Adsorption and redox reactions of heavy metals on synthesized Mn oxide minerals

Several Mn oxide minerals commonly occurring in soils were synthesized by modified or optimized methods. The morphologies, structures, compositions and surface properties of the synthesized Mn oxide minerals were characterized. Adsorption and redox reactions of heavy metals on these minerals in relation to the mineral structures and surface properties were also investigated. The synthesized birnessite, todorokite, cryptomelane, and hausmannite were single-phased minerals and had the typical morphologies from analyses of XRD and TEM/ED. The PZCs of the synthesized birnessite, todorokite and cryptomelane were 1.75, 3.50 and 2.10, respectively. The magnitude order of their surface variable negative charge was: birnessite> or =cryptomelane>todorokite. The hausmannite had a much higher PZC than others with the least surface variable negative charge. Birnessite exhibited the largest adsorption capacity on heavy metals Pb(2+), Cu(2+), Co(2+), Cd(2+) and Zn(2+), while hausmannite the smallest one. Birnessite, cryptomelane and todorokite showed the greatest adsorption capacity on Pb(2+) among the tested heavy metals. Hydration tendency (pK(1)) of the heavy metals and the surface variable charge of the Mn minerals had significant impacts on the adsorption. The ability in Cr(III) oxidation and concomitant release of Mn(2+) varied greatly depending on the structure, composition, surface properties and crystallinity of the minerals. The maximum amounts of Cr(III) oxidized by the Mn oxide minerals in order were (mmol/kg): birnessite (1330.0)>cryptomelane (422.6)>todorokite (59.7)>hausmannite (36.6).     

Adsorption of Cd to natural biofilms in the presence of EDTA: effect of pH, concentration, and component addition sequence

Both dissolved organic matters (DOM) and natural biofilms are important substances in controlling the behavior of trace metals in natural aquatic environments. In this study, ethylenediaminetetraacetic acid (EDTA) was selected as a typical DOM to investigate the effect of DOM on the adsorption of trace metals to the biofilms in natural waters. The adsorption of Cd to biofilms, including adsorption isotherm at a fixed pH (pH?=?6.0) and pH-edge adsorption (pH ranging from 4.3 to 9.0) with different adsorption sequences, was determined without EDTA and in the presence of EDTA ([EDTA]?=?0.5 μmol/L for isotherms measurement and [EDTA]?=?0.5 and 2.0 μmol/L for pH-dependent adsorption). The presence of EDTA generally decreased the adsorption of Cd, and the effect was determined by solution pH, concentration of EDTA, and adsorption sequence. Higher concentration or higher pH usually resulted in a more significant decrease. The influence of adsorption sequence on the effect of EDTA was insignificant in lower pH range, while the adsorption usually decreased in the order of Cd only adsorption > Cd first adsorption > EDTA first adsorption ≈ simultaneous adsorption in higher pH range. The effect of EDTA could be attributed to the conversion of Cd speciation, the competition with the biofilms for Cd, and the dissolution of Mn oxides from the biofilms. EDTA affected the adsorption of Cd to natural biofilms, and the effect could be fairly significant. The role of Mn oxides in determining the behavior of trace metals might be underestimated.     

Deriving freshwater quality criteria for copper,cadmium, aluminum and manganese for protection of aquatic life in Malaysia

