除氟活性铝氧化物（AlOxHy-Fn）的吸附除砷性能

以活性铝氧化物AlOxHy处理某高氟地下水的中试实验获得的吸附剂废料AlOxHy-Fn为对象,考察其对三价砷（As（Ⅲ））和五价砷（As（Ⅴ））吸附去除性能,并对吸附机理进行了探讨。研究显示,AlOxHy-Fn为多孔无定型且具有不规则表面的絮状结构,比表面积为218．88m2／g,零电荷点pHZPC在pH为8左右;AlOxHy-Fn可快速吸附As（Ⅲ）和As（Ⅴ）,且反应24h后的平衡吸附量分别为0．60和3．41mg／g,朗格缪尔模型可以很好地描述As（Ⅲ）和As（Ⅴ）在AlOxHy-Fn表面的吸附,且As（Ⅲ）和As（Ⅴ）的最大吸附容量分别为13．63和63．27mg／g;AlOxHy-Fn在pH=4～10范围内对As（Ⅴ）去除率在90％以上,As（Ⅲ）在中性和弱碱性pH范围内吸附效果较好,但去除率仍在32％以下。AlOxHy-Fn表面性质、砷形态分布特征等对As（Ⅲ）与As（Ⅴ）的吸附有重要影响,电负性As（Ⅴ）较电中性As（Ⅲ）更容易吸附在AlOxHy-Fn表面。AlOxHy-Fn吸附除砷过程中,在pH为6时氟溶出量最低（0．40mg／g）,过高或过低pH均会导致氟溶出量增大;氟溶出量与As（Ⅴ）吸附量之间有明显正相关关系（R2=0．97）,但与As（Ⅲ）吸附量无相关关系;铝溶出量在pH为4～10范围内均很低。将AlOxHy-Fn回用作为除砷吸附剂去除工业含砷废水的砷具有良好的技术经济可行性,且将As（Ⅲ）氧化为As（Ⅴ）是提高去除效果的重要手段。     

除氟活性铝氧化物(AlO_xH_y-F_n)的吸附除砷性能

以活性铝氧化物AlOxHy处理某高氟地下水的中试实验获得的吸附剂废料AlOxHy-Fn为对象,考察其对三价砷(As(Ⅲ))和五价砷(As(Ⅴ))吸附去除性能,并对吸附机理进行了探讨。研究显示,AlOxHy-Fn为多孔无定型且具有不规则表面的絮状结构,比表面积为218.88 m2/g,零电荷点pHZPC在pH为8左右;AlOxHy-Fn可快速吸附As(Ⅲ)和As(Ⅴ),且反应24 h后的平衡吸附量分别为0.60和3.41 mg/g,朗格缪尔模型可以很好地描述As(Ⅲ)和As(Ⅴ)在AlOxHy-Fn表面的吸附,且As(Ⅲ)和As(Ⅴ)的最大吸附容量分别为13.63和63.27 mg/g;AlOxHy-Fn在pH=4~10范围内对As(Ⅴ)去除率在90%以上,As(Ⅲ)在中性和弱碱性pH范围内吸附效果较好,但去除率仍在32%以下。AlOxHy-Fn表面性质、砷形态分布特征等对As(Ⅲ)与As(Ⅴ)的吸附有重要影响,电负性As(Ⅴ)较电中性As(Ⅲ)更容易吸附在AlOxHy-Fn表面。AlOxHy-Fn吸附除砷过程中,在pH为6时氟溶出量最低(0.40 mg/g),过高或过低pH均会导致氟溶出量增大;氟溶出量与As(Ⅴ)吸附量之间有明显正相关关系(R2=0.97),但与As(Ⅲ)吸附量无相关关系;铝溶出量在pH为4~10范围内均很低。将AlOxHy-Fn回用作为除砷吸附剂去除工业含砷废水的砷具有良好的技术经济可行性,且将As(Ⅲ)氧化为As(Ⅴ)是提高去除效果的重要手段。     

三价铁改性活性炭对水中微量砷的吸附特性

研究了三价铁改性对不同活性炭(颗粒和粉末)对水中砷的吸附特性的影响。结果表明,三价铁改性有效提高了活性炭对不同形态砷的吸附性能。其中,对于2种活性炭,As(Ⅲ)和As(Ⅴ)的最佳铁离子改性浓度分别为0.1和0.05 mol/L。此时,通过Langmuir等温线方程拟合得到:粉末和颗粒活性炭对As(Ⅲ)的最大吸附量qm分别为2.38 mg/g和9.39 mg/g;而对As(Ⅴ)的qm分别为5.12 mg/g和2.32 mg/g。此外,当溶液的p H从3升高到9的过程中,吸附量先增加后有所下降,当p H为7时,改性前后的活性炭对砷的吸附量达到最高。     

