Atrazine, isoproturon, mecoprop, 2,4-D, and bentazone adsorption onto iron oxides

Iron oxides are important components influencing the adsorption of various inorganic and organic compounds in soils and sediments. In this study the adsorption on iron oxides of nonionic and ionic pesticides was determined as a function of solution pH, ionic strength, and pesticide concentration. The investigated iron oxides included two-line ferrihydrite, goethite, and lepidocrocite. Selected pesticides comprised atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine), isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea)], mecoprop [(RS)-2-(4-chloro-2-methylphenoxy)propionic acid], 2,4-D (2,4-dichlorophenoxyacetic acid), and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide]. The adsorption of the nonionic pesticides (atrazine and isoproturon) was insignificant, whereas the adsorption of the acidic pesticides (mecoprop, 2,4-D, and bentazone) was significant on all investigated iron oxides. The adsorption capacity increased with decreasing pH, with maximum adsorption reached close to the pKa values. The addition of CaCl2 in concentrations from 0.0025 to 0.01 M caused the adsorption capacity to diminish. The adsorption of bentazone was significantly lower than the adsorption of mecoprop and 2,4-D, illustrating the importance of a carboxyl group in the pesticide structure. The adsorption capacity on the iron oxides increased in the order: lepidocrocite < goethite < two-line ferrihydrite. The maximum adsorption capacities of meco-prop and 2,4-D on goethite were found to be equivalent to the site density of singly coordinated hydroxyl groups on the faces of the dominant (110) form, suggesting that singly coordinated hydroxyl groups are responsible for adsorption. Differences in adsorption capacities between iron oxides can be explained by differences in the surface site density of singly coordinated hydroxyl groups. The maximum measured adsorption capacity of mecoprop on two-line ferrihydrite was equivalent to 0.2 mol/mol Fe.     

Phosphorus retention mechanisms of a water treatment residual

Water treatment residuals (WTRs) are a by-product of municipal drinking water treatment plants and can have the capacity to adsorb tremendous amounts of P. Understanding the WTR phosphorus adsorption process is important for discerning the mechanism and tenacity of P retention. We studied P adsorbing mechanism(s) of an aluminum-based [Al2(SO4)3 x 14H2O] WTR from Englewood, CO. In a laboratory study, we shook mixtures of P-loaded WTR for 1 to 211 d followed by solution pH analysis, and solution Ca, Al, and P analysis via inductively coupled plasma atomic emission spectroscopy. After shaking periods, we also examined the solids fraction by X-ray diffraction (XRD) and electron microprobe analysis using wavelength dispersive spectroscopy (EMPA-WDS). The shaking results indicated an increase in pH from 7.2 to 8.2, an increase in desorbed Ca and Al concentrations, and a decrease in desorbed P concentration. The pH and desorbed Ca concentration increases suggested that CaCO3 controlled Ca solubility. Increased desorbed Al concentration may have been due to Al(OH)4 formation. Decreased P content, in conjunction with the pH increase, was consistent with calcium phosphate formation or precipitation. The system appeared to be undersaturated with respect to dicalcium phosphate (DCP; CaHPO4) and supersaturated with respect to octacalcium phosphate [OCP; Ca4H(PO4)3 x 2.5H2O]. The Ca and Al increases, as well as OCP formation, were supported by MINTEQA2 modeling. The XRD and EMPA-WDS results for all shaking times, however, suggested surface P chemisorption as an amorphous Al-P mineral phase.     

