Comparative sorption and desorption behaviors of PFHxS and PFOS on sequentially extracted humic substances

The sorption and desorption behaviors of two perfluoroalkane sulfonates（PFSAs）, including perfluorohexane sulfonate（PFHx S） and perfluorooctane sulfonate（PFOS） on two humic acids（HAs） and humin（HM）, which were extracted from a peat soil, were investigated. The sorption kinetics and isotherms showed that the sorption of PFOS on the humic substances（HSs） was much higher than PFHx S. For the same PFSA compound, the sorption on HSs followed the order of HM 〉 HA2 〉 HA1. These suggest that hydrophobic interaction plays a key role in the sorption of PFSAs on HSs. The sorption capacities of PFSAs on HSs were significantly related to their aliphaticity, but negatively correlated to aromatic carbons,indicating the importance of aliphatic groups in the sorption of PFSAs. Compared to PFOS,PFHx S displayed distinct desorption hysteresis, probably due to irreversible pore deformation after sorption of PFHx S. The sorption of the two PFSAs on HSs decreased with an increase in p H in the solution. This is ascribed to the electrostatic interaction and hydrogen bonding at lower p H. Hydrophobic interaction might also be stronger at lower p H due to the aggregation of HSs.     

Adsorptive removal of hydrophobic organic compounds by carbonaceous adsorbents: A comparative study of waste-polymer-based, coal-based activated carbon, and carbon nanotubes

Adsorption of the hydrophobic organic compounds (HOCs) trichloroethylene (TCE), 1,3-dichlorobenzene (DCB), 1,3-dinitrobenzene (DNB) and γ-hexachlorocyclohexane (HCH) on five different carbonaceous materials was compared. The adsorbents included three polymer-based activated carbons, one coal-based activated carbon (F400) and multiwalled carbon nanotubes (MWNT). The polymerbased activated carbons were prepared using KOH activation from waste polymers: polyvinyl chloride (PVC), polyethyleneterephthalate (PET) and tire rubber (TR). Compared with F400 and MWNT, activated carbons derived from PVC and PET exhibited fast adsorption kinetics and high adsorption capacity toward the HOCs, attributed to their extremely large hydrophobic surface area (2700 m²/g) and highly mesoporous structures. Adsorption of small-sized TCE was stronger on the tire-rubber-based carbon and F400 resulting from the pore-filling effect. In contrast, due to the molecular sieving effect, their adsorption on HCH was lower. MWNT exhibited the lowest adsorption capacity toward HOCs because of its low surface area and characteristic of aggregating in aqueous solution.     

Effect of Na+ impregnated activated carbon on the adsorption of NH4+-N from aqueous solution

Two kinds of activated carbons modified by Na+ impregnation after pre-treatments involving oxidation by nitric acid or acidification by hydrochloric acid (denoted as AC/N-Na and AC/HCl-Na, respectively), were used as adsorbents to remove NH4+-N. The surface features of samples were investigated by BET, SEM, XRD and FT-IR. The adsorption experiments were conducted in equilibrium and kinetic conditions. Influencing factors such as initial solution pH and initial concentration were investigated. A possible mechanism was proposed. Results showed that optimal NH4+-N removal efficiency was achieved at a neutral pH condition for the modified ACs. The Langmuir isotherm adsorption equation provided a better fit than other models for the equilibrium study. The adsorption kinetics followed both the pseudo second-order kinetics model and intra-particle kinetic model. Chemical surface analysis indicated that Na+ ions form ionic bonds with available surface functional groups created by pre-treatment, especially oxidation by nitric acid, thus increasing the removal efficiency of the modified ACs for NH4+-N. Na+-impregnated ACs had a higher removal capability in removing NH4+-N than unmodified AC, possibly resulting from higher numbers of surface functional groups and better intra-particle diffusion. The good fit of Langmuir isotherm adsorption to the data indicated the presence of monolayer NH4+-N adsorption on the active homogenous sites within the adsorbents. The applicability of pseudo second-order and intra-particle kinetic models revealed the complex nature of the adsorption mechanism. The intra-particle diffusion model revealed that the adsorption process consisted not only of surface adsorption but also intra-particle diffusion.     

