微气泡曝气 O3/ H2O2处理 RO 浓水的效能及影响因素简

采用O₃/H₂O₂高级氧化工艺处理炼油厂反渗透（RO）浓水，用溶气泵加压溶气并产生微气泡强化传质，确定装置运行条件，考察气体中臭氧浓度、H₂O₂/O₃初始摩尔比、pH和温度对O₃/H₂O₂处理RO浓水效果的影响，并对RO浓水处理效能进行研究。结果表明，随着气体中臭氧浓度的增加，COD的去除率基本呈线性增加；加入适当量H₂O₂能提高臭氧氧化RO浓水的效果，H₂O₂/O₃初始摩尔比在0~0.8范围内，COD的去除率先增加后下降，H₂O₂/O₃初始摩尔比为0.5时COD去除率最大；pH从6.84增加到9.01，COD去除率逐渐增大，pH为10.03时COD去除率反而降低；在14~28℃范围内，温度低时，升高温度COD去除率增加较大，温度较高时，升高温度对COD去除率的影响较小。为考察该工艺的稳定性，在H₂O₂/O₃初始摩尔比为0.5、溶液pH为8~9、臭氧浓度为80~100 mg/L、温度为10~28℃条件下，对COD为90~140 mg/L的RO浓水氧化处理4~10 h，出水COD维持在39.9~49.9 mg/L，达到《城镇污水处理厂污染物排放标准（GB 18918-2002）》中的一级A标准；去除1 g COD消耗O₃ 1.4~3.3 g，消耗O₃与H₂O₂的总氧量为2.2~4.4 g。     

氨吹脱-Fenton氧化预处理阿奇霉素废水的研究

采用氨吹脱-Fenton试剂氧化法对阿奇霉素废水进行预处理，考察了各种因素对处理效果的影响。实验结果表明：在pH值为11，吹脱时间160 min，温度30℃的条件下，氨氮浓度从2 458.7 mg/L降低到421.7 mg/L，去除率可达82.85%；Fenton氧化吹脱出水的适宜工艺条件：初始pH值为3、反应时间90 min、FeSO₄·7H₂O投加量为0.01 mol/L、H₂O₂/Fe²⁺的投加比16∶1，此时，COD去除率为72.6%；废水经预处理后，有效地改善了废水水质，提高了废水的可生化性，由初始的0.1增至0.37，为后续废水的生化处理提供了有利条件。     

UV-Fenton光催化氧化处理高浓度邻苯二甲酸二辛酯生产废水

采用UV-Fenton技术光催化氧化高浓度邻苯二甲酸二辛酯（DOP）生产废水，确定最佳操作条件为：初始pH=3.8，H₂O₂浓度为9.99 g/L，H₂O₂/Fe²⁺摩尔比为20∶1，光照反应60 min。此条件下的废水COD去除率为89.1%，出水COD值在570 mg/L左右。经正交试验确定影响处理效果各因素的重要性顺序为：H₂O₂浓度＞H₂O₂/Fe²⁺摩尔比＞光照反应时间＞pH。UV的加入与单独的Fenton体系存在正相关的协同作用。废水降解的表观过程符合一级反应动力学模式。     

O3/UV预处理磺酰脲类除草剂生产废水的研究

采用O₃/UV工艺预处理磺酰脲类除草剂生产废水，考察了初始pH值、臭氧投量、叔丁醇投加等因素对废水处理效果的影响，并初步探讨了该工艺处理废水的反应机理。实验结果表明，在废水初始pH为13.59和臭氧投量为65.08 mg/min的条件下，预处理80 min后废水COD去除率达63.47%，BOD₅/COD由0.03提高至0.56，EC50从11%提高至55%。随着叔丁醇浓度的增加，废水COD去除率明显降低，证明该反应体系有?OH存在；体系中加入MnO₂后废水COD去除率下降了16%，氧化效率明显下降，证明该反应体系内中间产物H₂O₂在O₃/UV降解有机废水过程中起到了重要的作用。     