水处理用活性炭改性研究

利用锆和氯化十六烷基三甲铵共同改性活性炭,制备一种新型去除污水中硝酸盐和磷酸盐的水处理吸附剂,并考察吸附剂加量、反应温度、pH值、共存阴离子等影响因素对吸附效果的影响。结果表明:锆-氯化十六烷基三甲铵改性活性炭(Zr-CTAC-AC)吸附剂适用于硝酸盐和磷酸盐浓度在100mg/L以下的污水,随着Zr-CTAC-AC加量的增加,硝酸盐、磷酸盐去除率逐渐增加,单位吸附量逐渐下降,Zr-CTAC-AC加量为8g/L时,硝酸盐去除率为79%,Zr-CTAC-AC加量为4.0g/L时,磷酸盐去除率可达91%,但应在较低的pH值范围内使用;反应温度对Zr-CTAC-AC的吸附效果影响不大;共存Cl-、HCO3^-和SO4^2-可使硝酸盐的吸附率降低,但对磷酸盐吸附率影响较小;1mol/L NaCl溶液可使吸附到Zr-CTAC-AC表面的硝酸盐90.9%左右被解吸出来,1mol/L NaOH溶液可使吸附到Zr-CTAC-AC表面的磷酸盐78.4%左右被解吸出来。Zr-CTAC-AC能够有效去除污水中硝酸盐和磷酸盐,制备方法简单,且可循环利用,处理成本低。     

Arsenic and chromium removal by mixed magnetite–maghemite nanoparticles and the effect of phosphate on removal

Adsorption of arsenic and chromium by mixed magnetite and maghemite nanoparticles from aqueous solution is a promising technology. In the present batch experimental study, a commercially grade nano-size ‘magnetite’, later identified in laboratory characterization to be mixed magnetite–maghemite nanoparticles, was used in the uptake of arsenic and chromium from different water samples. The intent was to identify or develop a practical method for future groundwater remediation. The results of the study showed 96–99% arsenic and chromium uptake under controlled pH conditions. The maximum arsenic adsorption occurred at pH 2 with values of 3.69 mg/g for arsenic(III) and 3.71 mg/g for arsenic(V) when the initial concentration was kept at 1.5 mg/L for both arsenic species, while chromium(VI) concentration was 2.4 mg/g at pH 2 with an initial chromium(VI) concentration of 1 mg/L. Thus magnetite–maghemite nanoparticles can readily adsorb arsenic and chromium in an acidic pH range. Redox potential and pH data helped to infer possible dominating species and oxidation states of arsenic and chromium in solution. The results also showed the limitation of arsenic and chromium uptake by the nano-size magnetite–maghemite mixture in the presence of a competing anion such as phosphate. At a fixed adsorbent concentration of 0.4 g/L, arsenic and chromium uptake decreased with increasing phosphate concentration. Nano-size magnetite–maghemite mixed particles adsorbed less than 50% arsenic from synthetic water containing more than 3 mg/L phosphate and 1.2 mg/L of initial arsenic concentration, and less than 50% chromium from synthetic water containing more than 5 mg/L phosphate and 1.0 mg/L of chromium(VI). In natural groundwater containing more than 5 mg/L phosphate and 1.13 mg/L of arsenic, less than 60% arsenic uptake was achieved. In this case, it is anticipated that an optimum design with magnetite–maghemite nanoparticles may achieve high arsenic uptake in field applications.     

Chemistry of inorganic arsenic in soils: II. Effect of phosphorus, sodium, and calcium on arsenic sorption

There are more than 10000 arsenic (As) contaminated sites in Australia. The ability of soils at these contaminated sites to sorb As is highly variable and appreciable amounts of As have been recorded in the subsurface soils. The potential risk of surface and ground water contamination by As at these sites is a major environmental concern. Factors that influence adsorption capacity of soils influence the bioavailability and subsequent mobility of As in soils. In the present study we investigated the effect of PO4(3-) and Na+ and Ca2+ on the sorption of AsV and AsIII by an Oxisol, a Vertisol, and two Alfisols. The presence of P (0.16 mmol L(-1)) greatly decreased AsV sorption by soils containing low amounts of Fe oxides (<100 mmol kg(-1)), indicating competitive adsorption between P and AsV for sorption sites. In contrast, the presence of a similar amount of P had little effect on the amount of AsV adsorbed by soils with high Fe content (>800 mmol kg(-1)). However, AsV sorption substantially decreased from 0.63 to 0.37 mmol kg(-1) as P concentration was increased from 0.16 to 3.2 mmol L(-1) in selected soils. This suggests increased competition between P and AsV for soil sorption sites, through either the higher affinity or the effect of mass action of the increasing concentration of P in solution. A similar effect of P on AsIII sorption was observed in the low sorbing Alfisol and high affinity Oxisol. However, the amount of AsIII sorbed by the Oxisol was much greater than the Alfisol for all treatments. The presence of Ca2+ increased the amount of AsV sorbed compared with that of Na+ and was manifested through changes in the surface charge characteristics of the soils. A similar trend in AsIII sorption was recorded with changes in index cation, although the effect was not as marked as recorded for AsV.     