Removal of phenol by activated carbons prepared from palm oil mill effluent sludge

The study was attempted to produce activated carbons from palm oil mill effluent （POME） sludge. The adsorption capacity of the activated carbons produced was evaluated in aqueous solution of phenol. Two types of activation were followed, namely, thermal activation at 300, 500 and 800%, and physical activation at 150% （boiling treatment）. A control （raw POME sludge） was used to compare the adsorption capacity of the activated carbons produced. The results indicated that the activation temperature of 800℃ showed maximum absorption capacity by the activated carbon （POME 800） in aqueous solution of phenol. Batch adsorption studies showed an equilibrium time of 6 h for the activated carbon of POME 800. It was observed that the adsorption capacity was higher at lower values ofpH （2--3） and higher value of initial concentration of phenol （200--300 mg/L）, The equilibrium data were fitted by the Langmuir and Freundlich adsorption isotherms. The adsorption of phenol onto the activated carbon POME 800 was studied in terms of pseudo-first and second order kinetics to predict the rate constant and equilibrium capacity with the effect of initial phenol concentrations. The rate of adsorption was found to be better correlation for the pseudo-second order kinetics compared to the first order kinetics.     

Insight into the adsorption of tetracycline onto amino and amino–Fe~(3+) gunctionalized mesoporous silica: Effect of functionalized groups

In order to study the influences of functionalized groups onto the adsorption of tetracycline,we prepared a series of amino and amino–Fe~(3+)complex mesoporous silica adsorbents with diverse content of amino and Fe~(3+)groups(named N,N-SBA15 and Fe-N,N-SBA15).The resulting mesoporous silica adsorbents were fully characterized by X-ray powder diffraction(XRD),Fourier transform infrared spectrometer(FTIR)and N_2adsorption/desorption isotherms.Furthermore,the effects of functionalized groups on the removal of TC were investigated.The results showed that the periodic ordered structure of SBA-15 was maintained after modification of amino/Fe~(3+)groups.The functionalized amino groups decreased the adsorption capacity while the coordinated Fe~(3+)increased the adsorption capacity.The adsorption kinetics of TC fitted pseudo-second-order model well and the equilibrium was achieved quickly.The adsorption isotherms fitted the Langmuir model well and with the Fe~(3+)content increased from 3.93%to 8.26%,the Q_(max)of the adsorbents increased from 102 to 188 mmol/kg.The solution p H affected the adsorption of TC onto amino complex adsorbents slightly while influenced the adsorption onto Fe-amine complex adsorbents greatly.The adsorption of TC on SBA15 and N,N-SBA15 may be related to the formation of outer-sphere surface complexes,while the adsorption of TC onto Fe-N,N-SBA15 was mainly attributed to the inner-sphere surface complexes.This study could offer potential materials that have excellent adsorption behavior for environmental remediation and suggested useful information for the preparing other adsorbents in environmental applications.     

Adsorption of three pharmaceuticals on two magnetic ion-exchange resins

The presence of pharmaceuticals in aquatic environments poses potential risks to the ecology and human health. This study investigated the removal of three widely detected and abundant pharmaceuticals, namely, ibuprofen (IBU), diclofenac (DC), and sulfadiazine (SDZ), by two magnetic ion-exchange resins. The adsorption kinetics of the three adsorbates onto both resins was relatively fast and followed pseudo-second-order kinetics. Despite the different pore structures of the two resins, similar adsorption patterns of DC and SDZ were observed, implying the existence of an ion-exchange mechanism. IBU demonstrated a combination of interactions during the adsorption process. These interactionswere dependent on the specific surface area and functional groups of the resin. The adsorption isothermfittings verified the differences in the behavior of the three pharmaceuticals on the two magnetic ion-exchange resins. The presence of Cl^- and SO₄^2- suppressed the adsorption amount, butwith different inhibition levels for different adsorbates. This work facilitates the understanding of the adsorption behavior andmechanismof pharmaceuticals onmagnetic ion-exchange resins. The results will expand the application of magnetic ion-exchange resins to the removal of pharmaceuticals in waters.     

