交联羧甲基玉米淀粉对水溶液中铅离子吸附性能的优化研究

以玉米淀粉为原料，采用先醚化后交联改性工艺合成了交联羧甲基玉米淀粉吸附剂。在单因素试验的基础上，采用Box-Benhnken的中心组合试验设计及响应面分析法，研究了交联羧甲基玉米淀粉吸附剂用量、吸附时间和pH值3因素对水溶液中铅离子吸附效果的影响，得出了吸附剂对铅离子吸附效果的回归模型。结果表明，最佳吸附工艺参数为吸附剂用量0.22 g，pH值为6.6，吸附时间32.9 min，交联羧甲基玉米淀粉对铅离子吸附容量可达44.72 mg/g，铅离子去除率达到98.38%。常温下吸附动力学模型符合Freundlich等温式Q=0.4152C^0.9894。采用0.9 mol/L盐酸溶液作为解析液，铅离子回收率可达97.55%。     

铝钒土—钢渣吸附剂去除铅的研究

天然铝钒土与钢渣混合制得的Al-Ca混合吸附剂性能稳定,能够有效地去除水中的铅离子。通过间歇式振荡吸附实验得到该吸附剂的最佳制作条件为:铝钒土/钢渣为1:2,在0.5mol/lH_2SO_4溶液中处理2小时后,500℃灼烧1小时。实验中对铅的最大吸附量达到746.6mg/g。     

膨胀石墨对U(Ⅵ)的吸附特性

高温加热可膨胀石墨制得膨胀石墨,用于去除溶液中的U(Ⅵ)。通过静态吸附实验,研究了初始p H、吸附剂投加量、U(Ⅵ)初始浓度、温度以及吸附时间对膨胀石墨吸附U(Ⅵ)效果的影响。实验结果表明,膨胀石墨吸附U(Ⅵ)的最佳p H为6.5,在温度为30℃,投加量为2.0 g/L,U(Ⅵ)初始质量浓度为10 mg/L时,对U(Ⅵ)的去除率达到98.08%,反应在4 h达到平衡。Langmuir等温吸附模型和准二级动力学模型较好地拟合了吸附过程,30℃时饱和吸附量为27.03 mg/g;热力学分析表明,膨胀石墨对U(Ⅵ)的吸附是自发的放热反应。比表面积测试、扫描电镜、X射线能谱与傅里叶红外光谱分析结果表明,膨胀石墨对U(Ⅵ)的吸附以物理吸附为主,表面官能团起辅助作用。解吸实验证明,膨胀石墨是可重复利用的吸附剂。     

改性纤维素吸附剂的合成及其对铜离子的吸附

建立了一种简单方便的纤维素改性的固相合成方法。采用普遍廉价的滤纸作为原料,用固相合成法将预处理后的滤纸纤维经琥珀酸酐进行酯化改性,制备成新型的纤维素吸附剂,通过质量增比、扫描电镜、傅里叶红外光谱仪和X射线衍射仪对制备的吸附剂进行了分析表征,并且探究了离子初始浓度、溶液p H和吸附时间对改性纤维素吸附铜离子的影响。结果表明,在室温下初始离子浓度为1 000 mg/L,离子溶液体积为50 m L,加入0.1 g纤维改性剂,p H为4.0~5.0,吸附平衡时间为50 min时,滤纸纤维改性后最大吸附铜离子质量可达470 mg/g,铜离子去除率达到94%。     

生物质基炭膜的制备及其对Pb(Ⅱ)的吸附

以生物质二层牛皮为原料,在控制热分解条件下制备了生物质基炭膜。利用TG/DTG、XRD、FT-IR、SEM、TEM和低温N_2吸附-脱附等方法对在不同炭化温度下(550~950℃)制备的生物质基炭膜形貌特征、孔隙结构及其表面化学性质进行了表征。考察了炭化温度、反应时间、溶液pH、加入量等因素对炭膜吸附溶液中铅离子的影响。表征结果表明:随着炭化温度的升高,生物质基炭膜碳微晶趋于石墨化发展,总孔容积持续增大,孔隙结构变得更加发达。实验结果表明:随炭化温度升高,生物质基炭膜对铅离子的吸附效果明显变好;在初始铅离子质量浓度为50 mg·L~(-1)、溶液pH为5.5、吸附剂加入量为1.5 g·L~(-1)、吸附时间为6 h的条件下,950℃下所制炭膜对铅离子有较好去除效果,去除率可达99.9%,吸附容量为32.76 mg·g~(-1)。     