天然锰砂去除水中的砷

天然锰砂是一种廉价、高效的水处理用材料,但尚未用于水中砷的去除。实验研究了反应时间、砷形态、初始砷浓度、温度、溶液初始pH对吸附过程的影响。结果表明,天然锰砂对As(Ⅲ)的吸附能力大于As(Ⅴ)。25℃时,固液比为10 g/L的条件下,天然锰砂对初始浓度为5.0 mg/L的砷溶液吸附过程经72 h基本达到平衡,平衡时对As(Ⅲ)和As(Ⅴ)的去除率分别达到94.5%和85.9%。吸附过程符合Lagergren准一级反应动力学模型和假二级反应动力学模型。相比之下,假二级动力学模型拟合程度更高。对As(Ⅲ)和As(Ⅴ),45℃时的吸附量均大于25℃时。不同温度下,天然锰砂对As(Ⅲ)和As(Ⅴ)的吸附过程更符合Freundlich等温吸附模型。在溶液初始pH为3～10范围内,锰砂对砷的吸附能力受pH的影响较小。实验结果表明,天然锰砂是一种具有实际应用潜力的除砷材料。     

铁改性竹炭去除水中的As(Ⅲ)和As(Ⅴ)

利用竹炭负载铁氧化物制备了复合吸附剂,并用粉末X射线衍射对负载的铁进行了表征。通过静态吸附实验,对比研究了改性竹炭对水溶液中As(Ⅲ)和As(Ⅴ)阴离子的吸附特性。结果表明,载铁竹炭对As(Ⅲ)和As(Ⅴ)的最佳吸附pH分别为8和2。改性竹炭对砷阴离子的吸附过程可符合准二级动力。Freundlich等温方程式能很好地描述As(Ⅲ)和As(Ⅴ)在改性竹炭上的吸附。在相同初始浓度和吸附剂投加量下,改性竹炭对As(Ⅴ)的吸附量大于As(Ⅲ)。     

基于岭脊分析的天然含铁锰矿改性优化及机制研究

采用水合肼法对天然含铁锰矿进行改性,并用岭脊分析法优化改性工艺,从而提高天然含铁锰矿的砷吸附去除性能。结果表明,水合肼投加量和高锰酸钾投加量对改性天然含铁锰矿的砷吸附性能有显著影响,岭脊分析得到的天然含铁锰矿最优改性条件为水合肼投加量1.5 mmol/g、H₂SO₄ 3 mol/L、高锰酸钾1.1 mmol/g,此条件下获取的改性天然含铁锰矿对As(Ⅲ)、As(Ⅴ)去除率分别可达97.42%±0.06%、97.47%±0.48%,对As(Ⅲ)和As(Ⅴ)饱和吸附容量分别为15.29、8.01 mg/g,均明显优于天然含铁锰矿。改性过程在溶解天然含铁锰矿中杂质的同时,也使得天然含铁锰矿表面活化,不仅提高了As(Ⅲ)氧化能力,也增大了As(Ⅴ)吸附作用。     

无定型纳米TiO2吸附去除饮用水中的低浓度As(Ⅲ)

研究了纳米无定型TiO2颗粒对饮用水中低浓度的三价砷As(Ⅲ)吸附行为。纳米TiO2颗粒吸附剂的BET表面积为205 m2/g,计算的BJH吸附平均孔径为4.02 nm(4 V/A)。对起始As(Ⅲ)浓度为150μg/L的模拟含砷水,经过5h的吸附处理后残余浓度不足4μg/L,As(Ⅲ)去除率达到97%。反应起始阶段吸附速率较快,84%的As(Ⅲ)能够在20min内去除。As(Ⅲ)吸附动力学较好地符合拟二级动力学模式。最佳As(Ⅲ)吸附pH为9.3,低于此值,随酸性增加吸附速率有所降低;而高于此值的强碱性pH对吸附有强烈抑制作用。在平衡浓度较低的情形下(10～220μg/L),Lang-muir,Freundlich和Dubinin-Radushkevich(D-R)吸附等温式均可较好拟合吸附行为,但中性和弱碱性条件下更符合Fre-undlich吸附等温式;平衡浓度大于220μg/L,吸附容量随平衡浓度增加而迅速增加,最大吸附容量在低浓度下达到4.79 mg/g。     

砷形态转化及其环境效应研究

砷在水环境中的形态转化受到许多物理化学因素的制约,并产生毒害程度不同的环境效应。对多种因素进行研究,寻找将高毒的As(Ⅲ)向低毒的As(Ⅴ)转化的有利条件,并控制As(Ⅴ)向As(Ⅲ)的转化。结果表明,自然敞口放置3d的As(Ⅲ)溶液中没有As(Ⅴ)的出现,As(Ⅲ)向As(Ⅴ)的转化是一个缓慢的过程。锰矿、粉煤灰等天然矿物能氧化As(Ⅲ),从而降低毒性。酸性或碱性条件都有利于As(Ⅲ)向As(Ⅴ)的转化,转化率超过90%。温度、可见光、超声波等外界条件对砷形态转化有一定影响。紫外光照射3d后的As(Ⅲ)完全转化成As(Ⅴ),且As(Ⅴ)没有向As(Ⅲ)转化,因此紫外光是降低砷毒性的有利条件。Fe2+能将As(Ⅴ)还原,升高水体砷的毒性;而Fe3+能将As(Ⅲ)氧化,并生成氢氧化物将砷吸附。     

