基于人工神经网络和遗传算法研究锰过氧化酶脱色甲基橙

基于锰过氧化物酶(MnP)氧化脱色偶氮类染料的原理,实验研究MnP对甲基橙的脱色工艺,采用人工神经网络(ANN)和遗传算法(GA)建立脱色模型并优化工艺。建立的ANN模型的误差、相关系数、均方根误差和绝对平均偏差分别为0.0009、0.9971、1.21和6.82,模型有效且能够用于预测和工艺优化。采用GA对ANN模型进行数值寻优,得到的最佳工艺条件为酶液量0.6 mL,Mn2+浓度4 mmol/L,H2O2浓度0.49 mmol/L。该条件下脱色率达到(90.74±0.59)%。ANN耦合GA有效地建立了锰过氧化物酶脱色甲基橙的模型,并优化了工艺参数,为甲基橙脱色的研究提供一定参考。     

Phanerochaete chrysosporium吸附载体的选择及染料降解研究

研究了游离细胞与载体吸附培养、不同载体材料对Phanerochaete chrysosporium进行连续染料脱色及产酶能力的影响。结果表明,P.chrysosporium可在载体上良好生长,甚至生长到载体内部。木屑、玉米芯、花生壳3种载体材料中,以木屑载体吸附培养物的持续脱色和产酶效果最佳,该培养物经三轮连续脱色后对染料RB5仍能达到最高95%的脱色率,并产生596 U/L锰依赖过氧化物酶（MnP）和1 326 U/L木质素过氧化物酶（LiP）,对染料的持续脱色和产酶能力明显优于游离细胞培养物。     

多能场协同紫外光催化降解甲基橙的实验研究

以甲基橙为模拟废水,负载型纳米TiO2为光催化剂,在自制的多能场组合反应器中,初步研究了电场和超声场协同紫外光催化降解水中甲基橙的特点和规律。结果表明,在偏置电场电压为20 v,超声场声频为21.33 kHz、声强为0.375 W/cm2,紫外光波长为366 nm,功耗为O.25 W/mL,TiO2催化降解负荷为1.25 mL/cm2的条件下,对浓度为4 mg/L的甲基橙溶液分别处理30 min和90 min,脱色率分别可达91.67％和95.36％;比单一紫外光催化降解脱色率分别提高86.59％和86.79％。     

三株白腐菌产锰过氧化物酶活性及其对多环芳烃的降解

比较研究了β-环糊精(β-CD)对3株黄孢原毛平革菌(Phanerochaete chrysosporium)CGMCC5.776、GIM3.383和GIM3.393产锰过氧化物酶(MnP)和降解多环芳烃(PAHs)的影响.结果表明:3株菌都能分泌出高活性的MnP,β-CD能显著提高MnP的活性.加入2.0 g/Lβ-CD的体系培养到第12天时.酶活性最高达到2 912.5 U/L;而且β-CD能显著提高PAHs的降解率,两者之间存在较好的相关性.加入1.0 g/L β-CD的体系对比不加β-CD的体系,PAHs的降解率提高了1～2倍.PAHs的降解同时受到MnP活性、PAHs表观溶解度和分子结构稳定性等因素的影响.     

微波促进含Cr(Ⅵ)-H2O2体系降解甲基橙溶液的研究

研究了微波辐射下Cr(Ⅵ)-H2O2催化降解甲基橙溶液的行为,探索了微波功率、微波辐射时间、pH值、H2O2浓度、Cr(Ⅵ)等对甲基橙溶液脱色率和COD去除率的影响.研究结果表明,Cr(Ⅵ)-H2O2能形成类Fenton体系;微波辐射可提高H2O2产生羟基自由基(·OH)的效率.1000 mg/L的甲基橙溶液,在Cr(Ⅵ)浓度为10.0 mmol/L、pH值为2.5、H2O2浓度为20.0 mmol/L、微波功率为700W下加热2 min,甲基橙溶液的脱色率为99.2%,COD去除率为82.8%.     

Fe(II)EDTA/H_2O_2电催化降解甲基橙模拟废水的研究

在无隔膜电解槽中,采用SPR(Ru-Ir-TiO_2)为阳极,石墨为阴极,考察了Fe(II)EDTA/H_2O_2电催化降解甲基橙(methyl orange)模拟废水的影响,发现EDTA很大程度上促进了类电Fenton试剂对甲基橙模拟废水的降解.实验研究表明,在外加电压为5.0v,EDTA:Fe~(2+) =2:1(摩尔比,Fe~(2+) =40 mmol/L),H_2O_2=48 mmol/L,电解质Na_2SO_4=40 mmol/L,废水pH值为(6.5±0.1)的条件下,降解260 mg/L的甲基橙模拟废水90 min,EDTA的加入可以使甲基橙模拟废水的脱色率由29.5%上升到78.4%,COD由571.429 mg/L降至80 mg/L,COD的降解率为86%,EDTA在此过程中既是催化剂又是反应物,可有效避免EDTA带来二次环境污染的可能性.     

