磷酸微波活化多孔生物质炭对亚甲基蓝的吸附特性简

以甘蔗渣为原料，采用微波辅助H₃PO₄活化法制备富含含氧酸官能团的中孔生物质炭。通过扫描电子显微镜SEM、傅立叶变换红外光谱FT-IR等技术对生物质炭物理化学性质进行表征，并通过静态实验法，探讨炭样对亚甲基蓝的吸附行为及热力学性质。结果表明，H₃PO₄活化制备蔗渣生物质炭的适宜条件为浸渍比1：1，烘干时间10 h，活化功率900 W，活化时间22 min，在此条件下制得的生物质炭得率为39.2%，碘值为817 mg/g，亚甲基蓝值为229 mg/g，为国家一级品标准的1.7倍。红外光谱分析表明，炭样表面以羟基、羰基、羧基等酸性官能团为主。静态吸附实验表明，Freundlich方程与Redlich-Peterson方程能较好地描述等温吸附行为，表现为优惠吸附。热力学研究表明，吸附吉布斯自由能（ΔG⁰）<0，说明吸附反应是自发过程，而吸附标准焓变（ΔH⁰）>70 KJ/mol，表明亚甲基蓝在制备炭样上的吸附是吸热反应，升温有利于吸附，且化学反应在吸附过程中发挥了重要作用。     

磷酸微波活化多孔生物质炭对亚甲基蓝的吸附特性

以甘蔗渣为原料，采用微波辅助H3PO4活化法制备富含含氧酸官能团的中孔生物质炭。通过扫描电子显微镜SEM、傅立叶变换红外光谱FT-IR等技术对生物质炭物理化学性质进行表征，并通过静态实验法，探讨炭样对亚甲基蓝的吸附行为及热力学性质。结果表明，H3PO4活化制备蔗渣生物质炭的适宜条件为浸渍比1：1，烘干时间10h，活化功率900W，活化时间22min，在此条件下制得的生物质炭得率为39．2％，碘值为817mg／g，亚甲基蓝值为229mg／g，为国家一级品标准的1．7倍。红外光谱分析表明，炭样表面以羟基、羰基、羧基等酸性官能团为主。静态吸附实验表明，Freundlich方程与Redlich—Peterson方程能较好地描述等温吸附行为，表现为优惠吸附。热力学研究表明，吸附吉布斯自由能（△G0）〈0，说明吸附反应是自发过程，而吸附标准焓变（△H0）〉70KJ／mol，表明亚甲基蓝在制备炭样上的吸附是吸热反应，升温有利于吸附，且化学反应在吸附过程中发挥了重要作用。     

KOH活化花生壳生物质炭对亚甲基蓝吸附性能研究

以花生壳生物质炭(P-BC)为原料,KOH为活化剂,采用化学活化法制得活化生物质炭(K-BC),通过考察对亚甲基蓝的吸附性能,研究了花生壳生物质炭的最佳活化条件,并利用N2吸附-脱附实验、SEM等对最佳活化条件下的生物质炭进行表征。结果表明,K-BC活化的最佳条件为碱炭比为1.5∶1,活化温度为800℃,活化时间为90 min,此时K-BC的比表面积达到597.93 m2/g,总孔容达到0.76 cm3/g。并考察了亚甲基蓝初始浓度、pH等对K-BC吸附亚甲基蓝的影响,随着初始浓度的增加,吸附平衡时间显著延长,亚甲基蓝去除率显著降低;当pH=6时,K-BC对亚甲基蓝的吸附量最大;K-BC对亚甲基蓝的吸附动力学曲线符合伪二阶动力学模型,吸附平衡时K-BC对亚甲基蓝的吸附能力为80~149.95 mg/g。     

酸改性泥炭对含亚甲基蓝废水的吸附净化作用

采用稀硝酸对泥炭进行改性处理获得酸改性泥炭,并将其用于处理亚甲基蓝废水。考察初始溶液pH、接触时间、酸改性泥炭投加量和亚甲基蓝溶液初始浓度等因素对酸改性泥炭吸附效果影响。结果表明,初始溶液pH、接触时间、酸改性泥炭投加量和亚甲基蓝溶液初始浓度对酸改性泥炭吸附性能都有一定的影响。在最佳的反应条件下(接触时间为60 min,反应温度为35℃,初始溶液pH为7.12,酸改性泥炭投加量为2 g),亚甲基蓝去除率可达90.88%,其吸附较好地符合Freundlich和Langmuir等温方程,拟合相关系数均大于0.9。通过热力学计算发现,ΔG<0、ΔS>0,表明该吸附反应是自发的、吸热反应。且该吸附过程符合准二级动力学方程(R2=0.98)。     

