生物炭质吸附剂对硝基苯的吸附

以花生壳为生物炭质(P-BC)原料,Zn Cl2为活化剂,采用化学活化法制备生物炭质吸附剂(Z-BC),并以其吸附水中的硝基苯,考察了p H值、吸附剂投加量和吸附时间等因素对Z-BC吸附硝基苯过程的影响。分别采用吸附动力学模型和吸附等温模型对吸附动力学和等温线进行了系统分析。结果表明:p H值对吸附的影响不大,吸附剂适宜投加量为2 g·L-1,吸附平衡时间为120 min;Z-BC对硝基苯的吸附动力学过程用准一级动力学模型能很好地描述,其计算平衡吸附量与实验值相符;颗粒内扩散模型表明,吸附过程受液膜扩散与颗粒内扩散联合控制,并以颗粒内扩散为主要速率控制步骤;Langmuir吸附等温模型能更好地描述硝基苯在Z-BC上的吸附平衡;吸附热力学方程计算得到吸附焓变(ΔH)0、吸附自由能变(ΔG)0和吸附熵变(ΔS)0,表明Z-BC对水中硝基苯的吸附为放热和熵值增加的自发过程。     

改性活性氧化镁的除氟效能及机制

通过静态吸附实验,研究了改性活性氧化镁的除氟效能,通过比表面积、孔容、孔径和表面元素及化合物含量分析,初步探讨了改性机制。结果表明,改性后的活性氧化镁吸附行为更符合Langmuir等温线的拟合,即吸附为单分子层吸附,饱吸附容量为88.50 mg/g,吸附平衡常数为0.3681 L/mg,吸附速率可用拟二级动力学方程描述;改性活性氧化镁的吸附除氟效果基本不受溶液中共存的Cl-、NO-3、SO2-4和HCO-3的影响,但HPO2-4对改性活性氧化镁等除氟效果影响较大,尤其当其浓度大于100 mg/L时,显著降低改性活性氧化镁的吸附容量。温度升高改性活性氧化镁的吸附容量增大,在实际饮用水处理中p H基本不会影响除氟效果。改性活性氧化镁吸附除氟的最佳温度为30℃,最适p H为6~9.5。比表面积和孔容的增大可能是改性活性氧化镁吸附容量提高的主要原因之一。     

海带对镉的吸附动力学与热力学研究

采用批量平衡法研究了海带对镉的吸附的动力学与热力学,并采用Lagrange假一级动力学方程、假二级动力学方程、Langmuir等温线方程、Freundlich等温线方程以及Dubimim-Radushkevich等温线方程对实验数据进行了拟合.结果表明,在4种温度下海带对镉的吸附率均随吸附反应时间增加而增大,在60 min时达到最大,此后基本保持不变,随着温度由20℃升高至50℃,其最大吸附率呈下降趋势,由90.2%降至77.5%;海带对镉的吸附动力学符合Lagrange假二级动力学方程;海带对镉的吸附热力学符合Langmuir等温线方程和Dubimim-Radushkevich等温线方程,表明吸附主要发生在海带表面的活性区位,属于单分子层吸附,其吸附平均活化自由能E为11.4 kJ/mol,表明该吸附过程为化学吸附,在4种温度下吉布斯自由能变化量△AG°均为负值,吸附焓变△H°也为负值,表明海带对镉的吸附为放热反应,能自发进行.     

葛根去除水溶液中亚甲基蓝的生物吸附机理和特性

对农副产品葛根吸附水溶液中亚甲基蓝的特性和机理进行了一系列的研究。考察了不同条件对吸附效果的影响;采用2种等温线模型和3种动力学模型对吸附机理和动力学特性进行了模拟分析,并计算了相关的热力学函数。结果发现,溶液pH值等实验条件对吸附效果有较大的影响;Langmuir方程能很好地描述其吸附等温线,吸附是一个符合二级动力学过程的物理吸附;热力学函数计算结果显示,此吸附是一个自发的放热过程。在3种不同温度下,由Langmuir方程计算的最大吸附量为98.23、91.04和87.28 mg/g,表明葛根是一种良好的,具有一定发展潜力的染料吸附剂。     

