二氧化氯销毁氰化物的应用研究

在弱碱性条件下，二氧化氯消毒剂将氰化物氧化成无毒的氰酸盐（OCN）、二氧化碳和氮气。研究了影响二氧化氯销毁氰化物的几种因素：pH在8—11的范围内，不影响二氧化氯对氰化物的销毁率；在所试验的反应温度（0-40℃）内，温度对反应速率表现出有限的影响；二氧化氯与氰离子的最佳质量比为2：1；当氰离子最高使用浓度小于0．5g／L时，废水中氰离子浓度达一级以上的排放标准。     

二氧化氯处理矿山含氰废水的实验研究

实验采用二氧化氯(ClO2)作为矿山含氰废水处理剂,含氰废水在pH值8.5～11.5范围之间,ρ(ClO2/CN-)≥3的条件下,搅拌反应30 min后,氰化物去除率达99%以上,pH值＜9,ρ(CN)＜0.5 mg/L,达到<污水综合排放标准>中的一级标准.实验表明,利用二氧化氯的强氧化性处理矿山含氰废水,具有投药量少、使用便捷、无二次污染等优点,并且处理效果明显优于传统次氯酸盐处理法.     

二氧化氯处理矿山含氰废水的实验研究

实验采用二氧化氯 ( Cl O2 )作为矿山含氰废水处理剂 ,含氰废水在 p H 8.5～ 11.5之间 ,Cl O2 /CN- ≥ 3 (质量比 )的条件下 ,搅拌反应 3 0 min后 ,氰化物去除率达 99%以上 ,p H<9,CN- <0 .5 mg/L,达到《污水综合排放标准》中的一级标准。实验表明 ,利用 Cl O2 的强氧化性处理矿山含氰废水 ,具有投药量少、使用便捷、无二次污染等优点 ,且处理效果明显优于传统次氯酸盐处理法。     

高效降氰菌群的构建及降解特性

从筛选到的降氰菌中构建出了优于单一菌种降氰活性的复配菌群CNR.研究了该复合菌群的生长条件,探讨了温度、pH、接种量、氰化物初始浓度及降解时间等因素对CNR降氰的影响.研究表明,复配菌群CNR适应碱性环境,可降解高浓度氰化物(CN-11 000 mg/L),并对金属氰化物和脂肪族腈具有极强的降解能力.在有氧、pH 11、33 ℃和接种量10%条件下.含CN-11 000 ng/L培养液经60 h降解后,CN-1浓度降为0.49 mg/L,降氰率高达99.96%,达到国家一级排放标准.     

次氯酸钠处理终冷水中氰化物硫化物的研究

以次氯酸钠为氧化剂,用正交实验研究了次氯酸钠处理终冷水中氰化物和硫化物,得出正交实验中各因素的主次关系及对除氰除硫的影响。研究结果表明,反应体系的pH是影响脱氰脱硫的重要因素。在最佳处理条件,即pH为10．0,反应温度为25℃,投氯量系数为1．4,反应时间为45min．能使氰化物的质量浓度降至0．267mg／L,脱氰率高达99．8％,硫化物的质量浓度降到0．387mg／L,脱硫率达92．0％,达到≤0．5mg／L的国家排放标准。文章还对工业化提出了一些设想。     

铜氰溶液的电子束辐照降解

研究了铜氰溶液中总氰初始浓度、pH、铜浓度等对总氰降解效率的影响,比较了KCN溶液和铜氰溶液的总氰降解率,初步推断了铜氰溶液在辐照过程中的降解机制.实验结果表明,在同样的辐照剂量下,随着总氰初始浓度的增加,总氰降解率降低,相应的总氰降解G值增大;铜浓度越低,总氰降解率越高;pH越小的铜氰溶液总氰降解率越高.电子束辐照KCN溶液和铜氰溶液的总氰降解反应属于表观一级反应.在相同的辐照剂量下,KCN溶液的总氰降解率比铜氰溶液要高得多.铜氰溶液的电子束辐照降解过程非常复杂,主要是铜氰络合离子逐步离解出的CN-与·OH的反应.     

液体高铁酸钠同时去除电镀废水中氰化物和重金属

采用自制的电化学装置在线制备液体高铁酸钠,然后将制得的高铁酸钠投加到电镀废水中进行处理,考察不同pH值和不同高铁酸钠投加量对废水中总氰化物、Cu~(2+)、Ni~(2+)去除率的影响;对比研究了高铁酸钠氧化法和次氯酸钠氧化法在处理低浓度含氰电镀废水的效果。结果表明,当pH为9~10,高铁酸钠的最佳投加量为0.O.24±0.048 mmol·L~(-1)时,总氰化物、Cu~(2+)和Ni~(2+)的同时去除率均在90%以上;在处理低浓度含氰电镀废水时,高铁酸钠对总氰化物、Cu~(2+)和Ni~(2+)的同时去除率均明显高于次氯酸钠。这是因为高铁酸钠能够有效地氧化多种络合态的氰化物,包括Cu(CN)_4~(3-)、Cu(CN)_4~,Ni(CN)_4~(2-)等使废水中的重金属转变为离子态;然后在碱性条件下在高铁酸盐还原产物-Fe(OH)_3助凝和絮凝作用下,反应生成沉淀达到同时去除氰化物和重金属的目的。     

离子交换纤维对金属氰络合物吸附性能的研究

采用强碱性离子交换纤维对含氰废水中主要离子铜氰络合物、锌氰络合物的吸附性能进行了研究.实验结果表明:含氰废水的pH在8～11范围内,纤维材料对金属氰络合物具有良好的吸附性能;纤维对铜氰络合物、锌氰络合物的吸附速率很快,4 min左右就可达吸附平衡;温度对铜氰络合物、锌氰络合物吸附影响不大,纤维的这些吸附特点对工业应用非常有利.     

焦化废水除氰工艺的优化研究

对某焦化厂生化出水进行了除氰研究。对硫酸亚铁混凝除氰法进行了优化,采用沉淀净化法对其出水进行深度处理,考察了工艺中不同影响因素对总氰化物(TCN)去除效果的影响。结果表明,硫酸亚铁混凝除氰法的最佳反应条件为pH 5.00、FeSO4·7H2O投加量500mg/L、反应时间15min、沉淀时间30min;在此条件下,当原水TCN质量浓度为3.1~4.1mg/L时,出水TCN质量浓度达到0.60~0.70mg/L,需作进一步的深度处理。采用沉淀净化法处理硫酸亚铁混凝除氰法出水的最佳反应条件为先同时投加药剂A和药剂B,投加量分别为150、0.75mg/L,反应15min后,再按2mg/L投加药剂C,继续反应3min,最终出水TCN质量浓度低于0.1mg/L,达到《炼焦化学工业污染物排放标准》(GB 16171—2012)要求(氰化物排放限值为0.2mg/L);在此条件下,单位废水处理的药剂成本合计约为0.25元/t。     

废水中总氰化物的测定

由于氰离子与有生命体的血液中氧化型细胞色素氧化酶结合,阻碍它还原成还原型细胞色素氧化酶,造成生命的死亡。因此,测定氰离子总量是有极重要的意义。 总氰化物的测定(测出的是CN~-离子)指简单氰化合物A(CN)_X(A为H~+、K~+、Na~+、Ca~(+2)、Ba~(+2)等)与络合氰化物[Ay·M(CN)_X](M为Fe~(+3)、Fe~(+2)、Cd~(+2)、Cu~(+1)、Cu~(+2)、Ni~(+2)、Zn~(+2)、Ag~(+1)、     

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.