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1.
The photoconversion of As(III) (arsenite) and As(V) (arsenate) over a mesoporous TiO(2) electrode was investigated in a photoelectrochemical (PEC) cell for a wide range of concentrations (μM-mM), under nonbiased (open-circuit potential measurements) and biased (short-circuit current measurements) conditions. Not only As(III) can be oxidized, but also As(V) can be reduced in the anoxic condition under UV irradiation. However, the reversible nature of As(III)/As(V) photoconversion was not observed in the normal air-equilibrated condition because the dissolved O(2) is far more efficient as an electron acceptor than As(V). Although As(III) should be oxidized by holes, its presence did not increase the photooxidation current in a monotonous way: the photocurrent was reduced by the presence of As(III) in the micromolar range but enhanced in the millimolar range. This abnormal concentration-dependent behavior is related with the fate of the intermediate As(IV) species which can be either oxidized or reduced depending on the experimental conditions, combined with surface deactivation for the water photooxidation process. The lowering of the photooxidation current in the presence of micromolar As(III) is ascribed to the role of As(IV) as a charge recombination center. Being an electron acceptor, the addition of As(V) consistently lowers the photocurrent in the entire concentration range. A global concentration-dependent mechanism is proposed accounting for all the PEC results and its relation with the photocatalytic oxidation mechanism is discussed.  相似文献   

2.
Arsenic sorption onto maghemite potentially contributes to arsenic retention in magnetite-based arsenic removal processes because maghemite is the most common oxidation product of magnetite and may form a coating on magnetite surfaces. Such a sorption reaction could also favor arsenic immobilization at redox boundaries in groundwaters. The nature of arsenic adsorption complexes on maghemite particles, at near-neutral pH under anoxic conditions, was investigated using X-ray absorption fine structure (XAFS) spectroscopy at the As K-edge. X-ray absorption near edge structure spectra indicate that As(III) does notoxidize after 24 h in any of the sorption experiments, as already observed in previous studies of As(III) sorption on ferric (oxyhydr)oxides under anoxic conditions. The absence of oxygen in our sorption experiments also limited Fenton oxidation of As(III). Extended XAFS (EXAFS) results indicate that both As(III) and As(V) form inner-sphere complexes on the surface of maghemite, under high surface coverage conditions (approximately 0.6 to 1.0 monolayer), with distinctly different sorption complexes for As(III) and As(V). For As(V), the EXAFS-derived As-Fe distance (approximately 3.35 +/- 0.03 A) indicates the predominance of single binuclear bidentate double-corner complexes (2C). For As(III), the distribution of the As-Fe distance suggests a coexistence of various types of surface complexes characterized by As-Fe distances of approximately 2.90 (+/-0.03) A and approximately 3.45 (+/-0.03) A. This distribution can be interpreted as being due to a dominant contribution from bidentate binuclear double-corner complexes (2C), with additional contributions from bidentate mononuclear edge-sharing (2E) complexes and monodentate mononuclear corner-sharing complexes (1V). The present results yield useful constraints on As(V) and As(III) adsorption on high surface-area powdered maghemite, which may help in modeling the behavior of arsenic at the maghemite-water interface.  相似文献   

3.
The speciation and partitioning of arsenic (As) in surface and subsurface environments are controlled, in part, by redox processes. Within soils and sediments, redox gradients resulting from mass transfer limitations lead to competitive reduction-oxidation reactions that drive the fate of As. Accordingly, the objective of this study was to determine the fate and redox cycling of As at the interface of birnessite (a strong oxidant in soil with a nominal formula of MnO(x), where x ≈ 2) and dissimilatory As(V)-reducing bacteria (strong reductant). Here, we investigate As reduction-oxidation dynamics in a diffusively controlled system using a Donnan reactor where birnessite and Shewanella sp. ANA-3 are isolated by a semipermeable membrane through which As migrates. Arsenic(III) injected into the reaction cell containing birnessite is rapidly oxidized to As(V). Arsenic(V) diffusing into the Shewanella chamber is then reduced to As(III), which subsequently diffuses back to the birnessite chamber, undergoing oxidation, and establishing a continuous cycling of As. However, we observe a rapid decline in the rate of As(III) oxidation owing to passivation of the birnessite surface. Modeling and experimental results show that high [Mn(II)] combined with increasing [CO(3)(2-)] from microbial respiration leads to the precipitation of rhodochrosite, which eventually passivates the Mn oxide surface, inhibiting further As(III) oxidation. Our results show that despite the initial capacity of birnessite to rapidly oxidize As(III), the synergistic effect of intense As(V) reduction by microorganisms and the buildup of reactive metabolites capable of passivating reactive mineral surfaces-here, birnessite-will produce (bio)geochemical conditions outside of those based on thermodynamic predictions.  相似文献   

