In-series columns adsorption performance of Kraft mill wastewater pollutants onto volcanic soil

Two in-series columns systems with volcanic soil were tested for wastewater pollutants adsorption capacity. The first system was tested with acidified volcanic soil and the second with a reactivated volcanic soil. The reactivated soil was obtained by washing the previous spent acidified soil system with an acid solution. The systems parameters were obtained using the Bohardt and Adams model for fixed-beds. The acidified soil parameters indicated an adsorption capacity q of 28 and 139 mg/g of phenolic compounds and color, respectively (for each column), compared to 12 and 39 mg/g for the reactivated soil system. The adsorption rate constant k ranged between 1.5x10(-6) and 2.8x10(-6) l/min mg and no significant difference was observed for each analysed column system and pollutant. Furthermore, the molecular weight distribution analysis of input and output samples of one acidified soil column indicated that the fraction >30000 Da is the most adsorbed until the breakpoint. Moreover, the CODs and tannins and lignin removal efficiencies at the breakpoint reached values between 60% and 70% in each column and each system, indicating that lower biodegradable compounds were retained effectively. The results indicate that it is possible to compare the acidified volcanic soil adsorption capacity with natural zeolites, and a preliminary costs evaluation indicates that volcanic soil could be also competitive, even when comparing with activated carbon.     

Factors impacting on pharmaceutical leaching following sewage application to land

Sewage effluent application to land is a treatment technology that requires appropriate consideration of various design factors. Soil type, level of sewage pre-treatment and irrigation rate were assessed for their influence on the success of soil treatment in removing pharmaceuticals remaining after conventional sewage treatment. A large scale experimental site was built to assess treatment performance in a realistic environment. Of the factors investigated, soil type had the biggest impact on treatment performance. In particular, carbamazepine was very efficiently removed (>99%) when irrigated onto a volcanic sandy loam soil. This was in contrast to irrigation onto a sandy soil where no carbamazepine removal occurred after irrigation. Differences were likely caused by the presence of allophane in the volcanic soil which is able to accumulate a high level of organic matter. Carbamazepine apparent adsorption distribution coefficients (K(d)) for both soils when irrigated with treated sewage effluent were determined as 25 L kg(-1) for the volcanic soil and 0.08 L kg(-1) for the sandy soil. Overall, a volcanic soil was reasonably efficient in removing carbamazepine while soil type was not a major factor for caffeine removal. Removal of caffeine, however, was more efficient when a partially treated rather than fully treated effluent was applied. Based on the investigated pharmaceuticals and given an appropriate design, effluent irrigation onto land, in conjunction with conventional sewage treatment may be considered a beneficial treatment for pharmaceutical removal.     

Adsorption of methabenzthiazuron on six allophanic and nonallophanic soils: effect of organic matter amendment

This article reports on methabenzthiazuron [1-(1,3-benzothiazol-2-yl)-1,3-dimethylurea] (MBT) adsorption process on six agricultural allophanic and nonallophanic soils. The effect of amendment with exogenous organic matter was also studied. Adsorption kinetic fits an hyperbolic model. MBT adsorption reached an apparent equilibrium within 2 h and followed a second-order reaction. The maximum adsorbed amounts for natural soils ranged from 32 to 145 microg g(-1). Rate constants were considered relatively low (0.27-1.5 x 10(-4) [microg g(-1)](1-n) s-1); the slow process was attributed to a combined effect of difussion and adsorption. MBT adsorption fits the Freundlich model with r values > or =0.998 at P < or = 0.001 significance levels. Kf and Freundlich exponents (l/n) ranged from 5.3 to 82.1 cm3 g(-1) and from 0.66 to 0.73, respectively. Kf values for soils with a low organic matter content were lower than that obtained from the only typical allophanic soil derived from volcanic ash under study. Lineal regression analysis between Kf and organic matter content of nonallophanic soils gave a correlation coefficient of 0.980 (P = 0.02). Dispersion of Kd values together with close values of K(OM) indicate that organic matter (OM) was the principal component responsible for MBT adsorption in unamended soils. Addition of peat decreased soil pH and increased adsorption capacity for allophanic and nonallophanic soils. Kinetic experiments showed enhancements of Xmax values and lower rate constants.     