Adsorption of 2,4-dichlorophenoxyacetic acid by an Andosol

To identify the important soil components involved in 2,4-dichlorophenoxyacetic acid (2,4-D) adsorption on Andosols, 2,4-D adsorption on a surface horizon of an Andosol was compared with that on hydrogen peroxide (H2O2)-treated (soil organic matter [SOM] was removed), acid-oxalate (OX)-treated (active metal hydroxides and SOM were removed), and dithionite-citrate-bicarbonate (DCB)-treated (free and active metal [hydr]oxides and SOM were removed) soil samples at equilibrium pHs ranging from 4 to 8. Although the untreated soil contained a large amount of organic C (71.9 g kg-1), removal of SOM had little effect on 2,4-D adsorption. Active surface hydroxyls, which were attached to the active and free metal (hydr)oxides and metal SOM complexes, were identified as the most important soil functional group for 2,4-D adsorption. The dominant mechanism of the 2,4-D adsorption was a ligand exchange reaction in which the carboxylic group of 2,4-D displaced the active surface hydroxyl associated with metals and formed a strong coordination bond between the 2,4-D molecule and soil solid phase. The ligand exchange reaction reasonably accounted for the selective adsorption of 2,4-D over Cl-, competitive adsorption of phosphate over 2,4-D, reduction in plant-growth-inhibitory activity of soil-adsorbed 2,4-D, and the high 2,4-D adsorption ability of Andosols. Although a humic acid purified from the soil did not adsorb 2,4-D, the presence of the humic acid increased 2,4-D adsorption on Al and Fe, probably by inhibiting the hydrolysis and polymerization of Al and Fe resulting in the preservation of available adsorption sites on these metals. The adsorption behavior of 2,4-D on soils could be a good index for predicting the adsorption behavior of other organic acids in soils.     

Leaching mechanisms of Cr(VI) from chromite ore processing residue

Batch leaching tests, qualitative and quantitative x-ray powder diffraction (XRPD) analyses, and geochemical modeling were used to investigate the leaching mechanisms of Cr(VI) from chromite ore processing residue (COPR) samples obtained from an urban area in Hudson County, New Jersey. The pH of the leaching solutions was adjusted to cover a wide range between 1 and 12.5. The concentration levels for total chromium (Cr) and Cr(VI) in the leaching solutions were virtually identical for pH values >5. For pH values <5, the concentration of total Cr exceeded that of Cr(VI) with the difference between the two attributed to Cr(III). Geochemical modeling results indicated that the solubility of Cr(VI) is controlled by Cr(VI)-hydrocalumite and Cr(VI)-ettringite at pH >10.5 and by adsorption at pH <8. However, experimental results suggested that Cr(VI) solubility is controlled partially by Cr(VI)-hydrocalumite at pH >10.5 and by hydrotalcites at pH >8 in addition to adsorption of anionic chromate species onto inherently present metal oxides and hydroxides at pH <8. As pH decreased to <10, most of the Cr(VI) bearing minerals become unstable and their dissolution contributes to the increase in Cr(VI) concentration in the leachate solution. At low pH ( <1.5), Cr(III) solid phases and the oxides responsible for Cr(VI) adsorption dissolve and release Cr(III) and Cr(VI) into solution.     

