偶联剂改性凹凸棒土处理含汞(Ⅱ)废水的研究

利用一种含氮硅烷偶联剂γ-氨丙基三乙氧基硅烷改性凹凸棒土,对凹凸棒土改性前后的表面性质进行了分析,并通过静态吸附实验研究了材料对水中汞离子的吸附性能.研究结果表明,酸活化增加了凹凸棒土吸附材料的孔道直径,使吸附速度加快,30 min即达到吸附平衡.通过硅烷偶联剂对凹凸棒土的改性,在材料表面引入了大量氨基,提高了材料对汞...     

β-环糊精接枝羧甲基壳聚糖吸附剂的制备及其性能

采用γ-氨丙基三乙氧基硅烷化学修饰活化后的硅胶,以戊二醛为交联剂,接上羧甲基壳聚糖,继而接枝上β-环糊精作为功能单体,制备了一种用于分离富集水样中Cu(Ⅱ)的固相萃取新材料。利用红外光谱(FT-IR)、比表面分析(BET)、X射线衍射光谱(XRD)以及热重分析(TG)等方法对吸附剂进行结构表征。采用火焰原子吸收(FAAS)作为检测手段,考察了溶液p H、振荡时间、吸附剂用量、样品流速、洗脱液浓度和体积等对吸附剂吸附Cu(Ⅱ)的影响。吸附剂饱和吸附容量为9.37 mg/g,最大富集倍数高达350。吸附过程能用准二级动力学模型和Langmuir等温吸附方程进行很好的拟合。应用于环境水样中Cu(Ⅱ)的分离富集与测定,回收率在96.8%~105.2%之间,效果较好。     

改性壳聚糖处理污水中Ni(Ⅱ)的效果

通过丁二酸酐与γ-氨丙基三甲氧基硅烷改性后的纳米SiO2(即可分散的纳米二氧化硅,简称DNS)反应,合成了羧基化的DNS,再经过与壳聚糖脱水生成酰胺的过程,合成了改性壳聚糖。通过红外光谱和扫描电镜对改性壳聚糖进行表征。研究了壳聚糖及改性壳聚糖微粒吸附Ni2+时溶液pH值、时间、吸附剂用量和Ni2+初始浓度等对吸附率的影响,并确定了最佳条件为:pH=7,吸附时间为120 min,吸附剂的投加量为0.3 g。改性壳聚糖比壳聚糖具有更强的吸附Ni2+的能力,吸附率达67.01%。     

APTES改性污泥基炭的表征及其对水中Pb(Ⅱ)的吸附特性

污泥炭(SC)灰分含量高,吸附性能差,因而限制了其应用范围。使用3-氨基丙基三乙氧基硅烷(APTES)对污泥炭进行改性,提高其对重金属的吸附能力。结果表明:APTES成功地负载到污泥炭上;在25℃时,APTES-SC对Pb(II)的吸附量是SC的8倍;吸附量随溶液pH (1～8)的增大而增强。APTES-SC对Pb(II)的吸附行为符合二级动力学模型,等温吸附曲线符合Langmuir模型,吸附过程是自发、吸热反应(ΔG0,ΔH0)。该方法制备的改性污泥基炭是一种能去除废水中Pb(II)的高效吸附剂。     

7种改性硅藻土对Cd2+、Pb2+、Cu2+的吸附性能对比

首次系统地研究了硅藻土经热活化、锰氧化物、Mg(OH)2改性、聚丙烯酰胺、氨丙基三乙氧基硅烷、微乳液和Cu2等7种方法改性后,在不同pH下对Cd2+、pb2+、Cu2+的吸附效果及其主要机理.在实验条件下,重金属吸附效果最佳的是锰氧化物和Mg(OH)2改性硅藻土.对于pb2+、Cu2+和Cd2+的吸附,前者的最大吸附量分别为98、84和78 mg/g,后者是79、76和91 mg/g.SEM、BET、XRD、FTIR结果显示,这2种改性硅藻土的比表面积大大增加,且拥有更多能提高其吸附性能的Si-O-H基团.Mg(OH)2改性硅藻土对Cd2+吸附等温线研究表明,其符合Langmuir等温吸附模型.提供的改性方法和实验结果,为硅藻土处理水体重金属污染提供了新的技术手段和理论依据.     

