Sorption and desorption kinetics of phthalates and phenol on water/sediment interface

Ｓｏｒｐｔｉｏｎａｎｄｄｅｓｏｒｐｔｉｏｎｋｉｎｅｔｉｃｓｏｆｐｈｔｈａｌａｔｅｓａｎｄｐｈｅｎｏｌｏｎｗａｔｅｒ／ｓｅｄｉｍｅｎｔｉｎｔｅｒｆａｃｅＹｅＣｈａｎｇｍｉｎｇ，ＺｈａｏＷｕｓｈａｎ，ＬｉＴｉｅ，ＬｅｉＺｈｉｆａｎｇ，ＹａｎＨａｉＲｅｓ...     

Effects of aging process on adsorption–desorption and bioavailability of fomesafen in an agricultural soil amended with rice hull biochar

Biochar has been introduced as an acceptable soil amendment due to its environmental benefits such as sequestering soil contaminants. However, the aging process in biochar amended soil probably decreases the adsorption capacity of biochar through changing its physico-chemical properties. Adsorption, leaching and bioavailability of fomesafen to corn in a Chinese soil amended by rice hull biochar after 0, 30, 90 and 180 days were investigated.Results showed that the addition of 0.5%–2% fresh biochar significantly increases the adsorption of fomesafen 4–26 times compare to unamended soil due to higher SSA of biochar. Biochar amendment also decreases fomesafen concentration in soil pore water by5%–23% resulting lower risk of the herbicide for cultivated plants. However, the aging process decreased the adsorption capacity of biochar since the adsorption coefficient values which was 1.9–12.4 in 0.5%–2% fresh biochar amended soil, declined to 1.36–4.16, 1.13–2.78 and 0.95–2.31 in 1, 3 and 6-month aged treatments, respectively. Consequently, higher desorption, leaching and bioavailable fraction of fomesafen belonged to 6-month aged treatment. Nevertheless, rice hull biochar was effective for sequestering fomesafen as the adsorption capacity of biochar amended soil after 6 months of aging was still 2.5–5 times higher compared to that of unamended soil.     

Predicting heavy metals’ adsorption edges and adsorption isotherms on MnO2 with the parameters determined from Langmuir kinetics

Although surface complexation models have been widely used to describe the adsorption of heavy metals, few studies have verified the feasibility of modeling the adsorption kinetics,edge, and isotherm data with one p H-independent parameter. A close inspection of the derivation process of Langmuir isotherm revealed that the equilibrium constant derived from the Langmuir kinetic model, K S-kinetic, is theoretically equivalent to the adsorption constant in Langmuir isotherm, K S-Langmuir. The modified Langmuir kinetic model(MLK model) and modified Langmuir isotherm model(MLI model) incorporating p H factor were developed. The MLK model was employed to simulate the adsorption kinetics of Cu(II), Co(II), Cd(II), Zn(II) and Ni(II) on Mn O2 at p H 3.2 or 3.3 to get the values of K S-kinetic. The adsorption edges of heavy metals could be modeled with the modified metal partitioning model(MMP model), and the values of K S-Langmuir were obtained. The values of K S-kinetic and K S-Langmuir are very close to each other, validating that the constants obtained by these two methods are basically the same. The MMP model with K S-kinetic constants could predict the adsorption edges of heavy metals on Mn O2 very well at different adsorbent/adsorbate concentrations. Moreover, the adsorption isotherms of heavy metals on Mn O2 at various p H levels could be predicted reasonably well by the MLI model with the K S-kinetic constants.     

Effect of an eco-friendly o/w emulsion stabilized with amphiphilic sodium alginate derivatives on lambda-cyhalothrin adsorption–desorption on natural soil minerals