O3、H2O2/O3及UV/O3在焦化废水深度处理中的应用

采用O₃、H₂O₂/O₃和UV/O₃等高级氧化技术(AOPs)对某焦化公司的生化出水进行深度处理，考察了O₃与废水的接触时间、溶液pH、反应温度等因素对废水COD去除率的影响，确定出O₃氧化反应的最佳工艺参数为：接触时间40 min，溶液pH 8.5，反应温度25℃，此条件下废水COD及UV₂₅₄的去除率最高可达47.14%和73.47%；H₂O₂/O₃及UV/O₃两种组合工艺对焦化废水COD及UV₂₅₄的去除率均有一定程度的提高，但H₂O₂/O₃系统的运行效果取决于H₂O₂的投加量。研究结论表明，单纯采用COD作为评价指标，并不能准确反映出O₃系列AOPs对焦化废水中有机污染物的降解作用。     

天然沸石负载La2O3-ZnO-TiO2光催化降解活性艳红K-2BP

利用80目天然斜发沸石作载体制备La₂O₃(0.5%)-ZnO(20%)-TiO₂/沸石复合光催化剂，以20 W紫外灯为光源，在自制的光催化反应器中降解活性艳红K-2BP，考察了光照时间、空气通入量、催化剂用量、溶液初始浓度、H₂O₂与Fe³⁺投加量等对活性艳红K-2BP光催化降解率的影响。结果表明，当溶液初始浓度为60 mg/L，催化剂投加量为12 g/L，通气量为1 200 mL/min，光照2.5 h，活性艳红K-2BP的降解率可达99.2%；H₂O₂和Fe³⁺投加量为4 mL/L和3 g/L时，光照1 h活性艳红K-2BP降解率分别为100%和97.2%。紫外可见吸收光谱显示，LZTZ光催化剂可有效降解印染废水。     

O3/H2O2降解阿特拉津影响因素研究

采用O3/H2O2氧化去除水中内分泌干扰物阿特拉津，考察了反应条件及水质对去除的影响，并对反应机制进行了初步探讨。阿特拉津初始浓度2 mg/L，投量为7.5 mg/L的O₃单独氧化去除率为27.2%；相同O₃投量下，控制H₂O₂/O₃摩尔比为0.75，5 min阿特拉津的去除率最高可达96.5%；pH 值为7.5～8.5，温度在25～40℃的范围内，都维持了较高的去除率，表明H₂O₂/O₃体系对阿特拉津的去除效果良好，降解速度快，反应条件温和。0.5 mg/L的腐殖酸，对阿特拉津的去除影响不大，腐殖酸浓度为1、2和5 mg/L时，平均去除率分别为63.4%、50.7%和30.2%；碳酸氢钠的浓度为50和200 mg/L时，去除率分别为88.1%和73.8%，说明水质对阿特拉津的去除影响较大。叔丁醇的浓度为5和20 mg/L时，阿特拉津的去除率分别降低到44.7%和27.5%，去除率随自由基抑制剂叔丁醇增加而降低，说明H₂O₂/O₃降解阿特拉津主要为该体系产生的羟基自由基的贡献。     

vis／H2O2／草酸铁处理活性艳红染料的实验研究

采用vis／H₂O₂／草酸铁法，对活性艳红染料废水进行处理。研究了H₂O₂、K₂C₂O₄和Fe₂(SO₄)₃·7H₂O的投加量、pH值和光照时间等因素对染料废水处理效果的影响和最佳处理条件。结果表明，pH值2.5；30%H₂O₂的投加量0.1 mL；0.1 mol/L Fe₂(SO₄)₃·7H₂O的投加量1.0 mL；0.1 mol/L K₂C₂O₄的投加量1.5 mL；光照时间40 min的最佳条件下，70 mg/L的活性艳红模拟染料废水脱色率可达99.82%。通过对vis／H₂O₂／草酸铁法和Fenton法、H₂O₂法、草酸铁法等方法进行对比实验，vis／H₂O₂／草酸铁法明显优于其他方法，是一项有研究价值和开发应用前景的污染治理新技术。     

