不同原料和炭化温度下制备的生物炭结构及性质

以麦秆、稻杆和松木屑3种生物质为原料,在控制热分解条件下制备生物炭利用TG/DTG、Boehm滴定、FTIR、XRD、TEM和吸附实验等方法对不同原料在350、550和750℃3个炭化温度下制备的生物炭形貌及其表面化学性质进行了表征。结果表明:最大热解速率所对应温度以松木屑为最高,表示热稳定性最好;不同原料在相同炭化温度下所制得的生物炭所含表面含氧官能团种类和总量相近,但pH值和吸附能力差别较大,其中麦秆制得的生物炭pH值最大,松木屑制得的生物炭吸附能力最强;随着炭化温度升高,相同原料制得生物炭表面含氧官能团总量减少,pH值升高,纤维素和半纤维素特征峰消失,芳构化程度增加,吸附性能总体呈先上升后下降的趋势。     

热解条件对茶叶渣生物炭特性及镉污染土壤钝化效果的影响

以泡饮过的废弃茶叶为实验原料,通过不同热解温度(300、400、500和600℃)和热解时间(1 h和2 h)制备生物炭,探讨不同热解条件对茶叶渣生物炭(TSBC)的特性及其对镉(Cd)污染土壤钝化效果的影响。结果表明:热解温度的升高可明显增加TSBC的p H和比表面积,降低生物炭的产率、电导率和表面官能团的数量,使TSBC具有弱碱性、较大比表面积和较强的稳定性,对改良酸性土壤和吸附重金属存在一定潜力;而热解时间对其特性没有明显差异,与对照组相比,添加TSBC明显增加了Cd污染土壤的p H、有机碳(SOC)和可溶性有机碳(DOC)含量,但随着制备温度的升高,Cd污染土壤中SOC和DOC增加幅度逐渐降低。添加TSBC显著降低Cd污染土壤中可交换态镉的比例,当热解温度为500~600℃时降幅最显著,其下降比例与对照相比最高可达25.56%;残渣态镉比对照增加了0.88~1.18倍。因此,TSBC对镉污染土壤有较好的钝化效果,这为重金属污染土壤的修复和生活废弃物的资源化利用提供了理论依据。     

不同热解温度下污泥基生物炭的性质及对Cd~(2+)的吸附特性

以市政污泥为原料,在300、500和700℃无氧气氛下热解制备污泥基生物炭,探讨不同热解温度对污泥基生物炭性质的影响,研究污泥基生物炭对水溶液中重金属Cd~(2+)的吸附特性。结果表明,随着热解温度升高,污泥基生物炭的产率降低,pH值增大,碳、氢、氧和氮含量降低,芳香化程度增强,亲水性和极性降低,稳定性增强;随热解温度的升高,比表面积不断增大,生物炭表面变得粗糙并且出现明显的孔隙,但平均孔径呈现先增大后减小。在700℃下制备的污泥基生物炭对水溶液中Cd~(2+)的吸附效果优于其他制备温度下获得的生物炭,温度为298.15 K时,最大吸附容量为27.47 mg·g~(-1)。污泥基生物炭对Cd~(2+)的吸附动力学符合准二级动力学方程模型,吸附速率主要由化学吸附控制。污泥基生物炭对Cd~(2+)的吸附表现为快速吸附过程,生物炭前10 min的吸附量超过饱和吸附量的80%。Langmuir吸附等温模型能很好的描述污泥基生物炭对Cd~(2+)的吸附行为,吸附容量随热解温度升高而增大。     

热解工艺对污泥制备生物炭物理结构的影响

热解污泥制备生物炭是一种污泥资源化利用的主要处置方式,不同的反应条件对制得生物炭的品质存在显著的差异。以乙酸钾为添加剂,对城市脱水污泥(含水率80%)进行低温热解制备生物炭,考察了乙酸钾添加量、热解温度、热解停留时间及升温速率对生物炭性质的影响。通过N2吸附脱附、SEM、FT-IR等手段对原料污泥及生物炭进行了表征,实验结果表明,乙酸钾具有一定的扩孔作用,生物炭表面粗糙度明显增加,比表面积增大,吸附性能显著提高。当乙酸钾添加量4%,热解温度350℃,热解停留时间120 min,升温速率3℃·min~(-1)时生物炭的亚甲基蓝吸附量和比表面积分别为90.45 mg·g~(-1)、31.402 m2·g~(-1)。     