Freshwater quality criteria for copper (Cu), cadmium (Cd), aluminum (Al), and manganese (Mn) were developed with particular reference to aquatic biota in Malaysia, and based on USEPA’s guidelines. Acute toxicity tests were performed on eight different freshwater domestic species in Malaysia, which were Macrobrachium lanchesteri (prawn), two fish – Poecilia reticulata and Rasbora sumatrana, Melanoides tuberculata (snail), Stenocypris major (ostracod), Chironomus javanus (midge larvae), Nais elinguis (annelid), and Duttaphrynus melanostictus (tadpole), to determine 96-h LC50 values for Cu, Cd, Al, and Mn. The final acute values (FAVs) for Cu, Cd, Al, and Mn were 2.5, 3.0, 977.8, and 78.3 μg L^?1, respectively. Using an estimated acute-to-chronic ratio (ACR) of 8.3, the value for final chronic value (FCV) was derived. Based on FAV and FCV, a Criterion Maximum Concentration (CMC) and a criterion Continuous Concentration (CCC) for Cu, Cd, Al, and Mn of 1.3, 1.5, 488.9, and 39.1 μg L^?1 and 0.3, 0.36, 117.8, and 9.4 μg L^?1, respectively, were derived. The results of this study provide useful data for deriving national or local water quality criteria for Cu, Cd, Al, and Mn based on aquatic biota in Malaysia. Based on LC50 values, this study indicated that R. sumatrana, M. lanchesteri, C. javanus, and N. elinguis were the most sensitive to Cu, Cd, Al, and Mn, respectively.     

Cu and Zn adsorption onto non-residual and residual components in the natural surface coatings samples (NSCSs) in the Songhua River, China

Natural surface coatings samples (NSCSs) from the surface of river shingles were employed to investigate the roles of non-residual and residual components of the NSCSs in controlling Cu and Zn adsorption via the selective extraction techniques and statistical analysis. The results indicate that the greatest contribution to metals adsorption on a molar basis was from Mn oxides in the non-residual fraction. Metals adsorption capacities of Mn oxides exceeded those of Fe oxides by one order of magnitude, fewer roles were found attributing to adsorption by organic materials (OM), and the estimated contribution of the residual fraction to metals adsorption was insignificant. These results implied that Mn oxides were the most important component in controlling heavy metals in aquatic environments. Experiments with Cu and Zn adsorption measured together showed that Cu severely interfered with Zn adsorption to the NSCSs and vice versa under the conditions of the two coexisted ions adsorption.     

Enhanced reductive dechlorination of DDT in an anaerobic system of dissimilatory iron-reducing bacteria and iron oxide

The transformation of DDT was studied in an anaerobic system of dissimilatory iron-reducing bacteria (Shewanella decolorationis S12) and iron oxide (α-FeOOH). The results showed that S. decolorationis could reduce DDT into DDD, and DDT transformation rate was accelerated by the presence of α-FeOOH. DDD was observed as the primary transformation product, which was demonstrated to be transformed in the abiotic system of Fe²⁺ + α-FeOOH and the system of DIRB + α-FeOOH. The intermediates of DDMS and DBP were detected after 9 months, likely suggesting that reductive dechlorination was the main dechlorination pathway of DDT in the iron-reducing system. The enhanced reductive dechlorination of DDT was mainly due to biogenic Fe(II) sorbed on the surface of α-FeOOH, which can serve as a mediator for the transformation of DDT. This study demonstrated the important role of DIRB and iron oxide on DDT and DDD transformation under anaerobic iron-reducing environments.     

Effective adsorbent for arsenic removal: core/shell structural nano zero-valent iron/manganese oxide

Recently, nano zero-valent iron (nZVI) has emerged as an effective adsorbent for the removal of arsenic from aqueous solutions. However, its use in various applications has suffered from reactivity loss resulting in a decreased efficiency. Thus, the aim of this study was to develop an effective arsenic adsorbent as a core/shell structural nZVI/manganese oxide (or nZVI/Mn oxide) to minimize the reactivity loss of the nZVI. As the major result, the arsenic adsorption capacities of the nZVI/Mn oxide for As(V) and As(III) were approximately two and three times higher than that of the nZVI, respectively. In addition, the As(V) removal efficiency of the nZVI/Mn oxide was maintained through 4 cycles of regeneration whereas that of the nZVI was decreased significantly. The enhanced reactivity and reusability of the nZVI/Mn oxide can be successfully explained by the synergistic interaction of the nZVI core and manganese oxide shell, in which the manganese oxides participate in oxidation reactions with corroded Fe²⁺ and subsequently retard the release of aqueous iron providing additional surface sites for arsenic adsorption. In summary, this study reports the successful fabrication of a core/shell nZVI/Mn oxide as an effective adsorbent for the removal of arsenic from aqueous solutions.     