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。     

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。     

聚醚酰亚胺功能化磁性纳米微球吸附富集及测定水中痕量镉

利用聚醚酰亚胺修饰纳米磁性微球,制备了一种磁性纳米吸附材料,将其作为固相萃取吸附剂用于富集水体中的痕量镉Cd(Ⅱ)离子,并通过等离子电感耦合发射光谱法测定。利用透射电子显微镜(TEM)、傅里叶变换红外光谱(FIIR)和热重分析仪(TGA)对材料进行了表征,并考察了吸附剂对Cd(Ⅱ)离子的吸附性能,研究了溶液pH值、吸附时间、饱和吸附量、干扰离子、洗脱条件等因素对吸附性能的影响。结果表明,当水样的pH值为5时,振荡吸附15 min达到平衡,饱和吸附容量为5.61 mg/g。吸附在磁性纳米材料上的Cd(Ⅱ)离子可用5 m L 1.0 mol/L盐酸溶液完全洗脱,然后用等离子电感耦合发射光谱法测定此洗脱液中Cd(Ⅱ)离子的含量。将该方法用于环境水样中痕量Cd(Ⅱ)离子的吸附富集和测定,加标回收率在95.3%~97.8%之间。     

氧化石墨烯-氧化锌净化铅离子废水

利用改性Hummers法制备氧化石墨,并成功地将氧化锌负载到氧化石墨上催化降解铅离子。利用SEM、XRD、FTIR等对氧化石墨烯-氧化锌的形貌进行表征,并用以净化铅离子废水。通过实验分析得知废水净化的原因有两方面:光催化效应和吸附理论,然后考察其影响净化过程的因素。结果表明,氧化石墨烯-氧化锌对溶液中铅离子在紫外光下有较强的吸附和催化降解能力,在t=4 h,p H=7条件下,其最大净化量可达到184 mg/g。     

改性松针对水体中铅(II)的吸附

探讨了改性松针(GXLsp)作为吸附剂对水体中铅离子的吸附性能,考察了吸附时间、溶液pH值、吸附剂用量、盐离子浓度、Pb(II)初始浓度及温度对改性松针吸附Pb(II)的影响。利用Langmuir和Freundlich等温线模型对实验数据进行非线性拟合分析,结果表明,Freundlich等温线模型能很好地描述松针对Pb(II)的吸附过程。热力学参数表明吸附是一个自发的吸热过程。改性松针对铅的吸附行为符合拟二级动力学方程,表明吸附过程是以化学吸附为主。在293K时松针对Pb(II)的饱和吸附量为318.3 mg/g,因此,GXLsp可作为一种高效低值生物质吸附剂以去除水体中重金属Pb(II)的污染。     

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.     

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.     

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.     

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.     

Biochemical interaction of six op delayed neurotoxicants with several neurotargets

Abstract

Five organophosphorous insecticides: Leptophos, EPN, Cyano‐fenphos, trichloronate and salithion proved to cause irreversible ataxia not only to chicken but also to mice and sheep. TOCP was included as a reference. Cyanofenphos blocked the catecholamine B‐receptor binding activity with ³H‐norepinephrine at a level similar to that of the specific inhibitor propranolol in the mouse heart preparation. In the lamb heart preparation, the B‐receptor was more sensitive to Leptophos, salithion and TOCP than to propranolol. The six compounds and their oxons were screened for their in‐vitro inhibition to monamine oxidase (MAO), acetyl cholinesterase (AChE) and neurotoxic esterase (NTE) in the brain of either mouse, lamb or chicken. It is believed that their AChE inhibition stands for their acute toxicity, while NTE inhibition is responsible for their paralytic ataxia.