热解吸对土壤中POPs农药的去除及土壤理化性质的影响

为探索土壤热解吸修复技术对POPs污染土壤的修复效果及修复后土壤可耕作性,选择北京某农药厂旧址的POPs农药污染土壤,研究了不同温度下热解吸处理后土壤中滴滴涕(DDTs)和六六六(HCHs)各组分的去除率以及土壤理化性质的变化。结果表明,热解吸修复技术可有效去除土壤中POPs农药,其中,p,p’-DDE与α-HCH组分去除率受热解吸温度的影响比其他组分更为明显。∑HCH与∑DDT在310℃、340℃时分别达到97%、99%的去除率,且此时土壤中的污染物含量低于我国《展览会用地土壤环境质量评价标准》,此后去除率受温度的影响不明显。热解吸温度对修复后土壤的理化性质有一定的影响,不同温度影响的程度各不相同,其中,有机质含量与全氮含量分别由0.78%、0.0352%降至0.14%、0.0107%;pH波动幅度较小,由7.80变至8.25;阳离子交换量变化存在波动,但呈整体下降趋势,由7.87 mg/kg降至5.00mg/kg;土壤中速效磷显著增加,由7.59 mg/kg升至21.8 mg/kg。而在最优温度条件下,土壤理化性质受热解吸温度的影响较小。由此可以说明,热解吸技术可以用于POPs污染土壤的修复,选择适当的热解吸温度对土壤的可耕作性影响有限,因而是一种潜在的绿色修复技术。     

热解吸毛细管气相色谱法检测室内空气中苯和总挥发性有机物影响因素分析

根据《室内空气质量标准》(GB/T 18883—2002),采用热解吸毛细管气相色谱法检测室内空气中苯和总挥发性有机物(TVOC)。从采样管活化、采样体积、解吸率、有效进样量、载气种类和纯度等方面分析探讨了对该方法的影响,并提出相应的建议。     

响应面法优化甘蔗渣-污泥复合活性炭的制备工艺

为了提高污泥活性炭的吸附性能以提升其实际应用价值,提出在污泥中掺杂甘蔗渣制备复合活性炭,并采用Plackett-Burman联用响应面法对影响复合活性炭碘值的条件进行筛选优化。通过Plackett-Burman实验筛选出热解温度、热解时间和甘蔗渣与污泥干重比为主要影响因素,对这3个因素进行Box-Behnken实验,经响应面优化得到影响碘值的二次响应曲面模型,模型显示热解温度与热解时间、热解温度与干重比的交互作用显著,并确定了最佳制备条件:热解温度550℃、热解时间30 min和干重比50%,此时复合活性炭碘值为814 mg/g,优于未优化条件下制备的复合活性炭。通过比表面积、孔结构和碘值的测定以及元素和扫描电镜分析得出,甘蔗渣的掺杂提高了复合活性炭的比表面积、微孔体积、碘值及含碳量。研究结果表明,甘蔗渣掺杂和制备条件优化是提高污泥活性炭吸附性能的有效手段。     

热解吸对污染土壤中不同形态汞的去除作用

选取贵州省万山矿区的汞污染土壤样品进行不同形态汞的热解吸去除行为研究。研究了热解吸过程中∑Hg的去除效果及动力学,以及温度和时间对污染土壤中不同形态汞的去除作用。结果表明,热解吸修复技术可有效去除土壤中的汞,土壤中∑Hg的热解吸过程符合二级动力学方程。固定热解吸时间在10 min时,随着热解吸温度的升高,土壤中水溶态汞、盐酸溶态汞和碱溶态汞含量呈现先下降后上升再下降的趋势,王水溶汞和盐酸溶态汞始终呈现下降趋势,说明不同形态的汞之间发生了转化。热解吸温度为250℃时,随着热解吸时间的增加,环境风险大的水溶态汞、盐酸溶态汞、碱溶态汞和硝酸溶态汞的去除率大幅增加,土壤的有机质损失较少,说明在低温下,延长热解吸时间,对生物毒性强的形态汞有良好的修复效果,且此温度下处理后的土壤更容易恢复农田耕作。     

低浓度有机硫恶臭物质的采样分析方法

有机硫是环境空气中重要的恶臭物质,它的挥发性、不稳定性等理化性质使得低浓度有机硫的采样检测存在很大难度,其检测方法还不完善。为此,建立一种低温捕集浓缩-热解吸-气相色谱检测技术,用于低浓度有机硫恶臭物质的检测分析。以甲硫醚和乙硫醇为代表,研究采样管的吸附-热解吸过程,优化采样条件。结果表明:在液氮为制冷剂形成的低温环境下,有机硫恶臭物质可有效富集在活性炭吸附采样管内,低温浓缩饱和吸附容量为0.1~0.3 g·g~(-1);在20 m L·min~(-1)氮气吹扫下最佳热解吸温度230℃,解吸时间200 min。采样浓度为50μg·L~(-1)~16 mg·L~(-1)时,分析方法对甲硫醚和乙硫醇的平均相对标准偏差小于5%,精密度检测限达到μg·L~(-1)级。     

