响应曲面法优化聚硅酸铁混凝剂处理腈纶废水

为了提高聚硅酸铁(PSF)混凝剂处理腈纶废水处理效果,采用响应曲面法对实验反应条件进行优化。实验选取原水pH值、混凝剂投加量、沉降时间为自变量,COD去除率和浊度去除率为响应值,采用Box-Behnken实验设计方法,分别建立了二次多项式响应曲面模型。方差分析结果表明,该模型方程显著,模型与实际情况拟合良好,实验误差较小,可以用此模型来分析和预测聚硅酸铁混凝剂处理腈纶生化出水的最佳反应条件。模型优化结果显示,在pH值为7.44,投加量为1.74 g·L~(-1),沉降时间为17.26 min的条件下,响应曲面模型预测最大COD去除率为57.88%,浊度去除率为95%。     

突变灰盖鬼伞过氧化物酶降解刚果红的响应面法优化分析简

酶法降解偶氮染料刚果红是一个复杂的过程,受温度、pH、酶量、刚果红浓度和双氧水浓度显著影响。为研究各因素及因素间交互作用对刚果红降解影响,提高刚果红的降解率,分别使用单因素法和响应面分析法对刚果红降解条件进行了优化。单因素实验结果显示灰盖鬼伞过氧化物酶降解刚果红的最适条件为：pH 5.0、32℃、酶量4.98 U、双氧水0.1 mmol/L、刚果红20 mg/L,此时刚果红最高降解率为34.84%。然后选双氧水浓度、刚果红浓度和灰盖鬼伞过氧化物酶量作为3个因素,通过中心组合设计实验,用响应面法对刚果红降解进行优化分析,最后得到一个拟合度良好的二次多项方程模型（R²=0.9900）。方差分析结果显示,刚果红浓度和酶量是影响最显著的因素,双氧水与酶以及染料与酶之间的交互作用极显著。响应面分析优化后的反应体系为：双氧水浓度0.15 mmol/L,刚果红浓度为27.21 mg/L,酶为2.0 7 U,在此条件下,刚果红降解率达58.13%。     

突变灰盖鬼伞过氧化物酶降解刚果红的响应面法优化分析

酶法降解偶氮染料刚果红是一个复杂的过程,受温度、pH、酶量、刚果红浓度和双氧水浓度显著影响。为研究各因素及因素间交互作用对刚果红降解影响,提高刚果红的降解率,分别使用单因素法和响应面分析法对刚果红降解条件进行了优化。单因素实验结果显示灰盖鬼伞过氧化物酶降解刚果红的最适条件为：pH5．0、32℃、酶量4．98u、双氧水0．1mmol／L、刚果红20mg／L,此时刚果红最高降解率为34．84％。然后选双氧水浓度、刚果红浓度和灰盖鬼伞过氧化物酶量作为3个因素,通过中心组合设计实验,用响应面法对刚果红降解进行优化分析,最后得到一个拟合度良好的二次多项方程模型（R2=0．9900）。方差分析结果显示,刚果红浓度和酶量是影响最显著的因素,双氧水与酶以及染料与酶之间的交互作用极显著。响应面分析优化后的反应体系为：双氧水浓度0．15mmol／L,刚果红浓度为27．21mg／L,酶为2．07U,在此条件下,刚果红降解率达58．13％。     

脂肽类生物表面活性剂液体发酵条件的响应面优化

通过Plackett-Burman和Box-Behnken实验对解淀粉芽孢杆菌XZ-173液体发酵生产表面活性素进行了响应面优化研究。首先使用Plackett-Burman实验对影响表面活性素产量的17个因素进行显著性筛选,结果表明,MnSO4、CuSO4、温度和转速为显著性因素。再运用Box-Behnken实验对这4个显著因素的取值进一步优化,得到各因素优化后的数值分别为4.4 mg/L(MnSO4)、0.18 mg/L(CuSO4)、29℃(温度)和163 r/min(转速)。响应面分析结果表明:该菌株产生表面活性素的最佳培养基为:葡萄糖15 g/L,蛋白胨5 g/L,L-谷氨酸钠6 g/L,KH2PO40.8 g/L,MgSO40.4 g/L,KCl 0.4 g/L,酵母提取物3 g/L,L-苯丙氨酸2.5 mg/L,MnSO44.4 mg/L,CuSO40.18 mg/L,FeSO40.12 mg/L;最适培养条件:pH 7.5,温度29℃,转速163 r/min,接种量5%,装液量50 mL/250 mL,摇床培养36 h。在优化后的条件下,表面活性素实际产量为336 mg/L,实际实验结果与模型预测结果相一致。表面活性素采用HPLC技术分离,发现其在浓度仅为50 mg/L时EI24就可达到70%以上,反映了表面活性素优异的乳化活性以及广阔的应用前景。     

响应面分析法优化絮凝酵母SPSC01去除Cr(Ⅵ)

采用响应面法对絮凝酵母SPSC01去除水中Cr(Ⅵ)的条件进行优化。根据Box-Behnken Design的中心组合实验设计原理,采用三因素三水平的响应面分析方法,优化絮凝酵母SPSC01对Cr(Ⅵ)的去除。二阶模型的方差分析表明,预测响应值和实际值相符合,针对初始浓度为50 mg/L的Cr(Ⅵ)废水,在絮凝酵母SPSC01用量为10.89 g/L干重、温度为40℃、初始pH为2时的去除条件最优,二阶模型分析预测絮凝酵母SPSC01在4 h时对Cr(Ⅵ)去除率可达95.47%,在此条件下,实测Cr(Ⅵ)的去除率达93.06%,说明利用响应面法优化絮凝酵母SPSC01对Cr(Ⅵ)的去除条件是可行的。     