Adsorption thermodynamics and kinetic investigation of aromatic amphoteric compounds onto different polymeric adsorbents

The adsorption behavior of p-aminobenzoic acid and o-aminobenzoic acid onto the different polymeric adsorbents was systematically investigated as a function of the solution concentration and temperature.Experimental results indicated that the equilibrium adsorption data of the four polymeric adsorbents fitted well in the Freundlich isotherm.The adsorption capacity of multi-functional polymeric adsorbent NJ-99 was the highest,which might be attributed to the strong hydrogen-bonding interaction between the amino groups on the resin and the carboxyl group of aminobenzoic acid.The adsorption capacity of o-aminobenzoic acid onto any adsorbent was higher than p-aminobenzoic acid.Thermodynamic studies suggested the exothermic,spontaneous physical adsorption process.Adsorption kinetics results showed that the adsorption followed the pseudo-second-order kinetics model and the intraparticle mass transfer process was the rate-controlling step.     

Experimental and molecular dynamic simulation study of perfluorooctane sulfonate adsorption on soil and sediment components

Soil and sediment play a crucial role in the fate and transport of perfluorooctane sulfonate (PFOS) in the environment. However, the molecular mechanisms of major soil/sediment components on PFOS adsorption remain unclear. This study experimentally isolated three major components in soil/sediment: humin/kerogen, humic/fulvic acid (HA/FA), and inorganic component after removing organics, and explored their contributions to PFOS adsorption using batch adsorption experiments and molecular dynamic simulations. The results suggest that the humin/kerogen component dominated the PFOS adsorption due to its aliphatic featureswhere hydrophobic effect and phase transfer are the primary adsorptionmechanism. Compared with the humin/kerogen, the HA/FA component contributed less to the PFOS adsorption because of its hydrophilic and polar characteristics. The electrostatic repulsion between the polar groups of HA/FA and PFOS anions was attributable to the reduced PFOS adsorption.When the soil organicmatterwas extracted, the inorganic component also plays a non-negligible role because PFOS molecules might form surface complexes on SiO₂ surface. The findings obtained in this study illustrate the contribution of organic matters in soils and sediments to PFOS adsorption and provided newperspective to understanding the adsorption process of PFOS on micro-interface in the environment.     

Effects of ZnO nanoparticles on perfluorooctane sulfonate induced thyroid-disrupting on zebrafish larvae

Perfluorooctane sulfonate(PFOS) and ZnO nanoparticles(nano-ZnO) are widely distributed in the environment.However,the potential toxicity of co-exposure to PFOS and nano-ZnO remains to be fully elucidated.The test investigated the effects of co-exposure to PFOS and nano-ZnO on the hypothalamic–pituitary–thyroid(HPT) axis in zebrafish.Zebrafish embryos were exposed to a combination of PFOS(0.2,0.4,0.8 mg/L) and nano-ZnO(50 mg/L)from their early stages of life(0–14 days).The whole-body content of TH and the expression of genes and proteins related to the HPT axis were analyzed.The co-exposure decreased the body length and increased the malformation rates compared with exposure to PFOS alone.Co-exposure also increased the triiodothyronine(T3) levels,whereas the thyroxine(T4)content remained unchanged.Compared with the exposure to PFOS alone,exposure to both PFOS(0.8 mg/L) and nano-ZnO(50 mg/L) significantly up-regulated the expression of corticotropin-releasing factor,sodium/iodidesymporter,iodothyronine deiodinases and thyroid receptors and significantly down-regulated the expression of thyroid-stimulating hormone,thyroglobulin(TG),transthyretin(TTR) and thyroid receptors.The protein expression levels of TG and TTR were also significantly down-regulated in the co-exposure groups.In addition,the expression of the thyroid peroxidase gene was unchanged in all groups.The results demonstrated that PFOS and nano-ZnO co-exposure could cause more serious thyroid-disrupting effects in zebrafish than exposure to PFOS alone.Our results also provide insight into the mechanism of disruption of the thyroid status by PFOS and nano-ZnO.     