纳米零价铁去除磷酸盐机理研究

纳米零价铁(nanoscale zero-valent iron,nZVI)颗粒具有独特核-壳结构,使其具有较强氧化还原特性,比表面积大和表面活性高等特点,因此被广泛用于不同环境介质中多种污染物的去除修复。本研究采用传统的液相化学还原法合成nZVI颗粒并用于去除水溶液中的磷酸盐。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线衍射仪(XRD)表征nZVI颗粒的性质。实验研究了nZVI投加量、PO3-4初始浓度、溶液初始pH值对nZVI去除PO3-4效率的影响及微米零价铁(micro-ZVI)和nZVI去除PO3-4的对比。实验结果表明,当PO3-4初始浓度为20mg/L时,随着nZVI投加量从200mg/L增加到1000mg/L,PO3-4去除效率从32.94%上升到90.17%;当nZVI投加量为600mg/L时,随着PO3-4初始浓度从10mg/L增加到100mg/L,PO3-4去除效率从87.33%下降到45.77%;当nZVI投加量为600mg/L且PO3-4初始浓度为20mg/L,溶液pH分别为3和4时,PO3-4去除效率分别为83.63%和92.36%;nZVI和mZVI投加量均为600mg/L且PO3-4初始浓度为10mg/L,nZVI的PO3-4去除率(87.33%)是mZVI(8.86%)的9.86倍。研究结果表明,nZVI能够高效去除水体中的磷酸盐,主要去除机理是吸附和化学沉淀的双重作用。     

Adsorption of isoxaflutole degradates to aluminum and iron hydrous oxides

Isoxaflutole is a preemergence herbicide that has been marketed as a substitute for atrazine. It is rapidly transformed to a more stable and soluble diketonitrile degradate (DKN) after field application and can further degrade to a benzoic acid degradate (BA) within soil. However, no previous research has been conducted to investigate DKN and BA sorption to metal oxide minerals. The primary objective of this research was to elucidate the interactions of DKN and BA with synthetic hydrous aluminum and iron oxides (HAO and HFO, respectively) to understand how variably charged minerals may influence adsorption of these compounds in soil. The herbicide degradates did adsorb to HAO and HFO, and the data were well described by the Freundlich model (R2 > 0.91), with Nvalues ranging from 0.89 to 1.2. Adsorption isotherms and Kd values demonstrate that BA is adsorbed to HFO to a greater extent than other degradate-mineral combinations that were studied. The degree of hysteresis between adsorption/desorption isotherms was characterized as slight (hysteresis index values < 1.7), suggesting weak DKN and BA retention to HFO and HAO oxide surfaces. Degradate adsorption was observed to greatly diminish as suspension pH increased. Attenuated total reflectance-Fourier transform infrared spectra show no evidence that DKN or BA adsorb to mineral surfaces as inner-sphere complexes under hydrated conditions. Instead DKN and BA adsorb to positively charged metal oxide surfaces as outer-sphere or diffuse ion swarm complexes via electrostatic attraction. This research indicates that metal oxides may serve as important retardants for DKN and BA migration through acidic soils enriched with aluminum and iron oxides.     

Removal of the hazardous dye rhodamine B through photocatalytic and adsorption treatments

This paper reports on photocatalytic and adsorptive treatment of a hazardous xanthene dye, Rohdamine B, in wastewater. The photocatalytic degradation was carried out in the presence of the catalyst TiO(2) and the effects of pH, concentration of the dye, amount of TiO(2), temperature and electron acceptor H(2)O(2) on the degradation process were observed. It was found that photocatalytic degradation by TiO(2) is an effective, economical and faster mode of removing Rohdamine B from aqueous solutions. Attempts were also made to utilize activated carbon and rice husk as potential adsorbents to remove Rhodamine B from wastewater. The adsorption studies were carried out at 40, 50 and 60 degrees C, and the effects of pH, temperature, amount of adsorbents, concentration of adsorbate, etc., on the adsorption were measured. On the basis of adsorption data the Langmuir and Freundlich adsorption isotherm models were also confirmed. The adsorption isotherm constants thus obtained were employed to calculate thermodynamic parameters like Gibb's free energy, change in enthalpy and entropy. In order to observe the quality of wastewater COD measurements were also carried out before and after the treatments. A significant decrease in the COD values was observed, which clearly indicates that both photocatalytic and adsorption methods offer good potential to remove Rhodamine B from industrial effluents.     