The effects of amphiphilic O/W emulsions,stabilized by the alkyl polyglycoside(APG)or cholesterol-grafted sodium alginate(CSAD)/APG systems,on lambda-cyhalothrin adsorption/desorption mechanisms on natural soil minerals(i.e.,illite and kaolinite)were investigated.Sorption and desorption of lambda-cyhalothrin onto soil minerals was studied via batch equilibration to give insight into the adsorption equilibrium,kinetics,and thermodynamics of lambda-cyhalothrin adsorption onto minerals.The results indicate the following:(i)The adsorption processes for the APG system and CSAD/APG system include:rapid adsorption,slow adsorption,and adsorption equilibrium.The adsorption kinetics of pesticide on illite and kaolinite are in accordance with the Ho and McKay model,and the adsorption isotherm conforms to the Freundlich model.In addition,the adsorption processes of pesticide for the two systems on minerals were spontaneous and feasible(ΔG~00),endothermic(ΔH~00),and mainly involved chemical bonding(ΔH~060).(ii)The equilibrium adsorption percentages of the pesticide on illite for the APG system and CSAD/APG system were 42.4%and 64.8%,and the corresponding equilibrium adsorption percentages on kaolinite were 40.8%and 61.8%,respectively.Moreover,the pesticide adsorption rate K_(2-CSAD/APG)was faster than K_(2-APG),and its adsorption capacity K_(f-CSAD/APG )was greater than K_(f-APG).Meanwhile,the pesticide desorption K_(fd)in the CSAD/APG system was smaller than that in the APG system.As a result,this eco-friendly O/W emulsion based on amphiphilic sodium alginate derivatives might provide a green pesticide formulation,since it could reduce the amount of lambda-cyhalothrin entering aquatic systems to threaten non-target fish and invertebrate species.     

CrⅥ adsorption on four typical soil colloids: equilibrium and kinetics

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Adsorption of chloroacetanilide herbicides on soil and its components Ⅲ. Influence of clay acidity, humic acid coating and herbicide structure on acetanilide herbicide adsorption on homoionic clays

Adsorption of chloroacetanilide herbicides on homoionic montmorillonite, soil humic acid, and their mixtures was studied by coupling batch equilibration and FT-IR analysis. Adsorption isotherms of acetochlor, alachlor, metolachlor and propachlor on Ca²⁺-, Mg²⁺ -. Al³⁺ -and Fe³⁺ -saturated clays were well described by the Freundlich equation. Regardless of the type of exchange cations, Kf decreased in the order of metolachlor ＞ acetolachlor ＞ alachlor ＞ propachlor on the same clay. FT-IR spectra showed that the carbonyl group of the herbicide molecule was involved in binding, probably via H-bond with water molecules in the clay interlayer. The type and position of substitutions around the carbonyl group may have affected the electronegativity of oxygen, thus influencing the relative adsorption of these herbicides. For the same herbicide, adsorption on clay increased in the order of Mg²⁺ ＜ Ca²⁺ ＜ Al³⁺ ≤ Fe³⁺ which coincided with the iucreasing aciditv of homoionic clays. Acidity of cations may have affected the protonation of water, and thus the strength of H-bond between the clay water and herbicide. Complexation of clay and humic acid resulted in less adsorption than that expected from independent adsorption by the individual constituents. The effect varied with herbicides, but the greatest decrease in adsorption occurred at a 60:40 clay-to-humic acid ratio for all the herbicides. Causes for the decreased adsorption need to be characterized to better understand adsorption mechanisms and predict adsorption from soil compositions.     

Response to comment on "Removal of heavy metals from aqueous solution by carbon nanotubes: adsorption equilibrium and kinetics"

We would like to thank Dr. Ho for his careful examination of our paper. We agree with the comment on our paper published in Journal of Environmental Sciences.     

Effect of silver nanoparticles on an integrated fixed-film activated sludge–sequencing batch reactor: Performance and community structure

The effects of silver nanoparticles(AgNPs) on reactor performance, extracellular polymeric substances composition and microbial community structure and function in integrated fixed-film activated sludge–sequencing batch reactors(IFAS–SBRs) were investigated.Results showed that the addition of AgNPs from 0.1 to 10 mg/L exhibited no significant effects on nutrient removal. The average overall removal of COD, NH4+–N and PO43-–P was96.6%, 99.9% and 98.8%, respectively. The introduction of AgNPs caused an increase in extracellular polymeric substances content for the sludge and biofilm of IFAS–SBRs. The release of Ag+from Ag NPs and lactate dehydrogenase test implied the low toxicity of AgNPs to IFAS–SBRs. High-throughput sequencing revealed that microbial community structure showed significant shifts at phylum and genus levels after long-term exposure to AgNPs,but core functional groups responsible for nutrient removal remained at high abundance.Bacterial function prediction indicated that the metabolic categories showed no significant shifts under AgNPs stress, therefore good process performance could still be achieved.     

Particle concentration effect in adsorption/desorption of Zn(Ⅱ) on anatase type nano TiO_2

Adsorption/desorption in a new Zn(Ⅱ)-TiO_2 adsorption system was investigated at different particle concentrations(C_p).TEM,SEM and XRD analyses revealed that the TiO_2 particles were an aggregation of nano-sized(approximately 10 nm)pure anatase-type TiO_2. Adsorption experiments were carried out with particle concentrations of 100,400 and 1000 mg/L,and their adsorption isotherms were found to decline successively,showing an obvious C_p effect.Desorption experiments indicated that adsorption in this system was irreversible,and the irreversibility increased with increasing C_p.These phenomena could be explained by the MEA(metastable equilibrium adsorption)theory and the C_p effect could be modeled well with an MEA-Freundlich-type C_p effect isotherm equation. This study may help understand environmental behavior of contaminants on ultrafine natural particles.     