生物炭对土壤吸附邻苯二甲酸二乙酯的影响

选择花生壳为原材料,采用限氧升温法在450、700℃温度下分别热解2、4、6 h制备6种生物炭,在对其表面性质和元素组成进行分析的基础上,重点考察生物炭对土壤吸附邻苯二甲酸二乙酯(diethyl phthalate,DEP)的影响。结果表明:生物炭的比表面积和总孔体积随着热解温度的升高而增加,热解时间的延长也会提高比表面积和总孔体积,而4 h是较为适宜的热解时间;生物炭中元素组成主要受热解温度的影响,热解时间的作用很小,热解温度的升高使生物炭的芳香性增强,极性降低;添加生物炭能显著提高土壤对DEP的吸附能力;Langmuir模型和Freundlich模型均能较好地拟合添加生物炭土壤对DEP的吸附特征;在不同的平衡浓度条件下,生物炭对土壤吸附DEP的贡献率介于82.07%~99.49%之间,表明生物炭对土壤中DEP的吸附发挥着主导作用。相关分析发现,吸附参数ΔKoc与生物炭的比表面积和总孔体积具有显著相关性,提高比表面积和改善孔隙结构可以增强生物炭对DEP的吸附能力。     

热解温度对污泥碳基材料表面性质及吸附性能的影响

以市政污泥为原料,在300、400、500、600、700和800℃无氧气氛下,热解制备了污泥基生物炭。采用BET、SEM、XPS、FT-IR对不同热解温度下污泥炭进行了表征分析;研究了不同热解温度下污泥炭对污水中有机物的吸附效果和动力学;探究了热解温度对污泥炭微观调控下吸附实际水体中有机物的匹配机质。结果表明,随热解温度的升高,C—H、C—C结合比例降低,C=C、C—O=C比例升高,芳香化程度增加,且比表面积、孔容及表面粗超度均有所增加,1～2 nm微孔比例增多,介孔向微孔发展趋势逐渐明显。800℃热解温度条件下制备的污泥炭对二沉池出水中有机物的吸附效果优于其他温度下制备的污泥炭。吸附温度为298.15 K时,最大吸附容量为282.5 mg·g~(-1),且符合准二级吸附动力学。高温下制备的污泥炭对水体中腐殖酸和富里酸具有较强的吸附效能。这主要是由于表面丰富的含氧官能团、芳香键与腐殖酸和富里酸发生了氢键、化学键缔合作用和π-π共轭作用,同时污泥碳表面发达的孔隙结构和较大的比表面积也提供了更多的活性结合位点,促进了污染物的吸附。     

枇杷籽生物炭制备、表征及其微生物吸附性能研究

炭化温度是影响生物炭结构的重要因素,以废弃的枇杷籽作为生物质原材料,在400～800℃炭化温度内制备生物炭,对其理化性质进行表征,并研究生物炭对微生物菌群的吸附率。结果表明：随着炭化温度的上升,枇杷籽生物炭的产率下降,含氧官能团减少,芳香性结构更完全;在400～600℃炭化温度下,孔道变化明显,表面更粗糙,比表面积和总孔体积增大,中、微孔数量增多;当炭化温度升高到600℃以上,生物炭表面孔状结构发生坍塌,表面变平整,比表面积和总孔体积减小;炭化温度为600℃下制得的枇杷籽生物炭对大肠杆菌发酵液的吸附率为70%左右,对大肠杆菌悬浮液的吸附率为80%以上,枇杷籽生物炭对微生物菌群的吸附效果良好,经过后续优化有作为微生物载体的潜力。枇杷籽具有开发为生物炭并进行进一步应用的潜在价值。     