An exploration of the relationship between adsorption and bioavailability of pesticides in soil to earthworm

A study was conducted to determine the adsorption/desorption of butachlor, myclobutanil and chlorpyrifos on five soils using a batch equilibration technique and to study the relationship between bioavailability to Allolobophora caliginosa and the adsorption/desorption of these three pesticides. The results showed that the adsorption/desorption processes of the tested compounds were mainly controlled by soil organic matter content (OM) and octanol/water-partitioning coefficient (K(ow)), and that the bioavailability of the pesticides was dependent on characteristics of pesticides, properties of soils, and uptake routes of earthworms. Bioconcentration of butachlor and myclobutanil was negatively correlated with Freundlich adsorption constant K(af) and K(df). However, only a slightly positive correlation between bioconcentration and K(af) and K(df) was observed for chlorpyrifos due to its high affinity onto soil.     

Sorption of thiamethoxam in three Indian soils

The sorption behavior of the insecticide thiamethoxam [3-(2-chloro-1,3-thiazol-5-ylmethyl)-5-methyl-1,3,5-oxadiazinan-4-ylidene(nitro)amine] on three Indian soils with different physico-chemical properties was investigated. The soils represent the major grapevine growing areas of India, where the vineyards frequently receive thiamethoxam applications as foliar spray, soil drenching and through drip irrigation for the management of various insect pests. The rate constants for adsorption and desorption at two different temperatures were obtained from the Lindstrom model, which simultaneously evaluated adsorption and desorption kinetics. The data for rate constants, activation energies, enthalpy of activation, entropy of activation and free energy indicated physical adsorption of thiamethoxam on soil. The adsorptivity of different soils might be attributed to the organic matter and clay contents. A good fit to the linear and Freundlich isotherms was observed for both adsorption as well as desorption. Thiamethoxam could be categorized as a chemical with medium leaching potential.     

Adsorption of phenolic compounds from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent

A water-compatible hypercrosslinked polymeric adsorbent (NJ-8) for adsorbing and removing phenolic compounds from their aqueous solutions was prepared. This product can be used directly without a wetting process. Its adsorption property toward four phenolic compounds, phenol, p-cresol, p-chlorophenol, and p-nitrophenol was tested using the commercial Amberlite XAD-4 as a reference. The capacities of equilibrium adsorption for all four phenolic compounds on the NJ-8 from their aqueous solutions are around two times as high as that of Amberlite XAD4 within the temperature range 283-323 K, which may contribute to their micropore structure and the partial polarity on the network. Freundlich isotherm equations, as well as relative adsorption capacities and isosteric adsorption enthalpies for the four phenolic compounds, indicate that the adsorption of phenolic compounds on the NJ-8 resin is a physical adsorption process. Mini-column adsorption studies for phenol on Amberlite XAD4 and NJ-8 resins show that the breakthrough adsorption capacities are 0.54 and 0.99 mmol/ml, and the total capacities are 0.62 and 1.37 mmol/ml, while no extra acetone was needed to remove the adsorbed phenol from NJ-8 as from Amberlite XAD4.     

Sequential treatment of olive oil mill wastewater with adsorption and biological and photo-Fenton oxidation

Olive oil mill wastewater (OMWW), a recalcitrant pollutant, has features including high phenolic content and dark color; thereby, several chemical or physical treatments or biological processes were not able to remediate it. In this study, the treatment efficiencies of three treatments, including adsorption, biological application, and photo-Fenton oxidation were sequentially evaluated for OMWW. Adsorption, biological treatment, and photo-Fenton caused decreasing phenolic contents of 48.69 %, 59.40 %, and 95 %, respectively. However, after three sequential treatments were performed, higher reduction percentages in phenolic (total 99 %) and organic contents (90 %) were observed. Although the studied fungus has not induced significant color reduction, photo-Fenton oxidation was considered to be an attractive solution, especially for color reduction. Besides, toxicity of OMWW treatment was significantly reduced.     