Particle concentration effect in adsorption/desorption of Zn（Ⅱ） on anatase type nano TiO2

Adsorption/desorption in a new Zn(II)-TiO2 adsorption system was investigated at different particle concentrations (Cp). TEM, SEM and XRD analyses revealed that the TiO2 particles were an aggregation of nano-sized (approximately 10 nm) pure anatase-type TiO2. Adsorption experiments were carried out with particle concentrations of 100, 400 and 1000 mg/L, and their adsorption isotherms were found to decline successively, showing an obvious Cp effect. Desorption experiments indicated that adsorption in this system was irreversible, and the irreversibility increased with increasing Cp. These phenomena could be explained by the MEA (metastable equilibrium adsorption) theory and the Cp effect could be modeled well with an MEA-Freundlich-type Cp effect isotherm equation. This study may help understand environmental behavior of contaminants on ultrafine natural particles.     

活性炭纤维处理甲苯废水的试验

采用活性炭纤维处理甲苯模拟废水，通过静态和动态吸附实验，测定了吸附等温线、动态穿透曲线，并研究了ｐＨ、温度、吸附时间对处理效果的影响。结果表明，溶液ｐＨ在３￣５范围内对吸附效率影响不大；温度升高，吸附效率有所降低，吸附时间存在最佳值，吸附饱和炭用蒸汽再生，重复使用７次，吸附效率无明显变化，活性炭纤维对甲苯的吸附容量大，吸附速率快，再生条件温和。     

CuO-modified activated carbon for the improvement of toluene removal in air

We used an impregnation method to prepare CuO/AC(activated carbon) composite materials of different CuO content and characterized them via scanning electron microscope(SEM), Brunauer–Emmett–Teller(BET), and Fourier transform infrared spectroscopy(FT-IR).The effect of CuO content on toluene adsorption/desorption was evaluated.We explored the reusability of AC and AC03(CuO modified AC with CuO loading 0.3 wt.%) adsorbents via toluene adsorption/desorption cycle testing.We used quasi-firstand quasi-second-order models, the Bangham model, and the Weber–Morris model to fit the toluene adsorption data.The introduction of CuO species evidently improved the adsorption performance of activated carbon toward toluene.The CuO content markedly affected the specific surface area, CuO dispersal, the numbers of oxygen-containing functional groups on the surface, and adsorption performance of the prepared composite adsorbents.Low CuO content was not favorable for the formation of active adsorption sites,while high content greatly reduced the specific surface area, and even covered active adsorption sites.The toluene adsorption performance varied in the order AC03 AC02 AC05 AC08 AC01(AC03, AC02, AC05, AC08 and AC01 are CuO modifying AC with CuO loading 0.3, 0.2, 0.5 0.8 and 0.1 wt.%, respectively).The breakthrough time and toluene adsorption capacity of the AC03 composite adsorbent were 94 min and 701.8 mg/g,respectively, and the recycling efficiency was 92.8% after thermal desorption at 200°C.The adsorption process was best described by the Bangham model and adsorption could be divided into three stages.     

基于孔结构调控强化BEAC工艺生物降解效能

为进一步提升生物增强活性炭工艺（BEAC）中炭表面的功能菌载持量及生物降解活性,通过CO₂接触氧化与深度活化相结合的压块炭制备改进工艺对煤质净水炭的孔结构进行调控.结果表明：基于改进工艺制备的XHIT型炭的中孔容积（0.7041cm³/g）及中孔容积率（63.95%）显著提高,其表面复合功能菌初始固定化生物量达到9.13mmol/g（以P计）,增殖速率为2.123mmol/（g·d）（以P计）.深度活化产生的高含氧量（9.96%）显著降低了XHIT型炭表面吸附作用对水中溶解氧亲和度（（0.42±0.07）mg DO/L）,功能菌生物降解对水中溶解氧的利用效率达到91.17%.基于XHIT型炭构建的BEAC工艺（通水倍数为39.50m³/kg）对松花江水源水中的微量有机污染物（COD_Mn）的平均去除率达到（70.65±15.22）%,有机污染物累积去除量达到94655.50mg COD_Mn/kg炭.     

