TEMPO氧化微晶纤维素和马来酸酐接枝微晶纤维素的制备及对Cu~(2+)的吸附

通过马来酸酐(MA)固相接枝和四甲基哌啶(TEMPO)氧化体系改性微晶纤维素(MCC)制备了两种重金属离子吸附剂,对比了MA和TEMPO氧化体系对MCC的改性后对铜离子的吸附效果。结果表明:两者对MCC的改性都有效果,在铜离子浓度小于500 mg/L时,经TEMPO改性的MCC吸附容量和吸附率明显大于MA改性的MCC。经TEMPO改性后的MCC对铜离子的吸附性能提高,在室温条件下,0.22 g改性后MCC对pH=5.77,浓度为20 mg/L的铜离子溶液最大吸附率为90.56%,最大吸附容量为9.1 mg/g。     

改性木屑对铜离子的吸附性能

用热解+Na OH浸泡的方法制备改性木屑,通过表征手段观察了改性后木屑表面结构的变化,并研究了改性木屑对水溶液中Cu2+的吸附性能。结果表明:改性木屑表面变光滑,羟基增多;与原木屑和活性炭相比,改性木屑的平衡时间缩短了60 min,吸附速率提高了50%;改性木屑对铜离子的吸附符合Langmuir等温模型,最大吸附量为31.25 mg·g~(-1),是原始木屑吸附量的8倍,是活性炭的3倍。     

阴-阳离子有机膨润土制备及其对铅离子的吸附

用十八烷基三甲基溴化铵（STAB）和十二烷基苯磺酸钠（SDBS）共同改性膨润土制备阴．阳离子有机膨润土,并用红外光谱分析法、热分析法和X粉晶衍射分析进行了表征;考察了阴-阳离子有机膨润土对铅离子的吸附性能。结果表明,用0．5CEC（cationexchangecapacity）十八烷基三甲基溴化铵和0．4CEC十二烷基苯磺酸钠改性的膨润土吸附铅的效果最佳;阴-阳离子有机膨润土吸附铅离子的能力比改性前明显增加,达到吸附平衡所需要的时间缩短;pH值强烈影响有机膨润土对铅离子吸附;有机膨润土对铅离子等温吸附过程符合Langmuir吸附模型;吸附热力学分析表明该吸附是一个放热过程,降低温度有利于铅离子的吸附。     

黄麻纤维活性炭对亚甲基蓝和甲基橙吸附动力学

以黄麻纤维为原料,采用磷酸活化法制备活性炭。研究黄麻纤维活性炭对亚甲基蓝和甲基橙2种染料的吸附行为。结果表明,采用磷酸制备的活性炭,由于表面含有羧基和含磷官能团等酸性基团,能够促进活性炭对亚甲基蓝的吸附;黄麻纤维活性炭对2种染料的平衡吸附量、初始吸附速率均随着初始浓度的增加而升高;相同条件下,黄麻纤维活性炭对亚甲基蓝的平衡吸附量大于甲基橙;黄麻纤维活性炭对两种染料的吸附行为更符合准二级动力学模型。     

聚甲亚胺酰胺树脂对水中Cu~(2+)的吸附

制备了聚甲亚胺酰胺树脂,对其进行傅里叶变换红外光谱分析。采用批处理方法实验了pH、铜离子初始浓度、吸附时间、吸附剂用量对吸附量的影响,研究了等温吸附模型和吸附动力学模型。优化后的吸附条件为:在铜离子溶液体积50 mL、初始浓度为300 mg/L、pH为6.0时,吸附剂投放量50 mg、吸附时间60 min,此时吸附量达到269.1 mg/g,去除率达89.7%。25℃时在研究浓度范围内,铜离子吸附过程用Langmuir等温线模型和Freundlich等温线模型描述均可;与准一级动力学方程、Elovich方程及内扩散方程相比,准二级动力学方程能更好地描述其吸附动力学过程。     

中空纤维吸附材料吸附去除水中铜离子

利用一种使用方便的绳状中空纤维作为吸附剂,考察了其吸附去除水中铜离子的过程,探讨了溶液pH、吸附时间、铜离子初始浓度和竞争离子等因素对吸附性能的影响,并初步评价了该纤维吸附剂的脱附性能。结果表明:该纤维对铜离子的最大吸附量为39.66mg/g;对初始质量浓度为50mg/L的铜离子吸附去除率可达99.9%,说明该纤维吸附材料可以有效地去除水中的铜离子。中空纤维对铜离子的吸附过程可以用Langmuir等温吸附模型很好地拟合,纤维表面分布的大量羧基是其吸附铜离子的主要贡献者。     