Removal and pre-concentration of phenolic species onto beta-cyclodextrin modified poly(hydroxyethylmethacrylate-ethyleneglycoldimethacrylate) microbeads

Poly(Hydroxyethylmethacrylate-Ethyleneglycoldimethacrylate), poly(HEMA-EGDMA), microbeads with 150-200 microm in size, was prepared by suspension polymerization. Beta-cyclodextrin was modified onto the polymeric microbeads using glutaraldahyde activation in an acidic medium at pH=2.5. FT-IR and TGA were used for the characterization of modified polymers and the determination of the nature of the interaction between phenolic compounds and the modified polymeric microbeads. Plain and beta-cyclodextrin modified microbeads were used in adsorption-desorption studies of phenolic species in single solution. Adsorption capacities of the phenolic species onto the plain microbeads were found to be 28.2, 17.0, 14.3, 9.8, and 1.92 mg/g polymer for o-chloro phenol, p-nitro phenol, p-chloro phenol, o-nitro phenol, and phenol, respectively. However, for beta-cyclodextrin modified microbeads, adsorption capacity of phenolic species was determined as 274, 365, 128, 182, and 87 mg/g for phenol, o-nitro phenol, p-nitro phenol, o-chloro phenol, and p-chloro phenol, respectively. Desorption ratio for the phenolic species was more than 90%, except for o-nitro phenol. Detection limits of the phenolic species were improved at least 500-fold for UV-Vis spectrophotometric detection, after the pre-concentration of all phenolic species used in this study. Adsorption time for the phenolic species onto beta-cyclodextrin-modified poly(HEMA-EGDMA) microbeads was found to be reasonable short (10-60 min) and suitable for the applications. Also, synthesized microbeads were useful for the repeated use for the removal and pre-concentration of phenolic species.     

工艺参数对表面活性剂洗涤修复PAHs污染土壤的影响

采用土壤洗涤(soil-washing)技术,分别用TritonX-100和Tween-80为强化洗涤剂研究了搅拌强度、洗涤时间、表面活性剂浓度、液固比、温度和间歇搅拌6个工艺参数对PAHs污染土壤洗涤效果的影响。通过一系列烧杯搅拌实验得到最佳洗涤工艺参数。TritonX-100和Tween-80的最佳洗涤时间分别是30 min和60 min,其他工艺参数最佳条件均相同。分别是搅拌强度为250 r/min,表面活性剂浓度为5 g/L,液固比为10∶1,温度为室温和连续搅拌。在此最佳工艺参数条件下,污染土中PAHs的残留率<10%,基本上满足目标污染物的修复目标。应用表面活性剂强化洗涤技术修复PAHs污染土壤是合理和可行的。     

Modeling batch leaching behavior of arsenic and selenium from bituminous coal fly ashes

Correctly predicting the leaching potential of arsenic (As) and selenium (Se) is critical for assessing the environmental impact of coal fly ash. This study investigated the impacts of several key environmental factors, including pH, leaching time, and ash washing on the batch leaching behavior of As and Se from bituminous coal fly ashes. The experimental results demonstrated that As and Se leaching from fly ash increased beyond the minimal leaching pH ranges. Increasing leaching time increased As leaching but decreased Se leaching in the alkaline pH condition. A speciation-based adsorption model was used to quantify the batch leaching data, and determine the intrinsic leaching parameters including the total batch leachable mass and the adsorption constant of As or Se. The modeling approach was validated by correctly predicting the independent batch leaching data in a broad pH range and a different L/S condition. Experimental and modeling results also demonstrated that ash washing and ash aging (longer leaching time) did not change the adsorption constants of As and Se on the ash surface. However, ash washing could increase the availability of As and Se for leaching.     

