多相组合膜生物反应器对精细化工废水处理的应用研究

通过多相组合膜生物反应器对精细化工废水的处理试验，分析了COD、NH3-N、TP指标的去除效果。在装置进水浓度COD为600—900mg／L、NH3-N20～40mg／L、TP2．0～6．0mg／L时，出水COD为80—120mg／L，NH3-N未检出，TP为0．5—2．0mg／L，COD的去除率稳定在87％左右，NH3-N的去除率大于99％，TP的去除率稳定在75％左右。研究表明，多相组合膜生物反应器非常适合精细化工废水的处理。     

混凝-生物接触氧化处理合成橡胶碱洗废水

对化学合成橡胶碱洗废水进行了有机组分和可生化性分析，废水主要含有氯甲烷、六甲苯、异丁醇、甲醇等污染物质，生化降解实验中废水TOC可在6d内从60．9mg／L下降至0．0mg／L，可生化降解性好，适于生化处理。选择混凝．生物接触氧化组合工艺对废水进行处理，采用优化条件（pH=8、PAC=40mg／L、PAM=8mg／L）进行混凝，碱洗废水COD去除率为9．95％～72．94％（平均31．51％）；混凝后的碱洗废水与冲洗废水1：5混合进行接触氧化处理，在HRT为36h的情况下，COD去除率为65．6％-72．6％（平均70．4％），出水COD为134～331mg／L，满足企业废水排放市政管网的要求；同时，实验发现COD去除率与COD容积负荷存在指数函数变化关系。     

O3氧化工艺处理黄连素制药废水研究

采用臭氧（O3）氧化法处理含高浓度黄连素和COD的制药废水，探讨了废水初始pH、O3投加量及初始黄连素浓度等因素对O3氧化过程的影响，确定了O3氧化技术处理黄连素制药废水的最佳操作条件。结果表明，O3能够有效分解废水中的黄连素，降低其COD浓度；黄连素浓度为700mg／L、COD为3500mg／L、pH为0．88的废水，进气O3浓度为14．05mg／（L·min），处理时间为180rain（即投加量为2529mg／L）时，黄连素和COD的降解率分别可达77．46％和41．28％，BOD，／COD比（B／C比）从0．06提高到0．34，增加了4．7倍；随着废水中初始黄连素浓度的升高，废水COD降解率逐渐降低。O3氧化法是一种有效的黄连素制药废水预处理技术，可以大大提高废水的可生化性。     

三维电极-好氧生物法联合处理酸性染料废水模拟研究

采用电解-好氧生物法联合处理酸性大红G模拟废水，三维电解反应器填料为活性炭与玻璃珠混合物，平板电极材料为石墨，通过正交实验确定的最佳实验条件为：电解时间150min，活性炭／玻璃珠体积比为2：1，槽电压20V、pH为5、Na2SO4投加量1．5g／L，进水初始浓度2000mg／L。此时COD去除率及色度去除率分别可达49．78％和81．45％，废水BOD，／COD由0．12提高到0．42。电解后的废水采用生物接触氧化法处理12h后，出水COD为48mg／L，色度120倍，达到综合污水排放二级标准。     

臭氧-曝气生物滤池处理酸性玫瑰红染料废水

在实验室配制含酸性玫瑰红染料的印染废水，采用臭氧氧化-曝气生物滤池工艺开展处理试验。试验运行结果表明，臭氧氧化处理能提高模拟废水的可生化性，BOD／COD值由原水的0．18上升到0．36。经组合工艺处理后出水COD〈40mg／L，色度40倍以下，SS约50mg／L，处理效果良好。     

生物质材料预处理餐饮废水

采用4种廉价的生物质材料（水葫芦、柚子皮、木屑、核桃壳）用于餐饮废水的预处理。通过静态烧杯实验，研究了各生物质材料预处理废水的效果及最佳处理条件。结果表明，生物质材料对废水中COD的去除率均在45％以上，油脂吸附量为4～16mg／g，最优吸附材料为水葫芦，COD去除率达65％，油脂吸附量为16mg／g；水葫芦和柚子皮的最佳处理条件为：粒径〈0．2mm，投加量为20g／L，废水pH为4，处理时间为2h，温度为20℃；木屑和核桃壳的最佳实验条件为：粒径〈0．2mm，投加量为28g／L，pH为2，处理时间为2．5h，温度为20℃。生物质对餐饮废水的预处理，为废水中大量有机物和废弃油脂的去除提供了新思路和途径。     

Fenton氧化深度处理高浓度造纸废水的中试实验

采用Fenton氧化开展了对高浓度造纸废水深度处理的中试实验，对Fenton氧化的COD的去除效果，各药剂加药量及成本，排泥量和装置运行的稳定性等进行探讨和分析，结果表明，一级Fenton氧化的COD去除率可达到90％以上，出水COD在100mg／L左右，总加药成本在6元左右，排泥量约为1～1．2kg／t废水；二级Fenton氧化的COD去除率在96％左右，出水COD小于60mg／L，总加药成本在8元左右，排泥量约为1．15～1．4kg／t废水，验证了Fenton氧化用于高浓度造纸废水深度处理达到新的排放标准的可行性。     

采用HSB菌种生化处理焦化废水

采用HSB微生物菌种技术和缺氧-好氧（O-O／A工艺）组合工艺处理焦化废水的研究，结果表明，该技术处理焦化废水有很好的效果，COD从2500mg／L左右降至130mg／L以下，去除率达94．8％以上；NH3-N从500mg／L降至15mg／L以下，去除率达97％以上；出水COD、氨氮、酚、氰、油等污染物均可达《污水综合排放标准》（GB8987--1996）二级标准。     

加热酸化-Fenton氧化处理乳化液废水

采用加热酸化-Fenton氧化处理乳化液废水，在加酸量为1．0mL98％H2SO4／100mL乳化液、加热温度95℃、加热时间1h条件下，初始COD〉20万mg／L，浊度〉8000NTU的乳化液COD降低到46592mg／L，浊度降低到20NTU，加热和酸化的联合过程达到了良好的破乳效果；破乳后的出水在ρ（Fe2＋）／ρ（H2O2）=1：30、ρ（H2O2）和（COD）=1．4、pH=4的条件下进行Fenton氧化，处理后的出水COD可降到18600mg／L，去除率达61．4％，其B／C可由破乳后的0．11提高到0．43，废水的可生化性大大提高，为后续处理创造了可能。     

Fenton氧化与生化组合技术处理油田采油废水的研究

采用Fenton氧化与生化组合技术处理生物难降解的采油废水的研究结果表明，Fenton氧化技术不但对采油废水中有机质有较好的去除率，而且大大地改善了废水的可生化性，在H2O2的投加浓度和Fe^2 与H2O2的摩尔比分别为10mmol／L和0．1的条件下，经过30min氧化后可使废水BOD值由原来的5mg／L上升至40mg／L；同时随着氧化时间的延长，废水中残余的有机物分子量逐渐降低。30min氧化后的废水经过生物处理，其出水COD值为102mg／L，可以满足国家综合污水外排标准，经济分析结果表明，该技术处理采油废水的运行成本为1．47元／t。这一技术在解决石油行业采油废水的外排达标方面具有很好的应用前景。     

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.