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1.
Cyromazine (CY) is a triazine pesticide used as an insect growth inhibitor for fly control in cattle manure, field crops, vegetables, and fruits. Sorption of CY onto humic acid (HA) may affect its environmental fate. In this study, HA was used to investigate the sorption of CY at different solution chemistry conditions (pH, ionic strength) and in the presence of foreign ions and norfloxacin. All sorption isotherms fitted well with the Freundlich and Langmuir models. The sorption reached a maximum at initial pH 4.0 over the initial pH range of 3.0–7.0, implying that the primary sorption mechanism was cation exchange interaction between CY+ species and the negatively charged functional groups of HA. Increasing Ca2+ concentration resulted in a considerable reduction in the K d values of CY, hinting that Ca2+ had probably competed with CY+ for the cation exchange sites on the surfaces of HA. The sorption of CY on HA in different ionic media followed the order of NH4Cl ≈ KCl > K2SO4 > ZnCl2 ≈ CaCl2 at pH 5.0. Spectroscopic evidence demonstrated that the amino groups and triazine ring of CY was responsible for sorption onto HA, while the carboxyl group and the O-alkyl structure of HA participated in adsorbing CY.  相似文献   

2.
Abstract

The formation of the insecticide methidathion (S-[(5-methoxy-2-oxo-1,3,4-thiadiazol-3(2H)-yl)methyl] O,O-dimethyl phosphorodithioate) complexes with inorganic cation-saturated (Mg2+, Ca2+, Cu2+, and Ni2+) montmorillonites was investigated. The nature and structure of the complexes was determined by X-ray diffraction and infrared spectroscopy. The arrangement of the pesticide molecule in the interlayer space was also considered from ab initio calculations using simpler related molecules. The insecticide methidathion penetrated the interlayer spaces of the homoionic clay samples. The ligand–cation interactions in these complexes depend on the nature and characteristics of the saturating cations. Mechanisms involving water bridges and direct coordination with the exchange cation were proposed for the adsorption of methidathion by inorganic cation-saturated montmorillonites. The effect of the inorganic cations on the sorption of the cationic surfactant tetradecyltrimethylammonium bromide (TDTMA) by montmorillonite was also studied and the subsequent sorption of methidathion in TDTMA+-Montmorillonite determined. Van der Waals bonds constitute the methidathion adsorption mechanism by montmorillonite saturated with TDTMA+. The arrangements of methidathion and of the cationic surfactant molecules in the montmorillonite interlayer space were demostrated.  相似文献   

3.
Quinoline sorption was measured on Na-saturated subsurface materials, a natural clay isolate, and montmorillonite, and was dominated by exchange of the quinolinium ion. In water/methanol and water/acetone mixtures, quinoline sorption on the subsoils and clays was lower than from water. In cosolvent, sorption followed the ionization fraction indicating the continued predominance of ion exchange. The reduction in quinoline sorption by cosolvent was similar for all the subsoils and clays indicating commonality in the surface-solute-solvent interaction. Conditional equilibrium constants (cKex) for quinoline exchange on the subsoils in water/methanol mixtures decreased log-linearly with mole percent cosolvent up to 20% methanol. This decrease closely followed the increase in quinoline solubility in the cosolvent mixtures. Acetone caused greater reduction in sorption than methanol, at comparable mole percent, in accordance with its lower dielectric constant and enhanced solvating power. A generalized thermodynamic approach based on the concept of transfer activity coefficients was developed to account for the cosolvent effect on cKex, and was successfully applied to the quinoline sorption data. The thermodynamic analysis suggested that enhanced solvation of the organic cation in the bulk solvent and desolvation of Na+ at the charged surface predominate the cosolvent effect.  相似文献   

4.
This study investigated the influence of solution salinity, pH and the sediment characteristics on the sorption and desorption of perfluorooctane sulfonate (PFOS). The results showed that the sorption of PFOS onto sediment increased by a factor of 3 as the CaCl2 concentration increased from 0.005 to 0.5 mol L−1 at pH 7.0, and nearly 6 at pH 8.0. Desorption hysteresis occurred over all salinity. The thermodynamic index of irreversibility (TII) values increased with increasing concentration of CaCl2. Maximum irreversibility was found in the sorption systems with CaCl2 in the concentration of 0.5 mol L−1. The results suggested that PFOS can be largely removed from the water with increasing salinity, and get trapped onto sediments irreversibly. These phenomena could be explained by salting-out effect and Ca-bridging effect. Studies also suggested that the content of total organic carbon is the dominant psychochemical properties of sediment controlling the sorption of PFOS.  相似文献   

