活性炭对含铅废水吸附特性研究

采用静态法用活性炭吸附处理含铅废水,考察了活性炭对含铅废水的吸附特性。结果表明:活性炭对铅离子吸附平衡时间为100 m in;吸附等温方程为:Ce/qe=0.4298+0.0594Ce(25℃),该方程符合Langmu ir型吸附模式,不同温度下吸附平衡参数0RL1,表示该吸附为有利吸附。实验数据应用数学模型拟合,二级相关系数R2=0.9998,显示吸附过程动力学与二级动力学模型相关性较好;计算不同温度下各热力学参数:△Hθ大于零、△Gθ小于零,证实该吸附过程是一个自发吸热过程。△Sθ大于零,表明铅离子在固液界面有序性减小、混乱度增大。△Hθ值很小,说明该过程为物理吸附。     

镇江斜发沸石对氨氮的吸附动力学及热力学研究

采用静态平衡法,开展了镇江斜发沸石对水中氨氮的吸附动力学和热力学研究.结果表明,吸附量随反应温度升高而增加,斜发沸石对氨氮吸附符合Freundlich等温线方程,对氨氮吸附实验数据与准二级动力学模型拟合更好(R2＞0.998),热力学参数吸附焓变△H=18.26 kJ/mol,熵变△S=0.0632 kJ/kmol,对...     

Mg/Al/Fe水滑石的焙烧产物对F~-的吸附

采用共沉淀法合成Mg-Al-Fe类水滑石,并通过不同焙烧温度制得焙烧类水滑石。采用XRD,FT-IR,SEM等方法进行了吸附材料表征。研究了焙烧温度,吸附剂投加量,吸附时间,吸附初始p H值,吸附动力学,吸附等温线、吸附热力学等因素对Mg-Al-Fe类水滑石及其焙烧产物吸附F-的效果。研究表明,500℃焙烧类水滑石吸附效果最好,0.2 g吸附剂是最佳投加量值,在p H变化范围为3~8内吸附量基本无变化。研究结果表明,焙烧水滑石吸附符合准二级动力学曲线,反应活化能为E_a=14.63 k J/mol。反应基本符合Langmuir吸附等温模型。△G~0为负值表明该反应是一自发进行过程。高温有利于吸附反应进行。     

二氧化氯对水中二价铁离子的氧化动力学

采用分光光度法和连续碘量法研究了二氧化氯（ClO2）氧化二价铁离子的反应动力学。研究结果表明,该化学反应计量关系为：5Fe2＋＋ClO2＋4H＋→5Fe3＋＋Cl-＋2H2O,建立了ClO2氧化二价铁离子的反应动力学方程为-rFe2＋≈1.6678×106EXP（-5179.7/T）[ClO2][Fe2＋]（pH=6.0）;在pH=6.0和T=293 K的条件下,该反应对于ClO2和二价铁离子均为一级,总反应级数为二级,二级反应速率常数k值为0.03556×103L/（mol.s）,该反应活化能Ea为43.1 kJ/mol;表明ClO2除铁的氧化反应在一般水处理条件下即能进行。     

活性炭对水中微量酰胺咪嗪吸附规律

选择3种商品活性炭(煤质炭MAC、杏壳炭XAC、椰壳炭YAC),从其对水中微量药物酰胺咪嗪(carbamaz-epine,CBZ)的吸附平衡、吸附等温式、吸附动力学和热力学等方面详细考察了不同种类活性炭对CBZ的吸附去除规律。实验结果表明,3种活性炭与CBZ接触反应10 h后均达到吸附平衡,对CBZ的平衡吸附量在8.3 mg/g左右;比较了Lang-muir和Freundlich两种吸附等温式,发现Langmuir方程更适合描述3种活性炭对CBZ的吸附过程;计算表明3种活性炭的吸附过程均符合拟二级动力学方程,Weber-Morris方程的模拟结果则说明膜扩散和内扩散共同限制了3种活性炭对CBZ的吸附速率;3种活性炭的Ea值分别为29.87 kJ/mol(MAC)、36.02 kJ/mol(XAC)和38.86 kJ/mol(YAC),表明3种活性炭吸附CBZ时同时发生了物理吸附和化学吸附作用,且以化学吸附为主;20～40℃时3种活性炭的△G均为负值,说明3种活性炭对CBZ的吸附反应可以自发进行;MAC、XAC、YAC的△H值分别为-3.10、-3.05和-3.02 kJ/mol,负值表明吸附过程放热,上述△H值较小则说明温度对CBZ的吸附影响不大;3种活性炭吸附CBZ过程的△S值为0.94 J/(mol.K)(MAC)、2.24 J/(mol.K)(XAC)和2.97 J/(mol.K)(YAC),说明吸附过程熵值增加,在外界条件不改变的情况下该吸附过程不可逆,同时可以看出在3种活性炭中,CBZ分子更倾向于吸附在YAC上。     

