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1.
Understanding adsorption processes of butyltins (BTs) such as monobutyltin (MBT) and dibutyltin (DBT) by black carbons is important for the evaluation of BT exposure risks to organisms and humans. However, relevant knowledge is scarce. In this study, the acidity constants pKa,1 = 2.3, pKa,2 = 3.5 and pKa,3 = 5.9 for MBT and pKa,1 = 3.0 and pKa,2 = 5.1 for DBT are estimated via potentiometric titration. Additionally, adsorption isotherms of BTs to a wheat charcoal were determined. The adsorption behavior was observed to be pH-dependent due to BT speciation and the pH-dependent surface charge of the charcoal. MBT adsorption to the charcoal decreases with increasing pH from 4 to 8, while the highest adsorption occurs at pH 6 for DBT. Adsorption of the BTs is successfully described in the pH range of 3-10 by using a newly developed pH-dependent Dual Langmuir model. The model has the potential to predict the interaction of BT species with charcoal, which can contribute to the risk assessments of BTs in the environment.  相似文献   

2.
Hojaji E 《Chemosphere》2012,89(3):319-326
The binding behavior of lignin for Pb, Cu, Co, Mn, Cd and Ni was studied using the diffusive gradients in thin films technique (DGT). Samplers with different structures of diffusive gel were used in the well-stirred systems containing known concentrations of metals along with (a) 10, 20 and 40 μM lignin and; (b) 0.64 and 6.47 μM Suwannee river fulvic acid + 40 μM lignin at an ionic strength of 0.01 M (NaNO3) and pH = 7. Diffusion coefficients of lignin complexes in acrylamide gels were estimated and found to be less than 5% of the equivalent coefficients for the uncomplexed metal ions. These values were used to calculate concentrations of labile metals from DGT measurements in solutions, where lignin could discriminate metals in the order of Pb+2 > Cu+2 > Cd+2 > Ni+2 > Co+2 > Mn+2. Stability constants (Log K) were calculated using Visual MINTEQ II and WHAM V software. The K values were compared with the stability constants from titration of Pb and Cd with 10 μM lignin aqueous samples and with those of humic substances in natural waters. The constants obtained from measurement of complexing capacities might bias the real corresponding values unless two line regression analyses on titration data are considered. The DGT study of fractionation of metal species at varying ratios indicated that the proportion of organic complexes decreased with increasing ratios and gradually more metals were exchanged with inorganic phases. Speciation of Pb and Cd is affected by the concentrations of FA, Cd is dominantly bound with FA while Pb is evenly partitioned between the ligands. The comprehensive knowledge of metal-lignin complexes sheds some light on in situ operational speciation information that can be achieved by DGT.  相似文献   

3.
F Wang  C Liu  K Shih 《Chemosphere》2012,89(8):1009-1014
Understanding the interaction of perfluorochemicals, persistent pollutants with known human health effects, with mineral compounds in surface water and groundwater environments is essential to determining their fate and transport. Kinetic experiments showed that adsorption equilibrium can be achieved within 48 h and the boehmite (AlOOH) surface is receptive to perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorption. The adsorption isotherms estimated the maximum adsorption capacities of PFOS and PFOA on boehmite as 0.877 μg m−2 and 0.633 μg m−2, respectively. Compared to the adsorption capacity on γ-alumina, the abundant hydroxyl groups on boehmite surfaces resulted in the 2-3 times higher adsorption of PFOS and PFOA. Increasing solution pH led to a moderate decrease in PFOS and PFOA adsorption, owing to an increase in ligand exchange reactions and the decrease of electrostatic interactions. The presence of NaCl and CaCl2 in solution demonstrated negative effects for PFOS and PFOA adsorption on boehmite surfaces, with potential mechanisms being electrical double layer compression, competitive adsorption of chloride, and the Ca2+ bridging effect between perfluorochemicals.  相似文献   