Kinetic model for phenolic compound oxidation by Fenton's reagent

A kinetic model is developed for the oxidation of phenolic compounds by Fenton's reagent. In the first stage a rigorous kinetic model is applied to calculate the different kinetic rate constants for the oxidation process of p-hydroxybenzoic acid. In a second phase a competitive method is applied to calculate these kinetic constants for another 10 phenolic compounds present in agroindustrial and pulp paper wastewaters. These 10 phenolic compounds were: beta-resorcylic acid, 3-(4-hydroxyphenyl)-propionic acid, ferulic acid, protocatechuic acid, caffeic acid, p-coumaric acid, vanillic acid, syringic acid, veratric acid and 3,4,5-trimethoxybenzoic acid.     

Extended geometric method: a simple approach to derive adsorption rate constants of Langmuir-Freundlich kinetics

A new and simple equation has been presented here for calculation of adsorption and desorption rate constants of Langmuir-Freundlich kinetic equation. The derivation of new equation is on the basis of extension and correction to the geometric method which has been presented by Kuan et al. [Kuan, W.-H., Lo, S.-L., Chang, C.M., Wang, M.K., 2000. A geometric approach to determine adsorption and desorption kinetic constants. Chemosphere 41, 1741-1747] for the kinetics of adsorption/desorption in aqueous solutions. The correction is to consider that the concentration of solute is not constant and changes as adsorption proceeds. The extension is that we applied Langmuir-Freundlich kinetic model instead of Langmuir kinetic model to consider the heterogeneity and therefore it is more applicable to the real systems. For solving Langmuir-Freundlich kinetic model, some geometric methods and also Taylor expansion were used and finally a simple and novel equation was derived (Eq. (20)) for calculation of adsorption rate constant. This new method was named "extended geometric method". The input data of the obtained equation can be simply derived from initial data of adsorption kinetics. Finally the adsorption of methyl orange onto granular activated carbon was carried out at dynamic and equilibrium conditions and the capabilities of extended geometric method were examined by the experimental data.     

Equilibrium and kinetic studies on the adsorption of aniline compounds from aqueous phase onto bifunctional polymeric adsorbent with sulfonic groups

In the present study, a hydrophilic bifunctional polymeric resin (LS-2) with sulfonic groups was synthesized, and the adsorption performance of three aniline compounds, aniline, 4-methylaniline, and 4-nitroaniline onto LS-2 was compared with that on the commercial Amberlite XAD-4. The uptake of the aniline compounds on LS-2 is a procedure of coexistence of physisorption and chemisorption and obeys the pseudo-second order rate equation, while the uptake of the compounds on XAD-4 is merely a physical adsorption and follows the pseudo-first order rate equation. All the isothermal data fit well with the Freundlich model, and the values of K(F) of the compounds adsorbing on LS-2 are much higher than those on XAD-4 suggesting the higher adsorbing capacities on LS-2 than those on XAD-4, which may be attributed to the microporous structure and the polar groups on the network of LS-2 resin. Dynamic adsorption and desorption studies for aniline on LS-2 show that the breakthrough adsorption capacity and the total adsorption capacity are 0.96 and 1.24 mmol per milliliter resin, respectively. Nearly 100% regeneration efficiency for the adsorbent was achieved by 5% hydrochloric acid.     

Acetochlor as a soil pollutant

Acetochlor is a widely used herbicide all over the world. Similarly to other organic pollutants, the environmental fate of the acetochlor is strongly related to its adsorption properties. Static adsorption equilibrium measurements were carried out at 25 degrees C on different types of Hungarian soils characterized by varying amounts of organic matter and pH values. Isotherms obtained under different conditions, as well as on various soils, exhibit a similar shape, thus indicating a two-step adsorption process. The plots cannot be interpreted according to the classes of isotherms suggested by Giles. The adsorption coefficients (K) were estimated from the initial slope of the curves. These values were determined not only by the type of the soil, but also by the composition of the aqueous media. The organic matter adsorption coefficients (Kom) were also calculated and they were approximately identical for soils of high organic matter. Due to the low value of the adsorption coefficients, the acetochlor is a rather mobile pollutant of the soil posing a potential danger to the aquatic environment. For soils with high organic content, the Kom values are similar to each other and, due to the significant coverage of the inorganic surfaces, the adsorption is controlled by the solute-organic substance interactions. The adsorption of weakly polar compounds, however, is remarkable even on those soils where the organic content is low. In this case, the binding is governed by the solute-inorganic surface interactions. This conclusion is nicely proved by the adsorption of the acetochlor on quartz. According to our hypothesis, the second part of the adsorption step is controlled by the solute-adsorbed solute interactions. The role of the organic matter in this region of the isotherm is probably negligible. As the organic matter content of the soils plays an important role in the acetochlor adsorption, humic substances must have a strong influence upon the transport of this compound. Experiments to obtain adsorption isotherms of further pesticides and the development of a quantitative model are in progress.     

