The pH-dependent adsorption of tributyltin to charcoals and soot

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.     

Adsorptive removal of an acid dye by lignocellulosic waste biomass activated carbon: equilibrium and kinetic studies

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 (K_F) 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.     

Enhancement of phosphorus sorption onto light expanded clay aggregates by means of aluminum and iron oxide coatings

Phosphorus (P) loading from non-point or point sources increases the eutrophication risk of natural waters. The functioning of constructed wetlands (CWs) used as natural water treatment systems can be improved by means of additional materials adsorbing soluble P. In this study, light expanded clay aggregates (LECA) and LECA coated with aluminum (Al) oxide (Al-LECA) or iron (Fe) oxide (Fe-LECA) were tested for their efficiency as P sorbents in the pH range 3–8. The oxide coatings duplicated the actual sorption capacity calculated from the sorption isotherms at the P concentration in the equilibrium solution of 20 μg L⁻¹, assumed to be the allowable P level in purified water. In the oxide-coated LECAs the sorption was fast and followed both the first- and second-order Lagergren kinetic models, suggesting that the formation of a binuclear surface complex was feasible. In LECA, sorption was markedly slower and followed the first-order kinetic model, indicating that retention occurred through a monodentate attachment. These findings were in harmony with the degree of P saturation (DPS) of the sorbent surfaces at the highest P addition level (200 μg L⁻¹), DPS being decisively higher for LECA than for the oxide-coated sorbents. Accordingly, at higher pH values the competition by hydroxyl ions diminished the sorption in LECA relatively more than that in the coated sorbents. In agreement with the acidity of Al³⁺ being 100 times lower than that of Fe³⁺, at elevated pH the sorption by Al-LECA proved to be less reversible than that by Fe-LECA. The results provide evidence that in CWs Al-coated sorbents are superior to Fe-coated ones that are also redox-sensitive and may lose their sorption properties in anoxic conditions.     

Cu sorption on Phragmites australis leaf and stem litter: a kinetic study

Decaying organic matter plays an important role in the cycling of metals in wetland ecosystems. Sorption kinetics of Cu(II) on Phragmites australis leaf and stem litter were studied. Fresh leaf and stem litter was sampled from a surface flow wetland at the end of the growing season. The effect of decomposition stage was studied with litter that had been decomposing for a period of 5 months. The Lagergren pseudo-first-order model, the pseudo-second-order model, the Elovich equation and two diffusion models based on spherical intra-particle diffusion were fitted to the experimental data. The sorption capacity was significantly affected by the decomposition of the litter. The sorption process was best described by the pseudo-second-order kinetics (R(2) approximately 0.99) but the rate constant was strongly dependent on the initial Cu concentration. The intra-particle diffusion model fitted the data only slightly less (R(2)>0.95) than the pseudo-second-order model. A theoretical comparison revealed that the good fit with the pseudo-second-order kinetics could be indicative of intra-particle diffusion. Sorption kinetics observed for the leaf and stem litter at different metal concentrations showed a fast initial sorption followed by a slow sorption phase.     

Enhanced sorption of perfluorooctane sulfonate (PFOS) on carbon nanotube-filled electrospun nanofibrous membranes

Multi-walled carbon nanotube-filled electrospun nanofibrous membranes (MWCNT-ENFMs) were prepared by electrospinning. The addition of MWCNTs (0.5 wt.% vs. ENFMs) doubled the specific surface area and tensile strength of the ENFMs. The MWCNT-ENFMs were used to adsorb perfluorooctane sulfonate (PFOS) in aqueous solutions. The sorption kinetics results showed that the sorption rate of PFOS onto the MWCNT-ENFMs was much higher than the sorption rate of PFOS onto the pure ENFMs control, and the pseudo-second-order model (PSOM) described the sorption kinetics well. The sorption isotherms indicated that the sorption capacity of the MWCNT-ENFMs for PFOS (16.29 ± 0.26 μmol g⁻¹) increased approximately 18 times, compared with the pure ENFMs (0.92 ± 0.06 μmol g⁻¹). Moreover, the solution pH significantly affected the sorption efficiency and sorption mechanism. The MWCNT-ENFMs were negatively charged from pH 2.0–10.0, but the electrostatic repulsion between the MWCNT-ENFMs and PFOS was overcome by the hydrophobic interactions between PFOS and the MWCNTs or nanofibers. The strong hydrophobic interactions between PFOS and the MWCNTs played a dominant role in the sorption process. For the pure ENFMs, the electrostatic repulsion was conquered by the hydrophobic interactions between PFOS and the nanofibers at pH > 3.1. In addition to the hydrophobic interactions, an electrostatic attraction between PFOS and the pure ENFMs was involved in the sorption process at pH < 3.1.     