Study on sulfur migration in activated carbon adsorption-desorption cycle: Effect of alkali/alkaline earth metals

Activated carbon (AC) has been widely used in the removal of SO₂ from flue gas owing to its well-developed pore structure and abundant functional groups. Herein, the effect of alkali/alkaline earth metals on sulfur migration was investigated based on the dynamic adsorption and temperature programmed desorption experiment. The adsorption and desorption properties of six types of AC (three commercial and three laboratory-made) were carried out on a fixed-bed experimental device, and the physical and chemical properties of samples were determined by X-ray fluorescence, X-ray diffraction, scanning electron microscopy/energy dispersive X-ray, and X-ray photoelectron spectroscopy analysis. The experimental results showed that the adsorbed SO₂ cannot be completely desorbed by increasing the regeneration temperature (350 – 850°C), while the SO₂ fixed in the AC combines with the Ca-based minerals in the ash to form a stable sulfate. For different samples, higher ash content, higher CaO content in the ash and a more developed pore structure lead to a higher SO₂ fixation rate. Moreover, the multiple adsorption-desorption cycles experiment showed that the effect of SO₂ fixation is mainly reflected in the first cycle, after which the adsorption and desorption amount are approximately the same. This study elucidates the effect of alkali/alkaline earth metals on the adsorption-desorption cycle of AC, which provides a deeper understanding of sulfur migration in the AC flue gas desulfurization process.     

Review of post-combustion carbon dioxide capture technologies using activated carbon

Carbon dioxide(CO_2) is the largest anthropogenic greenhouse gas(GHG) on the planet contributing to the global warming. Currently, there are three capture technologies of trapping CO_2 from the flue gas and they are pre-combustion, post-combustion and oxy-fuel combustion. Among these, the post-combustion is widely popular as it can be retrofitted for a short to medium term without encountering any significant technology risks or changes.Activated carbon is widely used as a universal separation medium with series of advantages compared to the first generation capture processes based on amine-based scrubbing which are inherently energy intensive. The goal of this review is to elucidate the three CO_2 capture technologies with a focus on the use of activated carbon(AC) as an adsorbent for post-combustion anthropogenic CO_2 flue gas capture prior to emission to atmosphere. Furthermore, this coherent review summarizes the recent ongoing research on the preparation of activated carbon from various sources to provide a profound understanding on the current progress to highlight the challenges of the CO_2 mitigation efforts along with the mathematical modeling of CO_2 capture. AC is widely seen as a universal adsorbent due to its unique properties such as high surface area and porous texture. Other applications of AC in the removal of contaminants from flue gas, heavy metal and organic compounds, as a catalyst and catalyst support and in the electronics and electroplating industry are also discussed in this study.     

Competitive effects of humic acid and wastewater on adsorption of Methylene Blue dye by activated carbon and non-imprinted polymers

Natural organic matter(NOM), present in natural waters and wastewater, decreases adsorption of micropollutants, increasing treatment costs. This research investigated mechanisms of competition for non-imprinted polymers(NIPs) and activated carbon with humic acid and wastewater. Three different types of activated carbons(Norit PAC 200,Darco KB-M, and Darco S-51) were used for comparison with the NIP. The lower surface area and micropore to mesopore ratio of the NIP led to decreased adsorption capacity in comparison to the activated carbons. In addition, experiments were conducted for single-solute adsorption of Methylene Blue(MB) dye, simultaneous adsorption with humic acid and wastewater, and pre-loading with humic acid and wastewater followed by adsorption of MB dye using NIP and Norit PAC 200. Both the NIP and PAC 200 showed significant decreases of 27% for NIP(p = 0.087) and 29% for PAC 200(p = 0.096) during simultaneous exposure to humic acid and MB dye. There was no corresponding decrease for NIP or PAC 200 pre-loaded with humic acid and then exposed to MB. In fact, for PAC 200, the adsorption capacity of the activated carbon increased when it was pre-loaded with humic acid by 39%(p = 0.0005). For wastewater, the NIP showed no significant increase or decrease in adsorption capacity during either simultaneous exposure or pre-loading. The adsorption capacity of PAC 200 increased by 40%(p = 0.001) for simultaneous exposure to wastewater and MB. Pre-loading with wastewater had no effect on MB adsorption by PAC 200.     