Effect of the Mn oxidation state and lattice oxygen in Mn-based TiO2 catalysts on the low-temperature selective catalytic reduction of NO by NH3

TiO₂-supported manganese oxide catalysts formed using different calcination temperatures were prepared by using the wet-impregnation method and were investigated for their activity in the low-temperature selective catalytic reduction (SCR) of NO by NH₃ with respect to the Mn valence and lattice oxygen behavior. The surface and bulk properties of these catalysts were examined using Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and temperature-programmed desorption (TPD). Catalysts prepared using lower calcination temperatures, which contained Mn⁴⁺, displayed high SCR activity at low temperatures and possessed several acid sites and active oxygen. The TPD analysis determined that the Brönsted and Lewis acid sites in the Mn/TiO₂ catalysts were important for the low-temperature SCR at 80～160 and 200～350 °C, respectively. In addition, the available lattice oxygen was important for attaining high NO to NO₂ oxidation at low temperatures.

Implications: Recently, various Mn catalysts have been evaluated as SCR catalysts. However, there have been no studies on the relationship of adsorption and desorption properties and behavior of lattice oxygen according to the valence state for manganese oxides (MnO_x). Therefore, in this study, the catalysts were prepared by the wet-impregnation method at different calcination temperatures in order to show the difference of manganese oxidation state. These catalysts were then characterized using various physicochemical techniques, including BET, XRD, TPR, and TPD, to understand the structure, oxidation state, redox properties, and adsorption and desorption properties of the Mn/TiO₂ catalysts.     

Dynamic behaviour of Cd2+ adsorption in equilibrium batch studies by CaCO3 −-rich Corbicula fluminea shell

This work presents the structural and adsorption properties of the CaCO₃ ^?-rich Corbicula fluminea shell as a natural and economic adsorbent to remove Cd ions from aqueous solutions under batch studies. Experiments were conducted with different contact times, various initial concentrations, initial solution pH and serial biosorbent dosage to examine the dynamic characterization of the adsorption and its influence on Cd uptake capacity. The characterization of the C. fluminea shell using SEM/EDX revealed that the adsorbent surface is mostly impregnated by small particles of potentially calcium salts. The dominant Cd adsorption mechanism is strongly pH and concentration dependent. A maximum Cd removal efficiency of 96.20 % was obtained at pH 7 while the optimum adsorbent dosage was observed as 5 g/L. The Langmuir isotherm was discovered to be more suitable to represent the experimental equilibrium isotherm results with higher correlation coefficients (R ²?>?0.98) than Freundlich (R ²?<?0.97).The correlation coefficient values (p?<?0.01) indicated the superiority of the Langmuir isotherm over the Freundlich isotherm.     

Cadmium adsorption by willow root: the role of cell walls and their subfractions

Plant cell walls may play an important role in the uptake and accumulation of heavy metals. This study was undertaken to obtain a better understanding of the role of the root cell walls (RCW) and their subfractions on adsorption of cadmium (Cd) in a promising woody phytoremediation species, Salix jiangsuensis J172. In order to examine how Cd binding was affected by pectin and hemicellulose, RCW were isolated and sequentially fractioned by removing pectin (RCW1), partial removal of hemicellulose (RCW2), and complete removal of hemicellulose (RCW3). The RCW and fractions were characterized by Fourier transform infrared spectroscopy, which suggested decomposition of hemicellulose and a decline in nitrogen content following cell wall isolation and fractionation. The adsorption affinity of Cd increased gradually following the sequential extraction of root cells, suggesting that hemicellulose negatively impacted Cd adsorption, while pectin and cellulose enhanced Cd adsorption. Cd adsorption dynamics and isotherms could be best described by the pseudo-second-order (R?>?0.99) and Freundlich (R?>?0.97) models, respectively. Thermodynamic properties (?G, ?H, and ?S), determined using the van’t Hoff equation, indicated that while Cd adsorption was endothermic, and spontaneous for RCW2 and RCW3, adsorption was not spontaneous for the root, RCW, and RCW1. The results provide evidence for the importance of the root cell walls in the adsorption of Cd by willow roots.     

