壳聚糖季铵盐改性河沙去除铜绿微囊藻的研究

以2,3-环氧丙基三甲基氯化铵和壳聚糖为原料制备了水溶性的壳聚糖季铵盐(HTCC),利用HTCC对河沙进行改性,并用于铜绿微囊藻的处理。结果表明:(1)在HTCC用量为7.5 mg/L、预处理河沙用量为0.500g/L的最佳条件下制备得到的HTCC改性河沙(简称改性河沙)对铜绿微囊藻具有良好的降藻效果,当藻密度为9.5×106个/mL、水温25℃左右、藻液pH为8左右时,降藻率达到最高(99.50%)。(2)改性河沙的加入能大大缩短絮体形成及沉降的时间,压实絮体,减少其上浮。(3)改性河沙具有较宽的pH适用范围(7~12)。(4)改性河沙适宜在水温为25~35℃的夏季对铜绿微囊藻进行降藻。(5)改性河沙悬浊液在2~8℃下存放不宜超过10d。(6)HTCC的氨氮溶出率较低(最高为1.77%),氨氮溶出风险较低。     

光辅助下TiO2-蒙脱土复合材料抑杀蓝藻

以TiCl4和钠基蒙脱土为原料,采用水解法制备了TiO2-蒙脱土复合材料,采用XRD、IR和TEM对其结构和性质进行表征;通过藻细胞的内含物含量、生长代谢活性和形态的变化以及藻细胞膜脂质过氧化分析,研究了TiO2-蒙脱土复合材料在光辅助下去除颤藻的性能.结果表明,TiO2-蒙脱土复合材料中一部分TiO2插入蒙脱层间,增加了蒙脱土的层间距,另一部分以锐钛矿相均匀分散在蒙脱土上;在紫外光辅助下,TiO2-蒙脱土的用量为50.0 mg/L,lh后颤藻的除藻率可达94.58％;TiO2-蒙脱土通过光催化作用破坏藻细胞膜、降解藻细胞内含物、降低藻细胞代谢活性和破坏藻细胞形态,从而产生抑藻作用.     

钙离子对混凝去除水体中铜绿微囊藻的影响

以铜绿微囊藻为对象,研究了钙离子对聚合氯化铝(polyaluminumchloride,PAC)混凝沉淀藻细胞的影响及其可能的机理。结果表明,添加钙离子对PAC混凝去除模拟水样藻细胞和浊度均具有促进作用。在PAC摩尔浓度较低时(0.02 mmol·L~(-1)),最高可将除藻率和除浊率分别提高66.4%和76.8%。三维荧光及总溶解性有机碳(total(dissolved organirc carbon,TDOC)分析表明钙离子对去除水中溶解性胞外有机物(dissolved extracellular organic matter,dEOM)没有显著作用。利用Zeta电位和絮体形态对其影响混凝除藻效果的可能机理进行探究,发现钙离子能通过压缩双电层和吸附电中和提高藻细胞表面的Zeta电位,从而促进胶体脱稳凝聚。推测钙离子通过与铜绿微囊藻表面的黏附型胞外有机物(bound extracellular organic matter,bEOM)发生阳离子架桥作用促进藻细胞脱稳混凝沉淀。钙离子能够促进铜绿微囊藻脱稳,但是絮体粒径、强度、恢复能力的主要影响因素还是PAC摩尔浓度。     

壳聚糖改性红壤去除铜绿微囊藻

研究了聚合氯化铝铁和壳聚糖改性对高岭土、海泡石和红壤去除水中铜绿微囊藻效果的影响。结果表明,壳聚糖改性的红壤对铜绿微囊藻的去除效果最好,其生成絮体密实度大,抗扰动能力强。当改性红壤的投加量为50 mg/L时,叶绿素a和铜绿微囊藻去除率分别达到98.0%、95.1%。该絮凝剂适应性好,在pH为3.0~6.0的范围内对铜绿微囊藻均可取得很好的去除效果,对叶绿素a和浊度的去除率可达90%以上。壳聚糖通过包裹红壤颗粒,借助壳聚糖的粘结架桥和电中和能力,大幅度提高了红壤的絮凝性能。该絮凝剂处理富藻水,具有絮凝效果明显、絮体密实度大、投加量少、绿色环保、经济等优点,在工程上具有较大的实用价值。     

木质纤维素/蒙脱土纳米复合材料对Cr(Ⅵ)吸附性能研究

利用X射线衍射(XRD)和扫描电镜(SEM)方法,对木质纤维素/蒙脱土纳米复合材料的结构进行表征,并研究了溶液pH、Cr(Ⅵ)初始浓度、吸附时间和吸附温度对木质纤维素/蒙脱土纳米复合材料吸附Cr(Ⅵ)的影响.结果表明:(1)木质纤维素和蒙脱土复合后形成了插层一剥离型的纳米复合材料;(2)在溶液pH为2、Cr(Ⅵ)初始质量浓度为100mg/L、吸附温度为30℃、吸附时间为180 min的条件下,木质纤维素/蒙脱土纳米复合材料对Cr(Ⅵ)的吸附量达5.72mg/g;(3)木质纤维素/蒙脱土纳米复合材料对Cr(Ⅵ)的吸附符合伪二级动力学模型和Freundlich吸附等温式.     