5.
To date, sorption of organic compounds to nanomaterials has mainly been studied for the nanomaterial in its pristine state. However, sorption may be different when nanomaterials are buried in sediments. Here, we studied sorption of Perfluorooctane sulfonate (PFOS) to sediment and to sediment with 4% multiwalled carbon nanotubes (MWCNTs), as a function of factors affecting PFOS sorption; aqueous concentration, pH and Ca2+ concentration. Sorption to MWCNT in the sediment–MWCNT mixtures was assessed by subtracting the contribution of PFOS sorption to sediment-only from PFOS sorption to the total sediment–MWCNT mixture. PFOS Log KD values ranged 0.52–1.62 L kg?1 for sediment and 1.91–2.90 L kg?1 for MWCNT present in the sediment. The latter values are relatively low, which is attributed to fouling of MWCNT by sediment organic matter. PFOS sorption was near-linear for sediment (Freundlich exponent of 0.92 ± 0.063) but non-linear for MWCNT (Freundlich exponent of 0.66 ± 0.03). Consequently, the impact of MWCNT on sorption in the mixture was larger at low PFOS aqueous concentration. Effects of pH and Ca2+ on PFOS sorption to MWCNT were statistically significant. We conclude that MWCNT fouling and PFOS concentration dependency are important factors affecting PFOS–MWCNT interactions in sediments.  相似文献   

6.
Salinity increases mobility of heavy metals in soils   总被引:11,自引:0,他引:11  
The effect of salinity induced by CaCl2, MgCl2, NaCl and Na2SO4 on the mobility of Cu, Cd, Pb and Zn was studied. An increase of ionic strength by any salts promoted a higher release of Cd than the others metals. When CaCl2 and NaCl were applied, Cd and Pb showed the highest degree of mobilization. When MgCl2 was applied, Cd and Cu were mobilized the most. Finally, an increase of Na2SO4 also promoted the strongest mobilization of Cd and Cu.As the total heavy metal content was higher, the percentage of Pb and Cu released upon salinization decreased, indicating that these metals are strongly bound to soil constituents. An increase of carbonates in the soil promoted a higher release of Pb for all used salts and for Zn when MgCl2 and NaCl were used. This indicates that Pb and Zn are adsorbed on the surface of carbonate crystals. An increase of fine particles promoted a decrease of percentage of released Cd for all salts, indicating that Cd is strongly retained in the fine fractions.The main mechanism regulating Pb and Cd mobility was competition with Ca2+ for sorption sites followed for metal chloro-complexation, association between the Cd/Pb-sulfates and competition with Mg2+. The main mechanism regulating Cu mobility was the formation of Cu-sulfate, followed by competition with cations (Mg > Ca) and chloride. For Zn, competition with Ca2+ for sorption sites was the most important process for its mobility; followed by Zn-sulfate association and, finally, chloride and competition with Mg with the same effect.  相似文献   

7.
The effect of exchangeable cation — Na+ and Ca 2+ — on the diffusive transport of I, Sr 2+ and 3H (as HTO) in compacted bentonite was examined using a through-diffusion method. Total intrinsic diffusion coefficients, Di, were determined from the steady-state flux of the diffusants through the clays, and apparent diffusion coefficients, Da, were obtained from the time lag technique. The clays were compacted to a dry bulk density of 1.3 Mg/m3, and Na-bentonite was saturated with a solution of 100 mol NaCl/m3 and Ca-bentonite with one of 50 mol CaCl2/m3. The Di values for all diffusants are 2 to 6 times higher in the Ca- than Na-clay. We attribute this to the larger quasicrystal, or particle, size of Ca- compared to Na-bentonite. Hence, Ca-bentonite has a greater proportion of relatively large pores; this was confirmed by Hg intrusion porosimetry. This means the diffusion pathways in Ca-bentonite are less tortuous than those in Na-bentonite. Moreover, in some cases the effective porosity, or the porosity available for diffusive transport, may be greater in Ca-bentonite. The Da values are inversely proportional to the distribution coefficients of the diffusants with the clays.  相似文献   

