颗粒羟基氧化锆的除氟性能

以羟基氧化锆粉末为原料,制备颗粒羟基氧化锆,评价了颗粒羟基氧化锆对溶液中F-的吸附性能。结果表明:颗粒羟基氧化锆除氟过程符合Freundlich吸附等温线模型和拟二级动力学模型,F-的吸附过程包括液膜扩散和颗粒内的孔扩散;pH在3～4时,颗粒羟基氧化锆的氟吸附量达到最大值27.72 mg/g,其他范围内pH的升高或降低都会导致氟吸附量的降低;Cl-对颗粒羟基氧化锆除氟过程无明显影响,而SO24-和PO34-对颗粒羟基氧化锆除氟过程影响较大,且浓度越高影响越大;扫描电镜和X射线能谱测试结果显示颗粒内随着颗粒深度的增加,F-含量逐渐降低,F-在颗粒内部的传质过程受到阻碍,SO24-和PO34-对颗粒羟基氧化锆除氟的干扰作用主要发生在颗粒表面。     

改性粘土除氟剂处理高氟地下水研究

利用自行制备的改性粘土除氟剂处理含氟量较高的配水,研究了改性粘土的优化制备条件和不同因素对其除氟效果的影响,并进行地下水原水除氟验证,最后考察了改性粘土除氟剂的再生性能.结果表明,将0.3 mol/L的Al2(SO4)3和2%(质量分数)的NaOH按1:3(质量比)混合制成改性溶液.再将改性溶液与粘土按1.0:3.0(质量比)混合后,在400℃下煅烧2 h所制得的除氟剂除氟效果最好,最高氟吸附容量可达0.216 8 mg/g;地下水出水氟质量浓度为0.807 mg/L,低于<生活饮用水卫生标准>(GB5749--2006)限值(1 mg/L);制得的改性粘土除氟剂对氟具有较好的吸附重复性,可实现多次再生.     

锆负载型树脂用于含氟废水深度处理的研究

本文研制了一种以火力发电厂废树脂为载体的锆负载型氟离子吸附剂 ,并在评价了该树脂对氟离子的吸附性能之后探讨了该树脂用于火力发电厂含氟废水深度处理的可能性。研究结果表明 ,锆的最佳负载的最佳浓度为0 .5mol/L ,该负载树脂的最佳吸附pH为 3.0— 4 .0 ,用填充柱进行的动态实验结果表明 ,pH =3时的吸附容量显著高于 pH=4时的值。利用该树脂对火力发电厂模拟含氟废水进行了双柱串联吸附工艺处理 ,当柱流量为 35mL/min(SV10 )、第二柱穿透时 ,第一柱的吸附容量为 10 2 2 8mg/L湿树脂 ;用 0 .1mol/L的NaOH溶液进行再生 ,柱流量选择为 35mL/min(SV10 )时 ,脱附率在 95 %以上。     

负载镧镁改性活性氧化铝的除氟性能

制备载镧镁改性活性氧化铝(MAA),研究其对氟的吸附性能,采用扫描电镜SEM、X射线衍射仪XRD和等离子发射光谱仪ICP-OES对改性活性氧化铝进行表征,探讨可能的除氟机理。实验结果表明:吸附时间120 min、投加量2.0 g·L~(-1),p H=7,振荡频率180 r·min-1,对10 mg·L~(-1)高氟水去除率为97.7%。与未改性活性氧化铝(AA)相比,改性活性氧化铝除氟效果提高1.0倍,最大饱和吸附量为8.56 mg·g-1。不同阴离子对除氟性能的影响力大小为:CO2-3SO2-4Cl-NO-3。吸附剂对F-的吸附符合准二级动力学。改性活性氧化铝的吸附等温线符合Langmuir模型,该吸附反应为吸热反应,温度越高,自发程度越大。     

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。     

煅烧的水滑石同时去除水体中砷和氟

为探讨水滑石类材料对水体中氟、砷离子的同时去除效果,采用共沉淀法合成(Mg∶Al=2∶1)纳米类水滑石(LDHs),用傅立叶转换红外光谱、电子扫描透射电镜、X射线晶体衍射等手段对合成的材料进行了表征,并研究纳米材料在不同初始浓度、pH、吸附时间、阴离子干扰条件下其同时除砷氟性能。结果表明,煅烧后的水滑石(LDOs)对砷最大吸附量为51.02 mg/g,对氟最大吸附量为36.63 mg/g。吸附动力学实验表明,煅烧水滑石对砷的吸附在前6 h内基本完成,对氟的吸附在前10 h内基本完成。砷氟共存溶液保持pH=4~10及pH=6~8时,水滑石分别对砷、氟保持良好的吸附效率。对比不同阴离子对水滑石共除砷氟效率的影响,水滑石除砷速率受到阴离子影响力大小为:HPO2-4CO2-3NO-3Cl-SO2-4;水滑石除氟速率受到阴离子影响力大小为:CO2-3HPO2-4SO2-4Cl-NO-3。材料再生循环利用4次后,对砷和氟的吸附效率均能达到90%以上。实验结果表明,所合成的水滑石是一种优秀的能共除砷氟的吸附剂。     