颗粒羟基氧化锆的除氟性能

以羟基氧化锆粉末为原料,制备颗粒羟基氧化锆,评价了颗粒羟基氧化锆对溶液中F-的吸附性能。结果表明:颗粒羟基氧化锆除氟过程符合Freundlich吸附等温线模型和拟二级动力学模型,F-的吸附过程包括液膜扩散和颗粒内的孔扩散;pH在3～4时,颗粒羟基氧化锆的氟吸附量达到最大值27.72 mg/g,其他范围内pH的升高或降低都会导致氟吸附量的降低;Cl-对颗粒羟基氧化锆除氟过程无明显影响,而SO24-和PO34-对颗粒羟基氧化锆除氟过程影响较大,且浓度越高影响越大;扫描电镜和X射线能谱测试结果显示颗粒内随着颗粒深度的增加,F-含量逐渐降低,F-在颗粒内部的传质过程受到阻碍,SO24-和PO34-对颗粒羟基氧化锆除氟的干扰作用主要发生在颗粒表面。     

Variation of MCPA, metribuzine, methyltriazine-amine and glyphosate degradation, sorption, mineralization and leaching in different soil horizons

Pesticide mineralization and sorption were determined in 75 soil samples from 15 individually drilled holes through the vadose zone along a 28 km long transect of the Danish outwash plain. Mineralization of the phenoxyacetic acid herbicide MCPA was high both in topsoils and in most subsoils, while metribuzine and methyltriazine-amine was always low. Organic matter and soil pH was shown to be responsible for sorption of MCPA and metribuzine in the topsoils. The sorption of methyltriazine-amine in topsoil was positively correlated with clay and negatively correlated with the pH of the soil. Sorption of glyphosate was tested also high in the subsoils. One-dimensional MACRO modeling of the concentration of MCPA, metribuzine and methyltriazine-amine at 2 m depth calculated that the average concentration of MCPA and methyltriazine-amine in the groundwater was below the administrative limit of 0.1 μg/l in all tested profiles while metribuzine always exceeded the 0.1 μg/l threshold value.     

Preparation of various thiol-functionalized carbon-based materials for enhanced removal of mercury from aqueous solution

In this work, biochar (BC), activated carbon (AC), and graphene oxide (GO) were thiol-functionalized using 3-mercaptopropyltrimethoxysilane (3-MPTS) (named as BCS, ACS, and GOS, respectively). BCS, ACS, and GOS were synthesized mainly via the interaction between hydrolyzed 3-MPTS and surface oxygen-containing functional groups (e.g., –OH, O–C=O, and C=O) and π-π interaction. The materials before and after modification were characterized and tested for mercury removal, including sorption kinetics and isotherms, the effects of adsorbent dosage, initial pH, and ionic strength. Pseudo-second-order sorption kinetic model (R² = 0.992~1.000) and Langmuir sorption isotherm model (R² = 0.964~0.998) fitted well with the sorption data of mercury. GOS had the most –SH groups with the largest adsorption capacity for Hg²⁺ and CH₃Hg⁺ (449.6 and 127.5 mg/g), followed by ACS (235.7 and 86.7 mg/g) and BCS (175.6 and 30.3 mg/g), which were much larger than GO (96.7 and 4.9 mg/g), AC (81.1 and 24.6 mg/g), and BC (95.6 and 9.4 mg/g). GOS and ACS showed stable mercury adsorption properties at a wide pH range (2~9) and ionic strength (0.01~0.1 mol/L). Mercury maybe removed by ligand exchange, surface complexation, and electrostatic attraction.

     

Kinetic and isotherm error optimization studies for adsorption of atrazine and imidacloprid on bark of Eucalyptus tereticornis L.