Sorption of Perfluorooctane sulfonate（PFOS） including its isomers on hydrargillite as a function of pH,humic substances and Na2SO4

Perfluorooctane sulfonate（PFOS） is a persistent organic pollutant（POP） and emergent contaminant that are widespread in the environment. Understanding the mechanisms controlling the distribution of PFOS and its isomers between hydrargillite and the water phase is important in order to study their redistribution and mobility in the environment. This study investigated the effects of pH, humic acid, fulvic acid and Na₂SO₄ on sorption of PFOS isomers to hydrargillite. A mixture...     

苯酚、苯在水／阴离子有机膨润土界面的环境行为研究

研究了苯酚在水／阴离子有机膨润土界面的吸附行为，初步探讨了阴离子有机膨润土对苯酚、苯的吸附性能、机理及影响因素。结果表明，阴离子表面活性剂改性后，膨润土中有机碳含量增加了10～38倍，对苯酚、苯的吸附能力大大提高。水中苯酚、苯在水／阴离子有机膨润土界面的吸附行为主要分配作用所致，其吸附等温线呈线性。     

An insight into the removal of fluoroquinolones in activated sludge process: Sorption and biodegradation characteristics

The detailed sorption steps and biodegradation characteristics of fluoroquinolones(FQs)including ciprofloxacin, enrofloxacin, lomefloxacin, norfloxacin, and ofloxacin were investigated through batch experiments. The results indicate that FQs at a total concentration of 500 μg/L caused little inhibition of sludge bioactivity. Sorption was the primary removal pathway of FQs in the activated sludge process, followed by biodegradation, while hydrolysis and volatilization were negligible. FQ sorption on activated sludge was a reversible process governed by surface reaction. Henry and Freundlich models could describe the FQ sorption isotherms well in the concentration range of 100–300 μg/L. Thermodynamic parameters revealed that FQ sorption on activated sludge is spontaneous, exothermic, and enthalpy-driven. Hydrophobicity-independent mechanisms determined the FQ sorption affinity with activated sludge. The zwitterion of FQs had the strongest sorption affinity, followed by cation and anion, and aerobic condition facilitated FQ sorption. FQs were slowly biodegradable, with long half-lives( 100 hr). FQ biodegradation was enhanced with increasing temperature and under aerobic condition,and thus was possibly achieved through co-metabolism during nitrification. This study provides an insight into the removal kinetics and mechanism of FQs in the activated sludge process, but also helps assess the environmental risks of FQs resulting from sludge disposal.     

Sorption of tylosin and sulfamethazine on solid humic acid

Tylosin(TYL) and sulfamethazine(SMT) are ionizable and polar antimicrobial compounds,which have seeped into the environment in substantial amounts via fertilizing land with manure or sewage. Sorption of TYL and SMT onto humic acid(HA) may affect their environmental fate. In this study, the sorption of TYL and SMT on HA at different conditions(pH, ionic strength) was investigated. All sorption isotherms fitted well to the Henry and Freundlich models and they were highly nonlinear with values of n between 0.5 and 0.8, which suggested that the HA had high heterogeneity. The sorption of TYL and SMT on HA decreased with increasing p H(2.0–7.5), implying that the primary sorption mechanism could be due to cation exchange interactions between TYL~+/SMT~+ species and the functional groups of HA.Increasing ionic strength resulted in a considerable reduction in the K_d values of TYL and SMT,hinting that interactions between H bonds and π–π EDA might be an important factor in the sorption of TYL and SMT on HA. Results of Fourier transform infrared(FT-IR) and ~13C-nuclear magnetic resonance(NMR) analysis further demonstrated that carboxyl groups and O-alkyl structures in the HA could interact with TYL and SMT via ionic interactions and H bonds,respectively. Overall, this work gives new insights into the mechanisms of sorption of TYL and SMT on HA and hence aids us in assessing the environmental risk of TYL and SMT under diverse conditions.     

