Physicochemical characteristics of carbonaceous adsorbent for dioxin-like polychlorinated biphenyl adsorption

It has been known that dioxin-like polychlorinated biphenyls (DL-PCBs) are present in almost all types of environments worldwide. Activated carbon treatment has been expected for the removal of DL-PCBs because it is a simple and low-cost removal technology. In the present study, the physicochemical properties of activated carbon were investigated to identify the characteristics of 16 different types of activated carbon on adsorption properties for DL-PCBs. To accomplish this, micropore volume, and pore diameter were calculated by t-plot analysis and the mesopore volume was analyzed by the Barrett-Joyner-Halenda (BJH) method. In addition, the Brunauer-Emmett-Teller (BET) surface area, pH, metal elements, and surface acid functional groups were analyzed. Then, adsorption experiments using DL-PCB in hexane solution were conducted, and the relationship between adsorption and physicochemical properties of activated carbon was investigated. The results showed that activated carbons having a surface area of 700-1200 m² g⁻¹ and micropores with diameters of about 0.7-0.8 nm exhibited high activity for the adsorption of PCBs. The results also clearly showed that the mesopore volume of activated carbon influenced the adsorption rate and the equilibrium adsorption.     

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.     

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.     

Minimization of the formation of disinfection by-products

The drinking water industry is required to minimize DBPs levels while ensuring adequate disinfection. In this study, efficient and appropriate treatment scheme for the reduction of disinfection by-product (DBPs) formation in drinking water containing natural organic matter has been established. This was carried out by the investigation of different treatment schemes consisting of enhanced coagulation, sedimentation, disinfection by using chlorine dioxide/ozone, filtration by sand filter, or granular activated carbon (GAC). Bench scale treatment schemes were applied on actual samples from different selected sites to identify the best conditions for the treatment of water. Samples were collected from effluent of each step in the treatment train in order to analyze pH, UV absorbance at 254 nm (UVA₂₅₄), specific UV absorbance at 254 nm (SUVA₂₅₄), dissolved organic carbon (DOC), haloacetic acids (HAAs) and trihalomethanes (THMs). The obtained results indicated that using pre-ozonation/enhanced coagulation/activated carbon filtration treatment train appears to be the most effective method for reducing DBPs precursors in drinking water treatment.     

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.     

Selective removal of diclofenac from contaminated water using molecularly imprinted polymer microspheres

A molecularly imprinted polymer (MIP) was synthesized by precipitation polymerization using diclofenac (DFC) as a template. Binding characteristics of the MIP were evaluated using equilibrium binding experiments. Compared to the non-imprinted polymer (NIP), the MIP showed an outstanding affinity towards DFC in an aqueous solution with a binding site capacity (Q_max) of 324.8 mg/g and a dissociation constant (K_d) of 3.99 mg/L. The feasibility of removing DFC from natural water by the MIP was demonstrated by using river water spiked with DFC. Effects of pH and humic acid on the selectivity and adsorption capacity of MIP were evaluated in detail. MIP had better selectivity and higher adsorption efficiency for DFC as compared to that of powdered activated carbon (PAC). In addition, MIP reusability was demonstrated for at least 12 repeated cycles without significant loss in performance, which is a definite advantage over single-use activated carbon.     

双氯芬酸的吸附去除过程与机制

研究了非甾体抗炎药双氯芬酸的吸附去除过程与机制。对吸附处理效果较好的活性炭与纳米羟基氧化铁（α-FeOOH）进行了比表面积、Zeta电位等表面特性的表征,研究比较了双氯芬酸在活性炭与α—FeOOH2种材料上的吸附去除效果与吸附机制。结果表明,在相同的实验条件下,活性炭与α-FeOOH对双氯芬酸吸附去除率可分别达到97．9％和84．3％;双氯芬酸在活性炭上的吸附主要是由于活性炭较大的比表面积与疏水分配作用,在α-FeOOH上的吸附主要是由于静电引力作用;活性炭与α-FeOOH对双氯芬酸的吸附去除效果均随pH的升高而降低;在pH=6时,活性炭与α-FeOOH对双氯芬酸钠的吸附等温线均符合Langmuir方程,单位饱和吸附量分别为109．98mg／g和58．96mg／g;活性炭对双氯芬酸具有更强的吸附能力。     

Influence of Suwannee River humic acid on particle properties and toxicity of silver nanoparticles