酚类化合物在2-羧基苯甲酰基修饰的超高交联树脂上的吸附

合成了一种用来吸附和去除水溶液中酚类化合物的 2 羧基苯甲酰基修饰的超高交联吸附树脂 (ZH 0 1) ,并从动力学和吸附容量角度比较了XAD 4、AM 1和ZH 0 1分别吸附浓度为 80 0mg/L苯酚的情况。实验结果表明 ,ZH 0 1吸附剂有利于吸附苯酚、对甲苯酚和对硝基苯酚之类的酚类化合物。动力学和热力学研究都得到了相同的结果 :ZH 0 1对苯酚和对甲苯酚吸附是化学吸附的过渡状态 ,而对对硝基苯酚的吸附是一种物理吸附过程 ,并且显示了ZH 0 1表面均孔特性。苯酚在ZH 0 1上的小柱吸附研究表明了吸附穿透容量和总吸附量分别为 2 .38mmol/g和 3.0 5mmol/g ,溶剂甲醇对吸附在ZH 0 1上苯酚的脱附效果较好。     

Modeling interactions at the tributyltin-kaolinite interface

Tributyltin (TBT) is a common pollutant in natural environments and the interaction with mineral surfaces largely determine its solubility, speciation, bioavailability, and transport in aqueous systems. The present work aimed at quantifying the TBT adsorption using kaolinite and a kaolinite-rich sediment as sorbent materials. Experiments were conducted under conditions that are important from an environmental perspective. Proton adsorption data were determined for kaolinite as a function of pH and electrolyte concentrations to ascertain intrinsic acidity constants and site density values. The pH(zpc) of kaolinite sample KGa was determined at 4.9 by surface titration. The generalized diffused double layer model (DLM) was used to quantify both, proton and TBT adsorption. Following intrinsic acidity and TBT binding constants resulting from the TBT/kaolinite system were used: >SOH ==> >SO- + H+, logK = -5.4; >SOH + H+ ==> SOH2+, logK = 4.6; >XNa + H ==> XH + Na+, logK(X/H+) = -1.1; >SO- + TBT+ ==> >SOTBT, logK = 3.5; >XNa + TBT+ ==> Na+, logK(X/TBT) = 1.0. All surface-active variable charge sites on kaolinite, namely >AlOH and >SiOH are grouped and collectively refer to as >SOH in this paper. >XNa refers to ion exchange sites. Modeling of TBT adsorption onto kaolinite was conducted distinguishing selective (high affinity) sites (>S(S)OH) in addition to non-selective sites (>SOH). The inclusion of >S(S)OH was essential in order to quantify TBT adsorption successfully, while the inclusion of >XNa was optional. The reduction of surface coverage values by a 10-fold TBT adsorption modeling is in agreement with the results of molecular model calculations of the system. Parameters calculated for the monophase kaolinite were subsequently used to quantify the TBT adsorption onto kaolinite-rich sediment.     