银杏叶生物炭对亚甲基蓝的吸附特性

以银杏叶为原料,在700℃下热解制备银杏叶生物炭(GBBC),研究其对溶液中亚甲基蓝(MB)的吸附。考察了pH、吸附时间、GBBC投加量等对吸附结果的影响。实验结果表明:GBBC是一种很好的吸附剂,适用的pH范围宽(2~12),达到吸附平衡时间短(30min);在初始MB质量浓度为50mg/L、GBBC投加量为2.0g/L时,对溶液中MB的去除率达99.2%。吸附过程符合准一级动力学模型(R~2=0.982 9),颗粒内扩散模型拟合结果进一步表明GBBC对MB的吸附受表面吸附和颗粒内扩散共同主导。等温吸附模型拟合发现,Langmuir-Freundlich模型能很好地描述GBBC对MB的吸附行为(R~2=0.989 1)。可见,GBBC是一种去除废水中MB的高效吸附剂。     

改性菌丝体对Ni2+的吸附特性研究

通过专利对菌丝体进行了改性.所制备的改性菌丝体对重金属离子具有良好的吸附效果.结果表明,其对Ni2+的吸附容量63.2 mg/g(初始水溶液中Ni2+浓度为200 mg/L),是甲壳素吸附剂的3.3倍(19.1 mg/g),与壳聚糖吸附剂相比吸附容量提高了135%,与D751与南开152相比吸附容量非常接近.用0.5%-0.2%的解吸剂便可以完全解吸,能够重复使用达6次以上.本文还研究了改性菌丝体对Ni2+的吸附过程中重要的影响因素,结果发现,在微碱性(pH=8-9)条件下,改性菌丝体可以把初始浓度高达800 mg/L的Ni2+溶液一次性降低到17 mg/L,为改性菌丝体在工业废水处理中的应用奠定了良好的基础.     

季铵化改性木屑纤维素的制备及对氟离子的吸附研究

以3-氯-2-羟丙基三甲基氯化铵(CTA)为醚化剂,对木屑纤维素进行了季铵化改性.探讨了季铵化改性木屑纤维素用量、pH、吸附温度、氟离子初始浓度和吸附时间对氟离子静态吸附率的影响,以及流速对氟离子动态吸附率的影响.结果表明:(1)静态吸附最佳工艺条件:季铵化改性木屑纤维素用量为3.0 g/L,pH为4.0～6.0,吸附温度为25 ℃,吸附时间为120 min.在此最佳工艺条件下,季铵化改性木屑纤维素对100 mL 50.00 mg/L氟离子溶液的吸附率最高可达90.11%.(2)在pH为5.0、25 ℃的条件下,将50.00 mg/L氟离子溶液以5 mL/min的流速流经装有3.0 g/L季铵化改性木屑纤维素的吸附柱,吸附率可达97.95%.(3)季铵化改性木屑纤维素对溶液中氟离子的吸附过程为放热过程,在吸附过程中存在着化学吸附.(4)木屑来源丰富、价格价廉,季铵化改性木屑纤维素对溶液中氟离子的吸附效果好,且吸附工艺简单、易于实现工业化,具有良好的应用前景.     

改性膨润土颗粒对微污染水中有机物和氨氮的吸附

采用粘结剂聚乙烯醇(PVA)、造孔剂碳酸氢钠(NaHCO3)和微波强化Al改性膨润土(以下简称M-Al-Bt)制备改性膨润土颗粒(以下简称MBG),研究MBG对微污染水中有机物和氨氮(NH4-N)的吸附效果,考察了不同投加量、反应时间、pH值对腐殖酸(HA)和NH4-N的去除效果影响.结果表明,投加量3 g/L,反应时间20 min,pH =7时,MBG对微污染水中20 mg/L HA和5mg/L NH4-N的去除率分别可达98％和20％以上.HA和NH4-N共存时,存在竞争吸附,HA影响了MBG对NH4-N的去除.     

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.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

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.     

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.     

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.     

Radionuclides and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

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.