Size distribution and sources of trace metals and n-alkanes in the Athens urban aerosol during summer

Size-resolved, 24-h aerosol samples were collected from June–July 2001 by means of an Andersen high-volume cascade impactor. Sampling was conducted in a central avenue (Patission) characterised by heavy traffic, 21 m above street level, in the Athens city centre. Samples were analysed by atomic absorption spectrometry and gas chromatography to determine the size distribution of nine metallic elements (Cd, Pb, V, Ni, Mn, Cr, Cu, Fe, Al) and n-alkanes (with carbon numbers in the range 18–35). The aerosol mass median diameter (MMD) was calculated by means of probit analysis on the cumulative mass concentration size distribution for each metals and n-alkane. The total n-alkane mass concentration (TNA) in total suspended particles (TSP) ranged from 72 to 1506 ng m⁻³ while the total metal concentration ranged from 5.6 to 28.6 μg m⁻³. The results showed that metals such as Cd, V and Ni are characterised by a MMD <1 μm, while the MMD for Pb and Mn are ∼1 μm. Such metals are generally considered to have anthropogenic emission sources. Other metals such as Al, Fe, Cu and Cr were found to have MMD=2–6 μm, which generally originate from soil dust or mechanical abrasion processes. The Carbon number profile of n-alkane compounds showed a strong anthropogenic source with only a minor biogenic influence. The concentration of most n-alkanes was characterised by high variability during the sampling period, in contrast to the concentration of most trace metals. Most n-alkanes had a unimodal size distribution with MMD=1–2 μm similar to those of some trace metals (Pb, Mn), which originate mostly from vehicle emissions. This is a strong indication that these species have a common source. Finally, gas–particle partitioning of n-alkanes was also examined for different particle sizes by means of the relationship between the partition constant K_p and saturation vapour pressure (p_L⁰) as proposed by current sorption models.     

Characterization of cadmium (Cd) distribution and accumulation in Tagetes erecta L. seedlings: Effect of split-root and of remove-xylem/phloem

Tagetes erecta has a high potential for cadmium (Cd) phytoremediation. Through several hydroponic experiments, characteristics of ¹⁰⁸Cd distribution and accumulation were investigated in T. erecta with split -roots or removed xylem/phloem. The results showed that ¹⁰⁸Cd transport from roots to aboveground tissues showed the homolateral transport phenomenon in split-root seedlings. ¹⁰⁸Cd content of leaves on the +¹⁰⁸Cd side and the −¹⁰⁸Cd side was not significantly different, which implied that there was horizontal transport of ¹⁰⁸Cd from the +¹⁰⁸Cd side to the −¹⁰⁸Cd side in cut-root seedlings. Like ¹⁰⁸Cd transport, the transport of ⁷⁰Zn was homolateral. Reduction of water consumption in the removed xylem treatment significantly decreased ¹⁰⁸Cd accumulation; whereas, the removed phloem treatment had no significant effect on water consumption, but did decrease ¹⁰⁸Cd accumulation in leaves of the seedlings. The removal of phloem significantly reduced distal leaf ¹⁰⁸Cd content, which was significantly lower than that in the basal leaves in both the split-root and unsplit-root seedlings. Overall, the results presented in this study revealed that the root to aboveground cadmium translocation via phloem is as an important and common physiological process as xylem determination of the cadmium accumulation in stems and leaves of marigold seedlings.     

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 PO₄³⁻, SiO₄⁴⁻, CO₃²⁻ 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 PO₄³⁻ and polymerized silica. However, these species could not impede the quantitative association of As with colloidal ferrihydrite in the soil effluents.     

