水力空化耦合电解抑藻工艺性能的初步研究

采用水力空化与电解耦合的工艺去除水体中的藻类。初步探索了包括空化管径和电解时间在内的处理工艺参数，改善了处理装置结构。试验选用天然水体优势藻种——铜绿微囊藻和水华鱼腥藻为研究对象，在优化后的水力空化条件下，水头压力0.33 MPa，电流密度为2.13 mA/cm²，处理10 L密度为3.0×106 mL^-1的铜绿微囊藻藻液。结果表明，该装置具有显著的抑藻效果，处理30 min的水样在处理后培养3 d可以达到76.9%的抑藻率，4 d后抑藻率上升到到97.5%。而对藻液分别进行单独空化30 min和单独电解30 min后培养4 d的抑藻率分别为27.7%和27.8%，表明空化耦合电解具有协同作用。通过比较该装置对不同藻种以及处于不同生长阶段的藻种的处理效果，发现装置对铜绿微囊藻的抑藻率显著优于水华鱼腥藻；对于铜绿微囊藻而言，处于对数生长期的藻细胞比稳定生长期更易被除去。     

可见光下亚微米Cu_2O微球光催化去除铜绿微囊藻

以乙酸铜为铜源、乙二醇和葡萄糖为还原剂,采用溶剂热法制备亚微米Cu_2O微球,并用X射线衍射(XRD)和透射电子显微镜(TEM)对其结构进行表征;通过藻细胞的内含物含量、生长代谢活性、形态的变化和藻细胞膜脂质过氧化分析,研究了亚微米Cu_2O微球在可见光下去除铜绿微囊藻的性能。结果表明:亚微米Cu_2O微球由10nm左右的Cu_2O纳米粒子聚集形成;在可见光下,亚微米Cu_2O微球的加入量为0.4g/L,3h后叶绿素a去除率可达到80.4%;亚微米Cu_2O微球通过光催化作用破坏藻细胞膜、降解藻细胞内含物、降低藻细胞代谢活性和破坏藻细胞形态,从而产生抑藻作用。     

柑橘类果皮水提液对铜绿微囊藻生长的影响

研究了柑橘类果皮水提液对铜绿微囊藻生长的影响。采用二倍稀释法将儿种柑橘类果皮水提液分成7个浓度组,每组3个平行,在温度(25.0±0.5)℃,光照强度3000 l×下培养铜绿微囊藻。结果表明,柑橘类果皮水提液能有效抑制铜绿微囊藻的生长,且随着浓度的增加其抑藻作用增强。其中,蜜桔皮、马水桔皮、蜜柚皮水提液质量浓度在6.25、3.13、6.25g/L时对铜绿微囊藻的生长具有极显著的抑制作用(P0.01)。实际应用时,柑橘类果皮水提液质量浓度为6.25g/L时较为合理。柑橘类果皮中存在一种或几种能有效抑制铜绿微囊藻叶绿素a合成的物质,从而抑制铜绿微囊藻的生长,此类物质在高温处理下仍能保持一定的抑藻活性,这为控制蓝藻药物的研发提供了一定参考。     

四羟甲基硫酸鏻去除铜绿微囊藻效果及其机制研究

研究了四羟甲基硫酸鏻对铜绿微囊藻(Microcystis aeruginosa)的去除效果及机制.结果表明,四羟甲基硫酸鏻半效应浓度(EC50)与藻细胞数目呈正相关,线性方程为:Y=0.628 2X+0.956 4,R2=0.997 3(其中Y为EC50,mg/L;X为处理48 h后铜绿微囊藻细胞数目,106个/mL).11.0 mg/L四羟甲基硫酸鏻处理铜绿微囊藻36 h后,藻细胞可溶性蛋白、超氧化物歧化酶(SOD)活性、丙二醛(MDA)较对照组分别提高10.47%、11.31%、140.98%,四羟甲基硫酸鏻能够显著破坏藻细胞膜通透性,提高酯酶活性.四羟甲基硫酸鏻通过破坏藻细胞膜,造成膜脂过氧化,干扰藻体正常代谢而除藻.     

金鱼藻中抑藻化感物质的研究

通过静态模拟实验,比较了单独培养和共生培养下,不同初始藻密度时金鱼藻生物量和铜绿微囊藻密度的变化.采用固相萃取的方法对金鱼藻种植水中的化感物质进行富集,经甲醇洗脱、高效液相色谱分析,发现在铜绿微囊藻生长的胁迫下,金鱼藻释放的化学物质组成和含量发生变化,强极性物质含量下降,弱极性物质含量增加.二氯甲烷洗脱物经色谱质谱分析后,检测出15种不同于铜绿微囊藻释放的化合物,其中N-苯基-2-萘胺、脱氢枞酸甲酯和脱氢枞酸乙酯已有文献报道对藻类具有化感作用.     