Degradation of para-hydroxybenzoic acid by means of mixed microbial cultures

Olive mill wastewater contains some phenolic compounds that cause antibacterial activity of a kind that prevents biological treatment without previous dilution. Among these phenolic compounds, p-hydroxybenzoic acid (PHB) is considered to be one of the most representative. This work examines the biodegradation of PHB by aerobic microbial mixed cultures previously acclimatized to glucose, which was used as an easily biodegradable model compound. Microbial growth runs were carried out in a batch reactor in the PHB concentration range of 200-1000 mg/L. In all the runs the PHB proved to be completely degradable. The specific growth rates obtained were in the range of 0.16-0.35 l/h. Experimental runs showed that the functional relationship between the specific growth rate and PHB concentration was that proposed by Monod. The kinetic constants of the Monod equation (mu(max) and K(S)) and biomass yield coefficient (Y) were determined experimentally. With the parameter values thus obtained, a mathematical model that also takes account of the duration of the lag phase was employed to describe both the microbial growth and the consumption of PHB. The concentration values of the model fit well with the data obtained experimentally.     

Effect of bubble-induced surface turbulence on gas-liquid mass transfer in diffused aeration systems.

Models that predict volatilization of organic compounds from wastewater treatment basins may underestimate emission rates if the surfaces are considered as quiescent. In reality, the water surface may be agitated by subsurface aeration, increasing mass transfer across the tank surface air-water interface. This study investigated the effect of turbulence, induced by diffused bubble aeration, on mass transfer at the water surface of a pilot aeration basin. The mass transfer of ammonia from an enclosed headspace over the basin to acidified water was measured when different diffuser types and airflow rates were applied. Oxygen-transfer tests were conducted immediately following each ammonia-transfer test. Increasing airflow rates through fine- and coarse-bubble diffusers had a significant effect on the ammonia mass-transfer rate. Experimental mass-transfer parameters (K(L)a's) for surface volatilization derived with aeration present were up to 48% higher than the K(L)a values for quiescent conditions over the range of conditions tested. No effect of diffuser type on ammonia transfer could be determined. The study results infer an effect on oxygen transfer into the water at the surface and potential transfer of volatile organic compounds, if present, from the water. The results of the ammonia mass-transfer experiments suggest that adjustments to the existing mass transfer correlations for surface volatilization from aeration basins may be in order. Such adjustments will have the greatest effect on predictions for the less volatile compounds, under conditions of low airflow rates.     

Solution factors affecting the adsorption of phenol onto a siltstone

Phenolic compounds are a major pollution by-product of the underground coal gasification process. The adsorption of phenol onto a siltstone was studied using batch techniques and 1:1 crushed siltstone to solution slurries. The siltstone used was associated with a Wyoming coal deposit of a type similar to that which could be gasified in situ. The pH of the solution was found to be the major factor controlling the adsorption of phenol onto the siltstone. Phenol was adsorbed when the solution pH was less than the pKa while no sorption was observed at higher pH. Since in situ gasification sites have an elevated pH post gasification, phenolic compounds may be transported by groundwater in these regions. Significant differences were also found for the adsorption of phenol onto initially wet or dry adsorbate. Desorption studies were also performed. Langmuir and Freundlich adsorption isotherms were used to model the data.     

Distribution coefficient of selenium in Japanese agricultural soils

In order to evaluate the selenium (Se) sorption level in Japanese soils, soil/soil solution distribution coefficients (K(d)s) were obtained for 58 agricultural soil samples (seven soil classification groups) using 75Se as a tracer. Although several chemical forms of Se are present in agricultural fields, selenite was used, because it is the major inorganic Se form in acid soils such as found in Japan. The Kd values obtained covered a wide range, from 12 to 1060l/kg, and their arithmetic mean was 315l/kg. Among the soil groups, Andosols had higher Kd values. The Kd values for all samples were highly correlated with soil active-aluminum (Al) and active-iron (Fe) contents. Thus, active-Al and active-Fe were considered to be the major adsorbents of Se. Then, a new sequential extraction procedure was applied to 12 soil samples in order to quantify the effect of soil components on Se adsorption. The sequential extraction results showed that 80-100% of the adsorbed Se was recovered as Al-bound Se and Fe-bound Se. The amount of Al-bound Se was the highest in the soils that showed high Kd values, though the relative contribution of Fe-bound Se tended to increase with decreasing Kd values. The high values of Kd seemed to be caused mainly by the adsorption of Se onto active-Al in Japanese soils.