改性花生壳对苯酚的吸附

以花生壳为原料,使用环氧氯丙烷、二甲胺及吡啶,以N,N-二甲基甲酰胺为反应介质改性花生壳。结果表明:改性花生壳对苯酚的去除效果优于未改性花生壳。在实验条件下,吸附剂的吸附量在溶液pH为9,吸附时间为120 min时达到最大;溶液离子强度对吸附的影响较大。分析了该反应体系的动力学和热力学参数,改性花生壳吸附苯酚过程拟用准二级动力学模型处理,计算得出平衡吸附量与实验值相符。改性花生壳对苯酚的吸附符合Langmuir和Freundlich等温模式,R2均大于0.98,Qmax在84.49～108.76 mg/g之间,Freundlich模式的吸附强度n值在1.211～1.262之间,热力学参数△G、△H、△S表明改性花生壳对苯酚的吸附过程是自发、吸热过程。     

镧改性钢渣对水中氟离子的吸附性能

为有效去除铁路隧道开挖过程中涌出的地下水中的氟离子,避免对当地环境和居民身体健康造成危害,利用镧改性钢渣得到一种除氟材料,通过扫描电镜、比表面积测定、能量散射光谱、X射线衍射及傅里叶红外光谱等方法对材料进行表征。此外,结合吸附热力学和吸附动力学模型拟合,探究了改性钢渣对水中氟离子的吸附机理。结果表明：改性钢渣的比表面积由未改性的0.549 9 m²·g^-1增大到23.367 5 m²·g^-1,小粒径的钢渣比例增大且表面粗糙程度增强。能谱分析表明通过改性,可成功的将镧负载于钢渣表面。吸附拟合模型表明,钢渣对氟离子的吸附遵循Langmuir模型,说明钢渣对氟离子的吸附更接近于单层吸附,且主要为化学吸附。热力学参数表明,吸附吉布斯自由能(?G⁰)>0,焓变(?H⁰)和熵变(?S⁰)<0,表明该反应是放热过程,改性钢渣的除氟过程符合伪二级动力学过程。改性钢渣有望成为一种具有应用前景的除氟材料。     

铁铜改性稻壳炭对双氯芬酸钠吸附性能

以稻壳为原料制备铁铜改性生物炭(FCBC300),采用扫描电子显微镜、元素组成分析仪、X-射线衍射光谱仪、傅里叶红外光谱仪对其进行了系列基础理化性质表征,通过批量吸附实验研究了FCBC300在不同pH和干扰离子及有机物腐殖酸(HA)等条件下对双氯芬酸钠(DCF)的去除效果和吸附机制。结果表明,改性后稻壳炭表面负载Fe₃O₄、γ-Fe₂O₃和CuO,芳香性增强、亲水性降低,对DCF的吸附性能大幅度提升。pH=5～9条件下,改性稻壳炭对DCF的吸附量约是未改性稻壳炭的20倍,吸附机制以静电作用为主;PO₄^3-的存在对吸附几乎无影响,SO₄^2-、Cl^-和HCO₃^-对DCF的去除虽有轻微抑制作用,但去除率下降幅度均低于5%,HA存在则明显抑制吸附能力;FCBC300对DCF的吸附过程,更符合准一级动力学模型和Langmuir等温吸附模型,预测最大吸附量为4...     

改性树脂对β-萘磺酸的吸附性能

将D301树脂与FeCl3-NaOH体系反应进行改性,制备一种改性树脂作为吸附剂,吸附去除废水中的β-萘磺酸的研究。通过SEM技术对改性树脂进行了结构表征;考察了pH值、吸附时间和温度因素对改性树脂吸附β-萘磺酸的影响:最佳的实验条件pH值为3、反应时间为7 h、温度为298 K,且最大吸附量达778 mg/g。改性树脂对β-萘磺酸的吸附等温线符合Freundlich方程;热力学实验数据:ΔG<0,ΔH<0,该吸附过程为放热、自发过程;吸附动力学符合二级动力学方程。     

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.     

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.     

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.     

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.