响应面法优化UV/H_2O_2光氧化法处理高浓度LAS废水

采用响应面法对UV/H2O2光氧化法处理高浓度LAS废水的工艺参数进行了系统研究。根据Box-Behnken Design(BBD)设计原理,以初始pH与H2O2投加量、反应时间和温度为主要影响因素,设计4因素3水平共29个实验点的实验方案,并建立了二次响应面拟合模型。方差分析表明,初始pH与H2O2投加量、反应时间和温度以及初始pH和H2O2投加量、H2O2投加量和温度之间的交互作用,对实验结果具有显著性影响。实验得到的光氧化高浓度LAS废水最佳工艺条件,pH为4.0,H2O2投加量为40 mmol/L,反应时间为90 min,温度为25℃,在此条件下,LAS的平均去除率为98.1%。     

响应面法优化白腐菌Pleurotus ostreatus降解六氯苯

采用响应面法优化白腐菌侧耳属菌株(Pleurotus oatreatus)降解六氯苯(HCB)的条件.结果表明,对HCB降解率影响显著性较大的是摇床转速和pH.在摇床转速125 r/min、pH为7.0、培养温度为28℃、HCB初始质量浓度为10 mg/L、接种量为5%(体积分数)、培养时间为2 d的优化条件下,HCB降解率和降解速率分别为92.73%和2.318 mg/(L·d).     

高PHAs合成性能菌株的筛选及其条件优化

通过尼罗蓝荧光筛选,从活性污泥体系中筛得Ace-6、But-1和But-17。经DNA分子鉴定,Ace-6缺陷短波单胞菌(Brevundimonas diminuta),But-1约氏不动杆菌(Acinetobacter Johnsonii),But-17蜡样芽孢杆菌(Bacillus cereus)。采用摇瓶平行发酵实验,确定了各自的最佳碳源和氮源,并通过多因素正交实验对其进行合成条件优化。结果表明,Ace-6菌株合成条件为温度30℃、乙酸钠30 g·L~(-1)、酵母粉0.35 g·L~(-1)、pH 7.0、接种量5%,PHAs的总量可达412.02 mg·L~(-1);But-1菌株的合成条件为温度35℃、乙酸钠20 g·L~(-1)、硫酸铵0.35 g·L~(-1)、pH 7.5、接种量8%,PHAs的合成量可达392.39 mg·L~(-1);But-17菌株合成条件为温度35℃、淀粉20 g·L~(-1)、氯化铵0.35 g·L~(-1)、pH 7.5、接种量5%,PHAs可达304.70 mg·L~(-1)。     

书虱伴生菌中纤维素酶产生菌的筛选、鉴定及最佳产酶发酵条件的优化

从以啃食树皮为生的书虱伴生菌中筛选得到5株产纤维素酶的菌株,编号分别为S2、S6、N10、N11和N12。结合菌株的形态学及16S r DNA序列分析等结果将这些菌株分别鉴定为Bacillus methylotrophicus,Streptomyces sp.,Pseudomans fluorescens,Bacillus sp.及Pseudomans sp.。分别使用单因素分析法和响应面分析法对纤维素酶活最高的S2菌株的产酶发酵条件进行了优化。单因素实验结果显示,B.methylotrophicus S2的最适产酶发酵条件为:0.01 g/m L的CMC碳源、10 g/L蛋白胨的氮源、48 h的发酵时间、28℃、初始pH为7.0,此时总纤维素酶活达到204.37 u/g。然后选取发酵时间、温度和初始pH作为3个因素,通过BBD实验,用响应面法对S2的发酵条件进行优化分析,最后得到一个拟合度良好的二次多项方程模型(R2=0.9948)。方差分析结果显示,发酵温度与培养基初始pH之间的交互作用极显著。响应面分析优化后的反应体系为:温度24℃、初始pH为7.7、发酵59 h,测得酶活力为303.18 u/g,比优化前单因素最佳纤维素酶活力提高45%。     

重捕剂SDTC的合成及其处理含铊废水的研究

以小分子胺类、二硫化碳和十二烷基苯磺酸钠(SDBS)为原料合成一种复配型重捕剂SDTC,用于处理烧结脱硫含铊废水。采用响应面法通过Box-Behnken(BBD)实验设计影响铊去除率的反应条件,对废水pH、SDTC投加量、反应时间和无机离子进行了优化分析,同时通过红外光谱和紫外光谱对SDTC及其与铊生成的螯合物(SDTC-Tl)结构进行表征。结果表明,二次多项式模型的回归系数R~2为0.982 8,模型对实验数据的拟合度高。采用响应面法优化得出处理1.20mg/L含铊废水的最佳条件并对其进行修正为:废水pH 9.00,SDTC投加量2.80g/L,反应时间25.0min,无机离子21.1g/L,该条件下铊去除率为99.89%,实验结果与模型预测值吻合。红外和紫外光谱分析结果表明,SDTC与铊会发生配位反应,生成的SDTC-Tl可较长时间放置,不易产生二次污染。     

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.     

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)