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。     

氯化钙改性凹凸棒处理亚甲基蓝废水的研究

采用氯化钙改性凹凸棒,并对其进行了透射电镜、红外光谱分析。用改性后的凹凸棒泥浆处理亚甲基蓝废水,讨论了动力学和热力学吸附性质。结果表明:(1)利用氯化钙改性凹凸棒,泥浆粘度在21Pa.s条件下对亚甲基蓝废水的吸附动力学和热力学性质进行了研究。在研究范围内,改性凹凸棒泥浆对亚甲基蓝的吸附符合准二级反应动力学方程,并且Langmuir等温方程能更好地描述吸附过程。(2)改性凹凸棒泥浆对亚甲基蓝的平衡吸附量随亚甲基蓝初始浓度的增加而增大,随pH的增大而减小。(3)改性凹凸棒泥浆对亚甲基蓝主要以表面吸附为主。ΔG00、ΔH00表明吸附过程可以自发进行,并且为放热反应。ΔS00意味着随温度的增加,改性凹凸棒泥浆对亚甲基蓝的吸附趋于有序性。     

稻壳基活性炭的制备及其对亚甲基蓝吸附的研究

以稻壳为原料，采用K2CO3活化法和H3P04活化法制备了比表面积为1312m^2／g和682m^2／g的活性炭，通过扫描电子显微镜（SEM）、X-射线衍射仪（XRD）对样品进行了表征，并将孔隙发达的活性炭样品用于对亚甲基蓝的吸附，结果表明，K2CO3活化法制备的活性炭样品具有更多的微孔结构；随着亚甲基蓝溶液初始浓度的增加、活性炭吸附时间的延长，亚甲基蓝的去除率呈现逐渐降低和逐渐增大的变化规律，当pH值为6时，活性炭对亚甲基蓝的吸附效果最佳；稻壳基活性炭对亚甲基蓝的吸附等温线符合Langmuir模型，Qm最高可达476．2mg／g；热力学参数△G^0△H^0和△S^0均为负值，表明稻壳基活性炭对亚甲基蓝的吸附是一个自发的放热反应。     

棉秆基活性炭的制备及其对2,4-二硝基苯酚的吸附

以棉秆为原料，以KOH为活化剂，制备了高比表面棉秆基生物质活性炭。分析了制得的活性炭的元素组成、表面官能团、吸附能力等物化性能，探讨了浸渍比，活化温度，活化时间等工艺参数对制备活性炭得率、表面官能团、碘值、亚甲基蓝值等性能的影响，并通过静态吸附实验比较了不同条件下制备活性炭对2，4-二硝基苯酚的吸附性能，探讨了典型炭样品对2，4-二硝基苯酚的等温吸附特性。结果表明，KOH活化棉秆基生物质活性炭的表面物化性质随浸渍比、活化温度等工艺参数变化而变化，活化适宜条件为浸渍比1：3、活化温度800℃、活化时间90 min，在此条件下制得的炭样的碘值为1 251 mg/g，亚甲基蓝吸附值为478 mg/g，分别是国家一级品标准的1.25倍与3.54倍；对2，4-二硝基苯酚的Langmuir最大吸附量为747 mg/g，与Freundlich模型相比，Langmuir模型能较好地描述2，4-二硝基苯酚在炭样上的吸附行为，表明制备活性炭样品表面吸附位的能量分布较为均一。     

NaOH活化栗苞生物质炭对亚甲基蓝的吸附性能

以栗苞炭化料(C-BC)为原料,以NaOH为活化剂制备栗苞活化生物质炭(Na-BC),研究其对水中亚甲基蓝的吸附行为。选取炭碱比、活化温度和活化时间为影响因素,通过正交试验确定了最佳活化工艺,即炭碱比为1∶4,活化温度为800℃,活化时间为30 min,此时Na-BC的最大吸附量为609.38 mg·g~(-1)。对最优条件下制备的生物质炭进行SEM、BET等表征,比表面积达1 563.78 m~2·g~(-1),总孔容达1.452 cm~3·g~(-1)。吸附实验结果显示,吸附反应能较好用Langmuir模型和准二级动力学方程模型进行模拟,Na-BC对亚甲基蓝的吸附为自发吸热反应。通过热法与碱法再生处理饱和吸附生物质炭,再生后的Na-BC对亚甲基蓝具有较好的吸附能力。     

城镇有机垃圾热解生物炭对水中亚甲基蓝的吸附

热解是一项极具前景的城镇垃圾资源化处理技术,对热解产物的合理利用有助于热解技术的推广应用。以1套垃圾分选、热解工程设备产生的生物炭为原料,研究生物炭对水中亚甲基蓝的吸附效果,分析吸附动力学和吸附等温线;通过红外光谱、比表面积、孔径及微观形貌的表征方法阐释其吸附机理,并进行经济性分析。结果表明,生物炭对亚甲基蓝的去除率随生物炭投加量的增加而增加,随亚甲基蓝溶液初始浓度的增加而降低,在pH为9时达到最高。生物炭对亚甲基蓝的吸附过程符合准二级动力学方程和Langmuir吸附等温线方程,为单分子层吸附,最大吸附量为35.7 mg·g~(-1)。生物炭具有较强的非均质性,其对亚甲基蓝的吸附主要发生在微孔中,且亚甲基蓝与生物炭表面的O—H、NH~(3+)、NH_2、C—O等基团发生了作用,说明亚甲基蓝在生物炭表面的吸附受生物炭孔结构和化学性质2个方面的影响。生物炭的制备过程可产生446～708元·t~(-1)的经济效益,作为废水处理的吸附剂具有较好的应用前景。     

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.