Adsorption of natural organic matter (NOM) on nanoparticles can have dramatic impacts on particle dispersion resulting in altered fate and transport as well as bioavailability and toxicity. In this study, the adsorption of Suwannee River humic acid (SRHA) on silver nanoparticles (nano-Ag) was determined and showed a Langmuir adsorption at pH 7 with an adsorption maximum of 28.6 mg g⁻¹ nano-Ag. It was also revealed that addition of <10 mg L⁻¹ total organic carbon (TOC) increased the total Ag content suspended in the aquatic system, likely due to increased dispersion. Total silver content decreased with concentrations of NOM greater than 10 mg TOC L⁻¹ indicating an increase in nanoparticle agglomeration and settling above this concentration. However, SRHA did not have any significant effect on the equilibrium concentration of ionic Ag dissolved in solution. Exposure of Daphnia to nano-Ag particles (50 μg L⁻¹ and pH 7) produced a linear decrease in toxicity with increasing NOM. These results clearly indicate the importance of water chemistry on the fate and toxicity of nanoparticulates.     

Adsorption of mono- and di-butyltin by a wheat charcoal: pH effects and modeling

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 pK_a,1 = 2.3, pK_a,2 = 3.5 and pK_a,3 = 5.9 for MBT and pK_a,1 = 3.0 and pK_a,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.     

Influence of anionic, cationic and nonionic surfactants on adsorption and desorption of oxytetracycline by ultrasonically treated and non-treated multiwalled carbon nanotubes

High adsorption capacity of carbon nanotubes (CNTs) may greatly determine the bioavailability and mobility of organic contaminants. The fate of contaminants adsorbed by CNTs may be substantially influenced by surfactants used both in the synthesis and dispersion of CNTs. The aim of this research was to determine the influence of surfactants (nonionic - TX100, cationic - CTAB and anionic - SDBS) on adsorption and desorption of oxytetracycline (OTC) by multiwalled carbon nanotubes (MWCNTs). The surfactants used had a substantial influence on both adsorption and desorption of OTC. The direction of changes depended clearly on the type of surfactant. In case of anionic SDBS, increased adsorption of OTC by MWCNTs was observed. The presence of TX100 and CTAB decreased the adsorption of OTC by MWCNTs significantly. The increase of OTC adsorption after ultrasonic treatment was observed in case of MWCNTs alone and MWCNTs with SDBS and TX100. However, ultrasonic treatment caused OTC adsorption decrease in the presence of CTAB. The change of pH had also an important effect on OTC adsorption in the presence of surfactants. Depending on the surfactant and pH, an increase or decrease of OTC adsorption was observed. The presence of surfactants increased OTC desorption from MWCNTs significantly as follows: SDBS = CTAB < TX100. The results obtained suggest new potential threats and constitute a basis for further research considering the bioavailability and toxicity of antibiotics in the presence of MWCNTs and surfactants.     

Characterization of dissolved organic matter using high-performance liquid chromatography (HPLC)-size exclusion chromatography (SEC) with a multiple wavelength absorbance detector

High-performance liquid chromatography-size exclusion chromatography (HPLC-SEC) coupled with a multiple wavelength absorbance detector (200-445 nm) was used in this study to investigate the apparent molecular weight (AMW) distributions of dissolved organic matter (DOM). Standard DOM, namely humic acid, fulvic acid and hydrophilic acid, from the Suwannee River were tested to ascertain the performance and sensitivity of the method. In addition to four compounds groups: humic substances (Peak 1, AMW 16 kD), fulvic acids (Peak 2, AMW 11 kD), low AMW acids (Peak 3, AMW 5 kD), and low AMW neutral and amphiphilic molecules, proteins and their amino acid building blocks (Peak 4, AMW 3 kD), an new group that appears to include low AMW, 6-10 kD, humic substances was found based on investigating the spectra at various elution times. The spectroscopic parameter S_>365 (slope at wavelengths >365 nm) was determined to be a good predictor of the AMW of the DOM. The detector wavelength played an important role in evaluating the AMW distribution. For some fractions, such as the humic and low AMW non-aromatic substances, the error in measurement was ±30% as determined by two-dimensional chromatograms detected at an artificially selected wavelength. HPLC-SEC with multiple wavelength absorbance detection was found to be a useful technique for DOM characterization. It characterized the AMW distributions of DOM more accurately and provided additional, potentially important information concerning the properties of DOM with varying AMWs.     