改性膨润土联合混凝剂处理微污染水中有机物

采用十二烷基多糖苷季铵盐作为改性剂制备改性膨润土,研究了改性膨润土联合混凝剂去除有机物的效果,考察了有机改性剂用量、微波辐射功率、辐射时间、膨润土投加量、pH值对有机物去除效果的影响,探讨了改性膨润土的改性和去除机理。结果表明,经微波改性后,实现了十二烷基多糖苷季铵盐阳离子对膨润土的插层,增大了层间距,提高了膨润土的吸附性能。联合混凝剂投加改性膨润土能够改善絮凝性能,显著提高有机物的去除效果。在最佳条件下,改性膨润土与PAC联合后的强化混凝,对初始浓度15.3 mg/L的微污染水中有机物的去除率达到95%以上,吸附符合Freundlich吸附等温方程。     

四羟甲基硫酸鏻去除铜绿微囊藻效果及其机制研究

研究了四羟甲基硫酸鏻对铜绿微囊藻(Microcystis aeruginosa)的去除效果及机制.结果表明,四羟甲基硫酸鏻半效应浓度(EC50)与藻细胞数目呈正相关,线性方程为:Y=0.628 2X+0.956 4,R2=0.997 3(其中Y为EC50,mg/L;X为处理48 h后铜绿微囊藻细胞数目,106个/mL).11.0 mg/L四羟甲基硫酸鏻处理铜绿微囊藻36 h后,藻细胞可溶性蛋白、超氧化物歧化酶(SOD)活性、丙二醛(MDA)较对照组分别提高10.47%、11.31%、140.98%,四羟甲基硫酸鏻能够显著破坏藻细胞膜通透性,提高酯酶活性.四羟甲基硫酸鏻通过破坏藻细胞膜,造成膜脂过氧化,干扰藻体正常代谢而除藻.     

大气压等离子体射流对水中铜绿微囊藻的灭活作用

以铜绿微囊藻为研究对象,将空气源大气压等离子体射流(APPJ)引入到液相,构建新型的大气压等离子体射流液相反应体系,考察了不同APPJ处理方式对铜绿微囊藻的灭活效率,观察了放电处理的藻细胞形态,分析了培养基p H的变化和液相产生的主要活性物质(H2O2和O3)对藻灭活的作用,并探讨了APPJ灭活铜绿微囊藻的作用机理。研究结果表明,当电压为7 k V,空气气体流速为4 L/min,藻液吸光度约为0.200,铜绿微囊藻的灭活率达到99.16%;处理后的藻发生细胞变形和破裂;处理后的藻液中产生H2O2和O3等活性物质,同时产生大量的NO-3和NO-2离子,导致液相p H迅速下降。通过考察主要活性物质(H2O2和O3)及藻液p H因素发现,单一因素灭活效果不佳,主要活性物质(H2O2和O3)和p H的组合因素是APPJ灭活水中铜绿微囊藻的主要原因。     

AgBiO3对铜绿微囊藻生长的致毒效应

研究了AgBiO3对铜绿微囊藻生长的致毒效应.结果表明,培养液中Ag 的胁迫使铜绿微囊藻的生长繁殖受到明显抑制;由于铜绿微囊藻自身的防御机制,在受到胁迫时其细胞密度随着Ag 浓度的升高呈不对称"V"形变化;在一定铜绿微囊藻密度范围内,Ag 96h半数有效浓度(96h-EC50(y))和投加AgBiO3时初始藻细胞密度(x)之间存在线性关系:y=0.049 7x-0.051 1;在投加Ag 24h后,培养液上清液中Ag 浓度低于<生活饮用水卫生标准>(GB5749-2006)限值.因此,可以利用AgBiO3对铜绿微囊藻生长的致毒效应,将投加银系杀藻剂作为铜绿微囊藻水华控制措施之一.     

羟基铋离子改性蒙脱土的制备及其对碘离子的吸附

水体的碘污染问题正日益引起人们的广泛关注。以Swy-2型钠基蒙脱土为载体,利用其层间离子交换特性,简单快速制备了羟基铋离子改性蒙脱土,并通过扫描电镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)对材料吸附碘前后的物化特性进行了表征,研究了材料对水体中碘离子的去除效果,探讨了相关吸附机理。结果表明:合成材料对碘离子的吸附动力学符合假二级动力学方程,吸附等温线符合Langmuir模型,其最大吸附量为107.5 mg·g~(-1),换算成氧化铋对碘的吸附量高达595.2 mg·g~(-1);因此,以Swy-2型钠基蒙脱土为载体,进行羟基铋离子改性,可以大大地提高铋利用效果。对吸附碘后材料的XPS和XRD进一步分析推测,羟基铋离子改性蒙脱土对碘离子的去除,可能是经由化学吸附,生成Bi_4I_2O_5所造成的。     

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.     

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.     

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 in deer and elk from Los Alamos national laboratory and the doses to humans from the ingestion of muscle and bone

Abstract

This paper summarizes radionuclide concentrations (³H, ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu, ²⁴¹Am, and ^totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p<0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% on LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y^‐1 (2.2 μSv y^‐1), deer bone = 3.8 mrem y^‐1 (38 μSv y^‐1), elk muscle = 0.12 mrem y^‐1 (1.2 μSv y^‐1), and elk bone = 1.7 mrem y^‐1 (17 μSv y^‐1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y^‐1 (1000 μSv y^‐1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E‐06, which is far below the Environmental Protection Agency upper level guideline of 1E‐04.     

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.