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。     

壳聚糖改性硅藻土对太湖含藻水体处理效果的研究

研究了壳聚糖改性硅藻土对太湖含藻水体中浊度和蓝藻的去除效果。结果表明:(1)在室内模拟实验中,综合叶绿素a的去除率和去除速率来看,较适宜的改性硅藻土投加量为50mg/L。在此投加量下,室内模拟实验中浊度去除率达到91.50%,叶绿素a去除率达到98.10%;(2)在原位实验中,投加改性硅藻土也能有效去除浊度和叶绿素a,表、中、下层3层水体的最终浊度去除率分别达到82.41%、79.09%、72.82%,叶绿素a去除率分别为92.43%、87.17%、65.62%。(3)无论在室内模拟实验还是原位实验中,投加改性硅藻土后水体的浊度去除和叶绿素a去除均呈现出显著的相关性(p0.01),即两者的去除具有一定的同步性。     

壳聚糖改性粘土对高藻水中藻类的絮凝去除

对壳聚糖改性粘土用于天然高藻水中藻类的絮凝去除进行了研究。实验表明,经壳聚糖改性后的粘土对高藻水中藻细胞有较好的去除效果。粘土的种类对除藻效果有一定影响,其中以高粘凹凸棒石为最佳,其最佳投加量为66mg/L(壳聚糖6 mg/L),此时的叶绿素去除率达到95.45%。相比单独投加壳聚糖,粘土的加入增加了絮体密实度,减少了絮体体积,并使絮体分布更均匀。粘土的粒径对絮凝效果基本没有影响,粒径范围在25～74μm时,改性粘土对藻细胞的凝聚效果是一致的。经壳聚糖改性的粘土在酸性条件下絮凝效果较好,当pH值大于7时,其絮凝能力迅速下降。     

阳离子化壳聚糖改性黏土絮凝去除藻华

壳聚糖改性黏土可以用于治理藻华,但未经改性的壳聚糖具有电荷密度小、溶解度小、pH适用范围较窄以及分子质量较小等缺点,影响了壳聚糖改性黏土除藻的性能。为了优化壳聚糖的絮凝除藻性能,以二甲基二烯丙基氯化铵为阳离子醚化剂,在微波条件下对壳聚糖进行改性合成阳离子型壳聚糖,并研究了阳离子壳聚糖溶解度随pH的变化,以及用它改性后的黏土颗粒的表面电位的变化,并对阳离子壳聚糖改性黏土和壳聚糖改性黏土的絮凝除藻性能进行比较。结果表明,阳离子壳聚糖在酸性和碱性条件下都具有很好的溶解性,经其改性后的黏土颗粒的等电点(pH 10.8)显著高于壳聚糖改性黏土的等电点(pH 9.5)。在絮凝实验中,阳离子壳聚糖改性黏土的最大除藻率达到99%,藻絮体粒径为978μm,即使在pH为10时,仍有87%的去除率。结果表明,阳离子壳聚糖改性黏土的除藻性能明显优于未改性的壳聚糖改性黏土。     

基于改性凹凸棒土的强化混凝处理高藻低浊原水工艺

针对水厂低浊高藻水的处理难题,研究了改性凹凸棒土(改性凹土)联合聚合氯化铝(PAC)强化混凝的除藻除浊效果。设计实验原水条件为叶绿素a(chl-a)浓度为98.58~110.35μg/L,浊度(5.6±0.5)NTU。考察了PAC和改性凹土的复配投加量、混凝沉淀时间、pH、投加顺序、搅拌速率等工艺参数对Chl-a和浊度耦合去除效果的影响。结果表明,"PAC+改性凹土"对Chl-a和浊度的去除效果明显优于单投PAC的效果。当PAC投药量12 mg/L,改性凹土投药量10 mg/L,沉淀时间20 min时,对Chl-a和浊度的去除率可分别达到92.5%和89.2%,可至少减少40%的PAC投量,且形成的矾花密实,沉降速度快,去除效率高。最适pH范围为7~8。投加顺序应为先投加改性凹土,混合搅拌转数宜慢速,可控制为50 r/min。     

藻类生长期对改性蛭石絮凝除藻的影响

以水华微囊藻为研究对象,采用壳聚糖改性蛭石,研究了藻类不同生长期的除藻效果及其影响机制,结果表明平均藻细胞去除率为:对数期稳定期衰亡期迟缓期衰亡后期,衰亡后期EOM含量是对数期的4.6倍,藻细胞去除率仅为30%左右,是对数期的1/3。其原因与不同生长期Zeta电位和胞外分泌物(EOM)的变化有关,衰亡后期的电负性显著增强,且EOM含量也显著增大。过量的EOM会增大改性蛭石的投加量,当达到相同去除率时,未移除EOM藻液的投加量是移除EOM藻液的3倍。EOM对絮凝除藻具有低促高抑的作用,低浓度(DOC10 m L)时EOM可发挥吸附架桥作用,利于絮凝;高浓度(DOC30 m L)时EOM的电负性发挥主导作用,抑制絮凝。     