固定化荧光假单胞菌降解阴离子表面活性剂的研究

用海藻酸钠法包埋适冷性微生物荧光假单胞菌株AIS-11,并用于处理阴离子表面活性剂废水,所有实验均在批式反应器中进行。以L_9(3~4)正交试验确定了其对阴离子表面活性剂十二烷基硫酸钠(SDS)和十二烷基苯磺酸钠(SDBS)的最佳包埋条件,并且对游离细胞和固定化菌体的降解过程进行了动力学分析和比较。结果表明,固定化珠体能将吸附和生物催化过程有机地耦联起来,有效地提高了阴离子表面活性剂的降解速率,将底物最大利用速度(mg/L·h)从游离细胞的5.75(SDS)和5.12(SDBS)分别提高至22.89和25.14。     

Cadmium sorption by sodium and thiourea-modified zeolite-rich tuffs

In the present investigation, two zeolite-rich tuffs from Guaymas and El Cajon(State of Sonora), which were conditioned with a sodium chloride solution and subsequently modified with a thiourea solution, were chosen to evaluate the removal of Cd from aqueous systems. The zeolitic materials were characterized by scanning electron microscopy and X-ray diffraction. The surface area was also determined. The experiments were performed in a batch system, and the influences of p H, contact time between phases, and the concentration of Cd in the solution on the adsorption by sodium or thiourea-modified zeolite-rich tuff were investigated. It was found that the efficiency of Cd ion removal from aqueous solutions is influenced by the p H of the aqueous systems. The Cd adsorption kinetic data were well fitted to a pseudo-second-order model in all cases. The Langmuir and Langmuir–Freundlich isotherms adequately described the Cd sorption behavior by the zeolite from El Cajon pretreated with Na Cl and the zeolite from Guaymas modified with thiourea, respectively.     

老化对污泥改良沙土吸附水中对硝基苯酚性能的影响探讨

以添加不同比例城市污泥并老化2年后的新疆沙土为研究对象,从有机碳含量及对硝基苯酚吸附能力2个方面探讨了污泥改良技术对沙土的影响。结果表明,模拟废水对硝基苯酚在沙土、污泥及污泥改良沙土中的吸附等温线均符合Langmuir和Freundlich等温式;与污泥和沙土单独老化过程(用于计算理论值)相比,混合老化后的改良沙土的性质发生了很大变化,当加入污泥含量为9.1%～50%时,污泥改良沙土中的有机碳含量比理论计算值减少了11.54%～29.02%;对硝基苯酚在混合老化的改良沙土中的饱和吸附量远大于理论计算值,但吸附系数却远小于后者,表明混合老化后表面吸附作用增强,而有机质的分配作用在总吸附作用中的贡献减小。     

Long-term tillage effects on atrazine and fluometuron sorption in Coastal Plain soils