Arsenic sorption by red mud-modified biochar produced from rice straw

Red mud-modified biochar (RM-BC) has been produced to be utilized as a novel adsorbent to remove As because it can effectively combine the beneficial features of red mud (rich metal oxide composition and porous structure) and biochar (large surface area and porous structure properties). SEM-EDS and XRD analyses demonstrated that red mud had loaded successfully on the surface of biochar. With the increasing of pH in solution, arsenate (As(V)) adsorption on RM-BC decreased while arsenite (As(III)) increased. Arsenate adsorption kinetics process on RM-BC fitted the pseudo-second-order model, while that of As(III) favored the Elovich model. All sorption isotherms produced superior fits with the Langmuir model. RM-BC exhibited improved As removal capabilities, with a maximum adsorption capacity (Q_max) for As(V) of 5923 μg g^?1, approximately ten times greater than that of the untreated BC (552.0 μg g^?1). Furthermore, it has been indicated that the adsorption of As(V) on RM-BC may be strongly associated with iron oxides (hematite and magnetite) and aluminum oxides (gibbsite) by X-ray absorption near-edge spectroscopy (XANES), which was possibly because of surface complexation and electrostatic interactions. RM-BC may be used as a valuable adsorbent for removing As in the environment due to the waste materials being relatively abundant.     

Distribution and Fractionation of Phosphorus,Cadmium, Nickel,and Lead in Calcareous Soils Amended with Composts

Abstract

Composts improve organic carbon content and nutrients of calcareous soils but the accumulation and distribution of phosphorus and heavy metals among various fractions in soil may vary under the south Florida conditions. The accumulation of P, Cd, Ni, and Pb with depth and the distribution of water soluble, exchangeable, carbonate, Fe–Mn oxides, organic and residual forms of each element were investigated in soils amended with municipal solid waste (MSW) compost, co-compost and biosolids compost and inorganic fertilizer (as control). Total concentrations of P, Cd, Ni, and Pb were higher in the 0–22 cm soil layers and decreased considerably in the rock layers. These elements were in the decreasing order of P ? Pb > Ni > Cd. Amounts of water soluble and exchangeable forms of P, Cd, Ni and Pb were negligible at 0–22 cm soil depths except for Cd in the 10–22 cm depth. Amending calcareous soil with either organic or inorganic amendments rendered phosphorus, nickle and lead in the residual form followed by Fe–Mn oxides form in the 0–10 and 10–22 cm soil layers. Cadmium was predominantly in the Fe–Mn oxides fraction followed by the residual and carbonate forms in both soil layers. A significant positive correlation was found between various organic carbon fractions and organic forms of P, Cd and Pb in the surface soil layer. Soil amended with MSW compost had higher concentration of Cd in the organic fraction whereas, co-compost and MSW compost amended soil had higher concentrations of organic Ni fraction in the 0–10 cm soil layer.     

Natural radionuclides distribution and environmental impacts of ferruginous sand-siltstone (raw material) and their manufactured Ahmer oxide used as wall paints

Commercially known Ahmer oxide paints are prepared from raw material mainly composed of red iron oxides (hematite) and iron oxyhydroxides. The raw material used in manufacturing of Ahmer oxide comes from some localities in southwest Sinai such as Abu Thor, Allouga, and El lehian. The adsorption of uranium and other radioelements on iron oxides could make the raw material (red iron oxides) and their products environmentally hazardous. The studied samples were subjected to radiometric analysis using NaI (Tl) gamma-ray spectrometer. The average activity concentration of U, Th, Ra, and K are 108.7, 458.8, 88.8, and 627.5?Bq?kg^?1, respectively in raw material and 136.4, 14.6, 58.3, and 95.9?Bq?kg^?1 in Ahmer oxide. High values of activity concentrations of ²³⁸U, ²²⁶Ra, and ⁴⁰K were recorded in Allouga and El lehian raw material. High radioactivities of Allouga and El lehian raw material are mainly attributed to the presence of torbernite, zircon, and monazite, in addition to adsorbed elemental uranium in Ahmer oxide. absorbed dose rate (D), annual effective dose equivalent, radium equivalent activity (Ra_eq), external hazard index (H_ex), and internal hazard index (H_in), as well as representative gamma index (Iγ) were determined from the activity concentrations of ²²⁶Ra, ²³²Th, and ⁴⁰K. Some of the studied samples do not satisfy the universal standards.     