室内空气总挥发性有机物净化实验装置设计及应用

为了探究进气流量和相对湿度对活性炭吸附法和光催化转化法动态净化室内空气中总挥发性有机物(TVOC)的影响,设计了一套包含活性炭吸附器和光催化反应器的多功能空气动态净化实验装置,并利用该装置进行了室内空气净化实验。通过设置不同进气条件(进气流量和相对湿度)对室内空气进行净化实验,采用气相色谱仪对样品TVOC浓度进行检测,并与未经净化处理的空气样品进行对比,计算TVOC去除率。结果表明:该实验装置能够实现连续进气且能对进气流量和相对湿度进行精准调节;随着进气流量增大,活性炭和光催化对TVOC去除率减小;随着进气相对湿度增大,活性炭对TVOC去除率减小,光催化对TVOC的去除率呈现先增大后减小的趋势。以上实验结果为气候舱空气净化系统、家用空气净化器及室内新风过滤系统等动态空气净化系统的设计提供了参考。     

热解温度和时间对污泥生物碳理化性质的影响

污泥热解制备生物碳是一种环境友好的污泥处理处置途径。重点考察了热解温度及时间等因素对生物碳品质的影响。污泥取自厦门某城市污水处理厂脱水污泥（初始含水率为80%）,热解实验结果表明,随着热解温度的升高（从300～700℃）,热解时间的增加（2～4 h）,生物碳产率均下降;低温热解时（300℃）,生物碳偏酸性,而高温热解时（700℃）,生物碳偏碱性;生物碳N含量随着热解温度的升高、热解时间的增加而降低,而P、K及微量元素随着热解温度的升高,热解时间的增加而增加。DTPA浸提实验结果表明,高温热解能降低污泥生物碳中微量元素的有效性。     

餐厨垃圾中典型组分的裂解液化特征研究

利用实验室规模的实验装置管式加热炉进行餐厨垃圾热解实验,实验分析了反应温度对餐厨垃圾热解产物分布的影响,米饭、白菜、猪肉、塑料和纸5种原料在最佳温度下可实现热解油质量产率的最大化,分别为45.02%、24.55%、61.19%、73.77%和24.86%。其中,米饭和白菜热解油含水率较高,可达到30%~40%,将含水率降到15%后,测定热值分别为25.51 MJ/kg和17.75 MJ/kg。塑料和纸混合热解时,塑料热解过程的放热效应可缩小纸的热解温度区间,增加热解油产量。红外光谱分析厨余热解油包含多种含氧有机物。通过气质联用仪(GC-MS)分析塑料热解油和塑料与纸混合热解油在180℃以下蒸馏出的液相产物,主要组分为烷烃和烯烃,从成分和热值分析,与汽油、柴油相近。     

废弃印刷线路板最佳分离参数的实验研究

为研究废弃印刷线路板的热解特性,确定金属和非金属分离的热解最佳参数,用差热-热重联用分析仪对FR-4型印刷线路板进行了热失重分析,并对影响废弃印刷线路板中金属和非金属分离效果的升温速率、颗粒尺寸、热解终温和保温时间等主要因素进行了实验研究。结果表明,FR-4型线路板在320~360℃区间热失重速率达到最大值;升温速率越高,热解起始温度、终止温度和失重峰温也越高,显著失重过程持续的时间越长;当热解终温相同时,升温速率对FR-4型线路板的热失重率影响很小。综合考虑FR-4型废弃印刷线路板中金属和非金属的分离效果、热解装置的设计、热解过程的能耗以及运行过程的控制等因素,最佳热解参数建议设定为升温速率为10℃/min,热解终温为500℃,保温时间取30 min为宜。     

