while at elevated CO(2) when stomatal conductance was reduced saturation may have been reached only at higher concentrations of atmospheric Hg degrees . Foliar Hg concentrations were not correlated to soil Hg exposures, except for one of the four species (Rudbeckia hirta). Higher soil Hg concentrations resulted in high root Hg concentrations and considerably increased the percentage of total plant Hg allocated to roots. The large shifts in Hg allocation patterns-notably under soil conditions only slightly above natural background levels-indicate a potentially strong role of plants in belowground Hg transformation and cycling processes.     

Comparison of mercury chemistry models

Five mercury (Hg) chemistry models are compared using the same data set for model initialisation. All five models include gas-phase oxidation of Hg(0) to Hg(II) (except for one model), fast reduction–oxidation aqueous reactions between Hg(0) and Hg(II), and adsorption of Hg(II) species to soot particles within droplets. However, the models differ in their detailed treatments of these processes. Consequently, the 48-h simulations reveal similarities but also significant discrepancies among the models. For the simulation that included all Hg species (i.e., Hg(0), Hg(II) and Hg(p)) as well as soot in the initial conditions, the maximum simulated Hg(II) aqueous concentrations ranged from 55 to 148 ng l⁻¹ whereas the minimum concentrations ranged from 20 to 110 ng l⁻¹. These results suggest that further experimental work is critically needed to reduce the current uncertainties in the formulation of Hg chemistry models.     

Antimony sorption at gibbsite-water interface

Antimony (Sb) is extensively used in flame retardants, lead-acid batteries, solder, cable coverings, ammunition, fireworks, ceramic and porcelain glazes and semiconductors. However, the geochemical fate of antimony (Sb) remained largely unexplored. Among the different Sb species, Sb (V) is the dominant form in the soil environment in a very wide redox range. Although earlier studies have examined the fate of Sb in the presence of iron oxides such as goethite and hematite, few studies till date reported the interaction of Sb (V) with gibbsite, a common soil Al-oxide mineral. The objective of this study was to understand the sorption behavior of Sb (V) on gibbsite as a function of various solution properties such as pH, ionic strength (I), and initial Sb concentrations, and to interpret the sorption-edge data using a surface complexation model. A batch sorption study with 20 g L⁻¹ gibbsite was conducted using initial Sb concentrations range of 2.03-16.43 μM, pH values between 2 and 10, and ionic strengths (I) between 0.001 and 0.1 M. The results suggest that Sb (V) sorbs strongly to the gibbsite surface, possibly via inner-sphere type mechanism with the formation of a binuclear monodentate surface complex. Weak I effect was noticed in sorption-edge data or in the isotherm data at a low surface coverage. Sorption of Sb (V) on gibbsite was highest in the pH range of 2-4, and negligible at pH 10. Our results suggest that gibbsite will likely play an important role in immobilizing Sb (V) in the soil environment.     

Adsorption of methabenzthiazuron on six allophanic and nonallophanic soils: effect of organic matter amendment

This article reports on methabenzthiazuron [1-(1,3-benzothiazol-2-yl)-1,3-dimethylurea] (MBT) adsorption process on six agricultural allophanic and nonallophanic soils. The effect of amendment with exogenous organic matter was also studied. Adsorption kinetic fits an hyperbolic model. MBT adsorption reached an apparent equilibrium within 2 h and followed a second-order reaction. The maximum adsorbed amounts for natural soils ranged from 32 to 145 microg g(-1). Rate constants were considered relatively low (0.27-1.5 x 10(-4) [microg g(-1)](1-n) s-1); the slow process was attributed to a combined effect of difussion and adsorption. MBT adsorption fits the Freundlich model with r values > or =0.998 at P < or = 0.001 significance levels. Kf and Freundlich exponents (l/n) ranged from 5.3 to 82.1 cm3 g(-1) and from 0.66 to 0.73, respectively. Kf values for soils with a low organic matter content were lower than that obtained from the only typical allophanic soil derived from volcanic ash under study. Lineal regression analysis between Kf and organic matter content of nonallophanic soils gave a correlation coefficient of 0.980 (P = 0.02). Dispersion of Kd values together with close values of K(OM) indicate that organic matter (OM) was the principal component responsible for MBT adsorption in unamended soils. Addition of peat decreased soil pH and increased adsorption capacity for allophanic and nonallophanic soils. Kinetic experiments showed enhancements of Xmax values and lower rate constants.     

