污泥基活性炭吸附Cu2+的应用研究

以城市污水处理厂剩余污泥为原料,以ZnCl₂为活化剂制取污泥基活性炭。以此污泥基活性炭为吸附剂,对含Cu²⁺的废水进行了吸附实验研究。考察了溶液pH值、Cu²⁺的起始浓度对Cu²⁺离子吸附量的影响;利用等温吸附实验作出吸附等温线,并考察了污泥基活性炭吸附剂吸附Cu²⁺的动力学方程。实验结果表明,污泥基活性炭对Cu²⁺具有良好的吸附性能。吸附的最佳pH值为5;吸附符合Langmuir和Freundlich吸附等温方程,吸附为优惠吸附,吸附量随着吸附质溶液浓度的增加而增大;吸附平衡时间为4 h,吸附动力学符合二级动力学方程。     

新型TCAS吸附树脂对水中Cd2+的吸附去除研究

通过静态吸附试验,研究一种由超分子受体化合物磺化硫杂杯芳烃（TCAS）与树脂结合的产物——新型TCAS吸附树脂对重金属Cd²⁺的吸附去除性能,并初步探讨了吸附机理。试验研究结果表明,TCAS吸附树脂对Cd²⁺的饱和吸附量为14.45 mg/g。当温度为20℃,0.5 g TCAS吸附树脂对10 mL浓度为5 mg/L的Cd²⁺溶液吸附60 min时, Cd²⁺的去除率可达到99%以上。pH值是影响TCAS吸附树脂吸附效果的重要因素,在pH=5～9时,Cd²⁺的去除率随着pH值的升高而增大。在试验范围内,TCAS吸附树脂对Cd²⁺吸附符合Freundlich方程。吸附在TCAS吸附树脂上的Cd²⁺可洗脱回收,TCAS吸附树脂也可再生利用。 TCAS吸附树脂对重金属Cd²⁺的吸附机理主要归因于TCAS对Cd²⁺的络合作用。     

水淬渣-累托石混合吸附剂处理含Cu2+冶金废水的研究

研究了以水淬渣-累托石为吸附剂对含Cu²⁺的冶金废水进行处理。实验结果表明，在不调节含Cu²⁺冶金废水pH值的条件下，水淬渣与累托石质量比为3∶1，吸附剂用量为0.03g/mL，作用时间为20 min, 温度为25℃（常温）时，Cu²⁺的去除率达99.8％，对Cu²⁺的吸附容量为0.302mg/g，处理后的水符合国家污水综合排放标准（GB8978-1996）一级标准。水淬渣-累托石混合吸附剂比水淬渣或累托石单一吸附剂除     

水环境中腐殖酸与镉离子结合作用的影响因素

通过测定不同化学条件下腐殖酸与镉离子作用后的游离态镉离子浓度及其结合率,研究各因素对腐殖酸与镉离子作用的影响。研究结果表明,pH值、离子强度、投加镉离子总浓度、腐殖酸浓度和反应温度均影响腐殖酸与镉离子的结合。pH值在4.5~6.5范围内,随pH值升高,腐殖酸与Cd²⁺的结合率增大,游离态Cd²⁺浓度减少。溶液的离子强度增大对结合反应有抑制作用。投加Cd²⁺总浓度的增大会导致结合态Cd²⁺浓度和游离态Cd²⁺浓度逐渐增加,而其结合率逐渐减小。腐殖酸浓度逐渐增大,使Cd²⁺和腐殖酸的结合率逐渐增大。在20℃~50℃范围内时,随反应温度升高,游离态Cd²⁺浓度逐渐减小,其结合率逐渐增加。     

不同pH值条件下Fe3+、Cu2＋和Zn2＋对厨余垃圾两相厌氧消化水解酸化过程的影响

通过间歇实验研究了在pH=7和不调节pH两种情况下添加不同浓度的Fe^3＋、Cu^2＋和Zn^2＋对厌氧消化水解酸化阶段有机酸组分和含量的影响。结果表明，pH=7时，添加50 mg/L Fe^3＋和30 mg/L Cu^2＋，有利于厨余垃圾水解酸化过程的进行，反应生成的VFA（挥发性脂肪酸）含量增加。不调节pH时，添加100 mg/L以下的Fe^3＋和Cu^2＋对VFA含量也有所促进，但乳酸含量也增加。在2种pH条件下添加Zn^2＋对反应的促进或抑制作用均不明显。     