Use of magnesia for boron removal from irrigation water

The risk of B phytotoxicity due to high levels of B in irrigation water can be avoided by removing B from the water, before its use, through adsorption on certain adsorbents, such as magnesia (industrial MgO), if the latter can be proven to be an effective and easy to handle means for B removal. In addition, if such a material is applied as a fertilizer after its use and the adsorbed B is easily released into the soil solution, B phytotoxicity could constitute a potential hazard. The objectives of this work were to: (a) establish the optimum working conditions (equilibration time, solution to adsorbent ratio, and particle size of the adsorbent) for B adsorption, (b) assess the magnitude of B adsorption by magnesia, both in capacity and intensity terms, as well as the influence of temperature, (c) study B desorbability from magnesia, spiked with B at two rates, 5 and 0.5 mg g(-1), and (d) compare the results from b and c to those obtained using reagent grade MgO. The results showed that the time to achieve equilibrium depended on the B concentration of the external solution and ranged from 6 h (for B /= 50 mg L(-1)). The percentage of B adsorbed decreased as the volume of external solution to adsorbent increased and a working ratio of 50:1 was selected. For magnesia, B adsorption was particle size dependent with the smallest fraction (<0.1 mm) sorbing more B than the other three fractions studied (0.1-1.0, 1.1-2.0, 2.1-4.0 mm). Boron adsorption was conducted under strongly alkaline pH (10.3 +/- 0.2 and 10.4 +/- 0.1 for the reagent and magnesia, respectively) and increased with temperature. Both adsorbents exhibited a high B adsorption capacity (Langmuir maximum values were 5.85 +/- 0.39 and 4.45 +/- 1.31 mg B g(-1) for the reagent and magnesia, respectively) comparable to other metal oxides. However, the reagent grade MgO seemed to be superior to magnesia in terms of capacity and strength of B retention. This superiority of the reagent was attributed to its greater surface area (34.7 compared with 5.8 m(2) g(-1) for magnesia) and to its conversion to Mg(OH)(2) during the adsorption process, whereas magnesia remained unaltered, as was evident from X-ray diffractograms. Based on this data, magnesia seems to be an effective means for removing excess B from irrigation water, particularly if a material of fine particle size is used. Boron desorbability after 240 h of desorption time was more pronounced for magnesia reaching up to 55 and 60% of the amount of B added, at the spiked rates of 5 and 0.5 mg g(-1), respectively. Although these figures indicate that approximately half of the amount of B added remained adsorbed, they cannot be easily extrapolated to field conditions, and if B-laden magnesia is applied to soils, the possibility of B phytotoxicity cannot be excluded.     

Adsorption and transport of arsenic(V) in experimental subsurface systems

The adsorption and transport of As(V) in a heterogeneous, iron oxide-containing soil was investigated in batch and column laboratory experiments. The As(V) adsorbed rapidly to the soil over the first 48 h, but continued to adsorb slowly over the next several weeks, clearly indicating the potential for rate-limited transport. The equilibrium As(V) adsorption isotherm was markedly nonlinear, further indicating the potential for nonideal transport. A model developed for the adsorption of As(V) to hydrous ferric oxide (HFO) was able to predict the pH-dependent adsorption of As(V) to the soil in batch experiments within 0.116 to 0.726 root mean square error (RMSE). Arsenic(V) was significantly retarded in column transport experiments. The column transport experiments were modeled using the one-dimensional advection-dispersion equation, considering both linear and nonlinear adsorption equilibrium. Although the nonlinear local equilibrium model (NLLE, RMSE = 0.273) predicted the data better than the linear local equilibrium model (LLE, RMSE = 0.317), As(V) breakthrough occurred more rapidly than predicted by either model due to adsorption nonequilibrium. However, due to the presence of an irreversible or slowly desorbing fraction, the peak aqueous As(V) concentration (0.624 mg L(-1)) and the total amount of As(V) recovered (44%) was lower than predicted based on the two equilibrium models (NLLE and LLE). For the conditions used in this study [1 mg L(-1) As(V), pH 4.5 and 9,0-0.25 mM PO4, 0.53-1.6 cm min(-1) pore water velocity], the effect on As(V) mobility and recovery increased in the order pH < pore water velocity < PO4.     