天然橄榄石对水体铜绿微囊藻的去除效果

为开发安全、高效、廉价的水华控制技术,选择铝土矿、磷铁矿、黄铁矿、铬铁矿及橄榄石等10种天然矿物材料,以水体铜绿微囊藻为研究对象,通过跟踪测定其叶绿素a的变化,研究了天然矿物对水体铜绿微囊藻去除特性,并探讨了天然橄榄石去除铜绿微囊藻的影响因素及去除机理。结果表明:相同条件下天然橄榄石具有最高的除藻能力;矿物用量及藻密度对橄榄石除藻过程影响最大,其次为pH及水温,光强影响最小;当橄榄石浓度为1.5 g·L-1,藻密度1.7×106 cells·mL-1、水温15℃、反应介质为弱酸性或中性(pH 5～7)时,吸附1 h后,叶绿素a去除率高于96%。进一步分析可知,天然橄榄石主要通过静电作用对铜绿微囊藻进行吸附,进而使藻细胞絮凝沉降,部分藻细胞破裂分解,同时天然橄榄石在反应过程中吸附培养基中的营养盐,造成藻细胞营养缺少,从而对藻细胞的生长造成一定的抑制作用。     

微波辅助改性壳聚糖的制备及其絮凝性能

以壳聚糖、阳离子醚化剂二甲基二烯丙基氯化铵为原材料,采用微波辐射的方法,制备了壳聚糖接枝共聚物(壳聚糖-二甲基二烯丙基氯化铵),并通过红外光谱分析对改性壳聚糖进行了表征。以接枝率为标准,确定改性壳聚糖的最佳反应条件,并以高岭土悬浊液和实际生活污水作为处理对象,测定了改性壳聚糖的絮凝性能。结果表明,壳聚糖接枝共聚物的最佳制备条件是微波反应温度55℃,反应时间20 min,壳聚糖0.5 g,微波功率270 W,阳离子醚化剂的浓度20%,在此条件下,合成的改性壳聚糖的接枝率为80%。红外光谱分析结果显示,已成功地合成了壳聚糖-二甲基二烯丙基氯化铵接枝共聚物。在絮凝实验中,壳聚糖接枝共聚物的去浊率最高达到91%,COD去除率最高达到77%。其结果表明,壳聚糖接枝共聚物的絮凝性能明显高于原料壳聚糖。     

改性膨润土对水中磷和藻类的同步去除

为快速去除富营养化水体中的磷和藻类,制备了絮凝剂-镧复合改性膨润土(聚合氯化铝铁-镧复合改性膨润土(PAFC-La)、聚合硫酸铝-镧复合改性膨润土(PAS-La)、聚合硫酸铁-镧复合改性膨润土(PFS-La)、聚合氯化铝-镧复合改性膨润土(PAC-La)),对材料进行表征,通过吸附动力学和等温吸附模型比较4种复合改性膨润土的除磷性能,并探究投药量和pH对复合改性膨润土除磷除藻的影响。结果表明,4种材料吸附磷的过程均能由准二级动力学模型和Langmuir等温吸附模型描述。其中,PAC-La的磷吸附容量最大(44.677 mg/g);投药量为300 mg/L时,总磷(TP)去除率最高的是PAC-La(94.1%),叶绿素a(Chla)去除率最高的是PFS-La(78.2%);在pH为5～10时,PAC-La除磷除藻效果受pH影响最小。实验结果表明,采用絮凝剂-镧复合改性膨润土能够同步去除富营养化水体中的磷和藻类,尤其是采用PAC-La性能最优。     

改性壳聚糖复合凹凸棒土絮凝油漆废水

将壳聚糖、阳离子淀粉和二甲基二烯丙基氯化铵(DMDAAC)进行三元接枝共聚,制备了三元接枝改性壳聚糖(CTS-DMDAAC-CS),通过红外光谱和扫描电镜对其结构进行了表征。并且将三元接枝改性壳聚糖与凹凸棒土进行优化复配,对油漆废水进行了絮凝实验,得出了当pH=12,沉降时间为20 min,复合絮凝剂投加量为0.2 g,三元接枝共聚物∶凹凸棒土=1∶10时,该复合絮凝剂对油漆去除率最佳能够达到89.3%,并且絮凝效果好,是一种新型绿色环保的有机-无机复合絮凝剂。     

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.