Adsorption-desorption behaviour of zinc(II) at iron(III) hydroxide-aqueous solution interface as influenced by pH and temperature

Batch studies were carried out to investigate the adsorption of zinc(II) from fresh waters on an iron(III) hydroxide surface maintained at the pH of zero point of charge of hydroxide (ZPC, 6.85) and also on both the acidic (5.5) and alkaline (8.2) sides of pH of ZPC, at 15 and 35 degrees C. Zinc(II) adsorption on iron(III) hydroxide increased with an increase in pH. The rise in temperature from 15 to 35 degrees C increased zinc(II) adsorption at pH 5.5 and 6.85, but decreased it at alkaline pH (8.2). In none of the cases did adsorption attain a maximum adsorption density. The results indicate the presence of heterogeneous sites of varying affinity on the adsorbent. Zinc(II) adsorption followed Langmuir behaviour only at small adsorption densities (less than 10(-2.95) M Zn/kg at pH 5.5) and at higher adsorption densities, the availability of strongest binding sites decreased. Nonspecifically adsorbed zinc(II) (reversible to Ba(II)) decreased with the increase in pH and temperature. Sequential desorption experiments also revealed that desorption of adsorbed zinc(II) decreased with an increase in pH.     

Thermodynamics of metal cation binding by a solid soil derived humic acid. 2. Binding of Mn(II), Co(NH3)6aq3+ and Hg(II)

Metal binding is an important function of humic acids (HAs) in soils, sediments and waters. At pH 2.0, Mn(II) and Co(NH3)6aq3+ bind tightly in one step labeled A to a solid humic acid NHA isolated from a New Hampshire soil. Two consecutive steps are observed for Hg(II) binding. All the binding isotherms fit the Langmuir model in the temperature range 10.0-50.0 degrees C. Stoichiometric site capacities indicate predominant binding by charge-neutralizing HA carboxylate groups for Mn(II) and the second step A of Hg(II) binding. The binding affinity order in step A is Co(NH3)(6)3+>Hg(II)>Mn(II). Metal binding enthalpy and entropy changes fit the linear correlation found previously for binding of other metal cations by solid HAs. Free energy buffering from cooperative enthalpy and entropy changes and lower enthalpies for metal-HA interactions in solution suggest that desolvation of the cations and HA binding sites as well as HA conformational changes to allow for inner-sphere complexation predominate metal binding by hydrated solid HAs.     

Comparison of the adsorption of lead,cadmium, copper,zinc and barium to freshwater surface coatings

Measurements were made regarding the adsorption of lead, cadmium, copper, zinc and barium to freshwater surface coatings (biofilms and associated minerals), which were collected in Nanhu Lake in Jilin Province, PR China, in order to investigate the variability of adsorption capacities of these heavy metals mentioned in the above surface coatings. The adsorption of lead and other heavy metals to the biofilms was observed to decrease in the following order: copper, lead, zinc, cadmium, and barium. Generally, the values of Gamma(max) (the maximum adsorption, micromol/m(2)) increased with the standard electrode potential of metal elements used and were recorded as 166.7, 40.0, 29.4, 10.8, and 1.8 for copper, lead, zinc, cadmium and barium, respectively. The values of 1/Gamma(max) increased linearly with the decrease in values of the standard electrode potential of metal elements with a significant correlation (n=5, p=0.01) and increased linearly with the increase in values of covalent radius of metal elements with a significant correlation (n=5, p=0.05). This indicates that standard electrode potential and covalent radius were two of the principal characteristics of metals employed, causing the variation of lead and other heavy metal adsorption to the surface coatings.     

A comparative study of the effects of chloride, sulfate and nitrate ions on the rates of decomposition of H2O2 and organic compounds by Fe(II)/H2O2 and Fe(III)/H2O2

The effects of chloride, nitrate, perchlorate and sulfate ions on the rates of the decomposition of hydrogen peroxide and the oxidation of organic compounds by the Fenton's process have been investigated. Experiments were conducted in a batch reactor, in the dark at pH < or = 3.0 and at 25 degrees C. Data obtained from Fe(II)/H2O2 experiments with [Fe(II)]0/[H2O2]0 > or = 2 mol mol(-1), showed that the rates of reaction between Fe(II) and H2O2 followed the order SO4(2-) > ClO4(-) = NO3- = Cl-. For the Fe(III)/H2O2 process, identical rates were obtained in the presence of nitrate and perchlorate, whereas the presence of sulfate or chloride markedly decreased the rates of decomposition of H2O2 by Fe(III) and the rates of oxidation of atrazine ([atrazine]0 = 0.83 microM), 4-nitrophenol ([4-NP]0 = 1 mM) and acetic acid ([acetic acid]0 = 2 mM). These inhibitory effects have been attributed to a decrease of the rate of generation of hydroxyl radicals resulting from the formation of Fe(III) complexes and the formation of less reactive (SO4(*-)) or much less reactive (Cl2(*-)) inorganic radicals.     