Removal of arsenic(III,V) by a granular Mn-oxide-doped Al oxide adsorbent: surface characterization and performance

In order to remove arsenic (As) from contaminated water, granular Mn-oxide-doped Al oxide (GMAO) was fabricated using the compression method with the addition of organic binder. The analysis results of XRD, SEM, and BET indicated that GMAO was microporous with a large specific surface area of 54.26 m^2/g, and it was formed through the aggregation of massive Al/Mn oxide nanoparticles with an amorphous pattern. EDX, mapping, FTIR, and XPS results showed the uniform distribution of Al/Mn elements and numerous hydroxyl groups on the adsorbent surface. Compression tests indicated a satisfactory mechanical strength of GMAO. Batch adsorption results showed that As(V) adsorption achieved equilibrium faster than As(III), whereas the maximum adsorption capacity of As(III) estimated from the Langmuir isotherm at 25 °C (48.52 mg/g) was greater than that of As(V) (37.94 mg/g). The As removal efficiency could be maintained in a wide pH range of 3~8. The presence of phosphate posed a significant adverse effect on As adsorption due to the competition mechanisms. In contrast, Ca²⁺ and Mg²⁺ could favor As adsorption via cation-bridge involvement. A regeneration method was developed by using sodium hydroxide solution for As elution from saturated adsorbents, which permitted GMAO to keep over 75% of its As adsorption capacity even after five adsorption–regeneration cycles. Column experiments showed that the breakthrough volumes for the treatment of As(III)-spiked and As(V)-spiked water (As concentration = 100 μg/L) were 2224 and 1952, respectively. Overall, GMAO is a potential adsorbent for effectively removing As from As-contaminated groundwater in filter application.

     

Deposition of Mn from Automotive Combustion of Methylcyclopentadienyl Manganese Tricarbonyl beside the Major Highways in the Greater Toronto Area,Canada

ABSTRACT

Methylcyclopentadienyl manganese tricarbonyl (MMT) has been used in Canada since 1976 as an antiknock agent in gasoline, completely replacing Pb in 1990. An early study of much higher Mn concentrations in gasoline showed that the combustion of MMT leads to the formation of inorganic manganese oxides, especially Mn₃O₄. Recent emission testing by Lawrence Livermore National Laboratory for Ethyl Corp. has shown that Mn is primarily emitted as a phosphate or sulfate along with minor amounts of oxides. The main objective of this research was to analyze the deposition of Mn from MMT to the terrestrial environment beside the major highways in the greater Toronto area (GTA), Canada. The results were compared with Pb and other trace elements such as Al, Ca, Fe, Mg, Cu, Zn, Na, and the Cl^- ion (water extractable) to study the behavior of Mn in soil. The study area was located near major Toronto highways 401 (urban) and 400 (rural), at 43° 67′ N and 79° 37′ W (latitude and longitude) (278,560 and 47,835 cars/day), respectively. Surface soil samples (0–5 cm depth) were collected at distances up to 40 m from the roadside. Parameters evaluated included total and available Mn and other trace elements, particle size, pH, organic content, and cation exchange capacity.     

Characteristics of re-suspended road dust and its impact on the atmospheric environment in Beijing