Influence of humified organic matter on copper behavior in acid polluted soils

The main purpose of this work was to identify the role of soil humic acids (HAs) in controlling the behavior of Cu(II) in vineyard soils by exploring the relationship between the chemical and binding properties of HA fractions and those of soil as a whole. The study was conducted on soils with a sandy loam texture, pH 4.3-5.0, a carbon content of 12.4-41.0 g kg⁻¹ and Cu concentrations from 11 to 666 mg kg⁻¹. The metal complexing capacity of HA extracts obtained from the soils ranged from 0.69 to 1.02 mol kg⁻¹, and the stability constants for the metal ion-HA complexes formed, log K, from 5.07 to 5.36. Organic matter-quality related characteristics had little influence on Cu adsorption in acid soils, especially if compared with pH, the degree of Cu saturation and the amount of soil organic matter.     

Photodegradation of perfluorooctanoic acid by synthesized TiO2-MWCNT composites under 365nm UV irradiation

Degradation of perfluorooctanoic acid (PFOA) is of great importance due to its global distribution, persistence and toxicity to bioorganisms. In present study, a composite TiO₂ with multiple wall carbon nano-tubes (MWCNTs) was synthesized using sol-gel method and it was used as photocatalyst to degrade PFOA in water. The prepared composite catalyst displayed significant absorption in UV to visible light region. The loading content of TiO₂ on MWCNTs could be adjusted by changing the ratio of precursor to MWCNTs. Due to the combined effect of the adsorption ability and e⁻ transport capacity of MWCNT, the composites displayed much higher photocatalytic ability to PFOA as compared to pure TiO₂ under UV irradiation. The photocatalyst prepared with 10:1 of tetrabutyl titanate/MWCNT was the most effective. With the optimal dosage at 1.6 g L⁻¹, almost 100% of PFOA was degraded in acid medium after irradiation for 8 h. It was proposed that PFOA were mainly degraded by stepwise losing a moiety of CF₂.     

Adsorption behavior of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) on boehmite

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.     

A comparative study on sorption of perfluorooctane sulfonate (PFOS) by chars, ash and carbon nanotubes

Perfluorooctane sulfonate (PFOS), as one of emerging contaminants, has been attracting increasing concerns in recent years. Sorption of PFOS by maize straw- and willow-derived chars (M400 and W400), maize straw-origin ash (MA) as well as three carbon nanotubes (CNTs) was studied in this work. The sorption kinetics of PFOS by the six adsorbents was well fitted by the pseudo-second-order model. CNTs reached equilibrium in 2 h, much faster than those by chars (384 h) and ash (48 h). According to the sorption isotherms, both single-walled carbon nanotubes (SWCNT) and MA had high sorption capacities (over 700 mg g⁻¹), while the two chars had low sorption capacities (below 170 mg g⁻¹) caused by their small BET surface area. In the case of MA, due to its positively charged surface, both hydrophobic interaction and electrostatic attraction involved in the sorption, and the formation of hemi-micelles further favored the sorption. This study suggested that SWCNT and MA were effective adsorbents for PFOS removal from water. Compared to SWCNT, MA is low cost and easy to obtain, so it could be a preferred adsorbent for PFOS removal.     

Ultraviolet absorbance as a proxy for total dissolved mercury in streams

Stream water samples were collected over a range of hydrologic and seasonal conditions at three forested watersheds in the northeastern USA. Samples were analyzed for dissolved total mercury (THg_d), DOC concentration and DOC composition, and UV₂₅₄ absorbance across the three sites over different seasons and flow conditions. Pooling data from all sites, we found a strong positive correlation of THg_d to DOC (r² = 0.87), but progressively stronger correlations of THg_d with the hydrophobic acid fraction (HPOA) of DOC (r² = 0.91) and with UV₂₅₄ absorbance (r² = 0.92). The strength of the UV₂₅₄ absorbance-THg_d relationship suggests that optical properties associated with dissolved organic matter may be excellent proxies for THg_d concentration in these streams. Ease of sample collection and analysis, the potential application of in-situ optical sensors, and the possibility for intensive monitoring over the hydrograph make this an effective, inexpensive approach to estimate THg_d flux in drainage waters.     

