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。     

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。     

13X分子筛对水体中钒离子的吸附

为研究分子筛对水体中重金属的吸附效果,选取了13X分子筛作为实验材料,研究其对钒离子的吸附效果。分别研究了在不同温度、时间、溶液pH值和初始钒浓度的条件下,13X分子筛对钒离子的吸附量,结果表明:酸性条件更利于13X分子筛对钒的吸附,溶液pH≥5时吸附量趋于0;随着反应温度的升高,13X分子筛对钒离子的吸附量逐渐增加;13X分子筛对钒离子的吸附符合Langmuir模型和拟二级动力学模型。13X分子筛对钒离子具有一定的吸附效果,在一定的处理工艺条件下,可作为水体钒污染的修复材料。但针对不同来源废水的特点,需对分子筛进行改性并进一步优化修复工艺条件以实际应用。     

氨基修饰的MCM-41和纯MCM-41的微波制备及去除废水中铜离子的研究

采用微波辅助水热法一步合成了具有大比表面积和孔径的氨基改性的MCM41(NH2-MCM41)和纯MCM-41,并用粉末X射线衍射、红外、氮气-吸脱附对其结构作了表征.将NH2-MCM-41和纯MCM-41用于吸附废水中的铜离子,其静态吸附实验表明:吸附量随温度的增加略有升高;铜离子在2种吸附剂上的吸附均符合Langmu...     

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.     

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.     

Radionuclides in deer and elk from Los Alamos national laboratory and the doses to humans from the ingestion of muscle and bone

Abstract

This paper summarizes radionuclide concentrations (³H, ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu, ²⁴¹Am, and ^totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p<0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% on LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y^‐1 (2.2 μSv y^‐1), deer bone = 3.8 mrem y^‐1 (38 μSv y^‐1), elk muscle = 0.12 mrem y^‐1 (1.2 μSv y^‐1), and elk bone = 1.7 mrem y^‐1 (17 μSv y^‐1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y^‐1 (1000 μSv y^‐1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E‐06, which is far below the Environmental Protection Agency upper level guideline of 1E‐04.     

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.