8.
Abstract

The adsorption isotherms of fenuron (l, l‐dimethyl‐3‐phenylurea) on three smectites (SWy and SAz montmorillonites and SH hectorite) differing in their layer charge (SH<SWy<SAz) and saturated with several inorganic and organic cations were determined. The isotherms and sorption parameters from Freundlich equation indicate low adsorptivity on inorganic clays, but medium sorption in organoclays (OCls). Fenuron adsorption on homoionic smectites increases with decreasing layer charge and hydratation power of the inorganic exchangeable cation (except Fe3+), indicating that fenuron adsorbs as neutral molecule on uncharged siloxane surface by hydrophobic bonding, with some contribution of polar bond (fenuron C=O group and water associated to exchangeable cation). In the case of Fe3+‐saturated smectite fenuron protonation, provided by the interlayer acidic environment, promotes further sorption of fenuron as cationic form. The sorption on organoclays is enhanced via hydrophobic interaction with organocations, which is favoured for high layer charge and basal spacing and organocation saturation close to CEC. Quaternary alkylamonium is more efficient in high layer charge smectite, whereas primary alkylammonium is more efficient in medium charge smectite. The low values of the maximum sorption obtained with homoionic inorganic and organic smectites (100 and 5000 μmol/Kg) represent one fenuron molecule for each 2000–200 exchange sites and indicate that fenuron sorption is mainly associated to the outer exchange sites. This low adsorptivity of fenuron, as consequence of its high water affinity (high water solubility) would suggest high mobility of fenuron in natural soil and water systems.  相似文献   

9.
Brazil is the largest sugarcane producer in the world in which hexazinone (3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-triazine-2,4-dione) and tebuthiuron (1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea) are heavily used. Sugarcane harvesting is changing from the manual system with previous straw burning to the mechanized system without straw burning. The lack of burning results in soil organic carbon accumulation mainly in clayey soils, which should affect herbicides availability and fate. Therefore, we evaluated sorption of these herbicides in soil samples with and without straw burning. Both herbicides presented low apparent sorption coefficients (mean Kd,app= 0.6 and 2.4 L kg?1 for hexazinone and tebuthiuron, respectively), suggesting that they may leach to groundwater. Moreover, their sorption correlated primarily with soil organic carbon (SOC), but iron oxide contents extracted with ammonium oxalate (Fe2O3AOX) also affected it (Kd,app = ?0.228 + 0.0397 SOC + 0.117 Fe2O3AOX for hexazinone and Kd,app = ?1.407 + 0.201 SOC + 0.348 Fe2O3AOX for tebuthiuron). Soil organic carbon accumulation due to straw maintenance in the field positively affected sorption of both herbicides, but its effects were not enough to classify them as “non-leachers.”  相似文献   

10.
Linear alkylbenzene sulfonates (LAS) are anionic high production volume surfactants used in the manufacture of cleaning products. Here, we have studied the effect of the characteristics of marine and estuarine sediments on the sorption of LAS. Sorption experiments were performed with single sediment materials (pure clays and sea sand), with sediments treated to reduce their organic carbon content, and with field marine and estuarine sediments. C12-2-LAS was used as a model compound. Sorption to the clays montmorillonite and kaolinite resulted in non-linear isotherms very similar for both clays. When reducing the organic content, sorption coefficients decreased proportionally to the fraction removed in fine grain sediments but this was not the case for the sandy sediment. The correlation of the sediment characteristics with the sorption coefficients at different surfactant concentrations showed that at concentrations below 10 μg C12-2-LAS/L, the clay content correlated better with sorption, while the organic fraction became more significant at higher concentrations.  相似文献   

