Decomposition of organochlorine compounds in flue gas from municipal solid waste incinerators using natural and activated acid clays

High-temperature particle control (HTPC) using a ceramic filter is a dust collection method without inefficient cooling and reheating of flue gas treatment; thus, its use is expected to improve the energy recovery efficiency of municipal solid waste incinerators (MSWIs). However, there are concerns regarding de novo synthesis and a decrease in the adsorptive removal efficiency of dioxins (DXNs) at approximately 300°C. In this study, the effect of natural and activated acid clays on the decomposition of monochlorobenzene (MCB), one of the organochlorine compounds in MSW flue gas, was investigated. From the results of MCB removal tests at 30–300°C, the clays were classified as adsorption, decomposition, and low removal types. More than half of the clays (four kinds of natural acid clays and two kinds of activated acid clays) were of the decomposition type. In addition, the presence of Cl atoms detached from MCB was confirmed by washing the clay used in the MCB removal test at 300°C. Activated acid clay was expected to have high dechlorination performance because of its proton-rich-composition, but only two clays were classed as decomposition type. Conversely, all the natural acid clays used in this work were of the decomposition type, which contained relatively higher di- and trivalent metal oxides such as Al₂O₃, Fe₂O₃, MgO, and CaO. These metal oxides might contribute to the catalytic dechlorination of MCB at 300°C. Therefore, natural and activated acid clays can be used as alternatives for activated carbon at 300°C to remove organochloride compounds such as DXNs. Their utilization is expected to mitigate the latent risks related to the adoption of HTPC, and also to contribute to the improvement of energy recovery efficiency of MSWI.

ImplicationsThe effect of natural and activated acid clays on MCB decomposition was investigated to evaluate their suitability as materials for the removal of organochlorine compounds, such as DXNs, from MSWI flue gas at approximately 300°C. More than half of the clays used in this study showed the decomposition characteristics of MCB. The presence of Cl atoms in the clay used in the MCB removal test at 300°C proved the occurrence of MCB decomposition. The results of this study suggest a novel flue gas treatment method to establish high-energy efficient MSWI systems.     

The electron density distribution in pyridinium and bipyridylium compounds and its relevance to their adsorption by expanding lattice clays

Abstract

Charge distributions in 1, 1'‐ethylene‐2, 2'‐bipyridylium (diquat), 1,1'‐dimethyl‐4,4'‐bipyridylium (paraquat) and 1‐methylpyridinium organocations were calculated by a Complete Neglect of Differential Overlap semi‐empirical quantum mechanical procedure. The data show that the positive charges in the organocations are distributed around the molecules and are greatest in the positions ortho and para to the heterocyclic nitrogen atoms. Earlier interpretations of the mechanisms of adsorption of paraquat and diquat by soils and clays assumed that the charges were located in the heterocyclic nitrogen atoms. Here some consideration is given to the influence of the charge delocalizations on the processes of adsorption by montmorillonite and vermiculite clay preparations.     

水质对紫外消毒在两种典型再生水中应用的影响

以大肠杆菌为对象,研究了再生水水质变化对紫外消毒效果和光复活的影响。结果表明,紫外对大肠杆菌有很强的灭活作用,在紫外剂量为4mJ／cm^2时,大肠杆菌的灭活率达到了4．41个对数级。腐殖酸、铁和2种再生水水体中其他溶解性物质会影响光吸收和紫外透射率,但对紫外消毒动力学无影响。在颗粒物浓度为0～200mg／L的范围内,外源高岭土和活性污泥等颗粒物的投加对紫外消毒效果影响较小,而再生水水样W1中原有的2．61／1：g／L的颗粒物则会极大地影响消毒效果,使UV对细菌的灭活出现明显的拖尾现象。腐殖酸会增强紫外损伤大肠杆菌的光复活能力,但2种再生水中细菌的光复活能力相对磷酸盐缓冲溶液（PBS）中减弱,减弱程度在不同水样中有所不同。     

Sorption of chlorimuron-ethyl on montmorillonite clays: effects of exchangeable cations,pH, and ionic strength