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。     

硅烷化改性沸石对重金属离子的吸附性能

制得一种用于重金属废水处理的新型硅烷化改性沸石吸附剂,成本低、效果显著且稳定。通过对改性沸石表征,分析了改性对沸石结构的影响。结果表明,改性一定程度降低了原沸石的晶体特征,但基本上保持了其结构组成;硅烷化改性成功地在沸石上接枝了氨基。对硅烷化沸石的特性研究,得出硅烷化沸石对Ni2+、Cu2+、Zn2+和Pb2+吸附最佳投加量为1、1、1.6和0.6 g/L,且此时对4种离子的去除率也较好;吸附动力学研究得出,其吸附过程可用二级动力学方程较好地拟合;吸附达到平衡时,4种金属离子的平衡吸附量分别为11.23、17.41、15.45和59.42 mg/g;硅烷化沸石对金属离子的吸附行为更符合Langmuir模型,为化学吸附;在酸性条件下(pH=2～6),硅烷化沸石仍保持一定的吸附能力,具有一定的耐酸性。     

锆(Ⅳ)负载交联壳聚糖吸附硫酸根的性能

以甲醛、苯甲醛为交联剂,制备交联壳聚糖树脂,再与锆(Ⅳ)离子反应制备锆负载交联壳聚糖吸附剂。采用静态吸附法考察了该吸附剂对水中硫酸根离子(SO24-)的吸附性能。实验发现,吸附时间2 h,SO24-溶液初始浓度500 mg/L,pH值3.0,溶液温度35℃为较优的吸附条件;吸附过程符合Langmuir等温吸附模型,属于优惠吸附型,吸附容量可达78.65 mg/g;吸附过程较好地符合拟二级动力学模型;锆负载前后交联壳聚糖对硫酸根的吸附量提高了约4.5倍;该吸附剂具有良好的耐酸性和再生性能。     

氨基修饰介孔分子筛SBA-15对水中Pb~(2+)吸附性能

以二乙烯三胺基丙基三甲氧基硅烷为偶联剂,利用后修饰方法,制备出氨基修饰SBA-15。利用傅立叶红外光谱仪,N2-吸附脱附对样品结构进行表征,并讨论了吸附动力学特性及吸附等温特性。结果表明,修饰后的SBA-15吸附水中Pb2+时在120 min内可以达到吸附平衡,吸附过程符合拟二阶动力学方程。Langmuir模型及Dubinin-Radushkevich(DR)模型很好地描述了Pb2+在修饰后SBA-15上的吸附行为,其中基于Langmuir模型计算得出的25℃时最大吸附量为84.25 mg/g。D-R模型计算得出的平均吸附自由能在25℃、35℃和45℃时分别为-13.9、-14.4和-16.0 kJ/mol,表明吸附可能属于表面络合作用,可以归为化学过程。     

改性亚麻处理孔雀石绿染料废水的研究

为了深度处理染料废水,以亚麻为原料,利用戊二醛对其进行改性,并对其进行傅立叶红外光谱仪(FTIR)扫描和扫描电子显微镜(SEM)表征。研究了吸附动力学、热力学以及吸附机理,同时还探索了吸附温度、吸附时间、孔雀石绿初始浓度以及吸附剂用量对吸附性能的影响。结果表明:改性亚麻吸附性能明显优于未改性亚麻,室温下,将经过0.05mol/L戊二醛改性得到的改性亚麻0.20g用于吸附100mg/L孔雀石绿溶液50mL,吸附360min,吸附量达到33.26mg/g,对孔雀石绿的去除率为99.78%;动力学研究表明,吸附过程符合准二级动力学方程,为化学吸附;热力学研究表明,吸附过程符合Freundlich吸附等温方程,为多层吸附,且为自发反应。     

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.     

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.     

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 and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

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.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

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 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.     

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.