Adsorption kinetics of the herbicide safeners, benoxacor and furilazole, to activated carbon and agricultural soils

Chloroacetamide herbicides, namely acetochlor and metolachlor, are common herbicides used on corn and soybean fields. Dichloroacetamide safeners, namely benoxacor and furilazole, are commonly used in formulations containing chloroacetamide herbicides. Extensive reports on adsorption of chloroacetamide herbicides are available, yet little information exists regarding adsorption potential of co-applied safeners. Herein, the adsorption and desorption characteristics of selected herbicide safeners to granular activated carbon (GAC) and in agricultural soils are reported. Further, soil column studies were performed to understand the leaching behaviour of the herbicide Dual II Magnum. Equilibrium sorption experiments of safeners to three agricultural soils and one GAC showed that adsorption was best fitted by the Freundlich isotherm. The Freundlich adsorption constant, K_f, for benoxacor and furilazole sorption onto three agricultural soils ranged from 0.1 to 0.27 and 0.1 to 0.13 (mg/g) × (mg/L)?(1/n), respectively. The K_f for benoxacor and furilazole to GAC was 6.4 and 3.4 (mg/g) × (mg/L)?(1/n), respectively, suggesting more favorable sorption of benoxacor to GAC than furilazole to GAC. The sorption to soils was reversible as almost 40%–90% of both safeners was desorbed from three soils. These results were validated in four replicated soil column studies, where S-metolachlor was shown to leach similarly to the safener benoxacor, originating from the herbicide formulation. The leaching of S-metolachlor and benoxacor was influenced by soil texture. Cumulatively, these results show that safeners will move through the environment to surface waters similarly to the active ingredients in herbicides, but may be removed during drinking water treatment via GAC.     

活性炭吸附二苯并呋喃的动力学

采用Norit RB1和Monolith两种活性炭吸附气相中低浓度的二苯并呋喃,测定了二苯并呋喃在2种活性炭上的吸附等温线和吸附动力学曲线,分析了气相主体浓度、温度和二苯并呋喃初始浓度等因素对固相有效扩散系数的影响.结果表明,Langmuir吸附等温线模型能够比较准确地描述二苯并呋喃在Norit-RB1和Monolith活性炭上的吸附相平衡;二苯并呋喃在活性炭上的吸附速率受固相扩散控制;固相有效扩散系数随温度的升高而增大,气相浓度和二苯并呋喃初始浓度对固相有效扩散系数影响较小.     

Effects of temperature and SO3 on re-emission of mercury from activated carbon under flue gas conditions

Mercury(Hg) is a toxic and bio-accumulating heavy metal that is predominantly released via the combustion of coal. Due to its toxicity, the Environmental Protection Agency(EPA)has introduced Mercury and Air Toxics Standards(MATS) Rule regarding allowable Hg emissions. In order to reduce emissions, power plants have widely adopted activated carbon(AC) injection. AC injection has proven to be an effective method to reduce Hg emissions, but the re-emission of previously adsorbed Hg during unit operation, likely due to changing temperature or flue gas composition, could be problematic. This study specifically examined the effects of temperature and sulfur trioxide(SO3) concentration,by ramping temperature and SO3 concentration independently and simultaneously, on AC samples that are already exposed to flue gas and saturated in presence of Hg, sulfur dioxide(SO2) and nitric oxide(NO). Of these two suspected factors to cause re-emission,temperature had the greater impact and resulted in re-emission of both elemental and oxidized Hg with a greater fraction of oxidized Hg, which can be attributed to elemental Hg being more strongly bonded to the AC surface. Surprisingly, exposing the samples to increasing concentrations of SO3 had nearly no effect under the conditions examined in this study, possibly as a result of the samples being already saturated with sulfur prior to the SO3 ramp tests to simulate transient conditions in the plant.     

活性炭对天然水体中甲基对硫磷和三氯乙烯的吸附特性研究

采用序批式试验研究了3种粉末活性炭(PAC)对天然水体中甲基对硫磷(MP)和三氯乙烯(TCE)的吸附平衡特性,利用均相表面扩散模型(HSDM)对不同投炭量下的吸附动力学进行拟合与预测,并探讨了天然有机物(NOM)对MP、TCE在PAC上的竞争吸附效应.研究结果表明,天然水体条件下,3种PAC对MP和TCE的吸附符合Langmuir模型和Freundlich模型;MP比TCE更易于被PAC吸附;3种PAC对MP、TCE的吸附能力由大到小依次为YK炭、SL炭和JC炭;HSDM模型可以很好地对吸附动力学进行拟合,并能够有效地预测不同投炭量时的吸附动力学;天然水体中的NOM会与MP和TCE在PAC上发生竞争吸附,NOM对MP的竞争吸附作用相对TCE更为显著.