Sorption interaction of chlorimuron-ethyl with montmorillonite clays was investigated under varied types of exchangeable cation, pH, and ionic strength conditions. Chlorimuron-ethyl sorption on bentonites exhibited pronounced cation dependency, and the sorption ability increased as the sequence Ca²⁺- < Na⁺- < Al³⁺- < Fe³⁺-bentonite, due to different sorption mechanisms, whereas the cation dependency was influenced by the clay type and much weaker for montmorillonites. The decrease of pH at the range of 4.0–6.0 prominently increased sorption of chlorimuron-ethyl on all cation-exchanged montmorillonite clays, and nearly a neglected sorption (about 2 %) can be observed at pH over 7.0. In the presence of CaCl₂, sorption of chlorimuron-ethyl on Fe³⁺-bentonite was promoted because of complexion of Ca²⁺ and the surface of Fe³⁺-bentonite. However, as the concentration of CaCl₂ increased, chlorimuron-ethyl sorption on Ca²⁺- and Fe³⁺-exchanged bentonite decreased, suggesting that Ca bridging was not the prevailing mechanism for sorption of chlorimuron-ethyl on these clays. Furthermore, chlorimuron-ethyl sorption was relatively sensitive to pH, and the change of pH may obscure effect of other factors on the sorption, so it was quite necessary to control pH at a constant value when the effect of other factor was being studied.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

Persistence of metsulfuron‐methyl in two soils

Abstract

The persistence of metsulfuron‐methyl in sandy loam and clay soil incubated at different temperatures and moistures contents was investigated under laboratory conditions using longbean (Vigna sesquipedalis L.) as bioassay species. A significant degradation of metsulfuron‐methyl was observed in non‐autoclaved soil rather than the autoclaved soil sample. At higher temperature, the degradation rate in non‐autoclaved soil improved with increasing soil moisture content. In non‐autoclaved sandy loam and clay soil, the half‐life was reduced from 9.0 to 5.7 and from 11.2 to 4.6 days, respectively when moisture level of sandy loam increased from 20 to 80% field capacity at 35°C. In the autoclaved soil, herbicide residue seems to have been broken down by non‐biological process. The rate of dissipation was slightly increased after the second application of the herbicide to non‐autoclaved soils but not in autoclaved soil, indicating the importance of microorganisms in the breakdown process.     

钱江隧道盾构废弃泥浆的混凝分离

为了实现钱江隧道盾构废弃泥浆的无害化处理,对盾构废弃的砂土泥浆和粘土泥浆分别进行混凝分离的实验条件研究,结果表明:对于砂土泥浆,密度为1.20 g/cm3有利于实现高效的泥水分离;PAM作为絮凝剂的分离效果最好;混凝分离的最优化分离条件为:投药量为150 mg/L,pH为8左右,水力条件为以300 r/min搅拌1 min,再以80 r/min搅拌20 min。对于粘土泥浆,密度为1.10 g/cm3有利于实现高效的泥水分离;PAM作为絮凝剂的分离效果最好;混凝分离的最优化分离条件为:投药量为150 mg/L,pH为6左右,水力条件为以300 r/min搅拌1 min,再以80 r/min搅拌20 min。该实验为废弃泥浆的进一步处理奠定了基础。     

Removal of cyanobacterial blooms in Taihu Lake using local soils. I. Equilibrium and kinetic screening on the flocculation of Microcystis aeruginosa using commercially available clays and minerals

Algal removal abilities of 26 clays/minerals were classified into three categories according to the 8-h equilibrium removal efficiency (Q8h) and removal rate at a clay loading of 0.7 g/L. Type I clays (sepiolite, talc, ferric oxide, and kaolinite) had a Q8h > 90%, a t50 (time needed to remove 50% of the algae) < 15 min, and a t80 < 2.5 h. Type II clays (6 clays) had a Q8h 50-90%, a t50 < 2.5 h, and a t80 > 2.5 h. Type III clays (14 clays) with Q8h < 50%, t50 > 8 h and t80 > 14 h had no practical value in removal of algal blooms. When the clay loading was reduced to 0.2 g/L, Q8h for all the 25 materials decreased to below 60%, except for sepiolite whose Q8h remained about 97%. The high efficiency for sepiolite to flocculate M. aeruginosa cells in freshwaters was due to the mechanism of netting and bridging effect.     