A sampling campaign of re-suspended road dust samples from 53 sites that could cover basically the entire Beijing, soil samples from the source regions of dust storm in August 2003, and aerosol samples from three representative sites in Beijing from December 2001 to September 2003, was carried out to investigate the characteristics of re-suspended road dust and its impact on the atmospheric environment. Ca, S, Cu, Zn, Ni, Pb, and Cd were far higher than its crustal abundances and Ca²⁺, SO₄²⁻, Cl⁻, K⁺, Na⁺, NO₃⁻ were major ions in re-suspended road dust. Al, Ti, Sc, Co, and Mg in re-suspended road dust were mainly originated from crustal source, while Cu, Zn, Ni, and Pb were mainly derived from traffic emissions and coal burning, and Fe, Mn, and Cd were mainly from industrial emissions, coal combustion and oil burning. Ca²⁺ and SO₄²⁻ mainly came from construction activities, construction materials and secondary gas-particle conversions, Cl⁻ and Na⁺ were derived from industrial wastewater disposal and chemical industrial emissions, and NO₃⁻ and K⁺ were from vehicle emissions, photochemical reactions of NO_X, biomass and vegetable burning. The contribution of mineral aerosol from inside Beijing to the total mineral aerosols was ∼30% in spring of 2002, ∼70% in summer of 2002, ∼80% in autumn of 2003, ∼20% in PM₁₀ and ∼50% in PM_2.5, in winter of 2002. The pollution levels of the major pollution species, Ca, S, Cu, Zn, Ni, Pb, Fe, Mn, and Cd in re-suspended road dust reached ∼76%, ∼87%, ∼75%, ∼80%, ∼82%, ∼90%, ∼45%, ∼51%, and ∼94%, respectively. Re-suspended road dust from the traffic and construction activities was one of the major sources of pollution aerosols in Beijing.     

A new approach for modelling potential effects in cation adsorption onto binary (hydr) oxides

The current approach for modelling ion adsorption onto binary (hydr)oxides using homogeneous surface complexation models involves the assumption of either an ideal mixture of the two surfaces (i.e. two surface sites on one surface) or a patchwise surface (i.e. two surfaces with one surface site on each surface). As the physical truth should be between these two limiting cases, a model which assumes a patchwise surface constituted of three patches is proposed. Two patches represent the distinct (hydr)oxides, and the third one a mixture of these distinct (hydr)oxides. Using the diffuse layer model, the three approaches are applied to literature data for Cd adsorption onto binary mixtures of alumina-coated silica at total constant Cd concentration and varying amounts of alumina coatings. For Cd adsorption onto these binary (hydr)oxide systems, the new approach explains the observed potential effects. The proposed model, which contains two additional adjustable parameters in terms of site concentrations or one adjustable parameter in terms of specific surface area, is more successful than the two limiting cases. The new model is then validated by predicting Ca and Zn behaviour on the same binary (hydr)oxide system.     

Study on fractions of adsorbed Pb and Cd onto natural surface coatings

The speciation and extent of migration of adsorbed Pb and Cd in natural surface coatings (NSCs) were investigated using sequential extraction procedure to provide an understanding of distribution of the adsorbed Pb and Cd. Extractions were conducted on NSCs before and after Pb and Cd adsorption treatment under controlled laboratory conditions with initial Pb and Cd concentrations ranging from 0.2-2.5 mol/l. The Langmuir adsorption isotherms were applied to estimate equilibrium coefficients of Pb and Cd adsorption to NSCs components. The results showed that 58.50% of adsorbed Pb in average existed in tightly adsorbed form, and the remaining Pb was mostly present as solid oxides/hydroxides (34.00%) and exchangeable and soluble form (7.50%) in NSCs, respectively. Large amount of adsorbed Cd (70.51% in average) was present in exchangeable and soluble form, following a decreasing order in tightly adsorbed form (18.61%), solid oxides/hydroxides (9.87%), and easily oxidizable solids/compounds (1.01%), respectively. No Cd was found in strongly held oxides and precipitates. Compared to the distribution of adsorbed Pb in NSCs, Cd distribution showed that less migration of Cd from exchangeable and soluble form to solid oxides/hydroxides after adsorbed to NSCs, indicating fewer sites for Cd to adsorb to NSCs and less affinity of Cd to the NSCs. These percent distributions of metals provided an additional interpretation to that Pb adsorption to the NSCs greater than that of Cd, less retention of Cd than that of Pb and less roles attributed for Pb/Cd adsorption by organic materials in NSCs, which were observed based on the selective extraction techniques in the independent investigations.