MCM-41介孔分子筛的合成及其对铜离子的吸附性能简

以微硅粉为硅源,CTAB和PEG-6000为模板剂,合成MCM-41介孔分子筛。采用XRD、N₂吸附-脱附曲线、FTIR以及TEM表征了其结构、比表面积、孔径分布及晶体形貌,并且以该样品为吸附剂,对含Cu²⁺的溶液进行了静态吸附实验。结果表明,以微硅粉为硅源成功合成了具有典型六方排列孔道结构的MCM-41,其比表面积为869.5 m²/g,孔容为0.97 cm³/g,平均孔径为3.3 nm;溶液pH为5~6时,MCM-41对Cu²⁺的去除效果最好;MCM-41对Cu²⁺的最大吸附吸附容量36.3 mg/g;MCM-41对Cu²⁺的吸附性能符合Langmuir吸附方程的特征。动力学研究表明,该过程符合准二级动力学模型。     

重金属杂质对磷酸铵镁结晶法处理制药废水的影响

磷酸铵镁沉淀法处理废水时常受众多因素影响,其中重金属类杂质对该过程影响较大。实验研究了Mn²⁺、Cu²⁺杂质存在条件下,用该法去除制药废水中PO₄^3-、NH₄⁺污染物,同时,用XRD、XRF、SEM等手段研究了所得鸟粪石晶体特征。结果表明,pH为9.5时,Mn²⁺、Cu²⁺杂质存在条件下,PO₄^3-去除率分别为88%和85%,投加晶种有利于回收特定晶形鸟粪石,Cu²⁺对磷酸铵镁结晶过程的影响较Mn²⁺存在时显著。     

用H2O2/Fe3+处理高浓度含甲醛废水的研究

研究采用H₂O₂/Fe³⁺催化氧化处理高浓度含甲醛废水,探讨了双氧水和催化剂投加量、反应pH及反应温度等操作条件对处理效果的影响,并通过酸溶解回用失活催化剂。结果表明,较优的操作条件为：H₂O₂/COD（质量比）=2.2～2.6,Fe³⁺/H₂O₂（摩尔比）=0.048～0.058,反应pH 1.80～2.68,反应温度50℃,反应时间40 min;在上述操作条件下,甲醛去除率达到99%以上,COD去除率达到85%以上。失活的催化剂可通过稀酸溶解后循环使用,其效果与三价铁盐作催化剂的基本相同。采用H₂O₂/Fe³⁺处理含甲醛废水具有比采用H₂O₂/Fe³⁺较优的效果。     

沸石负载淀粉对Pb2+、Cu2+和Ni2+的吸附性能

将淀粉负载到沸石表面得到新型重金属离子复合吸附剂ZLS。分别从沸石与淀粉质量比、吸附温度、吸附时间、pH与重金属初始浓度不同方面考察了复合吸附剂ZLS吸附 Pb²⁺、Cu²⁺、Ni²⁺的影响。实验结果表明:当沸石与淀粉质量比为10:1,pH为6,吸附温度在30℃时,复合型吸附剂ZLS对Pb²⁺、Cu²⁺和Ni²⁺ 3种重金属离子的吸附效果最好;吸附动力学研究发现,ZLS对Pb²⁺、Cu²⁺和Ni²⁺的吸附行为均符合准二级动力学以及颗粒内部扩散模型;等温吸附数据符合Freundlich模型,吸附状态属于多层吸附。     

Cu2+、Zn2+对生物脱氮系统的影响

Cu²⁺和Zn²⁺是污水处理工艺中经常遇到的金属离子。在驯化好的活性污泥系统中,研究了金属离子Cu²⁺和Zn²⁺在0～100 mg/L浓度下对活性污泥生物脱氮系统的影响。试验发现Cu²⁺＞5 mg/L、Zn²⁺＞30 mg/L时,对硝化过程具有明显的抑制作用,在同样浓度的试验条件下Cu²⁺对硝化过程的抑制作用比Zn²⁺大。Cu²⁺≤0.5 mg/L时对反硝化过程具有一定的促进作用,有助于提高TN的去除效果;Cu²⁺＞0.5 mg/L时,对反硝化产生抑制作用,随着浓度的增加,TN去除率逐渐下降。Zn²⁺不影响反硝化过程,仅在大于30 mg/L时,对硝化过程产生抑制作用。重金属Cu²⁺对生物脱氮系统的影响明显强于Zn²⁺。     

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.     

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.     

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.     

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)