4.
Ham JE  Wells JR 《Chemosphere》2011,83(3):327-333
Indoor environments are dynamic reactors where consumer products (such as cleaning agents, deodorants, and air fresheners) emit volatile organic compounds (VOCs) that can subsequently interact with indoor oxidants such as ozone (O3), hydroxyl radicals, and nitrate radicals. Typically, consumer products consist of mixtures of VOCs and semi-VOCs which can react in the gas-phase or on surfaces with these oxidants to generate a variety of oxygenated products. In this study, the reaction of a pine-oil cleaner (POC) with O3 (100 ppb) on a urethane-coated vinyl flooring tile was investigated at 5% and 50% relative humidity. These results were compared to previous α-terpineol + O3 reactions on glass and vinyl surfaces. Additionally, other terpene and terpene alcohol mixtures were formulated to understand the emission profiles as seen in the POC data. Results showed that the α-terpineol + O3 reaction products were the prominent species that were also observed in the POC/O3 surface experiments. Furthermore, α-terpineol + O3 reactions generate the largest fraction of oxygenated products even in equal mixtures of other terpene alcohols. This finding suggests that the judicial choice of terpene alcohols for inclusion in product formulations may be useful in reducing oxidation product emissions.  相似文献   

5.
Nethaji S  Sivasamy A 《Chemosphere》2011,82(10):1367-1372
Chemically prepared activated carbon material derived from palm flower was used as adsorbent for removal of Amido Black dye in aqueous solution. Batch adsorption studies were performed for the removal of Amido Black 10B (AB10B), a di-azo acid dye from aqueous solutions by varying the parameters like initial solution pH, adsorbent dosage, initial dye concentration and temperature with three different particle sizes such as 100 μm, 600 μm and 1000 μm. The zero point charge was pH 2.5 and the maximum adsorption occurred at the pH 2.3. Experimental data were analyzed by model equations such as Langmuir, Freundlich and Temkin isotherms and it was found that the Freundlich isotherm model best fitted the adsorption data and the Freundlich constants varied from (KF) 1.214, 1.077 and 0.884 for the three mesh sizes. Thermodynamic parameters such as ΔG, ΔH and ΔS were also calculated for the adsorption processes and found that the adsorption process is feasible and it was the endothermic reaction. Adsorption kinetics was determined using pseudo first-order, pseudo second-order rate equations and also Elovich model and intraparticle diffusion models. The results clearly showed that the adsorption of AB10B onto lignocellulosic waste biomass from palm flower (LCBPF) followed pseudo second-order model, and the pseudo second-order rate constants varied from 0.059 to 0.006 (g mg−1 min) by varying initial adsorbate concentration from 25 mg L−1 to 100 mg L−1. Analysis of the adsorption data confirmed that the adsorption process not only followed intraparticle diffusion but also by the film diffusion mechanism.  相似文献   

6.
Soil acidification has been of concern in the oil sands region in Alberta due to increased acid deposition. Using the canopy budget model, and accounting for H+ canopy leaching by organic acids, we determined sources and sinks of H+ in throughfall in jack pine (Pinus banksiana) and trembling aspen (Populus tremuloides) stands in two watersheds from 2006 to 2009. In pine stands, H+ deposition was greater in throughfall than in bulk precipitation while the opposite was true in aspen stands. The annual H+ interception deposition was 148.8-193.8 and 49.7-70.0 molc ha−1 in pine and aspen stands, respectively; while the annual H+ canopy leaching was 127.1-128.7 and 0.0-6.0 molc ha−1, respectively. The greater H+ supply in pine stands was caused by greater interception deposition of SO42− and organic acids released from the pine canopy. Such findings have significant implications for establishing critical loads for various ecosystems in the oil sands region.  相似文献   

