滩涂石油污染高级氧化修复技术

在模拟原沉积物弱碱性及含水率的条件下,分别研究了2种高级氧化反应体系:H_2O_2辅助加入催化剂Fe SO4或Fe2(SO4)3及Na2S2O8辅助加入催化剂Fe SO4或Ca O及热催化对污染滩涂沉积物中石油烃的去除效果及其影响因素。同时,还模拟研究了长江口潮汐作用对滩涂石油污染修复效果的影响。研究表明:H_2O_2与样品的质量投加比为0.05,FeSO4和Fe2(SO4)3与H_2O_2摩尔投加比均为0.1时,石油烃去除率分别达到48.9%和57.4%;Na2S2O8本身氧化能力较强,单一Na2S2O8与样品的质量比大于0.01时,石油烃去除率达到46%以上;而在Na2S2O8最佳投加比条件下,Fe SO4、Ca O与Na2S2O8摩尔比为0.05和0.9时,去除率分别达到60.4%和51.3%以上,同时最佳催化温度为50℃。潮汐作用对芬顿试剂氧化修复滩涂石油污染具有促进作用,而高浓度污染滩涂区域建议采用阻隔修复。     

沸石对降雨径流中氨氮的吸附特性

城市面源污染是重要水体污染源之一,降雨发生时,雨水径流会携带累积在路面、屋面的含有机物、氮磷、重金属等污染物质进入水体,其中氮磷是造成水体富营养化的重要因素。针对这一情况,采用不同种类沸石,对雨水径流中的氮磷进行了吸附研究,着重考察了沸石对氨氮的吸附动力学,吸附等温线特征,并考察了p H、共存阳离子以及COD对吸附能力的影响。结果表明,Na型改性沸石吸附性能优于其他2种,饱和吸附量达到9.09 mg/g,沸石的吸附过程符合准二级动力学模型。Mg2+、Ca2+对Na型改性沸石的影响较大,Na型改性沸石吸附氨氮的适宜p H为5~8。本研究为探索用物化方法来处理雨水提供了依据,Na型改性沸石可以作为吸附雨水中氨氮的优选吸附剂。     

Mg2+对克雷伯氏菌NIII2及其诱变菌产絮凝剂特性的影响

研究了Mg2+对克雷伯氏菌NIII2及其诱变株NIII2-1、NIII2-2发酵产絮凝剂特性的影响作用。实验表明,发酵液未外加或投加较少量Mg2+时,3菌株均不分泌黄色物质,且易产酸,致使絮凝剂产量低,小于1.5 g/L。发酵液中加入Mg2+的浓度在0.5~0.7 mmol/L范围,絮凝剂产生时,伴随黄色分泌物出现,发酵液p H稳定在7.5左右,同时絮凝剂产量大大提高,可达9.7 g/L。未投加Mg2+,3菌株所产絮凝剂Zeta电位负值较大,分别为-59.2、-56.6、-52.1 m V,且蛋白质与糖含量比值小于0.5,絮凝活性低;而投加Mg2+所产絮凝剂Zeta电位值可升至-48.0 m V,3菌株所产絮凝剂中蛋白和糖含量比值分别可提高到1.87、3.29、2.03,对高岭土所产生的SS去除率均大于93%。未投加Mg2+时,诱变株NIII2-1、NIII2-2所产絮凝剂含有相当多的O-链接和N-链接的结构,而其他情况下所产絮凝剂则主要是O-链接结构。     

纳米零价铁颗粒除磷反应机理

从溶液化学与固相表征两方面对纳米零价铁(NZVI)去除水中磷酸根(PO3-4)的机理进行初步探究。分别研究不同初始p H值、溶解氧(DO)对NZVI除磷效果的影响,结果表明,酸性环境(p H为3.0~7.0)有利于NZVI除磷,且初始p H值越低,磷去除率越高;好氧环境较厌氧环境更利于磷的去除,DO8.0 mg/L时对磷酸根的去除率是厌氧条件(DO0.1 mg/L)下的2倍。采用Na OH对反应后含磷NZVI进行解析,发现磷解析率不到30%,说明吸附并非NZVI除磷惟一作用机理。微米铁、NZVI和Ca(OH)2等7种不同去除材料中以Ca(OH)2的共沉淀作用去除率最大(99.9%),NZVI次之(87.2%),表明NZVI除磷机理中还存在共沉淀作用。采用多种固相表征手段对NZVI除磷前后进行分析:扫描电子显微镜(SEM)显示反应后出现不规则颗粒;X射线衍射(XRD)表明Fe3(PO4)2是主要反应产物;X射线光电子能谱(XPS)分析未发现磷被还原成低价态。研究表明,NZVI可有效去除水中磷酸根,主要去除机理包括:NZVI对磷酸根的吸附作用、NZVI在水中腐蚀产生的Fe2+离子对磷酸根的化学沉淀作用及铁氢氧化物与磷酸根的共沉淀作用。     

MgCl2和脱水矿泥对赤泥盐碱性的调控

针对赤泥盐碱性过高造成资源化利用难的问题,采用MgCl2和氧化铝工业固体废物脱水矿泥对赤泥进行盐碱性调控,并依据赤泥的pH、电导率、碱性阴离子(OH-、CO32-、HCO3-、AlO2-)和可溶性盐分阳离子(K+、Ca2+、Na+、Mg2+)质量分数以及黑麦草种子发芽率结果表征盐碱性调控效果.结果表明,当赤泥投加7‰M...     