Exploitation of Trichoderma harzianum mycelial waste for the removal of rhodamine 6G from aqueous solution

The harvested mycelial waste of Trichoderma harzianum was used as an adsorbent for the removal of rhodamine 6G and was studied in batch mode. The effects of agitation time and initial dye concentration, adsorbent dosage and pH were examined. The study revealed that the amount of dye adsorbed (mgg(-1)) increased with increase in agitation time and reached equilibrium after 120 min, for dye concentrations of 10-50 mg L(-1). The adsorbent dosage of 1.0 g/50 mL and pH of 8.0 were found to be optimum for maximum dye removal. The batch mode adsorption data followed both the Langmuir and Freundlich isotherms. The pseudo first- and second-order rate kinetics were applied to the adsorbent system. The adsorption kinetics of rhodamine 6G showed that the pseudo-second-order kinetic model provided the best correlation of the equilibrium data. The study implies that it is possible to develop a dye removal system by using T. harzianum biomass, which occurs as sludge in waste stream of fermentation industries.     

Quantifying constraints imposed by calcium and iron on bacterial reduction of uranium(VI)

Uranium is a redox active contaminant of concern to both human health and ecological preservation. In anaerobic soils and sediments, the more mobile, oxidized form of uranium (UO(2)(2+) and associated species) may be reduced by dissimilatory metal-reducing bacteria. Despite rapid reduction in controlled, experimental systems, various factors within soils or sediments may limit biological reduction of U(VI), inclusive of competing electron acceptors and alterations in uranyl speciation. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite, and hematite) varying in free energies of formation. Observed pseudo first-order rate coefficients for U(VI) reduction vary from 12 +/- 0.60 x 10(-3) h(-1) (0 mM Ca in the presence of goethite) to 2.0 +/- 0.10 x 10(-3) h(-1) (0.8 mM Ca in the presence of hematite). Nevertheless, dissolved Ca (at concentrations from 0.2 to 0.8 mM) decreases the extent of U(VI) reduction by approximately 25% after 528 h relative to rates without Ca present. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Ferrihydrite, in contrast, acts as a competitive electron acceptor and thus, like Ca, decreases uranium reduction. However, while ferrihydrite decreases U(VI) in solutions without Ca, with increasing Ca concentrations U(VI) reduction is enhanced in the presence of ferrihydrite (relative to its absence)-U(VI) reduction, in fact, becomes almost independent of Ca concentration. The quantitative framework described herein helps to predict the fate and transport of uranium within anaerobic environments.     

Ultraviolet irradiation effects incorporation of nitrate and nitrite nitrogen into aquatic natural organic matter

One of the concerns regarding the safety and efficacy of ultraviolet radiation for treatment of drinking water and wastewater is the fate of nitrate, particularly its photolysis to nitrite. In this study, N NMR was used to establish for the first time that UV irradiation effects the incorporation of nitrate and nitrite nitrogen into aquatic natural organic matter (NOM). Irradiation of (15)N-labeled nitrate in aqueous solution with an unfiltered medium pressure mercury lamp resulted in the incorporation of nitrogen into Suwannee River NOM (SRNOM) via nitrosation and other reactions over a range of pH from approximately 3.2 to 8.0, both in the presence and absence of bicarbonate, confirming photonitrosation of the NOM. The major forms of the incorporated label include nitrosophenol, oxime/nitro, pyridine, nitrile, and amide nitrogens. Natural organic matter also catalyzed the reduction of nitrate to ammonia on irradiation. The nitrosophenol and oxime/nitro nitrogens were found to be susceptible to photodegradation on further irradiation when nitrate was removed from the system. At pH 7.5, unfiltered irradiation resulted in the incorporation of (15)N-labeled nitrite into SRNOM in the form of amide, nitrile, and pyridine nitrogen. In the presence of bicarbonate at pH 7.4, Pyrex filtered (cutoff below 290-300 nm) irradiation also effected incorporation of nitrite into SRNOM as amide nitrogen. We speculate that nitrosation of NOM from the UV irradiation of nitrate also leads to production of nitrogen gas and nitrous oxide, a process that may be termed photo-chemodenitrification. Irradiation of SRNOM alone resulted in transformation or loss of naturally abundant heterocyclic nitrogens.     

