pH和温度对2,2’,4,4’-四溴联苯醚在土壤中吸附和解吸行为的影响研究

研究了pH和温度对2,2’,4,4’-四溴联苯醚(BDE-47)在土壤中的吸附和解吸行为的影响。结果表明,pH和温度都可以影响BDE-47在受试土壤中的吸附和解吸行为。pH升高或降低均会使土壤对BDE-47的吸附能力提高,且在碱性环境中提高的程度更大;酸性或碱性条件下BDE-47在土壤中的解吸滞后性显著增强。温度降低后,土壤对BDE-47的吸附能力提高,5℃时的单点分配系数(Kd,表征土壤对BDE-47的吸附能力)是25℃时的1.03~1.67倍;温度由25℃降低到5℃后,BDE-47在土壤中的解吸滞后性增强。     

吸油草对海水中柴油的吸附及其影响因素研究

以柴油污染的海水为对象,研究了吸油草对海水中柴油的吸附、解吸规律,考察了海水盐度、温度和pH三因素对吸附的影响,并根据吸附等温线和吸附热力学的分析探讨了其吸附机理.研究结果表明,吸油草对海水中柴油的吸附及解吸均符合二级反应模式,达到吸附平衡仅需要10～20 min,而达到解吸平衡需要2～3 h,解吸平衡时间是吸附平衡时...     

十溴联苯醚共存条件下水中Zn(Ⅱ)的生物吸附

研究了十溴联苯醚(BDE-209)共存条件下嗜麦芽窄食单胞菌对水中Zn2+的吸附特性,并通过对菌体进行失活处理、红外光谱和X-光电子能谱分析,探讨了吸附机理。结果表明,Zn2+的吸附符合Freundlich吸附模式;嗜麦芽窄食单胞菌对Zn2+吸附作用明显,2.5 g/L菌体在2 h时,对初始浓度为2.0 mg/L Zn2+的去除率达92%。BDE-209对菌体吸附Zn2+有一定的抑制作用。各因素对嗜麦芽窄食单胞菌吸附Zn2+的影响程度由大到小依次为:投菌量>pH>BDE-209浓度。菌体对Zn2+的吸附除表面吸附外,还存在跨细胞壁细胞膜的主动运输和积累等作用。菌体中的酰胺基与羟基均参与了Zn2+吸附,而且菌体表面Ca2+与Zn2+发生了离子交换,吸附后Zn2+的价态不变。     

好氧污泥对17β-雌二醇吸附性能的研究

研究了好氧活性污泥与失活好氧污泥对17β-雌二醇的吸附性能.17β-雌二醇初始质量浓度为500～10 000 ng/L,采用失活好氧污泥进行吸附,考察了吸附平衡时间、pH与温度对吸附的影响.研究结果表明,失活好氧污泥对17β-雌二醇的吸附在30 min内达到平衡;pH在6～9时对吸附没有影响,pH为9以上时,随着pH升高吸附量减少;温度升高吸附能力降低;其吸附符合Freundlich吸附,且呈线性吸附.在10、20、30 ℃时,Freundlich吸附常数KF分别为91.81、80.65、61.49 L/kg,分配系数Kd分别为561.80、 435.60、306.70 L/kg.另外研究了20 ℃时好氧活性污泥的KF与Kd,它们分别为91.72、514.90 L/kg,与同温下失活好氧污泥的KF和Kd差别均小于20%.     

EDTA络合铜在无机柱撑膨润土上的吸附研究

利用天然膨润土、羟基铁和羟基铁铝柱撑膨润土,进行吸附EDTA络合铜离子(EDTA-Cu)的实验.研究了溶液中EDTA与Cu2 摩尔比、pH值、吸附时间对吸附过程的影响和吸附等温线的变化规律.结果表明,达到吸附平衡的时间为1 h;pH值对天然膨润土的吸附影响甚小,柱撑膨润土的最佳吸附pH在6～8之间;膨润土的分配系数随着溶液中EDTA与Cu2 的摩尔比的增加而减少,当摩尔比＞2后,分配系数趋于稳定;柱撑膨润土羟基吸附位的活性是决定吸附性能的关键因素;吸附过程符合Langmuir和Freundlich等温吸附模型,吸附容量的大小和吸附作用强弱的顺序为:羟基铁铝膨润土＞羟基铁膨润土＞天然膨润土.     