4.
5.
Analysis of arsenic concentrations in New Jersey well water from the Newark Basin showed up to 15% of the wells exceed 10 microg L(-1), with a maximum of 215 microg L(-1). In some geologic settings in the basin, this mobile arsenic could be from the weathering of pyrite (FeS2) found in black shale that contains up to 4% arsenic by weight. We hypothesized that under oxic conditions at circumneutral pH, the microbially mediated oxidation of sulfide in the pyrite lattice would lead to the release of pyrite-bound arsenic. Moreover, the oxidation of aqueous As(III) to As(V) by aerobic microorganisms could further enhance arsenic mobilization from the solid phase. Enrichment cultures under aerobic, As(III)-oxidizing conditions were established under circumneutral pH with weathered black shale from the Newark Basin as the inoculum source. Strain WAO, an autotrophic inorganic-sulfur and As(III)-oxidizer, was isolated and phylogenetically and physiologically characterized. Arsenic mobilization studies from arsenopyrite (FeAsS) mineral, conducted with strain WAO at circumneutral pH, showed microbially enhanced mobilization of arsenic and complete oxidation of released arsenic and sulfur to stoichiometric amounts of arsenate and sulfate. In addition, WAO preferentially colonized pyrite on the surface of arsenic-bearing, black shale thick sections. These findings support the hypothesis that microorganisms can directly mobilize and transform arsenic bound in mineral form at circumneutral pH and suggest that the microbial mobilization of arsenic into groundwater may be important in other arsenic-impacted aquifers.  相似文献   

6.
Laboratory experiments and modeling studies were performed to investigate the redox transformations of arsenic and iron in water treatment sludge during aging, and to evaluate the impact of those transformations on the leachability of arsenic determined with the U.S. EPA toxicity characteristic leaching procedure (TCLP). When the backwash suspension samples collected from a California surface water treatment plant were aged in closed containers for a few weeks, soluble arsenic increased from less than 5 microg/L to as high as 700 microg/L and then decreased dramatically because of biotic reduction of arsenate [As(V)], ferric oxyhydroxide, and sulfate. The experimental results and the thermodynamic models showed that arsenic mobility can be divided into three redox zones: (a) an adsorption zone at pe > 0, which is characterized by strong adsorption of As(V) on ferric oxyhydroxide; (b) a mobilization (transition) zone at -4.0 < pe < 0, where arsenic is released because of reduction of ferric oxyhydroxide to ferrous iron and As(V) to arsenite [As(III)]; and (c) a reductive fixation zone at pe < -4.0, where arsenic is immobilized by pyrite and other reduced solid phases. The TCLP substantially underestimated the leachability of arsenic in the anoxic sludge collected from sludge ponds because of the oxidation of Fe(II) and As(III) by oxygen. The leaching test should be performed in zero-headspace vessels or under nitrogen to minimize the transformations of the redox-sensitive chemical species.  相似文献   

7.
An electrochemically prepared water treatment reagent containing a high concentration of Al(13) polymer and active chlorine (PACC) showed promising potential for the removal of As(III) due to the combined function of oxidation and coagulation. The results indicated that PACC was effective for As(III) removal through oxidation by the active chlorine and subsequent removal of As(V) by coagulation with the Al(13) polymer. The As(III) was oxidized to As(V) by active chlorine in PACC, with a stoichiometric rate of 0.99 mg Cl(2)/mg As(III). The Al(13) polymer was the most active Al species responsible for As(V) removal in PACC. To meet As drinking water standards the stoichiometric weight ratio of Cl(2)/Al within PACC was 0.09 for the treatment of As(III). Considering the process of As(III) oxidation and As(V) coagulation together, the optimal pH conditions for the removal of As by PACC was within the neutral range, which facilitated the reaction of As(III) with active chlorine and favored the formation of Al hydroxide flocs. The presence of humic acid reduced the As(III) removal efficiency of PACC due to its negative influence on subsequent As(V) coagulation, and disinfection byproduct yields were very low in the presence of insufficient or stoichiometric active chlorine.  相似文献   