11.
用高压电弧放电产生的低温等离子体对含偶氮染料的废水进行了处理,以甲基橙为例研究了电压幅值、处理时间、溶液初始浓度、溶液初始pH值、投加Fe^2+和Fe^3+对染料脱色的影响。实验结果表明,甲基橙浓度为50mg/L时其降解率随时间和电压幅值的增加而增加。溶液初始浓度对染料去除效果影响较为明显,同等条件下初始浓度越低降解率越高。酸性条件下有利于低温等离子体处理甲基橙。Fe^2+和Fe^3+对低温等离子体降解甲基橙有一定的催化作用。电压8kV处理3min,Fe^2+为20mg/L时去除率由89.64%增至99.72%。Fe2(SO4),的最佳投加量为5mg/L(以Fe^3+计),而FeCl,的最佳投加量为80mg/L(以Fe^3+计)。  相似文献   

12.
Impacts of simulated acid rain on recalcitrance of two different soils   总被引:2,自引:0,他引:2  
Laboratory experiments were conducted to estimate the impacts of simulated acid rain (SAR) on recalcitrance in a Plinthudult and a Paleudalfs soil in south China, which were a variable and a permanent charge soil, respectively. Simulated acid rains were prepared at pH 2.0, 3.5, 5.0, and 6.0, by additions of different volumes of H2SO4 plus HNO3 at a ratio of 6 to 1. The leaching period was designed to represent 5 years of local annual rainfall (1,200 mm) with a 33 % surface runoff loss. Both soils underwent both acidification stages of (1) cation exchange and (2) mineral weathering at SAR pH?2.0, whereas only cation exchange occurred above SAR pH?3.5, i.e., weathering did not commence. The cation exchange stage was more easily changed into that of mineral weathering in the Plinthudult than in the Paleudalfs soil, and there were some K+ and Mg2+ ions released on the stages of mineral weathering in the Paleudalfs soil. During the leaching, the release of exchangeable base cations followed the order Ca2+?>?K+?>?Mg2+?>?Na+ for the Plinthudult and Ca2+?>?Mg2+?>?Na+?>?K+ for the Paleudalfs soil. The SARs above pH?3.5 did not decrease soil pH or pH buffering capacity, while the SAR at pH?2.0 decreased soil pH and the buffering capacity significantly. We conclude that acid rain, which always has a pH from 3.5 to 5.6, only makes a small contribution to the acidification of agricultural soils of south China in the short term of 5 years. Also, Paleudalfs soils are more resistant to acid rain than Plinthudult soils. The different abilities to prevent leaching by acid rain depend upon the parent materials, types of clay minerals, and soil development degrees.  相似文献   

13.
Oxidative transformation of organic contaminants by manganese oxides was commonly investigated with pure MnO2 suspension, which deviates from the fact that natural manganese oxides are seldom present as a pure form in the natural environment. In this study, we prepared manganese oxide-coated sand (MOCS) and evaluated its oxidative capacity using bisphenol A (BPA) as the model compound. BPA was transformed by MOCS and the reaction followed an exponential decay model. The reaction was pH dependent and followed the order of pH 4.5?>?pH 5.5?>?pH 6.5?>?pH 7.5?>?pH 8.6?>?pH 9.6, indicating that acidic conditions facilitated BPA transformation while basic conditions disfavored the reaction. Coexisting metal ions exhibited inhibitory effects and followed the order of Fe3+ > Zn2+ > Cu2+ > Ca2+ > Mg2+ > Na+. Transformation of BPA by MOCS was much slower than that by pure MnO2 suspension. However, similar transformation products were identified in both studies, suggesting the same reaction pathways. This work suggests that the reactivity of MnO2 in the environment might be overestimated if extrapolating the result from the pure MnO2 suspension because natural MnO2 is mainly present as coating on the surface of soils and sediments.  相似文献   

14.
Nanocomposite hydrogels based on poly(methacrylamide-co-acrylic acid) and nano-sized montmorillonite were prepared by aqueous dispersion and in situ radical polymerization. Optimum sorption conditions were determined as a function of montmorillonite content, contact time, pH, and temperature. The equilibrium data of Cu2+ and Ni2+ conformed to the Freundlich and Langmuir isotherms in terms of relatively high regression values. The maximum monolayer adsorption capacity of the nanocomposite hydrogel (with 3 wt% montmorillonite content), as obtained from the Langmuir adsorption isotherm, was found to be 49.26 and 46.94 mg g?1 for Cu2+ and Ni2+, respectively, at contact time?=?60 min, pH?=?6.8, adsorbent dose?=?100 mg/ml, and temperature?=?318 K. Kinetic studies of single system indicated that the pseudo-second order is the best fit with a high correlation coefficient (R 2?=?0.97–0.99). The result of five times sequential adsorption–desorption cycle shows a good degree of desorption and a high adsorption efficiency.  相似文献   

15.