The aim of this study was to establish the bark of Eucalyptus tereticornis L. (EB) as a low cost bio-adsorbent for the removal of imidacloprid and atrazine from aqueous medium. The pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich and intra-particle diffusion (IPD) models were used to describe the kinetic data and rate constants were evaluated. Adsorption data was analysed using ten 2-, 3- and 4-parameter models viz. Freundlich, Jovanovic, Langmuir, Temkin, Koble–Corrigan, Redlich–Peterson, Sips, Toth, Radke–Prausnitz, and Fritz-Schluender isotherms. Six error functions were used to compute the best fit single component isotherm parameters by nonlinear regression analysis. The results showed that the sorption of atrazine was better explained by PSO model, whereas the sorption of imidacloprid followed the PFO kinetic model. Isotherm model optimization analysis suggested that the Freundlich along with Koble–Corrigan, Toth and Fritz-Schluender were the best models to predict atrazine and imidacloprid adsorption onto EB. Error analysis suggested that minimization of chi-square (χ²) error function provided the best determination of optimum parameter sets for all the isotherms.     

Blood mercury levels among fish consumers residing in areas with high environmental burden

Mercury is a ubiquitous, persistent toxicant found in the environment. In water, mercury bioaccumulates up the food chain and leads to high concentrations in fish. Consumption of contaminated fish is the major source of exposure to mercury in the US. The objective of this study was to enroll persons living in areas selected by the Environmental Protection Agency (EPA) to have high mercury concentrations and who consume at least 6 oz of locally caught fish per week to determine the feasibility of monitoring future trends among a population identified as highly exposed. Blood samples were collected at time of interview and analyzed for mercury. Participants (n = 287) were enrolled from North Carolina, Maryland, and South Dakota. Participants reported eating an average of five servings of fish per week. The overall geometric mean for total mercury was 0.75 μg L⁻¹, with North Carolina having the highest mean level (2.02 μg L⁻¹). Overall, 42% of the study population had levels greater than the US geometric mean 0.83 μg L⁻¹. The number of servings of fish consumed was not found to be associated with blood mercury levels. We were able to identify some persons with elevated mercury concentrations living in areas identified by EPA; however, identifying and monitoring a highly exposed population over time would be challenging.     

Sorption kinetic characteristics of polybrominated diphenyl ethers on natural soils

Sorption kinetic characteristics of BDE-28 and BDE-47 on five natural soils with different organic carbon fractions were investigated, and could be satisfactorily described by a two (fast and slow)-compartment first-order model with the ratio of rate constants ranged from 9 to 94 times. The fast compartment made a dominant contribution (71% ∼ 94%) to the total sorption amount in the whole process, and accounted for over 90% of the increase in the total sorption amount at initial 5 h. The influence of the slow compartment on the increase in the total sorption amount became principal (above 90%) in the subsequent stage approximately from 9 h or 25 h to the apparent equilibrium at 265 h. The results proposed the different sorption behaviors of the mathematically classified compartments for BDE-28 and BDE-47, which may correspond to the different soil components, such as soil organic fractions with amorphous and condensed structures, respectively.     

Use of carbonised beet pulp carbon for removal of Remazol Turquoise Blue-G 133 from aqueous solution

Carbonised beet pulp (BPC) produced from agricultural solid waste by-product in sugar industry was used as adsorbent for the removal of Remazol Turquoise Blue-G 133 (RTB-G 133) dye in this study. The kinetics and equilibrium of sorption process were investigated with respect to pH, temperature and initial dye concentration. Adsorption studies with real textile wastewater were also performed. The results showed that adsorption was a strongly pH-dependent process, and optimum pH was determined as 1.0. The maximum dye adsorption capacity was obtained as 47.0 mg g^?1at the temperature of 25 °C at this pH value. The Freundlich and Langmuir adsorption models were used for describing the adsorption equilibrium data of the dye, and isotherm constants were evaluated depending on sorption temperature. Equilibrium data of RTB-G 133 sorption fitted very well to the Freundlich isotherm. Mass transfer and kinetic models were applied to the experimental data to examine the mechanisms of adsorption and potential rate-controlling steps. It was found that both external mass transfer and intra-particle diffusion played an important role in the adsorption mechanisms of dye and adsorption kinetics followed the pseudo second-order type kinetic model. The thermodynamic analysis indicated that the sorption process was exothermic and spontaneous in nature.     