7.
Wang C  Zhang S  Wang P  Hou J  Qian J  Ao Y  Lu J  Li L 《Chemosphere》2011,84(1):136-142
In this study, the alterations in nutrient elements content, reactive oxygen species level and antioxidant response were studied in leaves of Vallisneria natans (Lour.) Hara exposed to salicylic acid (SA, 10 or 100 μM), or Pb (50 μM) or their combinations for 4 d. No significant alterations in Mn and Ca content were observed but content of Cu, Zn, Fe and P decreased in plants exposed to SA alone. SA application inhibited the uptake of Pb and partially reversed Pb-induced the alterations in Mn, Ca and Fe content in leaves of V. natans exposed to 50 μM Pb. The decreased chlorophyll (a + b) and increased malondialdehyde and O2− and H2O2 content were detected in plants exposed to 100 μM SA, 50 μM Pb, 10 μM SA + 50 μM Pb or 100 μM SA + 50 μM Pb. Application SA partially inhibited Pb-induced the increase of malondialdehyde, O2− and H2O2 content. 100 μM SA decreased the activity of NADH oxidase and the content of non-protein thiols, carotenoids and ascorbic acid and increased the content of dehydroascorbate in plants treated with or without Pb. SA alone decreased the ascorbate peroxidase activity and increased the catalase and peroxidase activity, while SA application increased catalase activity but had no significant effect on ascorbate peroxidase and peroxidase activity in V. natans exposed to Pb. The results indicate that SA involves in the regulation of Pb uptake, nutrient balance and oxidative stress.  相似文献   

8.
Widespread use of tributyltin (TBT) poses a serious environmental problem. Adsorption by black carbon (BC) may strongly affect its behavior. The adsorption of TBT to well characterized soot and two charcoals with specific surface area in the range of 62-111 m2 g−1 have been investigated with main focus on pH effects. The charcoals but not soot possess acidic functional groups. TBT adsorption reaches maximum at pH 6-7 for charcoals, and at pH > 6 for soot. Soot has between 1.5 and 15 times higher adsorption density (0.09-1.77 μmol m−2) than charcoals, but charcoals show up to 17 times higher sorption affinities than soot. TBT adsorption is successfully described by a new pH-dependent dual Langmuir model considering electrostatic and hydrophobic adsorption, and pH effects on TBT speciation and BC surface charge. It is inferred that strong sorption of the TBTOH species to BC may affect TBT toxicity.  相似文献   

9.
The adsorption behavior of 241Am, 60Co, 137Cs and 85Sr in the presence and absence of chelating ligands (ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, iminodiaceiticacid and methyliminodiacetic acid) was investigated. Sorption affinity in the absence of chelating ligands followed: Am(III) > Co(II) > Cs(I) > Sr(II). The presence of chelating ligands generally had little effect on sorption of 85Sr and 137Cs with Kd values 110 and 690 mL g−1, respectively. But at 0.02 M of ethylenediaminetetraacetic or hydroxyethyliminodiacetic, the Kd decreased to 5 or 63 mL g−1, respectively, where thermochemical modeling indicated almost all 85Sr is complexed with these ligands. The Kd values for 241Am and 60Co generally decreased with increasing chelating agent concentrations. In notable cases, the Kd values for Am increased at specific concentrations of 10−3 M for IDA, MIDA and 10−4 M for EDDA. This is proposed to be due to formation of a ternary surface complex.  相似文献   

10.
The protective effect of hydroxytyrosol (HT), a strong antioxidant compound from extra virgin olive oil, against TCDD induced toxicity was investigated in human peripheral blood mononuclear cells (PBMC). PBMC (1 × 106 cells mL−1) were divided into four groups and were incubated in a CO2 incubator (5% CO2) for 12 h with vehicle, TCDD (10 nM), TCDD + HT (10 nM + 100 μM) and HT alone (100 μM) respectively. To clarify the role of HT against TCDD induced cytotoxicity, oxidative stress and the levels of antioxidant enzymes were assessed. Incubation of PBMC with TCDD significantly decreased cell viability, catalase (CAT) and glutathione peroxidase (GPx) and increased the levels of superoxide dismutase (SOD), glutathione reductase (GR) and oxidative stress markers such as lipid peroxidation products (LPO), protein carbonyl content (PCC) and reactive oxygen species (ROS). Whereas, HT had an effective antioxidant property as observed by the increased cell viability, normalization of antioxidant enzymes and decreased levels of LPO, PCC and ROS in PBMC co-treated with HT and TCDD. Apoptosis detection and comet assay results shows that HT, by acting as an antioxidant, prevents the damage to DNA induced by TCDD. In addition light microscopic and histopathological observations revealed that the cells are apoptotic and degenerated during TCDD treatment, whereas cells showed intact morphology during co-treatment with HT. On the whole, the results reveal that HT exerts a promising antioxidant potential in protecting the PBMC against TCDD induced oxidative stress, which might be due to the presence of catechol moiety in its structure.  相似文献   