Comparison of zinc complexation properties of dissolved natural organic matter from different surface waters

The zinc binding characteristics of natural organic matter (NOM) from several representative surface waters were studied and compared. NOM samples were concentrated by reverse osmosis. The samples were treated in the laboratory to remove trace metals. Square wave anodic stripping voltammetry (SWASV) was used to study zinc complexing properties of those NOM samples at fixed pH, ionic strength, and dissolved organic carbon (DOC) concentrations. Experimental data were compared to the predictions from the Windermere Humic Aqueous Model (WHAM) Version VI. At the same pH, ionic strength, and temperature, the zinc titration curves for NOM samples from different surface water sources tested in our study almost overlapped each other, indicating similarity in zinc binding properties of the NOM. A discrete two-site model gave good fits to our experimental titration data. Non-linear fitting by FITEQL 4.0 shows that the conditional zinc binding constants at the same pH are similar for NOM from different sources, indicating that zinc complexation characteristics of the NOM used in our study do not depend on their origin and one set of binding parameters can be used to represent Zn-NOM complexation for NOM samples from those different surface water sources representing geographically diverse locations. In addition, the total ligand concentrations (L(1,T), L(2,T), and L(T)) of all NOM show no observable gradation with increasing pH (L(1,T)=2.06+/-0.80 mmol/g carbon; L(2,T)=0.12+/-0.04 mmol/g carbon; L(T)=2.18+/-0.78 mmol/g carbon), while the conditional binding constants of zinc by NOM (logK(ZnL)(c)) show a linear increase with increasing pH(logK(1)(c)(pH=6.0)=4.69+/-0.25; logK(1)(c)(pH=7.0)=4.94+/-0.10; logK(1)(c)(pH=8.0)=5.25+/-0.006; logK(2)(c)(pH=6.0)=6.29+/-0.13; logK(2)(c)(pH=7.0)=6.55+/-0.08; logK(2)(c)(pH=8.0)=6.86+/-0.023) with a slope of ca. 0.28, indicating the zinc-NOM complexes become more stable at higher pH. The WHAM VI predicted free zinc ion activities at high zinc concentrations agree with our experimental results at pH 6.0, 7.0, and 8.0. However, the zinc binding of these NOM samples is over estimated by WHAM VI at zinc concentrations below 10(-6) M at pH 8.0.     

Ligand-assisted degradation of carbon tetrachloride by microscale zero-valent iron

Degradation of carbon tetrachloride (CT) by microscale zero-valent iron (ZVI) was investigated in batch systems with or without organic ligands (ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, malic acid and oxalic acid) at pHs from 3.5 to 7.5. The results demonstrated that at 25°C, the dechlorination of CT by microscale ZVI is slow in the absence of organic ligands, with a pseudo-first-order rate constant of 0.0217 h(-1) at pH 3.5 and being further dropped to 0.0052 h(-1) at pH 7.5. However, addition of organic ligands significantly enhanced the rates and the extents of CT removal, as indicated by the rate constant increases of 39, 31, 32, 28 and 18 times in the presence of EDTA, citric acid, tartaric acid, malic acid and oxalic acid, respectively, at pH 3.5 and 25°C. The effect of EDTA was most significant; the dechlorination of CT at an initial concentration of 20 mg l(-1) increased from 16.3% (no ligands) to 89.1% (with EDTA) at the end of 8h reaction. The enhanced CT degradation in the presence of organic ligands was primarily attributed to the elimination of a surface passivation layer of Fe(III) (hydr)oxides on the microscale ZVI through chelating of organic ligands with Fe(III), which maintained the exposure of active sites on ZVI surface to CT.     