Utilization of Modified Attapulgite for the Removal of Sr(II), Co(II), and Ni(II) Ions from Multicomponent System,Part I: Kinetic Studies

Radionuclide sorption by natural and modified clays is extensively accepted to be an important process from the radioactive waste point of view. This work focused on modification of natural attapulgite with a layered double hydroxide to produce a novel chemisorbent for Sr2+, Ni2+, and Co2+ removal from multicomponent solution. The structural and surface characteristics of both attapulgite (ATP) and modified attapulgite (LDH-ATP) were investigated using XRD, FTIR, SEM, and thermal analysis. Comparison of sorption features of Sr2+, Ni2+, and Co2+ onto ATP and LDH-ATP was achieved; the results indicated that LDH-ATP was the most efficient sorbent for Sr2+, Ni2+, and Co2+. Kinetic studies established that the sorption is fast and reaching >90% within 30 min. The sorption of Sr2+, Ni2+, and Co2+ are well defined by non-linear pseudo-second-order model and controlled by an intra-particle diffusion mechanism. The diffusivity was determined using homogeneous surface diffusion (HSDM) model and found in the order 10−13 m2/min; this confirmed that the sorption of the three ions is chemisorption process. LDH-ATP can be employed as a candidate chemisorbent for the removal of some metal ions from waste solution.     

Modelling of diffusion-limited retardation of contaminants in hydraulically and lithologically nonuniform media

A new reactive transport modelling approach and examples of its application are presented, dealing with the impact of sorption/desorption kinetics on the spreading of solutes, e.g. organic contaminants, in groundwater. Slow sorption/desorption is known from the literature to be strongly responsible for the retardation of organic contaminants. The modelling concept applied in this paper quantifies sorption/desorption kinetics by an intra-particle diffusion approach. According to this idea, solute uptake by or release from the aquifer material is modelled at small scale by a "slow" diffusion process where the diffusion coefficient is reduced as compared to the aqueous diffusion coefficient due to (i) the size and shape of intra-particle pores and (ii) retarded transport of solutes within intra-particle pores governed by a nonlinear sorption isotherm. This process-based concept has the advantage of requiring only measurable model parameters, thus avoiding fitting parameters like first-order rate coefficients.In addition, the approach presented here allows for modelling of slow sorption/desorption in lithologically nonuniform media. Therefore, it accounts for well-known experimental findings indicating that sorptive properties depend on (i) the grain size distribution of the aquifer material and (ii) the lithological composition (e.g. percentage of quartz, sandstone, limestone, etc.) of each grain size fraction. The small-scale physico-chemical model describing sorption/desorption is coupled to a large-scale model of groundwater flow and solute transport. Consequently, hydraulic heterogeneities may also be considered by the overall model. This coupling is regarded as an essential prerequisite for simulating field-scale scenarios which will be addressed by a forthcoming publication.This paper focuses on mathematical model formulation, implementation of the numerical code and lab-scale model applications highlighting the sorption and desorption behavior of an organic contaminant (Phenanthrene) with regard to three lithocomponents exhibiting different sorptive properties. In particular, it is shown that breakthrough curves (BTCs) for lithologically nonuniform media cannot be obtained via simple arithmetic averaging of breakthrough curves for lithologically uniform media. In addition, as no analytical solutions are available for model validation purposes, simulation results are compared to measurements from lab-scale column experiments. The model results indicate that the new code can be regarded as a valuable tool for predicting long-term contaminant uptake or release, which may last for several hundreds of years for some lithocomponents. In particular, breakthrough curves simulated by pure forward modelling reproduce experimental data much better than a calibrated standard first-order kinetics reactive transport model, thus indicating that the new approach is of high quality and may be advantageously used for supporting the design of remediation strategies at contaminated sites where some lithocomponents and/or grain size classes may provide a long-term pollutant source.     

The influence of mariculture on mercury distribution in sediments and fish around Hong Kong and adjacent mainland China waters

To study the influence of mariculture on mercury (Hg) speciation and distribution in sediments and cultured fish around Hong Kong and adjacent mainland China waters, sediment samples were collected from six mariculture sites and the corresponding reference sites, 200-300 m away from the mariculture sites. Mariculture activities increased total mercury, organic matter, carbon, nitrogen and sulfur concentrations in the surface sediments underneath mariculture sites, possibly due to the accumulation of unconsumed fish feed and fish excretion. However, methylmercury (MeHg) concentrations and the ratio of MeHg to THg (% MeHg) in sediments underneath mariculture sites were lower than the corresponding reference sites. The % MeHg in sediments was negatively correlated (r = −0.579, p < 0.05) with organic matter (OM) content among all sites, indicating that OM may have inhibited Hg methylation in surface sediments. Three mariculture fish species were collected from each mariculture site, including red snapper (Lutjanus campechanus), orange-spotted grouper (Epinephelus coioides) and snubnose pompano (Trachinotus blochii). The average MeHg concentration in fish muscle was 75 μg kg⁻¹ (wet weight), and the dietary intake of MeHg through fish consumption for Hong Kong residents was 0.37 μg kg⁻¹ week⁻¹, which was lower than the corresponding WHO limits (500 μg kg⁻¹ and 1.6 μg kg⁻¹ week⁻¹).     