Conservation tillage (CnT) management practices are known to increase levels of soil organic matter (SOM) in southeastern Coastal Plain soils. Plant residues in CnT systems accumulate at the surface and, with time, will form a layer enriched in SOM. The authors hypothesize that herbicide sorption will be highest in this SOM-enriched zone of CnT systems when compared to sorption at a similar depth in conventional tillage (CT) systems. The objective was to characterize the impact of two different tillage systems, CnT and CT, on sorption of atrazine [6-chloro-N-ethyl-N′-(1-methylethyl)-1,3,5-triazine-2,4-diamine] and fluometuron [N,N-dimethyl-N′-3-(trifluoromethyl)phenyl urea] in plots of Norfolk loamy sand (fine-loamy, siliceous thermic Typic Kandiudult). The plots have been under CnT and CT management for 18 yrs. Bulk (0–15 cm) and five equal incremental soil samples to a 15 cm depth were collected from 10 CnT and 10 CT plots, and the atrazine (ATR) and fluometuron (FLMT) sorption coefficients (K_d) were measured using batch equilibration. Significantly higher herbicide K_d values occurred in the CnT 0–3 cm samples, indicating that the highest amount of herbicide sorption occurred in the top few cm of soil. This corresponded to the stratified soil organic carbon (SOC) contents in topsoil of the CnT plots. In addition, analyses of covariance using SOC as the covariant to test for tillage effects indicated complex interactions among SOC, tillage, and depth. Those results confirm that tillage and soil depth will affect SOC contents of a Norfolk loamy sand, which correspondly will influence the magnitude of ATR and FLMT sorption.     

Effect of application rate and irrigation on the movement and dissipation of indaziflam

Indaziflam is a new preemergence herbicide for the control of annual grass and broadleaf weeds in various cropping systems including pecan orchards. The objectives of this study were to (1) determine the mobility and dissipation of indaziflam and (2) evaluate herbicide efficacy in a flood-irrigated pecan orchard in southern New Mexico, USA. Indaziflam was applied at 0, 36.5, and 73.1 g/ha in areas with (impacted) and without (unimpacted) tree injury symptoms. Soil samples were collected at 0–15, 15–30, and 30–46 cm depths 26, 63, 90, and 126 days after the first herbicide application. Additional soil samples were collected 4, 30, and 56 days after the second application. Indaziflam was detected in soil samples collected at each depth, suggesting movement with irrigation water. Indaziflam concentrations decreased with increasing soil depth and time. Indaziflam mass recoveries were greater in the unimpacted area than in the impacted area after the first and second applications. Dissipation half-lives of indaziflam in the soil ranged from 30 to 86 days for total indaziflam recovered from the entire soil profile after the first and second applications in both areas. The percent weed control was similar in the impacted and unimpacted areas for both rates of indaziflam on 26 and 63 days after application; however, on 90 days after the application, percent weed control was lower in the impacted than unimpacted area.     

根据水/辛醇分配系数(KOW)估算有机化合物的吸着系数(KOC)

根据５５４ 种有机化合物的实测资料，研究了这些化合物水／辛醇分配系数（ＫＯＷ）值与土壤／沉积物吸着系数（ＫＯＣ）值之间的定量关系，建立了根据ＫＯＷ值估算有机化合物ＫＯＣ的定量模型，讨论了模型的误差和稳健性。研究证实，有机化合物的ｌｏｇＫＯＷ与ｌｏｇＫＯＣ之间存在很好的线性关系，根据已知ＫＯＷ值可以较准确估算ＫＯＣ值。对所研究的５５４ 种化合物，模型估算ＫＯＣ的平均误差为０．４８ 个对数单位，６２％ 的化合物误差小于０．５ 个对数单位。四种方式的ｊａｃｋｋｎｉｆｅ检验证明模型具有较高的稳健性。     

脱乙酰甲壳质回收处理含铜废水

本文研究了利用脱乙酰甲壳质处理含铜污水时酸度、吸附时间及脱乙酰基程度对脱乙酰甲壳质吸附Ｃｕ２＋量的影响．获得结果：吸附量可达６５．０ｍｇ／ｇ，洗脱被吸附的Ｃｕ２＋后，脱乙酰甲壳质可再生；同时回收得纯度较高的ＣｕＳＯ４，Ｃｕ２＋的回收率可达９９．９８％；将脱乙酰甲壳质装柱处理含Ｃｕ２＋废液，流出液中Ｃｕ２＋的含量远远低于国家排放标准．