花生壳活性炭对亚甲基蓝的吸附特性

以花生壳为原料,氯化锌为活化剂制备花生壳活性炭,采用高分辨电子扫描电镜(SEM)和氮吸脱附曲线对花生壳活性炭进行了表征.从热力学和动力学的角度,研究了花生壳活性炭对亚甲基蓝溶液的吸附行为.热力学研究表明,花生壳活性炭对亚甲基蓝的吸附符合Langmuir等温吸附方程,该吸附是自发吸热过程,吸附自由能为-52.4017～-95.1765 kJ/mol,吸附熵变为214 J/(mol·K),吸附焓变为57.49796 kJ/mol.动力学研究表明,花生壳活性炭对亚甲基蓝的吸附符合二级反应动力学方程反应特征.     

改性木屑对水中Cr(Ⅵ)的吸附性能

在木屑上接枝季氨基团制备了改性木屑,并用傅里叶红外光谱(FT-IR)对其进行了表征。通过静态实验研究了改性木屑对水溶液中六价铬Cr(Ⅵ)的吸附特性,并探讨了温度、pH、多组分共存离子等对Cr(Ⅵ)吸附效果的影响。结果表明,在30℃时,改性木屑对Cr(Ⅵ)的饱和吸附容量为218.33 mg/g,吸附规律符合Langmuir等温方程式。在pH为3~10时,改性木屑对Cr(Ⅵ)均有显著的吸附效能,吸附过程符合准二级动力学方程,反应活化能为21.71 kJ/mol,对吸附热力学参数△G0、△H0和△S0的计算表明,吸附过程是吸热的自发过程。多组分干扰离子共存时,对Cr(Ⅵ)的吸附影响不大。     

甲基红在壳聚糖上吸附富集的研究

研究了pH、初始浓度、时间及温度对甲基红在壳聚糖上吸附富集的影响。结果表明,pH是影响甲基红吸附富集的重要因素,最佳pH3．4。其动力学行为更好地符合Lagergren准二级反应动力学模型,随着温度增加,平衡吸附量减少。吸附过程的表观活化能（Ea）为7．518kJ／mol。壳聚糖对甲基红的吸附过程较好地符合Freundlich吸附等温方程。计算得到吸附过程的热力学参数△G0、△H0。和△S0分别为-24．88kJ／mol（303K）、-22．15kJ／mol和8．783J／（mol·K）,表明壳聚糖对甲基红的吸附是一个自发的放热过程。红外光谱分析得到,壳聚糖吸附甲基红的过程中,壳聚糖分子中存在的大量羟基和氨基发挥了主要作用。     

改性膨胀石墨对含铅废水吸附特性

采用微波法在1 000 W下微波膨胀60 s制备了膨胀石墨,以乙醇为分散剂,采用超声沉淀法制备了纳米氢氧化镁,同时将纳米氢氧化镁负载到膨胀石墨孔隙中,制备出一种新型吸附剂,并采用静态吸附的方法研究了该吸附剂对铅离子的吸附效果,实验证明当改性膨胀石墨的用量为0.035 g,铅溶液的pH=4,铅溶液初始浓度为300 mg/L,吸附温度为25℃时,该吸附剂对铅离子的去除率能达到48%,吸附容量能达到105 mg/g左右。同时该吸附反应能够较好地符合Lang-muir吸附等温式以及二级动力学模型。     

硫酸活化市政污泥吸附Pb2+

以城市污水厂脱水剩余污泥为原材料,采用硫酸活化法制备活化剩余污泥,讨论了溶液初始pH、铅离子的浓度、接触时间和吸附剂投加量等因素对处理含铅废水效能影响,探讨了其吸附动力学特征.结果表明,活化剩余污泥对铅离子有较好吸附效果,10 min内吸附率达到75%,45 min内吸附基本达到平衡,在偏酸性或中性条件下,吸附容量随着初始pH增大而增大.采用4种动力学方程(准一级吸附动力学方程、准二级吸附动力学方程、颗粒扩散吸附动力学方程、Elovich动力学方程)对其吸附数据进行吸附动力学拟合,通过分析得出,准二级吸附动力学方程能较好地反映该吸附过程,其相关系数R2均达到0.999以上.     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

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.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

Radionuclides in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.