Pilot-scale study of the effect of selective catalytic reduction catalyst on mercury speciation in Illinois and Powder River Basin coal combustion flue gases

A study was conducted to investigate the effect of selective catalytic reduction (SCR) catalyst on mercury (Hg) speciation in bituminous and subbituminous coal combustion flue gases. Three different Illinois Basin bituminous coals (from high to low sulfur [S] and chlorine [Cl]) and one Powder River Basin (PRB) subbituminous coal with very low S and very low Cl were tested in a pilot-scale combustor equipped with an SCR reactor for controlling nitrogen oxides (NOx) emissions. The SCR catalyst induced high oxidation of elemental Hg (Hg0), decreasing the percentage of Hg0 at the outlet of the SCR to values <12% for the three Illinois coal tests. The PRB coal test indicated a low oxidation of Hg0 by the SCR catalyst, with the percentage of Hg0 decreasing from approximately 96% at the inlet of the reactor to approximately 80% at the outlet. The low Cl content of the PRB coal and corresponding low level of available flue gas Cl species were believed to be responsible for low SCR Hg oxidation for this coal type. The test results indicated a strong effect of coal type on the extent of Hg oxidation.     

Mercury conversion processes in Amazon soils evaluated by thermodesorption analysis

This paper reports on the speciation study and the Hg redox behavior in Amazon soils not influenced by gold mining and collected near Manaus, AM, Brazil. The samples were incubated by adding Hg(0) and HgCl₂ to dry soil. Solid phase Hg speciation analysis was carried out using a Hg thermodesorption technique with the aim of distinguishing elemental Hg(0) from Hg(II) binding forms. In the first case, we observed the conversion of Hg(0) to Hg(II) binding forms in the range of 28–68% and a correlation between the percent of oxidation and OM content. Samples incubated with Hg(II) showed the formation of Hg(I) and/or Hg(0) in the range of 19–69%. The lowest values corresponded to the samples with the lowest clay contents. The kinetics of conversion of Hg(0) as well as HgCl₂ were roughly fitted to the two first order reactions, a fast one and a slow one. It was not possible to evaluate differences between sampling sites and types of soils, but the mean half-life of the first order reaction obtained by the addition of Hg(II) was slower (t_1/2 = 365 d) than the one obtained by the addition of Hg(0) (t_1/2 = 148 d). Previous studies have shown the predominance of organically bound Hg in these samples. Thus, the kinetic difference between Hg oxidation and reduction in combination with the efficient retention processes by OM may explain the high background values found in Amazon soils.     

Mercury exposure in the freshwater tilapia Oreochromis niloticus

Mercury (Hg) can be strongly accumulated and biomagnified along aquatic food chain, but the exposure pathway remains little studied. In this study, we quantified the uptake and elimination of both inorganic mercury [as Hg(II)] and methylmercury (as MeHg) in an important farmed freshwater fish, the tilapia Oreochromis niloticus, using ²⁰³Hg radiotracer technique. The dissolved uptake rates of both mercury species increased linearly with Hg concentration (tested at ng/L levels), and the uptake rate constant of MeHg was 4 times higher than that of Hg(II). Dissolved uptake of mercury was highly dependent on the water pH and dissolved organic carbon concentration. The dietborne assimilation efficiency of MeHg was 3.7-7.2 times higher than that of Hg(II), while the efflux rate constant of MeHg was 7.1 times lower. The biokinetic modeling results showed that MeHg was the greater contributor to the overall mercury bioaccumulation and dietary exposure was the predominant pathway.     

Adsorption,desorption, and mobility of two insecticides in Malaysian agricultural soil

Laboratory studies utilizing radioisotopic techniques were conducted to determine the adsorption, desorption, and mobility of endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxanthiepin3-oxide) and methamidophos (O,S-dimethyl phosphorothioate) in sandy loam and clay soils of the Cameron Highlands and the Muda rice-growing area, respectively. High Freundlich adsorption distribution coefficients [Kads(f)] for endosulfan (6.74 and 18.75) and low values for methamidophos (0.40 and 0.98) were obtained in the sandy loam and clay soils, respectively. The observed Koc values for endosulfan were 350.85 (sandy loam) and 1143.19 (clay) while Koc values of 20.92 (sandy loam) and 59.63 (clay) were obtained for methamidophos. Log Kow of 0.40 and 1.25 were calculated for endosulfan as well as -1.96 and -1.21 for methamidophos in the sandy loam and clay soils, respectively. Desorption was common to both pesticides but the desorption capacity of methamidophos from each soil type far exceeded that of endosulfan. Soil thin layer chromatography (TLC) and column studies showed that while methamidophos was very mobile in both soils, endosulfan displayed zero mobility in clay soil.