8.
Due to their redox reactivity, surface sorption characteristics, and ubiquity as corrosion products or as minerals in natural sediments, iron(II)-bearing minerals control to a large extent the environmental fate of actinides. Pu-L(III)-edge XANES and EXAFS spectra were used to investigate reaction products of aqueous (242)Pu(III) and (242)Pu(V) reacted with magnetite, mackinawite, and chukanovite under anoxic conditions. As Pu concentrations in the liquid phase were rapidly below detection limit, oxidation state and local structure of Pu were determined for Pu associated with the solid mineral phase. Pu(V) was reduced in the presence of all three minerals. A newly identified, highly specific Pu(III)-sorption complex formed with magnetite. Solid PuO(2) phases formed in the presence of mackinawite and chukanovite; in the case of chukanovite, up to one-third of plutonium was also present as Pu(III). This highlights the necessity to consider, under reducing anoxic conditions, Pu(III) species in addition to tetravalent PuO(2) for environmental risk assessment. Our results also demonstrate the necessity to support thermodynamic calculations with spectroscopic data.  相似文献   

9.
XAS speciation of arsenic in a hyper-accumulating fern   总被引:1,自引:0,他引:1  
The coordination environment and the redox speciation of arsenic in a newly discovered arsenic hyper-accumulating fern (Pteris vittata L) were investigated by X-ray absorption spectroscopy. This method allowed us to probe arsenic directly, i.e., with minimal sample preparation. The results indicate that arsenic is predominantly accumulated as As(III) in the leaves. XANES and EXAFS results show that As(III) in the leaves is primarily present as aqueous arsenite species. The plant actively maintains arsenic in this reduced oxidation state, because after sample collection and subsequent aging and drying of the plant material, As(III) is gradually oxidized to As(V). We think that these arsenite species are sequestered in vacuoles. At extremely high As concentrations (ca. 1% As per dry weight) arsenic in the fern leaves is coordinated to a significant degree by sulfur in addition to oxygen. This spectral signature indicates that thiol-rich compounds are implicated in the biochemical transformations of arsenic within the plant.  相似文献   

10.
An estimated 30-50 million people in Bangladesh consume groundwater with arsenic contents far above accepted limits. A better understanding of arsenic redox kinetics and simple water treatment procedures are urgently needed. We have studied thermal and photochemical As(III) oxidation in the laboratory, on a time scale of hours, in water containing 500 micrograms/L As(III), 0.06-5 mg/L Fe(II,III), and 4-6 mM bicarbonate at pH 6.5-8.0. As(V) was measured colorimetrically, and As(III) and As(tot) were measured by As(III)/As(tot)-specific hydride-generation AAS. Dissolved oxygen and micromolar hydrogen peroxide did not oxidize As(III) on a time scale of hours. As(III) was partly oxidized in the dark by addition of Fe(II) to aerated water, presumably by reactive intermediates formed in the reduction of oxygen by Fe(II). In solutions containing 0.06-5 mg/L Fe(II,III), over 90% of As(III) could be oxidized photochemically within 2-3 h by illumination with 90 W/m2 UV-A light. Citrate, by forming Fe(III) citrate complexes that are photolyzed with high quantum yields, strongly accelerated As(III) oxidation. The photoproduct of citrate (3-oxoglutaric acid) induced rapid flocculation and precipitation of Fe(III). In laboratory tests, 80-90% of total arsenic was removed after addition of 50 microM citrate or 100-200 microL (4-8 drops) of lemon juice/L, illumination for 2-3 h, and precipitation. The same procedure was able to remove 45-78% of total arsenic in first field trials in Bangladesh.  相似文献   

