热解吸对土壤中POPs农药的去除及土壤理化性质的影响

为探索土壤热解吸修复技术对POPs污染土壤的修复效果及修复后土壤可耕作性,选择北京某农药厂旧址的POPs农药污染土壤,研究了不同温度下热解吸处理后土壤中滴滴涕(DDTs)和六六六(HCHs)各组分的去除率以及土壤理化性质的变化。结果表明,热解吸修复技术可有效去除土壤中POPs农药,其中,p,p’-DDE与α-HCH组分去除率受热解吸温度的影响比其他组分更为明显。∑HCH与∑DDT在310℃、340℃时分别达到97%、99%的去除率,且此时土壤中的污染物含量低于我国《展览会用地土壤环境质量评价标准》,此后去除率受温度的影响不明显。热解吸温度对修复后土壤的理化性质有一定的影响,不同温度影响的程度各不相同,其中,有机质含量与全氮含量分别由0.78%、0.0352%降至0.14%、0.0107%;pH波动幅度较小,由7.80变至8.25;阳离子交换量变化存在波动,但呈整体下降趋势,由7.87 mg/kg降至5.00mg/kg;土壤中速效磷显著增加,由7.59 mg/kg升至21.8 mg/kg。而在最优温度条件下,土壤理化性质受热解吸温度的影响较小。由此可以说明,热解吸技术可以用于POPs污染土壤的修复,选择适当的热解吸温度对土壤的可耕作性影响有限,因而是一种潜在的绿色修复技术。     

某典型化工污染场地土壤修复方案研究

以典型化工污染场地为研究对象,构建适合该场地的修复技术筛选体系,筛选最佳修复方法。根据特征污染筛选结果、场地修复目标及业主需求等因素,通过室内模拟实验、施工现场微调等方法,确定污染场地最优修复方案。结果表明,作为Cd、苯并[a]芘复合污染场地,根据筛选体系结合Topsis法进行评估,确定场地修复技术为异位化学淋洗。运用响应曲面法,采用BoxBehnken设计多因素实验进行室内模拟,确定最佳修复条件。采用0.6mol/L柠檬酸与20g/Lβ-环糊精进行复配的淋洗剂,在pH=3.0、淋洗温度35.00℃、液固比(淋洗剂与土壤的体积质量比)6.00mL/g、搅拌强度320.00r/min下,淋洗4次,每次淋洗3.4h,对某化工污染场地进行修复,修复后土壤中Cd、苯并[a]芘的去除量分别为69.88、39.20mg/kg,去除率分别达80.14%、70.50%,达到预期修复目标。     

化学氧化法治理焦化厂PAHs污染土壤

针对焦化类工业场地多环芳烃(PAHs)污染土壤治理问题,选取北京某焦化厂PAHs污染土壤,对其进行化学氧化修复治理的室内模拟研究,实验采用高锰酸钾、Fenton试剂、双氧水和过硫酸钠4种氧化剂,测试了氧化剂的土壤氧化剂需求量(SOD),分析了4种氧化剂对15种PAHs的氧化效果以及反应过程中土壤总PAHs浓度和土壤有机质含量(SOM)随反应时间的变化。结果表明,北京某焦化厂PAHs污染土壤过硫酸钠SOD低于高锰酸钾SOD;Fenton试剂和双氧水对PAHs的总去除率分别为59.53%和62.72%,且对三环PAHs的去除率较好,高锰酸钾对PAHs的总去除率为59.24%,对蒽和苯并(a)芘的去除效果较好,活化过硫酸钠对PAHs的总去除率为68.87%;土壤有机质可通过对PAHs的吸附影响氧化剂的处理效果。     

射频加热强化土壤气相抽提技术的应用

热强化土壤气相抽提技术是一种高效的土壤治理技术,广泛应用于包气带土壤中挥发性有机污染物的去除。在天津某有机污染场地开展射频加热强化土壤气提技术应用研究,研究了射频阳极连接方式对场地加热效果的影响,并考察了该技术对实验场地的实际修复效果。结果表明,射频阳极采用并联方式连接对场地的加热效果较好,加热10 d后,场地温度升高约40℃;随着SVE系统工作时间的延长,场地温度逐渐下降,土壤气中TVOCs的浓度逐渐下降;经过约2个月的修复,中浅层土壤中污染物的总去除率约90%,氯仿去除率达95%,深层土壤中的污染物去除率约64%。     

活化过硫酸钠去除长期污染土壤中的TPH

探讨了利用过硫酸钠氧化修复实际污染场地长期高浓度石油类(TPH)污染土壤的可行性。研究了过硫酸钠的活化方式、添加量、添加方式、土壤初始p H等因素对TPH降解效率的影响,并采用探针化合物研究了活化过硫酸钠对TPH的氧化去除机制。结果表明:Fe~(2+)活化方法对TPH去除效果最好,反应24 h最高去除率达40.8%;碱活化效果次之,去除率可达35.2%;过氧化氢活化效果一般,去除率为21%左右;热活化效果较差,去除率仅为15.6%。Fe~(2+)活化过硫酸钠去除土壤中TPH的反应在5 min内基本完成,最佳过硫酸钠用量为2.5 mmol·g-1土,过硫酸钠/硫酸亚铁/柠檬酸投加量之比为4∶1∶1,一次添加氧化剂的方式较多次添加效果好。实验场地土壤初始p H对TPH降解效果影响不大,自由基探针实验证实反应中硫酸根自由基、羟基自由基、还原性物质的存在。对于本场地污染土壤的修复,利用Fe~(2+)活化过硫酸钠修复是较为有效、快速的方法。     