The influence of lipids on the energetics of uptake of polycyclic aromatic hydrocarbons by natural organic matter

Although most of the organic carbon in soils and sediments may be composed of humic substances, their interaction with other compounds, especially their sorption interactions, may be significantly affected by the presence of small amounts of the other components of natural organic matter (NOM). In this investigation, the influence of the lipid fraction of NOM on the sorption thermodynamics of fluorene, phenanthrene, and pyrene to several geosorbent samples was examined before and after extraction of lipids. Batch experiments were performed at the same concentration for all polycyclic aromatic hydrocarbons (PAHs) (0.025 x their solubility in water) at different temperatures (10, 20, 30, and 40 degrees C), and the thermodynamic parameters were calculated. Removal of the lipids increases the sorption capacity of the samples as well as the exothermicity of the process. The free energy change was negative for all the samples and no significant differences were noticed on lipid removal. The entropy changes were small and positive for the whole geosorbent samples, but even smaller or more negative when the lipids were removed. This indicates that the interaction of PAHs with soils and sediments in the absence of extractable lipids is stronger and the mechanisms involved may be different, changing from a partitioning-like mechanism to specific adsorption. Because of the competition between lipids and PAHs for the same sorption sites, the lipids can be viewed as an "implicit sorbate."     

Magnetic composite prepared from palm shell-based carbon and application for recovery of residual oil from POME

Magnetic separation combined with adsorption by activated carbon has been found to be a useful method for removing pollutants. In this paper, the use of palm shell as a source of activated carbon for the removal and recovery of oil from palm oil mill effluent (POME) is studied. In the first part of the study, the properties of samples of activated carbon prepared from palm shell under a variety of different conditions were characterized for their hydrophobicity, surface areas and pore size distribution. The most effective of the activated carbon samples was prepared by impregnation with ZnCl(2) followed by combined physical/chemical activation under carbon dioxide flow at 800 °C. Four grams of these samples adsorbed 90% of the oil from 50 mL POME. In the second part, the palm shell-based carbon samples were given magnetic properties by the technique of iron oxide deposition. Ninety-four percent of the activated carbon/iron oxide composite containing the adsorbed oil could be extracted from the POME by a magnetic bar of 0.15 T. Four grams of the composite can remove 85% of oil from 50 mL POME and a total of 67% of the initial oil can then be recovered by hexane extraction. Powder X-ray diffractometry showed the presence of magnetite and maghemite in the activated carbon/iron oxide composite.     

Metal immobilization in soils using synthetic zeolites

In situ immobilization of heavy metals in contaminated soils is a technique to improve soil quality. Synthetic zeolites are potentially useful additives to bind heavy metals. This study selected the most effective zeolite in cadmium and zinc binding out of six synthetic zeolites (mordenite-type, faujasite-type, zeolite X, zeolite P, and two zeolites A) and one natural zeolite (clinoptilolite). Zeolite A appeared to have the highest binding capacity between pH 5 and 6.5 and was stable above pH 5.5. The second objective of this study was to investigate the effects of zeolite addition on the dissolved organic matter (DOM) concentration. Since zeolites increase soil pH and bind Ca, their application might lead to dispersion of organic matter. In a batch experiment, the DOM concentration increased by a factor of 5 when the pH increased from 6 to 8 as a result of zeolite A addition. A strong increase in DOM was also found in the leachate of soil columns, particularly in the beginning of the experiment. This resulted in higher metal leaching caused by metal-DOM complexes. In contrast, the free ionic concentration of Cd and Zn strongly decreased after the addition of zeolites, which might explain the reduction in metal uptake observed in plant growth experiments. Pretreatment of zeolites with acid (to prevent a pH increase) or Ca (to coagulate organic matter) suppressed the dispersion of organic matter, but also decreased the metal binding capacity of the zeolites due to competition of protons or Ca.