Metal contamination of short-term snow cover near urban crossroads: correlation analysis of metal content and fine particles distribution

Snow samples were collected near crossroads in Novi Sad, Serbia, during December 2009 to assess metal concentrations (Ca, K, Zn, Fe, Cu, Mn, Al, Pb and Na), fine particle distribution and pH value. The filtered samples of melted snow were analysed, with a focus on particles smaller than a few μm. The most common values of the frequency number distribution curve were either in the range of 0.05-0.07 μm or one order of magnitude higher (0.2-0.5 μm). At examined locations metal concentrations varied from 0.0004 mg L⁻¹ for Pb to 18.9 mg L⁻¹ for Na. Besides Na, which mostly originated from de-icing salt, Ca is found to be the most abundant element in snow indicating the dominant influence of natural factors on snow chemistry. No significant difference was found in concentration of the elements at locations near crossroads with either low or high traffic volume, except for Na and Zn.To investigate how metals were related a correlation analysis was done for the concentrations of metals and with respect to the particle size distribution parameters and pH values. The major influence on the fine particle volume (mass) was concluded to be due to the elements from anthropogenic sources. This conclusion was based on the significant positive correlation between Fe, Zn and Al and the fine particle volume based distribution parameters.     

Nonideal transport of contaminants in heterogeneous porous media: 9 - impact of contact time on desorption and elution tailing

A series of miscible-displacement experiments was conducted to examine the impact of sorption contact time on desorption and elution of trichloroethene from a well-characterized soil. A large number of contact times were examined, spanning 1 h to 4 years (∼2 × 10⁶ h). Effluent trichloroethene concentrations were monitored over a range of greater than six orders of magnitude, allowing characterization of potential asymptotic tailing. The results of the column experiments showed that trichloroethene exhibited extensive elution tailing for all experiments. Each increase in contact time resulted in a successive increase in the extent of tailing. In total, the number of pore volumes of water flushing required to reach the analytical detection limit increased from approximately 1000 for the 1-h contact time to almost 9000 for the 4-year contact time. These results indicate that a contact time of less than 1 h produced a sorbed phase that is relatively resistant to desorption, and that a progressive increase in resistance to desorption occurred with increased contact time. A mathematical model incorporating nonlinear, rate-limited sorption/desorption described by a continuous-distribution reaction function was used to successfully simulate the measured data. The nonlinear sorption, the apparent rapid development of desorption resistance, and the progressive increase in resistance with increasing contact time are consistent with behavior anticipated for sorbate interactions with hard-carbon components of the soil.     

Polycyclic aromatic hydrocarbon (PAH) deposition to and exchange at the air-water interface of Luhu, an urban lake in Guangzhou, China

Urban lakes are vulnerable to the accumulation of semivolatile organic compounds, such as PAHs from wet and dry atmospheric deposition. Little was reported on the seasonal patterns of atmospheric deposition of PAHs under Asian monsoon climate. Bulk (dry + wet) particle deposition, air-water diffusion exchange, and vapour wet deposition of PAHs in a small urban lake in Guangzhou were estimated based on a year-round monitoring. The total PAH particle deposition fluxes observed were 0.44-3.46 μg m⁻² day⁻¹. The mean air-water diffusive exchange flux was 20.7 μg m⁻² day⁻¹. The vapour deposition fluxes of PAHs ranged 0.15-8.26 μg m⁻² day⁻¹. Remarkable seasonal variations of particulate PAH deposition, air-water exchange fluxes and vapour wet deposition were influenced by seasonal changes in meteorological parameters. The deposition fluxes were predominantly controlled by the precipitation intensity in wet season whereas by atmospheric concentration in dry season.     

Antimony sorption at gibbsite-water interface

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