污泥连续式微波热解制备生物气

采用升温迅速的微波能作为热源,利用自主设计微波设备对含水率为82%(m/m)的湿污泥进行高温热解实验。采用单因素实验法,探究热解终温、停留时间、活性炭添加量对污泥热解生物气组分和含量的影响规律,确定连续式运行的最佳工况条件:热解终温900℃,停留时间50 min,活性炭添加比例为30%,热解功率1 600 W;在此基础上进行连续12h微波高温热解实验,共热解污泥56 kg,产生生物气32.26 kg,热解油10.98 kg,固体残渣12.66 kg,产气转化率高达57.8%,生物气组分H_2+CO含量高达67%,热解产物具有良好的工业利用价值。污泥热解生物气中H2S浓度超标10倍以上,而NH_3浓度未超标,硫化氢的去除技术研究值得关注。     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Phytoextraction of lead-contaminated soil using vetivergrass (<Emphasis Type="Italic">Vetiveria zizanioides</Emphasis> L.), cogongrass (<Emphasis Type="Italic">Imperata cylindrica</Emphasis> L.) and carabaograss (<Emphasis Type="Italic">Paspalum conjugatum</Emphasis> L.)

Background, Aims and Scope The global problem concerning contamination of the environment as a consequence of human activities is increasing. Most of the environmental contaminants are chemical by-products and heavy metals such as lead (Pb). Lead released into the environment makes its way into the air, soil and water. Lead contributes to a variety of health effects such as decline in mental, cognitive and physical health of the individual. An alternative way of reducing Pb concentration from the soil is through phytoremediation. Phytoremediation is an alternative method that uses plants to clean up a contaminated area. The objectives of this study were: (1) to determine the survival rate and vegetative characteristics of three grass species such as vetivergrass, cogongrass and carabaograss grown in soils with different Pb levels; and (2) to determine and compare the ability of the three grass species as potential phytoremediators in terms of Pb accumulation by plants. Methods The three test plants: vetivergrass (Vetiveria zizanioides L.); cogongrass (Imperata cylindrica L.); and carabaograss (Paspalum conjugatum L.) were grown in individual plastic bags containing soils with 75 mg kg⁻¹ (37.5 kg ha⁻¹) and 150 mg kg⁻¹ (75 kg ha⁻¹) of Pb, respectively. The Pb contents of the test plants and the soil were analyzed before and after experimental treatments using an atomic absorption spectrophotometer. This study was laid out following a 3 × 2 factorial experiment in a completely randomized design. Results On the vegetative characteristics of the test plants, vetivergrass registered the highest whole plant dry matter weight (33.85–39.39 Mg ha⁻¹). Carabaograss had the lowest herbage mass production of 4.12 Mg ha⁻¹ and 5.72 Mg ha⁻¹ from soils added with 75 and 150 mg Pb kg⁻¹, respectively. Vetivergrass also had the highest percent plant survival which meant it best tolerated the Pb contamination in soils. Vetivergrass registered the highest rate of Pb absorption (10.16 ± 2.81 mg kg⁻¹). This was followed by cogongrass (2.34 ± 0.52 mg kg⁻¹) and carabaograss with a mean Pb level of 0.49 ± 0.56 mg kg⁻¹. Levels of Pb among the three grasses (shoots + roots) did not vary significantly with the amount of Pb added (75 and 150 mg kg⁻¹) to the soil. Discussion Vetivergrass yielded the highest biomass; it also has the greatest amount of Pb absorbed (roots + shoots). This can be attributed to the highly extensive root system of vetivergrass with the presence of an enormous amount of root hairs. Extensive root system denotes more contact to nutrients in soils, therefore more likelihood of nutrient absorption and Pb uptake. The efficiency of plants as phytoremediators could be correlated with the plants’ total biomass. This implies that the higher the biomass, the greater the Pb uptake. Plants characteristically exhibit remarkable capacity to absorb what they need and exclude what they do not need. Some plants utilize exclusion mechanisms, where there is a reduced uptake by the roots or a restricted transport of the metals from root to shoots. Combination of high metal accumulation and high biomass production results in the most metal removal from the soil. Conclusions The present study indicated that vetivergrass possessed many beneficial characteristics to uptake Pb from contaminated soil. It was the most tolerant and could grow in soil contaminated with high Pb concentration. Cogongrass and carabaograss are also potential phytoremediators since they can absorb small amount of Pb in soils, although cogongrass is more tolerant to Pb-contaminated soil compared with carabaograss. The important implication of our findings is that vetivergrass can be used for phytoextraction on sites contaminated with high levels of heavy metals; particularly Pb. Recommendations and Perspectives High levels of Pb in localized areas are still a concern especially in urban areas with high levels of traffic, near Pb smelters, battery plants, or industrial facilities that burn fuel ending up in water and soils. The grasses used in the study, and particularly vetivergrass, can be used to phytoremediate urban soil with various contaminations by planting these grasses in lawns and public parks. ESS-Submission Editor: Dr. Willie Peijnenburg (wjgm.peijnenburg@rivm.nl)