11.
H2 thresholds for microbial respiration of arsenate (As(V)) were investigated in a pure culture of Sulfurospirillum arsenophilum. H2 was consumed to threshold concentrations of 0.03-0.09 nmol/L with As(V) as terminal electron acceptor, allowing for a Gibbs free-energy yield of 36-41 kJ per mol of reaction. These thresholds are among the lowest measured for anaerobic respirers and fall into the range of denitrifiers or Fe(III)-reducers. In sediments from an arsenic-contaminated aquifer in the Red River flood plain, Vietnam, H2 levels decreased to 0.4-2 nmol/L when As(V) was added under anoxic conditions. When As-(V) was depleted, H2 concentrations rebounded by a factor of 10, a level similar to that observed in arsenic-free controls. The sediment-associated microbial population completely reduced millimolar levels of As(V) to arsenite (As-(III)) within a few days. The rate of As(V)-reduction was essentially the same in sediments amended with a pure culture of S. arsenophilum. These findings together with a review of observed H2 threshold and steady-state values suggest that microbial As(V)-respirers have a competitive advantage over several other anaerobic respirers through their ability to thrive at low H2 levels.  相似文献   

12.
Mobilization of arsenic from freshwater and estuarine sediments during the transition from oxic to anoxic conditions was investigated using recently developed diffusive sampling techniques. Arsenic speciation and Fe(II) concentrations were measured at high resolution (1-3 mm) with in situ diffusive gradients in thin films (DGT) and diffusive equilibration in thin films (DET) techniques. Water column anoxia induced Fe(II) and As(III) fluxes from the sediment. A correlation between water column Fe(II) and As(III) concentrations was observed in both freshwater (r(s) = 0.896, p < 0.001) and estuarine (r(s) = 0.557, p < 0.001) mesocosms. Porewater sampling by DGT and DET techniques confirmed that arsenic mobilization was associated with the reductive dissolution of Fe(III) (hydr)oxides in the suboxic zone of the sediment; a relationship that was visible because of the ability to measure the coincident profiles of these species using combined DGT and DET samplers. The selective measurement of As(III) and total inorganic arsenic by separate DGT samplers indicated that As(III) was the primary species mobilized from the solid phase to the porewater. This measurement approach effectively ruled out substantial As(V) mobilization from the freshwater and estuarine sediments in this experiment. This study demonstrates the capabilities of the DGT and DET techniques for investigating arsenic speciation and mobilization over a range of sediment conditions.  相似文献   

13.
Bacterial reduction of arsenic(V) and iron(III) oxides influences the redox cycling and partitioning of arsenic (As) between solid and aqueous phases in sediment-porewater systems. Two types of anaerobic bacterial incubations were designed to probe the relative order of As(V) and Fe(III) oxide reduction and to measure the effect of adsorbed As species on the rate of iron reduction, using hydrous ferric oxide (HFO) as the iron substrate. In one set of experiments, HFO was pre-equilibrated with As(V) and inoculated with fresh sediment from Haiwee Reservoir (Olancha, CA), an As-impacted field site. The second set of incubations consisted of HFO (without As) and As(III)- and As(V)- equilibrated HFO incubated with Shewanella sp. ANA-3 wild-type (WT) and ANA-3deltaarrA, a mutant unable to produce the respiratory As(V) reductase. Of the two pathways for microbial As(V) reduction (respiration and detoxification), the respiratory pathway was dominant under these experimental conditions. In addition, As(III) adsorbed onto the surface of HFO enhanced the rate of microbial Fe(III) reduction. In the sediment and ANA-3 incubations, As(V) was reduced simultaneously or prior to Fe(III), consistent with thermodynamic calculations based on the chemical conditions of the ANA-3 WT incubations.  相似文献   

14.
While a high efficiency of contaminant removal by nanoscale zerovalent iron (nZVI) has often been reported for several contaminants of great concern, including aqueous arsenic species, the transformations and translocation of contaminants at and within the nanoparticles are not clearly understood. By analysis using in situ time-dependent X-ray absorption spectroscopy (XAS) of the arsenic core level for nZVI in anoxic As(III) solutions, we have observed that As(III) species underwent two stages of transformation upon adsorption at the nZVI surface. The first stage corresponds to breaking of As-O bonds at the particle surface, and the second stage involves further reduction and diffusion of arsenic across the thin oxide layer enclosing the nanoparticles, which results in arsenic forming an intermetallic phase with the Fe(0) core. Extended X-ray absorption fine-structure (EXAFS) data from experiments conducted at different iron/arsenic ratios indicate that the reduced arsenic species tend to be enriched at the surface of the Fe(0) core region and had limited mobility into the interior of the metal core within the experimental time frame (up to 22 h). Therefore, there was an accumulation of partially reduced arsenic at the Fe(0)/oxide interface when a relatively large arsenic content was present in the solid phase. These results illuminate the role of intraparticle diffusion and reduction in affecting the chemical state and spatial distribution of arsenic in nZVI materials.  相似文献   