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。     

改性丝瓜络纤维对水体日落黄的吸附特性

采用化学改性的方法将丝瓜络制备为阴离子吸附剂,并将其用于水体日落黄(SY)染料的吸附,分别考察了吸附剂的用量、日落黄染料的初始浓度(C0)、p H值、温度(K)、时间(T)5个因素对吸附效果的影响。通过模拟吸附等温曲线、吸附动力学以及热力学方程并通过比表面积(BET)和红外光谱(FTIR)分析改性丝瓜络吸附染料前后和丝瓜络改性前后的变化情况以此探究其吸附机理。结果表明,p H对吸附效果影响不明显;最大吸附量随温度升高而增大,在298 K温度时最大吸附量达到137 mg/g,是未改性丝瓜络的9.78倍。Langmuir方程拟合吸附过程描述最好,吸附类别为化学吸附。吸附过程符合伪二级动力学,是一个自发和吸热的过程。改性丝瓜络可以有效去除水体中的日落黄染料。     

铝锰复合氧化物负载沸石对氨氮和磷的同步吸附特性

采用氧化还原-共沉淀法将铝锰复合氧化物负载到沸石表面制成颗粒型吸附材料,探究了该吸附剂同步去除氨氮(NH_4~+-N)和磷(P)的吸附动力学和吸附等温线特征,并讨论了吸附剂投加量和溶液p H值对吸附效果的影响。结果表明:铝锰复合氧化物改性沸石(aluminum-manganese bimetal oxide coated zeolite,AMOCZ)对NH_4~+-N及P的吸附动力学曲线均符合拟二阶吸附动力学方程的特征;NH_4~+-N的吸附等温线数据可用Freundlich方程进行较好地拟合,而Langmuir方程更适用于描述P的吸附等温线特征。NH_4~+-N和P共存时,两者在AMOCZ表面的饱和吸附量分别从单独体系下的1.24和6.43mg·g~(-1)变为8.17和6.51 mg·g~(-1)。这说明P的存在可显著促进AMOCZ对NH_4~+-N的吸附,而NH_4~+-N的存在对P的吸附无显著影响。此外,复合污染条件下,P的存在在p H=3~10范围内均能促进AMOCZ对NH_4~+-N的吸附;NH_4~+-N在p H为3~8时对P的吸附起促进作用,p H大于8时则会抑制AMOCZ对P的吸附。     

MgAl型层状化合物对六价铬的吸附性能

尿素-水热法制备层状双金属氢氧化物Mg Al-LDH,系统考察了焙烧温度、p H值、初始Cr(VI)浓度、吸附时间和吸附温度对样品的吸附性能的影响。并对其吸附热力学、动力学和吸附机理进行研究。采用傅里叶红外光谱(FT-IR)对吸附Cr(VI)前后的Mg Al-LDH进行表征。Mg Al-LDH的最佳吸附条件为p H=2.5,吸附过程符合Langmuir等温模型,最大吸附容量为105.15 mg·g-1,其对Cr(VI)的吸附为放热过程,并遵守准二级动力学模型,化学吸附为主导。Mg Al-LDH对Cr(VI)的吸附主要在酸性条件下进行,吸附机理主要为静电作用和离子交换:在酸性条件下,Mg Al-LDH表面带正电荷,并通过静电作用吸附Cr(VI)阴离子,同时Mg Al-LDH的层间CO2-3和NO-3与溶液中的Cr(VI)阴离子进行离子交换。     

改性伊利石对活性艳蓝K-GR的吸附

采用十六烷基三甲基溴化铵(CTMAB)对伊利石进行改性,利用红外光谱、扫描电镜、X射线衍射及热重分析对吸附剂进行结构表征。研究了改性吸附剂对活性艳蓝K-GR的吸附性能。结果表明,最佳吸附条件为:p H 3,吸附剂用量0.3 g,CTMAB/伊利石质量比0.125。吸附过程符合准二级动力学方程,吸附等温线可以很好地用Langmuir模型描述。在热力学研究中,ΔG00,ΔH00,ΔS00,说明吸附过程是自发、吸热和熵增加的过程。     

好氧污泥对活性艳兰KN-G的吸附特性研究

实验研究了活性艳兰KN-G在好氧污泥上的吸附等温线和吸附动力学,考察了pH对好氧污泥吸附活性艳兰KN-G的影响。结果表明,好氧污泥对活性艳兰KN-G的吸附Freund lich和Langmu ir方程准确性较高,但是从模型的准确性和稳定性两方面考虑,Freund lich方程更适合描述好氧污泥吸附活性艳兰KN-G。应用伪一级、伪二级反应动力学和颗粒内扩散方程模型对实验数据进行验证,表明好氧污泥吸附活性艳兰KN-G更符合伪二级反应动力学模型。pH值对活性艳兰KN-G的吸附影响很大,pH值与吸附量呈负相关。     

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.