Optimization and treatment of wastewater of crude oil desalting unit and prediction of scale formation

In this article, one of Iran’s southwest oil fields that produces 3200 barrels per day (bbl/d) of wastewater from oil and gas processing was investigated. Experimental analysis of oil reservoir water and desalting wastewater disposal of crude oil desalting unit was performed. First, water was treated with a reverse osmosis membrane. As a result, the purified water, with lower total dissolved solids (TDS) and pH, was a suitable candidate for injection into the adjacent wells of the crude oil desalting unit. The effectiveness and compatibility of this wastewater to the formation water of the oil field wells were simulated. Finally, we studied and identified the formation, the amount, and the type of mineral scale deposits. These are the most important problems during water injection into the wells. The analysis shows that the refined water from the reverse osmosis (RO) process was a suitable and low-cost economical option for injection in onshore and offshore fields, due to the low amount of salts, the concentration of susceptible ions in scaling formation, and the appropriate pH. This oil field, which is in the second half of life, requires enhanced oil recovery methods (EOR) for the maintenance of pressure and an increase in oil recovery.

     

The efficiency of electrocoagulation in treating wastewater from a dairy industry,Part I: Iron electrodes

Iron electrodes were used for electrocoagulation (EC) treatment of wastewater from a dairy plant. Electrolysis time, pH, current density and distance between electrodes were considered to assess the removal efficiency of chemical oxygen demand (COD), total solids (TS) and their fractions and turbidity. Samples were collected from the effluent of a dairy plant using a sampling methodology proportional to the flow. The treatments were applied according to design factorial of half fraction with two levels of treatments and three repetitions at the central point. The optimization of parameters for treating dairy industry effluent by electrocoagulation using iron electrodes showed that electric current application for 15 minutes, an initial sample pH close to neutral (pH 7.0) and a current density of 50 A ^{. m?2} resulted in a significant reduction in COD by 58 %; removal of turbidity, suspended solids and volatile suspended solids by 95 %; and a final treated effluent pH of approximately 9.5. Negative consequences of the type of electrode used were the emergence of an undesirable color and an increase in the proportion of dissolved solids in the treated effluent.     

Removal of harmful cyanobacterial blooms in Taihu Lake using local soils. III. Factors affecting the removal efficiency and an in situ field experiment using chitosan-modified local soils

Effects of ionic strength, pH, organic content, cell concentration, and growth phase on the removal of MA cells using chitosan-modified sepiolite were studied in the laboratory. The MA removal efficiency increased with the increase of salinity for normal clay flocculation. In contrast, for chitosan-modified clays/soils, MA removal efficiency increased with the decrease of salinity. The removal efficiency of chitosan-modified sepiolite was not significantly affected by pH (6-9), but dropped dramatically beyond pH 10. Humic acid had a small negative effect on the removal of MA cells. Cells were removed more effectively by clays around the early senescence growth phase than other growth stages. The removal efficiency increased as the cell concentration increased. In a field enclosure of Taihu Lake, a loading of 0.025 g/L chitosan-modified local soils removed 99% algal cells and no increase of chlorophyll-a was observed during the following one month's monitoring process.     

Sorption of Pesticides on Kaolinite and Montmorillonite as a Function of Hydrophilicity

Pesticides and other organic species are adsorbed by soil via different mechanisms, with bond strengths that depend on the properties of both the soil and the pesticide. Since the clay fraction in soil is a preferential sorbent for organic matter, reference kaolinite and montmorillonite are useful models for studying the mechanism and the strength of sorption. This paper presents the results of batch experiments to investigate the interactions of kaolinite KGa-1 and montmorillonite SWy-1 with the following pesticides and organic species resulting from the natural degradation of pesticides in the environment: atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine), simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine), diuron [1,1-dimethyl-3-(3,4-dichlorophenyl)urea], aniline, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol. Each of these chemicals has different hydrophilicity. Systems containing 2.0 g of clay were put in contact with 100.0 mL of solutions of the pesticides at known concentration ranging from 1.0 to 5.0 mg/L, and the amount of solute adsorbed was evaluated through RP-HPLC analysis of the pesticide still present in the aqueous suspension. To test for electrostatic interactions between the clay surface and the pesticides, potentiometric titration was used to determine the permanent surface charge of clays. Experiments were performed at different pH values. The results indicate that, for the chemicals studied, neutral molecules are preferentially retained relative to ionized ones, and that montmorillonite is a more effective sorbent than kaolinite.     