Biochar (BC) and activated carbon (AC) were both produced from corn straw. Biochar-supported zerovalent iron (BC-ZVI) and activated carbon-supported zerovalent iron (AC-ZVI) were synthesized and applied for Se(IV)/Se(VI) removal. The sorption capacity of BC-ZVI for Se(IV) and Se(VI) was reported at 62.52 and 35.39 mg g?1, higher than that of AC-ZVI (56.02 and 33.24 mg g?1), respectively, due to its higher iron content and more positive charges. The spectroscopic analyses showed that Se(IV)/Se(VI) were reduced to Se(0)/Se(-II) of less toxicity and solubility. The effects of various factors such as pH, ionic strength, co-existing cations and anions, and natural organic matter (NOM) were also investigated. Ionic strength showed no significant effect on Se(IV)/Se(VI) removal, but pH was critical. The presence of NO3? and SO42? did not cause obvious inhibition to the removal, while PO43? inhibited the sorption capacity of BC-ZVI and AC-ZVI for Se(IV)/Se(VI) significantly. Common cations (K+, Ca2+, and Mg2+) were found to slightly enhance the removal, while NOM significantly decreased the sorption capacity of BC-ZVI and AC-ZVI for Se(IV)/Se(VI). Besides, NOM showed stronger inhibition effect on AC-ZVI than that on BC-ZVI. These results indicated that BC-ZVI, compared with AC-ZVI, could be a promising sorbent to remove Se(IV)/Se(VI) due to its low cost and high efficiency.

  相似文献   

16.
The ability of free ferrous ion activated persulfate (S2O82−) to generate sulfate radicals (SO4) for the oxidation of trichloroethylene (TCE) is limited by the scavenging of SO4 with excess Fe2+ and a quick conversion of Fe2+ to Fe3+. This study investigated the applicability of ethylene-diamine-tetra-acetic acid (EDTA) chelated Fe3+ in activating persulfate for the destruction of TCE in aqueous phase under pH 3, 7 and 10. Fe3+ and EDTA alone did not appreciably degrade persulfate. The presence of TCE in the EDTA/Fe3+ activated persulfate system can induce faster persulfate and EDTA degradation due to iron recycling to activate persulfate under a higher pH condition. Increasing the pH leads to increases in pseudo-first-order-rate constants for TCE, S2O82− and EDTA degradations, and Cl generation. Accordingly, the experiments at pH 10 with different EDTA/Fe3+ molar ratios indicated that a 1/1 ratio resulted in a remarkably higher degradation rate at the early stage of reaction as compared to results by other ratios. Higher persulfate dosage under the EDTA/Fe3+ molar ratio of 1/1 resulted in greater TCE degradation rates. However, increases in persulfate concentration may also lead to an increase in the rate of persulfate consumption.  相似文献   

17.
Carbonic anhydrase II (CA II) can catalyze the reversible hydration reaction of CO2 at a maximum of 1.4?×?106 molecules of CO2 per second. The crude intracellular enzyme extract containing CA II was derived from Chlorella vulgaris. A successful CO2 capture experiment with the presence of calcium had been conducted on the premise that the temperature was conditioned at a scope of 30?C40?°C, that the biocatalyst-nurtured algal growth period lasted 3?days, and that pH ranged from7.5 to 8.5. Ions of K+, Na+, Ca2+, Co2+, Cu2+, Fe3+, Mg2+, Mn2+, and Zn2+ at 0.01, 0.1, and 0.5?M were found to exhibit no more than 30?% inhibition on the residual activity of the biocatalyst. It is reasonable to expect that calcification catalyzed by microalgae presents an alternative to geological carbon capture and sequestration through a chain of fundamental researches carried on under the guidance of sequestration technology.  相似文献   