15.
We investigated the stoichiometry, kinetics, and mechanism of arsenite [As(III)] oxidation by ferrate [Fe(VI)] and performed arsenic removal tests using Fe(VI) as both an oxidant and a coagulant. As(III) was oxidized to As(V) (arsenate) by Fe(VI), with a stoichiometry of 3:2 [As(III):Fe(VI)]. Kinetic studies showed that the reaction of As(III) with Fe(VI) was first-order with respect to both reactants, and its observed second-order rate constant at 25 degrees C decreased nonlinearly from (3.54 +/- 0.24) x 10(5) to (1.23 +/- 0.01) x 10(3) M(-1) s(-1) with an increase of pH from 8.4 to 12.9. A reaction mechanism by oxygen transfer has been proposed for the oxidation of As(III) by Fe(VI). Arsenic removal tests with river water showed that, with minimum 2.0 mg L(-1) Fe(VI), the arsenic concentration can be lowered from an initial 517 to below 50 microg L(-1), which is the regulation level for As in Bangladesh. From this result, Fe(VI) was demonstrated to be very effective in the removal of arsenic species from water at a relatively low dose level (2.0 mg L(-1)). In addition, the combined use of a small amount of Fe(VI) (below 0.5 mg L(-1)) and Fe(III) as a major coagulant was found to be a practical and effective method for arsenic removal.  相似文献   

16.
Oxidation of arsenite, As(III), to arsenate, As(V), is required for the efficient removal of arsenic by many water treatment technologies. The photocatalyzed oxidation of As(III) on titanium dioxide, TiO2, offers an environmentally benign method for this unit operation. In this study, we explore the efficacy and mechanism of TiO2-photocatalyzed As(III) oxidation at circumneutral pH and over a range of As(III) concentrations approaching those typically encountered in water treatment systems. We focus on the effect of As adsorption on observed rates of photooxidation. Adsorption (in the dark) of both As(III) and As(V) on Degussa P25 TiO2 was examined at pH 6.3 over a range in dissolved arsenic concentrations, [As]diss, of 0.10-89 microM and 0.2 or 0.05 g L(-1) TiO2 for As(III) and As(V), respectively. Adsorption isotherms generally followed the Langmuir-Hinshelwood model with As(III) exhibiting an adsorption maxima of 32 micromol g(-1). As(V) adsorption did not reach a plateau under the experimental conditions examined; the maximum adsorbed concentration observed was 130 micromol g(-1). The extent of As(III) and As(V) adsorption observed at the beginning and end of the kinetic studies was consistent with that observed in the adsorption isotherms. Kinetic studies were performed in batch systems at pH 6.3 with 0.8-42 microM As(III) and 0.05 g L(-1) TiO2; complete oxidation of As(III) was observed within 10-60 min of irradiation at 365 nm. The observed effect of As(III) concentration on reaction kinetics was consistent with surface saturation at higher concentrations. Addition of phosphate at 0.5-10 microM had little effect on either As(III) sorption or its photooxidation rate but did inhibit adsorption of the product As(V). The selective use of hydroxyl radical quenchers and superoxide dismutase demonstrated that superoxide, O2-, plays a major role in the oxidation of As(III) to As(V).  相似文献   

17.
Arsenite retention mechanisms within estuarine sediments of Pescadero, CA   总被引:2,自引:0,他引:2  
Arsenic, a toxic metalloid, is commonly associated with sulfide minerals in anoxic sediments. Here we characterize arsenic(III) retention on sediments from a sulfidic estuarine marsh using a series of sorption experiments, and probe the structure of retained arsenite with X-ray absorption spectroscopy. Although the extent of sorption varied with sampling locations, several adsorption characteristics were apparent. A fraction of arsenite adsorbed over the entire pH range examined, although it was most extensive at pH greater than 7, and conformed to a Langmuir isotherm. Iron sulfide phases were responsible for As partitioning in these sediments. Initially, an FeAsS-like precipitate formed with a structure similar to those reported for As(III) sorbed on iron sulfides, a complex that is highly reactive. Following reaction for 21 d, much of the FeAsS-like precipitate was converted to As2S3. A drop in the redox potential accompanied this conversion, suggesting that the evolution of sulfide and other reduced species stabilizes bound arsenic. Processes discerned in this study reveal the importance of sulfide minerals in As sequestration within anoxic environments.  相似文献   