Fenton氧化技术修复六氯环己烷污染土壤特性研究

为研究六氯环己烷(HCHs)在污染土壤中的Fenton氧化特性及其影响因素,以中国西南地区已停产的某HCHs生产企业厂区的污染土壤为研究对象,分析Fenton氧化作用下Fenton氧化时间、催化剂种类、催化剂投加量和H_2O_2投加量等因素对HCHs去除率的影响。结果表明:(1)延长Fenton氧化时间可以促进HCHs的去除,其去除率在100min后达到稳定;Fe~(2+)的催化效率优于Fe~(3+)和Fe~0,最佳催化剂为FeSO_4·7H_2O晶体;催化剂投加量最佳为5%(质量分数);较高投加量的H_2O_2有利于产生更多的HO·,H_2O_2投加量最佳为20g/mL。(2)Fenton氧化对HCHs的去除机制具有一致性,但不同HCHs异构体的去除率存在差异。在以FeSO_4·7H_2O晶体为催化剂、Fenton氧化时间为100min、催化剂投加量为5%、H_2O_2投加量为20g/mL的最优条件下,β-HCH去除率最高(96.7%),α-HCH去除率次之(79.2%),γ-HCH和δ-HCH去除率分别为54.8%和51.3%。(3)Fenton氧化技术是一种优秀的HCHs污染土壤修复技术,具有较高的可行性、经济性和环境友好性,具有较大的HCHs污染场地原位修复应用前景。     

Fenton氧化技术处理稠油污染土壤

利用Fenton氧化技术对稠油污染土壤进行氧化处理,分析对后续微生物修复的促进作用。向1 000 g石油类含量为8%的稠油污染土壤中加入10.0 mL 18 mmol/L Fe2+溶液与10.0 mL 30%H2O2,反应时间为2 h。氧化处理后土壤中石油烃的总去除率可达到31.38%,胶质去除率为45.22%,沥青质去除率为51.26%,胶质的分子量由1 841下降到1 472,沥青质的分子量由5 831下降到5 073。Fenton氧化可使土壤酶活、各类微生物的数量及呼吸强度有不同程度的下降,但在氧化后30 d内,土壤各类微生物数量都超过了原有水平,其中细菌数量最高达到9.84×105CFU/g,是氧化前的数量的1.57倍。以上实验结果表明,Fenton氧化可以有效去除土壤中胶质和沥青质,并且使土壤中微生物的生长速率加快。因此,Fenton氧化能够促进后续的微生物修复。     

异位类Fenton化学氧化在多环芳烃污染场地修复中的应用

多环芳烃作为土壤的主要污染源之一,其修复技术的研究对土壤可持续利用具有重要的意义;但目前的研究主要基于室内小试实验,对具体修复技术在实际现场中的应用少有报道。基于上海青浦区西虹桥沈海高速东侧17-02污染场地的工程实践,结合室内实验,详细地介绍了原场异位类Fenton化学氧化修复多环芳烃污染土壤施工工艺。处理结果表明:以柠檬酸为催化助剂的类Fenton化学氧化能够有效地处理场地污染土壤中的苯并(a)蒽、苯并(a)芘、苯并(b)荧蒽和茚并(1, 2, 3-cd)芘等超标污染物;修复后场地土壤各项物理指标相比修复前变化较小;同时,类Fenton氧化反应放热,修复过程中土壤微生物能够将有机柠檬酸快速降解,有效降低了化学氧化对土壤p H的影响。     

微波修复原油污染土壤的均匀设计实验

采用均匀设计实验方法,研究了微波修复原油污染土壤时原油去除率与微波能耗、含水率和含炭率等因素的关系,并应用MATLAB编程拟合出经验公式。结果分析表明:微波能耗在0～288 kJ范围内,污染土壤的原油去除率随微波能耗线性增加;在含水率为6%、含炭率为4%、微波能耗从0增加到288 kJ时,原油去除率从0%增加至92.3%;含炭率在0%～4%范围内原油去除率与含炭率成线性关系,在微波能耗为288 kJ、含水率为6%、含炭率从0%增加到4%时,原油去除率从12.3%增加至92.3%;原油去除率与含水率成二次曲线关系且开口向下,微波修复原油污染土壤的最佳含水率为6.6%。研究结果对微波修复原油污染土壤技术的优化提供了有价值的参考。     

PAHs污染土壤的热修复可行性

以某煤制气厂污染场地中16种US EPA优先控制多环芳烃(Σ16 PAHs)为目标污染物进行了热修复批量实验和可行性实验。热修复批量实验结果表明,当热修复温度为400℃、加热时间为8 h时,土壤中的Σ16 PAHs去除率达99.9%。热修复可行性实验选择重污染、中污染和轻污染土壤以400℃作为目标温度,恒温72 h进行实验。热修复前后不同程度污染土壤的Σ16 PAHs的总去除率均可达到99.9%,但重污染土壤浓度非常高,部分苯并类物质未达到修复目标值,需进一步延长加热时间或提高加热温度保证达到修复目标值。土壤土工参数影响分析结果表明,热修复后土壤颗粒粒径呈增大趋势,土壤稳定性、抗压强度均增强。此外,土壤中可溶性盐含量增多,盐渍化程度增大。     

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.