TiO2/CdS复合半导体光催化剂降解甲基橙的实验研究

采用Sol-Gel法制备TiO2/CdS复合半导体光催化剂,以8 W-365 nm的紫外灯为光源、甲基橙溶液模拟染料废水、在自制的光催化反应器中研究TiO2/CdS的光催化活性和光催化降解甲基橙的特点和规律.结果表明,当CdS掺入量为0.5%(摩尔比)时,TiO2/CdS的光催化活性最高;当CdS的掺入量＞3.5%(摩尔比)时,TiO2/CdS光催化剂的光催化活性低于TiO2的光催化活性;对初始浓度为15 mg/L的甲基橙溶液处理2.5 h后,脱色率可达44%;甲基橙的光催化降解反应符合Y=A B1×X B2×X2动力学模型.     

载体吸附培养黄孢原毛平革菌(Phanerochaete chrysosporium)和云芝(Trametes versicolor)对染料的脱色

比较研究了不同载体吸附培养的黄孢原毛平革菌(Phanerochaete chrysosporium)和云芝(Trametes versicolor)对染料连续脱色的效果。结果表明:(1)白腐真菌黄孢原毛平革菌和云芝分别在含有球形的木屑、玉米芯和花生壳载体的液体环境中振荡培养,菌体以膜状或团状形式大量附着生长在载体表面。(2)连续4轮脱色过程中,不论黄孢原毛平革菌还是云芝,都是木屑为载体的培养液的持续脱色和产酶能力最好,宜选择木屑为载体。其中,木屑为载体的黄孢原毛平革菌培养液经过2轮连续12d脱色后对活性黑RB5的最高脱色率仍能达到97%,在第3轮脱色中对活性红M-3BE的最终脱色率接近96%,并且能产生最高611U/L的锰依赖过氧化物酶(MnP)和1 477U/L的木质素过氧化物酶(LiP)。(3)在实际应用中应该将木屑为载体的黄孢原毛平革菌和云芝培养液都投加到含染料废水处理系统中,强化生物处理效果。     

多能场协同紫外光催化降解甲基橙的实验研究

以甲基橙为模拟废水，负载型纳米TiO2为光催化剂，在自制的多能场组合反应器中，初步研究了电场和超声场协同紫外光催化降解水中甲基橙的特点和规律。结果表明，在偏置电场电压为20V，超声场声频为21．33kHz、声强为O．375W／cm^2，紫外光波长为366nm，功耗为0．25W／mL，TiO2催化降解负荷为1．25mL／cm^2的条件下，对浓度为4mg／L的甲基橙溶液分别处理30min和90min，脱色率分别可达91．67％和95．36％；比单一紫外光催化降解脱色率分别提高86．59％和86．79％。     

Fe（Ⅱ）EDTA／H2O2电催化降解甲基橙模拟废水的研究

在无隔膜电解槽中，采用SPR（Ru—Ir—TiO2）为阳极，石墨为阴极，考察了Fe（Ⅱ）EDTA／H2O2电催化降解甲基橙（methylorange）模拟废水的影响，发现EDTA很大程度上促进了类电Fenton试剂对甲基橙模拟废水的降解。实验研究表明，在外加电压为5．0V，EDTA：Fe2＋=2：1（摩尔比，Fe2＋=40mmol／L），H202=48mmot／L，电解质Na2SO4=40mmol／L，废水pH值为（6．5±0．1）的条件下，降解260mg／L的甲基橙模拟废水90min，EDTA的加入可以使甲基橙模拟废水的脱色率由29．5％上升到78．4％，COD由571．429mg／L降至80mg／L，COD的降解率为86％，EDTA在此过程中既是催化剂又是反应物，可有效避免EDTA带来二次环境污染的可能性。     

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 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.     

A History of Dry Cleaners and Sources of Solvent Releases from Dry Cleaning Equipment

Approximately 25, 000-35, 000 dry cleaning facilities currently operate in the U.S. The release of perchloroethylene and other solvents from these establishments represents a major source of soil and groundwater contamination. The manner in which dry cleaning solvents escape from dry cleaning plants is, for all practical purposes, identical for chlorinated and petroleum hydrocarbon solvents and is related to one of the following events: the catastrophic failure of a component of the dry cleaning system, the improper installation, operation or maintenance of the dry cleaning equipment or a combination of all of these causes. Acceptable customs, codes and regulations can also dictate what is authorized for operation of a dry cleaning facility in a particular community, geographic area during a particular time frame. Environmental litigation dealing with the origin of a solvent release from dry cleaners tends to focus on the design and manufacture of dry cleaning industry machines such as washers, washer extractors, tumblers, solvent filters, water separators, stills and spotting boards. A thorough analysis of the daily operations of dry cleaners often reveals that poor maintenance, failure to follow the manufacturer's instructions and the actions of the operator are the most likely causes of soil and groundwater pollution. In order to forensically evaluate the most probable origins of a solvent release and to examine issues regarding liability, a thorough understanding of the history of dry cleaning and a detailed analysis of the operation and maintenance of the dry cleaning equipment are necessary. The discovery of solvent plumes in the vicinity of dry cleaning plants may suggest that the solvent source is the dry cleaning plant; however, the presence of these plumes does not necessarily indicate that the dry cleaning equipment was defectively designed or manufactured. A thorough review of the type of equipment used over the life of the dry cleaning plant and verifiable solvent mileage records frequently indicates that operators of the plant have disposed of solvent and contaminated solids into the municipal sewer or on ground surfaces.     

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.