用H2O2/Fe3+处理高浓度含甲醛废水的研究

研究采用H₂O₂/Fe³⁺催化氧化处理高浓度含甲醛废水，探讨了双氧水和催化剂投加量、反应pH及反应温度等操作条件对处理效果的影响，并通过酸溶解回用失活催化剂。结果表明，较优的操作条件为：H₂O₂/COD（质量比）=2.2～2.6，Fe³⁺/H₂O₂（摩尔比）=0.048～0.058，反应pH 1.80～2.68，反应温度50℃，反应时间40 min；在上述操作条件下，甲醛去除率达到99%以上，COD去除率达到85%以上。失活的催化剂可通过稀酸溶解后循环使用，其效果与三价铁盐作催化剂的基本相同。采用H₂O₂/Fe³⁺处理含甲醛废水具有比采用H₂O₂/Fe³⁺较优的效果。     

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%。     

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 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.     

Influence of crop residues on trifluralin mineralization in a silty clay loam soil

Trifluralin is typically applied onto crop residues (trash, stubble) at the soil surface, or onto the bare soil surface after the incorporation of crop residues into the soil. The objective of this study was to quantify the effect of the type and amount of crop residues in soil on trifluralin mineralization in a Wellwood silty clay loam soil. Leaves and stubble of Potato (Solanum tuberosum) (P); Canola (Brassica napus) (C), Wheat (Triticum aestivum) (W), Oats (Avena sativa), (O), and Alfalfa (Medicago sativa) (A) were added to soil microcosms at rates of 2%, 4%, 8% and 16% of the total soil weight (25 g). The type and amount of crop residues in soil had little influence on the trifluralin first-order mineralization rate constant, which ranged from 3.57E-03 day^?1 in soil with 16% A to 2.89E-02 day^?1 in soil with 8% W. The cumulative trifluralin mineralization at 113 days ranged from 1.15% in soil with 16% P to 3.21% in soil with 4% C, again demonstrating that the observed differences across the treatments are not of agronomic or environmental importance.     

Concurrent nitrate and Fe(III) reduction during anaerobic biodegradation of phenols in a sandstone aquifer

The biodegradation of phenols (5, 60, 600 mg l⁻¹) under anaerobic conditions (nitrate enriched and unamended) was studied in laboratory microcosms with sandstone material and groundwater from within an anaerobic ammonium plume in an aquifer. The aqueous phase was sampled and analyzed for phenols and selected redox sensitive parameters on a regular basis. An experiment with sandstone material from specific depth intervals from a vertical profile across the ammonium plume was also conducted. The miniature microcosms used in this experiment were sacrificed for sampling for phenols and selected redox sensitive parameters at the end of the experiment. The sandstone material was characterized with respect to oxidation and reduction potential and Fe(II) and Fe(III) speciation prior to use for all microcosms and at the end of the experiments for selected microcosms.The redox conditions in the anaerobic microcosms were mixed nitrate and Fe(III) reducing. Nitrate and Fe(III) were apparently the dominant electron acceptors at high and low nitrate concentrations, respectively. When biomass growth is taken into account, nitrate and Fe(III) reduction constituted sufficient electron acceptor capacity for the mineralization of the phenols observed to be degraded even at an initial phenols concentration of 60 mg l⁻¹ (high) in an unamended microcosm, whereas nitrate reduction alone is unlikely to have provided sufficient electron acceptor capacity for the observed degradation of the phenols in the unamended microcosm.For microcosm systems, with solid aquifer materials, dissolution of organic substances from the solid material may occur. A quantitative determination of the speciation (mineral types and quantity) of electron acceptors associated with the solids, at levels relevant for degradation of specific organic compounds in aquifers, cannot always be obtained. Hence, complete mass balances of electron acceptor consumption for specific organic compounds degradation are difficult to confine. For aquifer materials with low initial Fe(II) content, Fe(II) determinations on solids and in aqueous phase samples may provide valuable information on Fe(III) reduction. However, in microcosms with natural sediments and where electron acceptors are associated with the sediments, complete mass-balances for substrates and electron acceptors are not likely to be obtained.