生物炭固定化解磷菌对Pb2+的吸附特性

以小麦秸秆和活性污泥为原料,在3种温度下热解制备生物炭,使用傅立叶红外光谱(FTIR)和扫描电镜(SEM)对其结构和性能进行表征,探究了以不同生物炭为载体,以解磷菌为固定化菌株制备的固定化微生物对Pb~(2+)的吸附能力,同时研究了吸附时间和热解温度对固定化微生物吸附Pb~(2+)的影响。结果表明:小麦秸秆生物炭较活性污泥生物炭的表面官能团更为丰富,且小麦秸秆生物炭的芳香化程度随热解温度升高而增加;随着热解温度的升高,小麦秸秆生物炭的微孔逐渐发展,孔壁变薄,孔隙结构更为发达;以700℃热解的小麦秸秆生物炭为载体制备的固定化微生物(IBWS700)对Pb~(2+)的吸附量最高,对Pb~(2+)的吸附量可达89.39mg/g;IBWS700对Pb~(2+)的吸附动力学符合准二级动力学方程;IBWS700对Pb~(2+)的吸附可以用Langmuir模型较好地拟合。     

生物黑炭-水泥固化稳定化石油污染土壤

石油在开采、储运、加工和使用过程中出现的漏油以及突发性泄漏事故对土壤造成了严重的污染。笔者考察生物黑炭(BC)和水泥联合固化稳定化修复石油污染土壤的可行性,发现黑炭制备的热解温度是影响生物黑炭吸附性能的直接因素。与400℃热解的生物黑炭(BC400)相比,600℃热解的生物黑炭(BC600)具有更加类似活性表(AC)的性能。AC、BC对石油污染土壤均有较好的稳定化效果,石油烃的浸出浓度随着稳定化剂添加量的增加而降低。水泥添加量是影响石油污染土壤固化稳定化效果的重要因素。当水泥添加量为50%,以2%的AC或BC600作为稳定化剂,均能有效固化稳定化石油污染土壤,处理后的固化产物满足可接受浸出浓度限值的要求,无侧限抗压强度达到卫生填埋和建筑回填土强度标准。生物黑炭可以替代活性炭用于石油污染土壤的固化稳定化。     

响应面法优化磷酸改性秸秆生物炭的制备

以秸秆为原料,磷酸为活化剂制备改性生物炭,利用基于Box-Behnken中心组合的响应面法对生物炭制备条件进行优化。根据响应面分析,热解温度、保留时间和磷酸质量分数对生物炭的吸附性能有显著影响,浸渍比影响不显著;保留时间与浸渍比、磷酸质量分数与浸渍比的交互作用对生物炭吸附能力也有显著影响。根据响应面法获得生物炭制备的最优条件为:热解温度884.32℃、保留时间82.61min、磷酸质量浓度40.74%、浸渍比1.74,此时生物炭最大碘吸附预测值为1 099mg/g,与验证实验实测结果(1 063mg/g)仅相差3.28%,表明响应面回归模型预测结果可靠。响应面法优化后制得的生物炭具有更高比表面积与总孔容,因此具有更高的吸附性能。     

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.     

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.     

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.     

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.     

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.     

Knowledge transfer initiative between molecular biologists and environmental researchers and regulators

A Natural Environment Research Council (NERC) funded Knowledge Transfer (KT) workshop was held in the United Kingdom (UK) to identify the needs and opportunities in the application of molecular biology and ‘omics’ techniques to environmental monitoring and risk assessment. Attendees highlighted a lack of effective communication between end-users and researchers as well as difficulties with data interpretation as reasons behind the slow uptake of molecular biology and omics techniques. A number of promising areas in which new techniques could be implemented at a practical level in the very near future were identified, thereby raising the profile of these recent technologies and providing vital proof of concept work. Molecular taxonomy, bacterial source tracking and pre-screening of chemicals for potential toxicities were all viewed as areas in which omics and molecular techniques could have immediate value, with the aim of reducing cost, increasing efficiency and providing more comprehensive data of improved quality.     

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.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.