天然氧化纤维素的吸附性能

重金属污染已成为最严重的环境问题之一。纤维素是一种可生物降解的天然高分子,含量极其丰富。将纤维素经TEMPO/Na Br/Na Cl O体系进行氧化改性,得到了一种新型吸附材料——天然纤维素氧化物。研究了其对废水中Cu2+和Fe3+的去除效果,并探究吸附剂投加量、p H、温度、初始浓度和吸附时间对去除效率的影响。结果表明,室温条件下,在Cu2+浓度为100 mg/L和p H为5~6的溶液中,加入0.175 g吸附材料,吸附时间为60 min,可以得到99%的吸附效率;而Fe3+的溶液需要调节到p H值为4~5,添加的吸附材料是0.15 g,吸附效率也是99%以上。动力学研究还表明,该材料对Cu2+和Fe3+的吸附过程与Freundlich型及Langmuir型吸附等温模型都能较好地拟合。该新型吸附材料在废水处理行业将会有广阔的应用前景。     

铁负载阴离子交换树脂高效除磷研究

针对污水处理生化出水高磷酸盐浓度对水体富营养化影响的问题,采用阴离子交换树脂(AER)为基质材料,利用树脂上—NH2官能团中的N原子与Fe3+发生配位聚合,制备了除磷聚合配位交换吸附剂(Fe—PLE)。并采用Langmuir和Freundlich等温吸附方程对Fe—PLE和原AER进行了比较,发现Fe—PLE更加趋向化学吸附类型,且Fe—PLE最大吸附容量达到93.05 mg/g,比AER提高了47.98%。通过SEM、EDS、FT-IR及TGA对吸附前后Fe—PLE和AER的表征比较,认为通过配位作用形成Fe—O配位键是Fe—PLE的可溶性无机磷吸附效率提高的主要原因。通过静态吸附实验考察了吸附时间、p H和竞争性阴离子对AER和Fe—PLE吸附的影响,结果显示,Fe—PLE吸附平衡时间为1.5 h,比AER稍高;2种吸附填料都在p H 7.0时效率最高,AER的磷吸附效率对p H较为敏感,Fe—PLE能够在相对较宽的p H范围内保持高去除率;竞争性阴离子对AER磷吸附的负面影响较大,而Fe—PLE依靠其Fe—O的配位作用具有一定的抗干扰能力。通过4次循环再生实验,Fe—PLE表现出良好再生能力的同时磷有较高的回收利用率。     

软水树脂再生废液提高印染污泥脱水性能的研究

研究了软水树脂再生废液和热处理对印染污泥脱水性能的影响。以污泥比阻(SRF)和毛细吸水时间(CST)作为评价污泥脱水性能的指标,通过测定污泥Zeta电位和FT-IR光谱来阐述污泥脱水机理。实验确定的最佳污泥脱水条件为:加热温度70℃,100 m L污泥添加30 m L软水树脂再生废液(软水树脂再生废液中Ca2+的量约为干污泥质量的11.9%),污泥比阻由2.52×1011m·kg~(-1)降至0.85×1011m·kg~(-1),污泥CST由15.2 s降至8.9 s。随着Ca2+浓度的增加,可使污泥表面电荷明显减少,较高的温度可能会加强这种影响。FT-IR光谱表明,Ca2+能与絮体的O—H官能团、蛋白质等相互作用。实验还对软水树脂再生废液与常用阳离子絮凝剂Fe Cl3和Al2(SO4)3的絮凝效果进行了比较。研究证明软水树脂再生废液可作为絮凝剂使用,是一种经济有效的改善污泥脱水性能的方法,且实现了废物利用。     

Fe~(2+)活化过硫酸钠原位修复氯苯污染地下水

通过建立土槽模型模拟实际污染场地,并采用Na2S2O8为氧化剂、柠檬酸螯合Fe2+为活化剂,研究了氯苯在地下水中的迁移分布规律、原位修复及其对地下水环境的影响。结果表明,氯苯在含水层水平纵向上的迁移作用大于横向迁移;随着时间的增加,地下水中氯苯浓度变化总趋势为先增加后减少并最终趋于稳定;随着迁移距离的增加,氯苯的浓度逐渐降低。柠檬酸螯合Fe2+活化Na2S2O8能够有效修复受氯苯污染的地下水和土壤;持续氧化36 h后,地下水和土壤中氯苯的去除率分别达到82.4%和80.3%。进一步研究发现,氧化处理后,出水的p H值基本稳定在3.5、SO2-4浓度为88.7mg/L,满足地下水Ⅱ类水质标准。     

天然沸石吸附氨氮的影响因素

对比研究了沸石对生活污水和人工配制氯化铵溶液中氨氮的吸附特性,考察了沸石投加量、反应时间、悬浮物、阳离子和阴离子对沸石吸附氨氮的影响。结果表明,沸石对生活污水中氨氮的吸附能力明显低于人工配制氯化铵溶液,氨氮去除率随着沸石投加量的增加而增加,但单位质量沸石的氨氮吸附量却随之减小,吸附过程呈现快速吸附,缓慢平衡的特点。生活污水中悬浮物的存在,会削减沸石对氨氮的吸附能力。不同类型的阳离子和阴离子的加入都能导致人工配制氯化铵溶液中氨氮在沸石上的吸附量存在差异。阳离子的影响趋势主要为价态的影响,即价态越高,对氨氮吸附阻碍作用越显著,当阳离子当量浓度〉2meq／L时,影响吸附强弱的顺序为Ca2＋〉Mg2＋ 〉Na＋;阴离子影响沸石吸附强弱的顺序受初始氨氮的浓度影响较大。Langmuir等温方程式较Freundich、DubininRadushkevich、KobleCorrigan和Temkin等温方程式更好地描述沸石吸附氨氮的行为。     

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.