核桃壳吸附废水氨氮的动力学和影响因素

对核桃壳吸附废水中氨氮的动力学和影响因素进行了研究。考察了p H、时间、Na+、Cr3+和温度等因素对模拟废水中氨氮的吸附行为的影响。研究结果显示,核桃壳对氨氮的吸附最佳p H为8.5,通过对吸附过程动力学参数的计算,吸附过程符合二级动力学过程,Langmuir模型能较好地反映吸附过程特征。285、300和310 K条件下最大吸附量分别为0.45、0.58和0.6 g/kg。说明核桃壳是具有潜在利用价值的生物质吸附材料。     

NaCl改性沸石对氨氮吸附性能的研究

采用NaCl溶液对天然沸石进行改性,考察了NaCl浓度、温度及沸石用量对改性效果的影响。通过表面特征分析、吸附机制分析、吸附等温试验和吸附动力学试验,进一步比较了天然沸石和改性沸石对氨氮的吸附性能。结果表明,在NaCl溶液为6%(质量分数)、温度为303 K、天然沸石用量为15 g(以100 mL的NaCl溶液计)的优化条件下,改性沸石对氨氮的吸附效果最佳。扫描电子显微镜(SEM)和比表面积(BET)分析可知,沸石经改性后表面变粗糙,平均吸附孔径变小,比表面积变大。2种沸石对氨氮的吸附过程均可用Langmuir、Freundlich吸附等温方程较好地拟合,在温度为303 K时,改性沸石比天然沸石单分子层饱和吸附量增幅为34%以上。颗粒内扩散是沸石吸附氨氮的限制性因素,其吸附动力学较符合准二级反应动力学方程,拟合结果表明改性沸石具有更好的动力学性能,其吸附速率常数略大于天然沸石。     

法库沸石对氨氮的吸附特性和阳离子交互过程

以0.9~2 mm和3.3~4 mm粒径沸石的天然法库沸石作为实验材料,开展了等温吸附实验、动力学实验和阳离子影响实验,探讨了天然沸石对氨氮(NH+4-N)的吸附特性及阳离子交互过程。结果表明,法库沸石对NH+4-N等温吸附线符合Langmuir和Freundlich吸附方程,最大吸附量为10.41 mg/g。吸附动力学过程符合准二级和颗粒内经扩散动力学方程,其吸附NH+4过程为物理吸附和化学吸附过程,并以化学吸附为主。对反应过程中各离子浓度监测发现,沸石中与NH+4发生离子交换的主要是Na+、Ca2+和K+,三者占离子交换总量的99%。共存阳离子在沸石吸附NH+4过程中,Ca2+和Mg2+对吸附过程影响最大,Na+影响最小。     

天然沸石对海水中氨氮的吸附特性

以天然沸石为吸附剂进行吸附海水中氨氮实验研究,考察了沸石粒径、反应液pH值和盐度对吸附效果的影响,对吸附动力学和热力学特性进行了探讨。实验结果表明,天然沸石粒径越小,越有利于其对海水中氨氮的吸附,反应液pH值对氨氮吸附影响较小,但在碱性条件下NH+4能够与海水中的Mg2+、PO3-4反应生成Mg NH4PO4·6H2O沉淀,导致反应液氨氮平衡浓度降低。随着海水盐度梯度增加,天然沸石对氨氮的吸附量呈显著下降趋势。天然沸石对海水中氨氮的吸附是快速吸附、缓慢平衡的过程,吸附过程较好地满足准二级动力学模型。吸附等温线更好地符合Langmuir等温吸附方程,通过热力学计算发现,△G0为负值,而△H0和△S0均为正值,说明天然沸石对海水中氨氮的吸附是吸热易发过程。     

氢氧化钠改性沸石对水中Cu~(2+)的吸附特性研究

利用氢氧化钠对天然沸石进行改性,将天然沸石和改性沸石用于吸附去除水中的Cu~(2+),分析了p H、温度、Cu~(2+)初始浓度、吸附时间对Cu~(2+)吸附性能的影响,并对吸附过程的吸附等温模型及吸附动力学进行研究。结果表明,改性沸石对Cu~(2+)的吸附性能明显优于天然沸石,当沸石投加量为10 g/L,Cu~(2+)为200 mg/L,p H为6.67,温度为50℃时,天然沸石和改性沸石对Cu~(2+)的吸附量分别为2.02、2.69 mg/g。Langmuir和Freundlich吸附等温模型均能较好地描述两种沸石对Cu~(2+)的吸附过程。天然沸石对Cu~(2+)的吸附行为更符合准一级动力学方程,而准二级动力学方程对改性沸石的吸附行为拟合度更好。两种沸石对Cu~(2+)的吸附均为非均相吸附,且内扩散过程不是唯一的速控步骤。     