11.
Qian Y  Posch T  Schmidt TC 《Chemosphere》2011,82(6):859-865
Sorption of polycyclic aromatic hydrocarbons (PAHs) to glass commonly used in laboratories was studied. Sorption coefficients (Kd) of five selected PAHs to borosilicate glass surfaces were measured using column chromatography. A linear relationship between log Kd and the corresponding water solubility of the subcooled liquid (log Sw) of the investigated PAHs was observed. Based on the determined sorption coefficients our data revealed that mass loss caused by sorption on glass walls strongly depends on the ratio of solution volume to contacted surface area (V/S). The influence of solution chemistry such as ionic strength, solution pH, presence of cosolvent, and the influence of temperature on the sorption process were investigated. In the presence of ionic strength, sorption coefficients concurrently increased but less than a factor of 2 up to 0.005 M calcium chloride concentration. However, further increasing ionic strength had no influence on Kd. The cosolvent reduced sorption at a concentration of methanol in water above 0.5% (v/v); however, for benzo[a]pyrene even with 10% (v/v) methanol the mass loss would be still higher than 10% (with a V/S ratio less than 0.25). Significant effects of the solution pH and temperature were not observed. These results suggest that van der Waal’s forces dominate the sorption process. In the analysis of highly hydrophobic PAHs in aqueous samples, mass loss due to sorption on glass walls should be accounted for in the final result if untreated glass is used. The presented relationship between log Kd and log Sw may help to decide if such a correction is necessary. Furthermore, the frequently used silanization of glass surfaces may not be sufficient to suppress sorption for large PAHs.  相似文献   

12.
This study investigated adsorption of fulvic acid (FA) by single-walled (SWCNT) and multi-walled carbon nanotubes (MWCNT) and activated carbon. Adsorption of FA depends greatly on the adsorbent surface area and solution pH. SWCNT has higher adsorption than MWCNT and activated carbon. Lower E4/E6 (absorbance at 465 nm to that at 665 nm) and higher E2/E3 (absorbance at 250 nm to that at 365 nm) ratios of the residual FA in solution after adsorption than that of original FA in low pH ranges suggest that aromatic rich FA fractions with polar moieties readily adsorb on the adsorbents. The apparent interaction mechanisms between FA and CNT surfaces include electrostatic, hydrophobic, π-π and hydrogen-bond interactions. FA adsorption was reduced greatly with increasing pH because of the increase of electrostatic repulsion and the decrease of hydrophobic and hydrogen-bond interactions.  相似文献   

13.
Oxidation of bisphenol F (BPF) by manganese dioxide   总被引:1,自引:0,他引:1  
Bisphenol F (BPF), an environmental estrogen, is used as a monomer in plastic industry and its environmental fate and decontamination are emerging concern. This study focused on the kinetics, influencing factors and pathways of its oxidation by MnO2. At pH 5.5, about 90% of BPF was oxidized in 20 min in a solution containing 100 μM MnO2 and 4.4 μM BPF. The reaction was pH-dependent, following an order of pH 4.5 > pH 5.5 > pH 8.6 > pH 7.5 > pH 6.5 > pH 9.6. Humic acids inhibited the reaction at low (≤pH 5.5) and high pH (≥pH 8.6) at high concentrations. In addition, metal ions and anions also suppressed the reaction, following the order Mn2+ > Ca2+ > Mg2+ > Na+ and HPO42− > Cl > NO3 ≈ SO42−, respectively. A total of 5 products were identified, from which a tentative pathway was proposed.  相似文献   