骨炭对水中不同形态Sb吸附和解吸的影响

采用骨炭作为吸附剂,研究其在不同骨炭用量、pH值和温度条件下对水中Sb（Ⅲ）和Sb（Ⅴ）吸附和解吸的影响。结果表明,骨炭对Sb（Ⅲ）的吸附效果远好于Sb（Ⅴ）,在0.2~8.0 mmol/L的Sb（Ⅲ）和Sb（Ⅴ）浓度下,骨炭对这2种形态Sb的去除率分别为46.1%~78.6%和9.6%~31.7%。采用Langmuir方程和Freundlich方程均可以很好地拟合骨炭对Sb（Ⅲ）和Sb（Ⅴ）的吸附,Sb（Ⅲ）和Sb（Ⅴ）的最大吸附容量分别为110.1034 mg/g和17.4167 mg/g。骨炭对Sb（Ⅲ）的解吸也大于对Sb（Ⅴ）的解吸。骨炭对Sb（Ⅲ）和Sb（Ⅴ）的吸附受不同骨炭用量、pH值和温度影响。     

膜蒸馏去除水中砷的研究

采用新型膜蒸馏技术对水中As（III）与As（Ⅴ）的去除展开了研究。实验结果表明,膜蒸馏对水中As (III)及As (Ⅴ)具有较高的去除能力：当产水中砷含量超过10 μg/L时,原水中As (III)与As (Ⅴ)的浓度可分别高达40 mg/L和2 000 mg/L。局部润湿现象的存在导致As (III)及As (Ⅴ)跨膜至产水侧,PVDF微孔膜在溶液中的负电性以及As (III)与 As (Ⅴ)在溶液中存在形式的不同导致膜蒸馏对两者去除能力的差异。360 h连续运行过程中产水通量及电导率稳定,且整个过程中As (III)均低于检测限,说明PVDF微孔膜具有良好的疏水性和稳定的除砷性能。     

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.     

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.     

土壤中砷的化学平衡

本文比较详细地综述了砷的化学特性,环境背景值及来源和循环,土壤中砷的三大化学平衡即沉淀溶解平衡,氧化还原平衡,吸附解吸平衡,以及微生物对砷的转化。     

Elemental uptake by edible herbs and lettuce (Latuca sativa)

The total concentration of toxic elements (aluminum, cadmium, chromium and lead) and selected macro and micro elements (iron, manganese, copper and zinc) are reported in six leafy edible vegetation species, namely lettuce, spinach, cabbage, chards and green and red types of Amaranth herbs. Although spinach and chards had greater than 125 mv of iron, both the amaranthus herbs recorded > than 320 μ g g^{? 1} dry weight. In both the spinach and chard species, the Mn and Zn levels were appreciable recording > 225 μ g g^{? 1} and 150 μ g g^{? 1} dry weight, respectively. Aluminum concentrations were (in μ g g^{? 1} dry weight) lettuce (10), cabbage (11), spinach (167), chards (65), amaranthus green (293) and amaranthus red (233). All the micro and macro elements and the toxic elements (Ni, Cr, Cd and Pb) elements analyzed, were below the recommended maximum permitted levels (RMI) in vegetables. Further the elemental uptake and distribution of the nine elements, at three growth stages of the lettuce plant grown on soil bed under controlled conditions are detailed. In the soil, except for iron (16%), greater than 33% of the other cations were in exchangeable form. Generally in the lettuce plant, roots retained much of the iron (> 224 μ g g^{? 1}) and aluminum (> 360 μ g g^{? 1}), while leaves had less than 200 μ g g^{? 1} of iron and 165 μ g g^{? 1} of Al. Although the concentrations of elements marginally decreased with growth, the lettuce leaves had significant amounts of Mn (30 μ g g^{? 1}), Zn (50 μ g g^{? 1}) and Cu (3.6 μ g g^{? 1}). Some presence of lead in leaves (2.0 μ g g^{? 1}) was noticed, but all the toxic and other elements analyzed were well below the RMI values for the vegetables.     

The dissipation of nonlyphenol in stream and pond water under simulated field conditions

Abstract

The dissipation of 1.0 ppm nonylphenol in stream and pond water, incubated in flasks at 16°C under simulated field conditions up to 44 days indicated that the half‐life was 2.5 days if the flasks were open, and 16 days if they were closed. A transformed product was detected in the closed flasks.

Translocation of nonylphenol in water occurred when treated water samples were incubated in the presence of sediment. After 10 days, nonylphenol was detected only in the sediment, but not in water (detection limit = 10 ppb). About 80% of the nonylphenol was degraded in 71 days, but no degradation occurred if the water and the sediment were autoclaved prior to incubation.