18.
湿法烟气脱硫反应过程的实验研究   总被引:1,自引:1,他引:0  
在石灰石/石膏湿法烟气脱硫中试台上,系统开展了浆液pH值、飞灰浓度、液气比、入口SO2浓度、烟气速度和氧化方式等对脱硫反应过程影响的实验研究。实验表明,脱硫效率随着石膏浆液pH值、液气比的升高而增加,且入口SO2浓度越高,液气比越低,影响效应越明显;脱硫效率随着烟气速度、烟气温度和入口SO2浓度的增加而下降;石膏浆液中飞灰含量对系统脱硫效率具有一定的促进作用:pH值>5.6,飞灰浸出液中Fe3+含量相对较低,Fe3+对脱硫反应过渡态催化氧化影响程度较轻,不同工况脱硫效率差别不大。pH值<5.6,飞灰浸出液中Fe3+含量随pH值降低而增大,增效效果逐渐显著;氧化方式对脱硫反应过程有明显的影响,强制氧化工艺的脱硫效率比自然氧化的高5%左右。  相似文献   

19.
This study presents oxidative transformation of carbamazepine by synthetic manganese oxide (??-MnO2) as well as impact of variables including initial MnO2 loading, pH, coexisting metal ions, and humic acid (HA) on transformation. Manganese oxide (??-MnO2) was synthesized and stored in the form of suspension. The oxidative reactions were conducted in 50?mL polyethylene (PE) centrifuge tubes with constant pH maintained by buffers. The kinetic experiment was carried out in the solution of pH 2.72 containing 5.0?mg/L of carbamazepine and 130.5?mg/L of MnO2. Effects of initial MnO2 loading (0?C130.5?mg/L), pH (2.72?C8.58) and 0.01?M of coexisting solutes (metal ions and HA) on carbamazepine oxidation were also determined. Reaction kinetics indicated that carbamazepine was rapidly degraded in the first 5?min, and approximately 95?% of carbamazepine was eliminated within 60?min. The reaction exhibited pronounced pH dependence and increased with decreasing pH values. The transformation of carbamazepine was also accelerated with increasing MnO2 loadings. Coexisting metal ions competed with carbamazepine for reactive sites leading to reduced carbamazepine removal, and the inhibitive capacity followed the order of Mn2+?>?Fe3+?>?Ca2+????Mg2+. Presence of HA in aqueous solution caused a significant reduction on the magnitude of carbamazepine transformation. This study indicated that carbamazepine can be effectively degraded by ??-MnO2, and transformation efficiency was strongly dependent on reaction conditions. It suggests that amendment of soil with MnO2 be a potential alternative to solve carbamazepine pollution.  相似文献   

20.

Introduction

Trends in precipitation pH and conductivity during 1992?C2009, and in ionic compositions from January 2007 to June 2009, are reported from Lushan Mountain, one of the highest mountains in mid-east China. Annual mean pH was in the range of 4.35?C5.01 and showed a statistically very significant (P?P?Results and discussions Over the period of study, Lushan Mountain received more rainfall in spring and summer. The pH values varied seasonally with winter minima. The winter multiyear seasonal mean pH was 4.35. The corresponding summer value was 4.88. SO 4 2? and NO 3 ? were the main anions, and NH 4 + and Ca2+ the main cations. The anion to cation ratio was 0.8?C1.0, and that of [SO 4 2? ] to [NO 3 ? ] was 2.4-3.0, much lower than that of the 1980s. However, sulfuric acid was still the main acid present. The ratio of [NH 4 + ] to [Ca2+] was about 1.0, suggesting that these two alkaline substances provided close acid neutralizing capacity. The ratio of [Cl?] to [Na+] was about 0.67, somewhat lower than that of natural precipitation.

Conclusions

Ionic composition varied seasonally and was closely correlated to the amounts of rainfall and pollution. Trajectory analyses showed that the trajectories to Lushan Mountain could be classified in six clusters and trajectories originating from the South Sea and the areas surrounding Lushan Mountain had the greatest impacts on precipitation chemistry.  相似文献   

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