14.
We examined the effect of ozone (O3) on Norway spruce (Picea abies) needle epicuticular wax over three seasons at the Kranzberg Ozone Fumigation Experiment. Exposure to 2× ambient O3 ranged from 64.5 to 74.2 μl O3 l−1 h AOT40, and 117.1 to 123.2 nl O3 l−1 4th highest daily maximum 8-h average O3 concentration. The proportion of current-year needle surface covered by wax tubes, tube aggregates, and plates decreased (P = 0.011) under 2× O3. Epistomatal chambers had increased deposits of amorphous wax. Proportion of secondary alcohols varied due to year (P = 0.004) and O3 treatment (P = 0.029). Secondary alcohols were reduced by 9.1% under 2× O3. Exposure to 2× O3 increased (P = 0.037) proportions of fatty acids by 29%. Opposing trends in secondary alcohols and fatty acids indicate a direct action of O3 on wax biosynthesis. These results demonstrate O3-induced changes in biologically important needle surface characteristics of 50-year-old field-grown trees.  相似文献   

15.
Cypermethrin is a widely used insecticide that has caused concern due to its toxicity in the aquatic environment. As with all land applied pesticides, the most significant source of water pollution is from the soil, either due to leaching or washoff. The behaviour of cypermethrin in the soil controls the likelihood of future pollution incidents, with two of the most significant processes being the formation of bound residues and microbial degradation. The formation of bound residues and mineralisation was measured in four organically managed soils from the UK. The formation of bound residues was measured using three different extraction solutions, 0.01 M CaCl2, 0.05 M HPCD and acetonitrile. Biodegradation was assessed by measurement of mineralisation of cypermethrin to CO2. The formation of bound residues varied according to extraction method, soil type and length of ageing. In two of the four soils studied, acetonitrile extractability decreased from 100% initially to 12-14% following 100 d ageing. The extent of mineralisation increased after 10-21 d ageing, reaching 33% of remaining activity in one soil, however following 100 d ageing the extent of mineralisation was significantly reduced in three out of the four soils. As with the formation of bound residues, mineralisation was impacted by soil type and length of ageing.  相似文献   

16.
This paper reports on the partitioning behaviour of 15 perfluorinated compounds (PFCs), including C4-C10 sulfonates and C5-C14 carboxylic acids, between water, sediment and fish (European chub, Leuciscus cephalus) in the Orge River (nearby Paris). Total PFC levels were 73.0 ± 3.0 ng L−1 in water and 8.4 ± 0.5 ng g−1 in sediment. They were in the range 43.1-4997.2 ng g−1 in fish, in which PFC tissue distribution followed the order plasma > liver > gills > gonads > muscle. Sediment-water distribution coefficients (log Kd) and bioaccumulation factors (log BAF) were in the range 0.8-4.3 and 0.9-6.7, respectively. Both distribution coefficients positively correlated with perfluoroalkyl chain length. Field-based biota-sediment accumulation factors (BSAFs) are also reported, for the first time for PFCs other than perfluorooctane sulfonate. log BSAF ranged between −1.3 and 1.5 and was negatively correlated with the perfluoroalkyl chain length in the case of carboxylic acids.  相似文献   

17.
Liao W  Liu HW  Chen HJ  Chang WY  Chiu KH  Wai CM 《Chemosphere》2011,82(4):573-580
Catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) with up to four fused benzene rings over high-density-polyethylene-stabilized palladium nanoparticles in supercritical carbon dioxide via in situ UV/Vis spectroscopy is presented. PAHs can be efficiently converted to saturated polycyclic hydrocarbons using this green technique under mild conditions at 20 MPa of CO2 containing 1 MPa of H2 at 40-50 °C. Kinetic studies based on in situ UV/Vis spectra of the CO2 phase reveal that the initial hydrogenation of a given PAH and the subsequent hydrogenations of its intermediates are pseudo-first-order. The hydrogenation rate of the latter is always much smaller than that of the former probably due to increasing steric hindrance introduced by the hydrogenated benzene rings of PAHs which impedes the adsorption process and hydrogen access to PAHs on catalyst surfaces.  相似文献   