18.
A novel Fe-Mn binary oxide adsorbent was developed for effective As(III) removal, which is more difficult to remove from drinking water and much more toxic to humans than As(V). The synthetic adsorbent showed a significantly higher As(III) uptake than As(V). The mechanism study is therefore necessary for interpreting such result and understanding the As(III) removal process. A control experiment was conducted to investigate the effect of Na2SO3-treatment on arsenic removal, which can provide useful information on As(III) removal mechanism. The adsorbent was first treated by Na2SO3, which can lower its oxidizing capacity by reductive dissolution of the Mn oxide and then reacted with As(V) or As(III). The results showed that the As(V) uptake was enhanced while the As(III) removal was inhibited after the pretreatment, indicating the important role of manganese dioxide during the As(III) removal. FTIR along with XPS was used to analyze the surface change of the original Fe-Mn adsorbent and the pretreated adsorbent before and after reaction with As(V) or As(III). Change in characteristic surface hydroxyl groups (Fe-OH, 1130, 1048, and 973 cm(-1)) was observed by the FTIR. The determination of arsenic oxidation state on the solid surface after reaction with As(III) revealed that the manganese dioxide instead of the iron oxide oxidized As(III) to As(V). The iron oxide was dominant for adsorbing the formed As(V). An oxidation and sorption mechanism for As(III) removal was developed. The relatively higher As(III) uptake may be attributed to the formation of fresh adsorption sites at the solid surface during As(III) oxidation.  相似文献   

19.
Arsenic removal by passive treatment, in which naturally present Fe(II) is oxidized by aeration and the forming iron(III) (hydr)oxides precipitate with adsorbed arsenic, is the simplest conceivable water treatment option. However, competing anions and low iron concentrations often require additional iron. Application of Fe(II) instead of the usually applied Fe(III) is shown to be advantageous, as oxidation of Fe(II) by dissolved oxygen causes partial oxidation of As(III) and iron(III) (hydr)oxides formed from Fe(II) have higher sorption capacities. In simulated groundwater (8.2 mM HCO3(-), 2.5 mM Ca2+, 1.6 mM Mg2+, 30 mg/L Si, 3 mg/L P, 500 ppb As(III), or As(V), pH 7.0 +/- 0.1), addition of Fe(II) clearly leads to better As removal than Fe(III). Multiple additions of Fe(II) further improved the removal of As(II). A competitive coprecipitation model that considers As(III) oxidation explains the observed results and allows the estimation of arsenic removal under different conditions. Lowering 500 microg/L As(III) to below 50 microg/L As(tot) in filtered water required > 80 mg/L Fe(III), 50-55 mg/L Fe(II) in one single addition, and 20-25 mg/L in multiple additions. With As(V), 10-12 mg/L Fe(II) and 15-18 mg/L Fe(III) was required. In the absence of Si and P, removal efficiencies for Fe(II) and Fe(III) were similar: 30-40 mg/L was required for As(II), and 2.0-2.5 mg/L was required for As(V). In a field study with 22 tubewells in Bangladesh, passive treatment efficiently removed phosphate, but iron contents were generally too low for efficient arsenic removal.  相似文献   

20.
为更全面深入地评价卷烟烟气中砷的危害,建立了一种砷形态分离测定方法。用超声溶剂提取剑桥滤片捕集的卷烟主流烟气中的砷,AB-8 大孔吸附树脂分离有机态和无机态砷,717 强碱阴离子交换树脂进一步分离无机态中的As(Ⅲ) 和As(Ⅴ)。对影响As(Ⅲ) 和As(Ⅴ) 分离的实验条件进行了研究,并确定了较佳分离条件。考察了分离方法的精密度和回收率,结果表明:该方法相对标准偏差(RSD,n=6)3.5%-4.7%,无机态砷加标回收率90.6%-102.4%。检出限和定量限分别为0.013μg/L 和0.043μg/L。该方法准确、可靠,可有效地用于卷烟主流烟气中砷的形态分析。   相似文献   

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