Laboratory studies on volatilization and mineralization of 14c‐p,p'‐DDT in soil,release of bound residues and dissipation from solid surfaces

Abstract

In support of field data, laboratory studies were conducted on volatilization, mineralization and binding of ¹⁴C‐p,p'‐DDT in soils at Sao Paulo. Incubation of soil for 6 weeks did not result in volatilized organics or mineralization; with >95% extractable radiocarbon in the form of p,p'‐DDT. Small amounts of bound residues (1.8%) were detected in soil. These data confirm the very slow dissipation of DDT in the field which presumably relates to the acidic pH of soil (4.5–4.8).

Bound ¹⁴C‐residues in soils treated with ¹⁴C‐p,p'‐DDT at Praia Grande and Sao Paulo could be released (5–21%) by sulphuric acid treatment. The released residue had the composition: 69–90% DDT, 7–32% DDD and 0–3% DDE. Incubation of soil bound ¹⁴C‐residues with fresh inoculum for 3 months did not result in release of ¹⁴C.

Dissipation from wooden surfaces was fairly slow. After 20 weeks, 74% of the applied radioactivity could be recovered; 44% hexane‐non‐extractable.     

Removal of cyanobacterial blooms in Taihu Lake using local soils. II. Effective removal of Microcystis aeruginosa using local soils and sediments modified by chitosan

After sepiolite was modified with Fe3+ to increase its surface charge, the initial algal removal rate increased significantly, but its Q8h was not improved substantially at clay loadings below 0.1 g/L. Modification on netting and bridging properties of clays by either chitosan or polyacrylamide (PAM) dramatically increased flocculation (Q8h) of MA cells in freshwaters. Algal removal efficiencies of different solids, including Type III clays, local soils and sediments, were all improved to a similar level of >90% at a total loading of 0.011 g/L (contained 0.001 g/L chitosan) after they were modified with chitosan, making the idea of clearing up algal blooms using local soils/sediments possible. The mechanism of netting and bridging was confirmed to be the most important factor in improving the removal efficiency of cells, whereas clays also played important roles in the sedimentation of the floc.     

Reduced Adsorption of Ametryn in Clay,Humic Acid,and Soil by Interaction with Ferric Ion Under Fenton Treatment Conditions

Previous work in our laboratory indicated a weak interaction between ferric ion and several triazine/triazinone herbicides during a Fenton treatment process, and the intensity of the interaction was calculated. To further support the existence of this weak interaction, the adsorption of ametryn, a triazine herbicide, was investigated in kaolinite clay, humic acid, and soil under pseudo-Fenton conditions. At a low addition rate of ferric ion, the adsorption of ametryn in clay, humic acid, and soil was enhanced due to the decreased pH resulting from the hydrolysis of ferric ion. But the pH effect was totally neutralized and the adsorption of ametryn was significantly reduced by further addition of ferric ion, demonstrating the existence of the weak interaction between ametryn and ferric acid. Further study showed that the adsorption-reduction effect of ferric ion existed not only with ametryn but also with several other triazine/triazinone herbicides. This weak interaction may accelerate the desorption process during the remediation of triazine/triazinone herbicide-contaminated soil using a Fenton/Fenton-like treatment, but it may also impede the degradation of these herbicides.     

Sorptive interactions and binding of δ‐endotoxin protein from bacillus thuringiensis subsp. kurstaki inforest soils

Abstract

The adsorption, desorption and binding of the insecticidal protein from Bacillus thuringiensis subsp. kurstaki (Btk toxin) onto autoclaved sandy and clay loam forest soils were studied at 23°C in a buffer medium (pH 10.2) using the precipitated protein mixture (active + inactive) obtained from a commercial Btk formulation. The active protein in the buffer solution was quantified by ELISA technique. Maximum adsorption of the toxin onto the sandy (301 μg/g) and clay (474 μg/g) loam soils was found to occur after 3 and 4 hours of agitation, respectively. Adsorption of the toxin was higher in the clay loam soil than in sandy loam. Adsorption parameters were calculated using the Freundlich and linear isotherm equations. The K_F and 1/n values for the soils were 1.12 and 1.48 (sandy), and 20.42 and 0.874 (clay), respectively, indicating stronger affinity of the toxin for the clay compared to the sandy loam soil. The linear model showed deviations at higher concentrations, nevertheless using the best fit, K_D and K_OC values were computed for the two soils. For sandy loam, the K_D and K_OC values were 9.38 and 391, respectively; the corresponding values for clay loam were 13.19 and 425, confirming the higher sorption affinity of the toxin for clay loam. The adsorption data did not fit the Langmuir equation because of heterogeneity of the soil surface. Desorption studies showed that more than half of the adsorbed toxic protein remained firmly attached to sandy (162.6 μg/g or 54.5%) and clay (314.0 μg/g or 67.4%) loam soils after six 0.5‐h washes (total 3.0 h wash time). Although the toxin appears to be a non‐leacher, its lateral mobility, soil persistence and biological consequences, including bioavailability of the bound residues, are poorly understood and require further investigation.     