18.
Bentonite clay is considered as possible backfill material for nuclear waste repositories in crystalline rock. The same material may also be a source of clay colloids, which may act as carriers for actinide ions possibly released from the repository. Depending on the geochemical parameters, these colloids may be retained by interaction with mineral surfaces of the host rock. In the present study interaction of carboxylated fluorescent latex colloids, used as a model for bentonite colloids, with natural Grimsel granodiorite and some of its component minerals is studied by fluorescence microscopy and SEM/EDX. The experiments are carried out by varying the pH from 2–10. Strong adsorption is observed at pH values close to or below the points of zero charge (pHpzc) of the mineral surfaces. The influence of Eu(III), used as a chemical homologue for trivalent actinide ions, on colloid adsorption is investigated. Depending on mineral phase and pH, a significant increase of colloid adsorption is observed in the presence of Eu(III).  相似文献   

19.
The migration behavior of the actinyl ions U(VI)O22+, Np(V)O2+ and Pu(V,VI)O2(+,2+) in the geosphere is to a large extend controlled by sorption reactions (inner- or outer-sphere adsorption, ion-exchange, coprecipitation/structural incorporation) with minerals. Here NpO2+ adsorption onto calcite is studied in batch type experiments over a wide range of pH (6.0–9.4) and concentration (0.4 μM–40 μM) conditions. pH is adjusted by variation of CO2 partial pressure. Adsorption is found to be pH dependent with maximal adsorption at pH 8.3 decreasing with increasing and decreasing pH. pH dependence of adsorption decreases with increasing Np(V) concentration. EXAFS data of neptunyl adsorbed to calcite and neptunyl in the supernatant shows differences in the Np(V)-O-yl distance, 1.85 ± 0.01 Å for the adsorbed and 1.82 ± 0.01 Å for the solution species. The equatorial environment of the neptunyl in solution shows about 5 oxygen neighbours at 2.45 ± 0.02 Å. For adsorbed neptunyl there are also about 5 oxygen neighbours at 2.46 ± 0.01 Å. An additional feature in the adsorbed species' R-space spectrum can be related to carbonate neighbours, 3 to 6 carbon backscatterers (C-eq) at 3.05 ± 0.03 Å and 3 to 6 oxygen backscatterers (O-eq2) at 3.31 ± 0.02 Å. The differences in the Np(V)-O-yl distance and the C-eq and O-eq2 backscatterers which are only present for the adsorbed species indicate inner-sphere bonding of the adsorbed neptunyl species to the calcite surface. Experiments on adsorption kinetics indicate that after a fast surface adsorption process a continuous slow uptake occurs which may be explained by incorporation via surface dissolution and reprecipitation processes. This is also indicated by the part irreversibility of the adsorption as shown by increased KD values after desorption compared to adsorption.  相似文献   

20.
Root and shoot lead concentrations and the impact of chelating agents on these were investigated in two populations of the novel metallophyte Matthiola flavida. Plants were exposed in hydroponics to Pb(NO3)2, supplied alone, or in combination with citric acid, or EDDS. When supplied at concentrations expected to bind about 95% of the Pb in a solution containing 1-μM Pb (1000 μM citrate or 3.1 μM EDDS, respectively), the root and shoot Pb concentrations were dramatically lowered, in comparison with a 1-μM free ionic Pb control exposure. A 1-mM EDDS + 1-μM Pb treatment decreased the plants’ Pb concentrations further, even to undetectable levels in one population. At 100 μM Pb in a 1-mM EDDS-amended solution the Pb concentration increased strongly in shoots, but barely in roots, in comparison with the 1-μM Pb + 1-mM EDDS treatment, without causing toxicity symptoms. Further increments of the Pb concentration in the 1-mM EDDS-amended solution, i.e. to 800 and 990 μM, caused Pb hyperaccumulation, both in roots and in shoots, associated with a complete arrest of root growth and foliar necrosis. M. flavida seemed to be devoid of constitutive mechanisms for uptake of Pb-citrate or Pb-EDDS complexes. Hyperaccumulation of Pb-EDDS occurred only at high exposure levels. Pb-EDDS was toxic, but is much less so than free Pb. Free EDDS did not seem to be toxic at the concentrations tested.  相似文献   

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