Decomposition of 2,2',4,4',5,5'-hexachlorobiphenyl with iron supported on an activated carbon from an ion-exchange resin

An activated carbon (AC) containing a high concentration (374 mg g⁻¹) of Fe was prepared by carbonization of an ion-exchange resin. To examine its chemical reactivity as a catalyst to decompose 2,2′,4,4′,5,5′-hexachlorobiphenyl (PCB-153), the decomposition parameters of temperature and time were varied under air or N₂. Decomposition at 350 °C was achieved within 15 min under air and 30 min under N₂, and the efficiency of PCB-153 decomposition was 99.7% and 98.0%, respectively. An analysis of inorganic chloride ions revealed that PCB-153 was mineralized effectively during the decomposition. The Brunauer-Emmett-Teller (BET) surface area and pore volume of the AC were measured to assess the adsorption capacity before and after the decomposition. The differences between decomposition under air and N₂ reflected the differences in the BET surface and pore volume measurements. A decomposition pathway was postulated, and the reactive characteristics of chlorine atoms loaded on the benzene rings followed the order of para > meta > ortho, which agrees with the calculated results from a density functional theory study.     

Sorption, desorption, and degradation of (4-chloro-2-methylphenoxy)acetic acid in representative soils of the Danubian Lowland, Slovakia

Herbicide leaching through soil into groundwater greatly depends upon sorption-desorption and degradation phenomena. Batch adsorption, desorption and degradation experiments were performed with acidic herbicide MCPA and three soil types collected from their respective soil horizons. MCPA was found to be weakly sorbed by the soils with Freundlich coefficient values ranging from 0.37 to 1.03 mg^1−1/n kg⁻¹ L^1/n. It was shown that MCPA sorption positively correlated with soil organic carbon content, humic and fulvic acid carbon contents, and negatively with soil pH. The importance of soil organic matter in MCPA sorption by soils was also confirmed by performing sorption experiments after soil organic matter removal. MCPA sorption in these treated soils decreased by 37-100% compared to the original soils. A relatively large part of the sorbed MCPA was released from soils into aqueous solution after four successive desorption steps, although some hysteresis occurred during desorption of MCPA from all soils. Both sorption and desorption were depth-dependent, the A soil horizons exhibited higher retention capacity of the herbicide than B or C soil horizons. Generally, MCPA sorption decreased in the presence of phosphate and low molecular weight organic acids. Degradation of MCPA was faster in the A soil horizons than the corresponding B or C soil horizons with half-life values ranging from 4.9 to 9.6 d in topsoils and from 11.6 to 23.4 d in subsoils.     

Suppressive effect of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and dioxin-like polychlorinated biphenyls transfer from feed to eggs of laying hens by activated carbon as feed additive

In this study, we investigated the suppressive effect of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs) transfer from the feed to the eggs of laying hens by using activated carbon as a feed additive. Four groups of six hens (White Leghorn egg-layers; age, 11 weeks) were housed as two control groups and two exposure groups for a period of 20 weeks. Two control groups were fed with either the basal feed “Control” or basal feed additing activated carbon “Control + C”. Another two exposure groups were fed with feed contaminated (about 6 ng TEQ kg⁻¹ feed) by standard solutions of PCDDs/PCDFs and DL-PCBs “Exposure” alone and contaminated feed adding activated carbon “Exposure + C”. There was no significant effect on each groups for the growth rate, biochemical blood components, and egg production: these were around the standard levels for poultry in general. Moreover the results in this study showed the availability of activated carbon as a feed additive owing to the reduction in the risk of food pollution by PCDDs/PCDFs and DL-PCBs. The concentration in the eggs of the Exposure group gradually increased following the start of egg-laying but reached a steady state after about 1 month. In contrast, the concentration for the Exposure + C group was stationary and below the maximum EU level (6 pg TEQ g⁻¹ fat). In comparison to the Exposure group, the Exposure + C group showed a significant decline in the percentage of bioaccumulation into the egg. This reduction due to activated carbon was also observed in the muscle and abdominal fat. The reductions were compound- and congener-dependent for DL-PCBs as follows: PCDDs/PCDFs, non-ortho-PCBs, and mono-ortho-PCBs were more than 90%, 80%, and 50%, respectively, irrespective of the type of tissues. Fat soluble vitamin concentrations in the eggs of the Exposure + C group showed lower trends than the Exposure group. The γ-tocopherol and α-tocopherol concentrations in eggs of Exposure + C group showed a significant reduction of about 40%. However, the addition of activated carbon into animal feed could obviate the remote potential for accidents causing unintentional food pollution with PCDDs/PCDFs and DL-PCBs.