花生壳吸附Cu^2＋的动力学和热力学研究

采用平衡吸附法,研究了pH、时间及温度对花生壳吸附水溶液中Cu2 的影响.结果表明,pH显著影响花生壳对Cu2 的吸附,pH为3.00～5.00时,吸附效果最好;初始吸附过程非常快,30 min时即达到最大吸附量的97%左右,其动力学行为更好地符合Lagergren准二级反应动力学模型,随着温度增加,初始吸附速率和平衡吸附量增加.吸附过程的表观活化能(Ea)为17.02 kJ/mol,表明花生壳吸附水溶液中Cu2 是吸热的化学过程.吸附活化熵为负值,表明Cu2 从水溶液本体中溶解的自由状态到被吸附的状态是有序增加的过程.吸附活化焓呈正值,意味着升温有利于吸附.花生壳对Cu2 的吸附较好地符合Langmuir吸附等温线.吸附过程中吉布斯自由能变化呈负值,说明吸附过程为自发的过程.     

活性炭吸附处理电镀废水中的EDTA

采用颗粒活性炭对模拟废水中EDTA进行批式吸附实验,在实验中考察了恒温振荡器的振荡速度、温度、pH值等因素对吸附的影响,同时探讨了吸附等温线模型和吸附动力学模型。实验结果表明,在25％时活性炭对EDTA的吸附平衡时间为40h。在pH值为5．0、温度为25℃、振荡器振荡速度为200r／min、活性炭粒径为1～2mm、活性炭加入量为10g／L的情况下,EDTA的浓度在48h内由368．8mg／L降低至76．34mg／L,对应的COD值从305．9mg／L降低为67．21mg／L,去除率达到了79．3％。活性炭对EDTA的吸附符合Langmuir吸附等温线模型,其吸附行为可以用准二级吸附动力学模型来描述。     

天然和巯基改性沸石吸附水溶液中重金属Hg2+的特征研究

为了提高沸石对汞的吸附性,利用半胱胺盐酸盐对天然斜发沸石进行改性,制得巯基改性沸石。研究了吸附剂用量、pH值、温度、Hg²⁺浓度和吸附时间对沸石和巯基改性沸石吸附Hg²⁺的影响,并进一步研究了吸附机理。结果表明,巯基改性沸石吸附Hg²⁺受pH值、温度的影响较小,吸附机制主要是沸石表面的硫与Hg²⁺的化学反应。而天然沸石对Hg²⁺的吸附主要是离子交换作用,受温度、pH值等的影响较大,随温度的升高吸附量下降。整个吸附过程以较快的速度进行。天然沸石在吸附时间为1 h、巯基改性沸石在0.5 h时基本达到吸附平衡。吸附条件试验和Langmuir等温吸附模型都表明,巯基改性沸石对Hg²⁺的吸附能力得到了很大的提高,吸附容量由8.06 mg/g 提高到19.88 mg/g,提高了146.65%。     

磺胺类抗生素的活性炭吸附过程研究

采用煤质活性炭对3种磺胺类抗生素(浓度在1～2 mg/L之间)的吸附处理过程做了深入研究。结果表明,3种磺胺类抗生素在2～3 h之内可以达到吸附平衡;准一级动力学对其吸附动力学的模拟结果良好,且SMZ、SM1和SM2的一级吸附动力学常数k1分别为0.029、0.024和0.017 min-1,3种抗生素的平衡吸附容量分别为3.75、3.23和2.95 mg/g,SMZ的平衡吸附容量最大,最先达到吸附平衡,且平衡浓度也最低。3种磺胺类抗生素的吸附过程中,吸附前期的阻力主要是内扩散,而吸附后期较低浓度的抗生素吸附过程的阻力主要来自于膜扩散;采用Freundlich等温线方程描述3种磺胺类抗生素的吸附过程更为合理。     

针铁矿对Pb~(2+)的吸附特征及影响因素研究

通过恒温振荡平衡法研究了Pb~(2+)在针铁矿上的等温吸附和吸附动力学特征,探讨了吸附的影响因素.结果表明:(1)随Pb~(2+)平衡浓度和pH的增大,针铁矿对Pb~(2+)的吸附量逐渐增大.(2)针铁矿对Pb~(2+)的等温吸附可用Freundlich和Langmuir方程较好地拟合.(3)在相同温度和pH下,随离子强度的提高,针铁矿对Pb~(2+)的吸附量增大.(4)在相同离子强度和pH下,针铁矿对Pb~(2+)的吸附量总体随温度升高而增大.针铁矿对Pb~(2+)的吸附是自发进行的吸热反应.(5)针铁矿吸附Pb~(2+)的过程可分为初始的快吸附和随后的慢吸附2个阶段.pH影响吸附反应快慢,随pH增大吸附速率增大;随着pH的增大,达到平衡吸附的时间缩短.吸附动力学方程用Elovich方程拟合最佳.     

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)