Seepage from deep bedded and poultry litter systems

Abstract

The work reported indicates that there could be a potential of ground water pollution by NO₃‐N from turkey facilities built on both sandy and clay soils. At four different depths (30.54, 61.08, 91.62, and 122.16 cm), the NO₃‐N levels for the clay soil were 1572, 497, 66, and 28 ppm, and those for the sandy soil were 293, 425, 324, and 164 ppm, respectively. No significant P increases were observed but there did exist a significant increase of K in the topsoil for both clay and sandy turkey structures. The results show that swine hoop houses with less than three or four years of age may not pose a threat to groundwater pollution due to the leaching of nutrients. The only dairy feedlot sampled in this study, although it has been used for more than 20 years, did not show leaching of NO₃‐N and P. However, it did show a significantly elevated concentration of potassium in the topsoil, as compared to the background sample. More sites should be investigated to verify this.     

不同工艺对含高浓度腐殖酸地下水处理的可行性

针对内蒙古农村地区高腐殖酸地下水的处理问题,分别对（pH调节）-PAC强化混凝、高锰酸钾预氧化／混凝、活性炭吸附／混凝、Fenton氧化等技术处理的可行性进行了研究,同时利用三维荧光和高效体积排阻色谱分析处理前后水中有机物的组成变化特征。有机分析结果显示,水中的有机物为腐殖酸类物质,分子量分别为1600和3500,腐殖酸类物质为水中色度的主要贡献者。原水PAC强化混凝、高锰酸钾预氧化／PAC混凝对有机物的去除效果不佳,处理前后水样DOC浓度无明显变化,而pH调节．PAC强化混凝、微米活性炭吸附和Fenton氧化均能有效去除有机物。将原水pH调节至6．5,经300mg／LPAC混凝后出水DOC降至5．99mg／L。活性炭投加量为0．6g／L时,DOC降至7．6mg／L,然后采用60mg／LPAC混凝出去高度分散而不易沉降的小颗粒活性炭。此外,当反应初始pH值为3,过氧化氢投加量为0．5％（v／v）,亚铁和双氧水摩尔比为0．05时,出水DOC降至5．6mg／L,氧化后有小分子有机物生成。     

Adsorption of picloram on clays nontronite,illite and kaolinite: equilibrium and herbicide-clays surface complexes

The picloram (PCM) adsorption on nontronite, illite and kaolinite was studied at pH 3, 5 and 7. The adsorption isotherms had well-fitted to Langmuir and Freundlich models equations. The interactions of PCM with the clay mineral surfaces exhibited an anionic profile adsorption, with a decrease in adsorption when the pH increases. The PCM adsorption capacity increases in the following order: kaolinite?<?illite?<?nontronite. The X-ray diffraction (XRD) analysis of PCM-clay samples revealed that the picloram molecule does not enter into the clays basal space. The interaction of PCM with clays surface sites through nitrogen of the pyridine ring was confirmed by X-ray photoelectron spectroscopy (XPS). Due to the anionic form of PCM, the adsorption onto the external and edges surface sites of the clay minerals was proposed.     

PAC与粘土矿物混凝去除颤藻及残余铝形态研究

研究了PAC与不同粒径的天然粘土矿物复合混凝去除给水中的颤藻。结果表明,两者复合除藻效果显著优于单加PAC。当PAC浓度为12 mg/L,矿物浓度为24 mg/L,粒径为160目时,除藻效果最好,浊度和叶绿素a去除率分别为98.2%和100%。两者复合后PAC形态含量都发生了变化,悬浮态铝含量相对增加,溶解态铝含量相对减少,总残余铝量减小。