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。     

壳聚糖包覆介孔微孔分子筛去除水中的氨氮

以壳聚糖包覆介孔-微孔复合分子筛(CS/MCM-41-A)为吸附剂去除水中的氨氮,研究了反应时间、溶液p H、溶液氨氮初始浓度、CS/MCM-41-A投加量、竞争离子对吸附的影响,分析了CS/MCM-41-A的吸附动力学和热力学特征。结果表明,298 K下,当CS/MCM-41-A投加量为5 g/L,溶液氨氮初始浓度50 mg/L,p H为7,吸附时间为40 min时,溶液中氨氮的去除率达到74.35%,CS/MCM-41-A对离子的选择吸附顺序为Mg2+K+Ca2+Na+。CS/MCM-41-A吸附氨氮符合拟二级动力学方程,吸附等温线更好地符合Freundlich方程,CS/MCM-41-A对氨氮的去除有良好的吸附性能。     

沸石联合微生物固定化去除微污染水体中氨氮的研究

将沸石联合经过驯化的活性污泥微生物固定化,通过静态实验.考察了不同粒径沸石及不同组分固定化方法对沸石联合微生物固定化去除氨氮的影响;通过动态实验,考察了沸石联合微生物固定化去除微污染水体中低浓度氨氮的机制.结果表明,活性污泥经过16 d的驯化,氨氮去除率为90%以上;沸石吸附氨氮为快速吸附,粒径<0.5 mm的沸石的吸附容量明显大于其他粒径的沸石;不同组分固定化小球对氨氮的去除效率不同,各组分均有贡献,吸附容量依次为:沸石固定化小球>沸石联合微生物固定化小球>微生物固定化小球;沸石联合微生物固定化去除微污染水体中低浓度氨氮可分为4个阶段,即沸石吸附阶段、吸附饱和及微生物适应阶段、硝化作用明显加强和沸石部分再生阶段、微生物作用良好和沸石进一步再生阶段,最终沸石吸附与生物再生处于良好的动态平衡中,氨氮去除率达到60%左右.     

改性沸石对水中微量汞的吸附性能

为了更好的去除水体中微量汞,研究了采用二氧化锰和壳聚糖对天然斜发沸石进行改性,着重考察了pH、温度、离子强度、Hg~(2+)初始浓度和时间对改性前后沸石吸附Hg~(2+)的影响,并研究了其吸附机理。结果表明,改性沸石受pH、温度和离子强度影响较小,在pH、温度、离子强度和初始浓度为6、25℃、0.05 mol·L~(-1)和50μg·L~(-1)时,二氧化锰+壳聚糖改性沸石(ZCM)对Hg~(2+)的去除率高达99%,符合国家饮用水标准,并且二氧化锰+壳聚糖改性沸石(ZCM)具有更好的解吸再生性。3种沸石均较好的符合Langmuir等温吸附模型和假二级动力学模型,其中改性沸石对汞的吸附主要为离子交换和表面官能团的络合作用,二氧化锰+壳聚糖改性沸石(ZCM)和壳聚糖改性沸石(ZC)饱和吸附量由1.43 mg·g~(-1)提高到5和3.3 mg·g~(-1),吸附平衡时间由10 h减少至1和4 h,为治理汞微污染地表水提供一定的理论支持。     

香蕉皮改性吸附剂对氨氮吸附特性

利用Na OH对香蕉皮进行改性,制备改性吸附剂,研究吸附时间、温度、p H等3个因素对其氨氮吸附性能的影响。实验结果表明,Na OH改性提高了该吸附剂对氨氮的吸附能力,在较广温度范围内,该改性吸附剂保持着较高的吸附效率,在吸附氨氮过程中氨氮去除率随着p H值增大呈上升趋势,水质呈中性和碱性时,改性吸附剂表现出较高的吸附效率。相同氨氮初始浓度条件下,在吸附剂投加量增加,氨氮去除率升高,在氨氮浓度为6 mg/L时,可达到96.78%。在20℃温度条件下,饱和吸附量理论值达到9.478 7 mg/g。改性香蕉皮吸附剂对氨氮的吸附符合伪二阶吸附动力模型,氨氮饱和吸附数据符合Langmuir和Freundlich等温吸附模型。     

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.     

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.     

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.     

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)