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。     

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.     

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.     

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.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State—Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, α and β endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino – Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6 % leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (α-endosulfan), 1.47E-162 (β-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.     

Endosulfan in China 2—emissions and residues

Background, aim, and scope  Endosulfan is one of the organochlorine pesticides (OCPs) and also a candidate to be included in a group of new persistent organic pollutants (UNEP 2007). The first national endosulfan usage inventories in China with 1/4° longitude by 1/6° latitude resolution has been reported in an accompanying paper. In the second part of the paper, we compiled the gridded historical emissions and soil residues of endosulfan in China from the usage inventories. Based on the residue/emission data, gridded concentrations of endosulfan in Chinese soil and air have been calculated. These inventories will provide valuable data for the further study of endosulfan. Methods  Emission and residue of endosulfan were calculated from endosulfan usage by using a simplified gridded pesticide emission and residue model—SGPERM, which is an integrated modeling system combining mathematical model, database management system, and geographic information system. By using the emission and residue inventories, annual air and soil concentrations of endosulfan in each cell were determined. Results and discussion  Historical gridded emission and residue inventories of α- and β-endosulfan in agricultural soil in China with 1/4° longitude by 1/6° latitude resolution have been created. Total emissions were around 10,800 t, with α-endosulfan at 7,400 t and β-endosulfan at 3,400 t from 1994 to 2004. The highest residues were 140 t for α-endosulfan and 390 t for β-endosulfan, and the lowest residues were 0.7 t for α-endosulfan and 170 t for β-endosulfan in 2004 in Chinese agricultural soil where endosulfan was applied. Based on the emission and residue inventories, concentrations of α- and β-endosulfan in Chinese air and agricultural surface soil were also calculated for each grid cell. We have estimated annual averaged air concentrations and the annual minimum and maximum soil concentrations across China. The real concentrations will be different from season to season. Although our model does not consider the transport of the insecticide in the atmosphere, which could be very important in some areas during some special time, the estimated concentrations of endosulfan in Chinese air and soil derived from the endosulfan emission and residue inventories are in general consistent with the published monitoring data. Conclusions  To our knowledge, this work is the first inventory of this kind for endosulfan published on a national scale. Concentrations of the chemical in Chinese air and agricultural surface soil were calculated for each grid cell. Results show that the estimated concentrations of endosulfan in Chinese air and soil agree reasonably well with the monitoring data in general. Recommendations and perspectives  The gridded endosulfan emission/residue inventories and also the air and soil concentration inventories created in this study will be updated upon availability of new information, including usage and monitoring data. The establishment of these inventories for the OCP is important for both scientific communities and policy makers.     

Impact of spiked concentrations of Cd,Pb, As and Zn in growth medium on elemental uptake of Nasturtium officinale (Watercress)

This study is aimed at investigating the impact of water quality on the uptake and distribution of three non-essential and toxic elements, namely, As, Cd and Pb in the watercress plant to assess for metal toxicity. The plant was hydroponically cultivated under greenhouse conditions, with the growth medium being spiked with varying concentrations of As, Cd and Pb. Plants that were harvested weekly for elemental analysis showed physiological and morphological symptoms of toxicity on exposure to high concentrations of Cd and Pb. Plants exposed to high concentrations of As did not survive and the threshold for As uptake in watercress was established at 5 ppm. Translocation factors were low in all cases as the toxic elements accumulated more in the roots of the plant than the edible leaves. The impact of Zn on the uptake of toxic elements was also evaluated and Zn was found to have an antagonistic effect on uptake of both Cd and Pb with no notable effect on uptake of As. The findings indicate that phytotoxicity or death of the watercress plant would prevent it from being a route of human exposure to high concentrations of As, Cd and Pb in the environment.     

Butyltin compounds in sediment and fish from the Polish Coast of the Baltic Sea

Concentrations of mono- (MBT), di- (DBT), and tri-(TBT) butyltin compounds were measured in eggs, liver, and muscle of nine species of fish from four regions of the Baltic Sea - the Firth of Vistula, the Gulf of Gdańsk, Puck Bay, and the mouth of the Vistula River. The overall concentration ranges among all the fish sampled from the four sites were: < 7 to 79 ng/g for MBT, 6 to 1100 ng/g for DBT, 7 to 3600 ng/g for TBT, and 16 to 4800 ng/g for total BTs, on a wet wt basis. The highest concentration of total BTs was found in herring liver from the Firth of Vistula (4800 ng/g, wet wt) and in roach muscle from Puck Bay (3300 ng/g, wet wt), while the least concentration was found in burbot eggs and liver from the Vistula River (39 and 32 ng/g, wet wt, respectively). TBT was the major form of BTs present in most samples analyzed. Sediment samples collected from shipyards in the Gulf of Gdańsk contained butyltin concentrations ranging from 1.2 to 46 μg/g (dry wt) for MBT, 2.0 to 42 μg/g for DBT, and 2.6 to 40 μg/g for TBT. As with the fish, the majority of the BTs in sediment were present as TBT, which suggested recent exposure of the aquatic environment of the region to TBT.     

Malathion-induced sublethal toxicity on the hematology of cricket frog (Fejervarya limnocharis)

The effect of malathion [diethyl(dimethoxythiophosphorylthio)succinate] at sublethal concentration (0.006 ppm) on hematological parameters of the cricket frog (Fejervarya limnocharis) was studied for 24 hrs to 240 hrs of exposure and remarkable hematological alterations were observed. The study on hematological parameters revealed a highly significant decrease (P < 0.01) in the total erythrocytes count in malathion-exposed animals from 24 hours to 96 hrs of exposure as compared to control. Significant decreases (P < 0.01) of hemoglobin and packed cell volume were also observed from 48 hrs to 240 hrs. A significant increase (P < 0.01) in leucocytes count was noted throughout the exposure period. Elevated numbers of lymphocytes and eosinophils as found in the present study revealed lymphocytosis as well as eosinophilia, suggesting that this was a result of direct stimulation of the immunological defense due to the presence of a toxic substance or may be associated with tissue damage. The cytomorphological and cytopathological study of erythrocytes and leucocytes in malathion-exposed frogs at 0.006 ppm concentration revealed various cytotoxic effects at different exposure times. It was noted that the size and the shape of the erythrocytes were subjected to variation in different blood disorders.     

Relation between forest vegetation, atmospheric deposition and site conditions at regional and European scales

Several monitoring programs have been set up to assess effects of atmospheric deposition on forest ecosystems. The aim of the present study was to evaluate effects on the understorey vegetation, based on the first round of a regional (the Netherlands) and a European forest monitoring program. A multivariate statistical analysis showed surprisingly similar results for both data sets; the vegetation appeared to be largely determined by the ‘traditional’ factors soil, climate, and tree species, but there was a small but statistically significant effect of atmospheric deposition. The effects of deposition include a slight shift towards nitrophytic species at high N deposition in the European network, and towards acidophytic species at high S-deposition in the Dutch network. The relatively small effect of atmospheric deposition is understandable in view of the very large natural variation in environmental conditions. Time series of both vegetation and environment are needed to assess deposition effects in detail.