铜绿微囊藻对香蒲叶片氮代谢相关酶活性的影响

采用共培养的实验方法,通过追踪测定香蒲(Typha orientalis Presl.)叶片中NO-3、NH+4、TN、可溶性蛋白的含量及硝酸还原酶(NR)、谷氨酰胺合成酶(GS)、谷氨酸脱氢酶(GDH)活性,研究了不同初始密度铜绿微囊藻(Microcystis aeruginosa)对香蒲叶片内各种形态氮含量及氮代谢相关酶活性的影响。结果表明,铜绿微囊藻初始密度为1.0×104cells/m L时,香蒲叶片NR、GS和GDH活性增加,可溶性蛋白及TN含量也增加,说明低密度铜绿微囊藻对香蒲叶片的氮代谢具有促进作用,香蒲吸收同化氮能力增强;铜绿微囊藻初始密度为1.0×107cells/m L时,香蒲叶片NR及GS酶活性降低,而GDH活性增强,NO-3、NH+4含量增加,而可溶性蛋白及TN含量降低,表明高密度铜绿微囊藻对香蒲叶片的氮代谢具有抑制作用,香蒲吸收同化氮能力减弱。     

氧活性粒子氧化NO生成HNO_3

采用强电离介质阻挡放电方法制取高浓度氧活性粒子(O+2、O3)并注入气体外排烟道中,实现O+2、O3氧化NO转化成资源酸(HNO3)的等离子化学反应。描述强电离放电的氧活性粒子产生器,讨论烟道中O+2、O3氧化NO成HNO3等离子体反应机制,分析回收酸液的NO-2、NO-3离子种类及浓度。考察强电离放电等离子体源的输入功率、水体积百分比、气体温度、气体流速对NOx氧化率的影响。氧化率为97.2%的最佳实验条件是:O+2浓度为1.38×1010个/cm3,O3浓度为210 mg/L,烟气温度为65℃,H2O体积浓度为5.6%,停留时间为0.94 s。     

曝气对遮光条件下藻类消亡的影响

以斜生栅藻和铜绿微囊藻为材料,分析低光照度范围内藻类光合作用特性和呼吸速率,研究曝气对遮光条件下藻类消亡过程的影响.结果表明,(25±1) ℃时斜生栅藻和铜绿微囊藻的光补偿点分别为600、720 lx,呼吸速率分别为89、57 μmol/(mg*h);光照度低于光补偿点,藻类内源呼吸导致水体DO浓度降低;单纯遮光(光照度为0 lx)处理7 d,斜生栅藻和铜绿微囊藻生物量去除率(以OD650计)分别为17.2%和39.1%;增加曝气措施后,斜生栅藻和铜绿微囊藻去除率分别上升到71.3%和92.0%,曝气能有效促进藻类消亡.实验数据拟合结果证明,藻细胞消亡符合藻细胞内源呼吸-衰减模型.     

共培养条件下黄菖蒲和狭叶香蒲对铜绿微囊藻光合系统的影响

采用共培养的实验方法,通过测定铜绿微囊藻(Microcystis aeruginosa)叶绿素a含量及叶绿素荧光参数,研究了黄菖蒲(Iris pseudacorus L.)和狭叶香蒲(Typha angustifolia L.)对铜绿微囊藻光合系统的影响。结果表明,共培养条件下,黄菖蒲和狭叶香蒲对铜绿微囊藻的光合系统具有明显的化感作用,表现为,处理组中铜绿微囊藻的叶绿素a含量从第4天开始显著(Paried t-test,p0.05)低于对照组;培养过程中,YⅡ(光系统Ⅱ有效量子产量)和Fv/Fm(光系统Ⅱ最大量子产量)值也呈现逐渐下降的趋势,说明黄菖蒲和狭叶香蒲对铜绿微囊藻产生了化感抑制,光合效率和光能转化效率下降;而Ik(半饱和光强)和α(光限制斜率)值呈现先增加后逐渐降低的趋势,从第4天开始显著(Paried t-test,p0.05)低于对照组,表明黄菖蒲和狭叶香蒲的化感作用在短时间内可以激发铜绿微囊藻对光强的耐受能力并能提高藻的光能利用效率,但是随着化感时间的延长,铜绿微囊藻对强光的耐受能力及光能利用效率下降。     

广玉兰、龙爪槐和黄杨化感物质对铜绿微囊藻生长的抑制

针对水华的主要物种——铜绿微囊藻,初步测定了60种植物的浸提液对其细胞增殖的抑制率。结果表明,8种植物的浸提液对铜绿微囊藻生长的抑制率达到90%以上。其中,广玉兰、龙爪槐和黄杨叶片浸提液对铜绿微囊藻生长的抑制率分别达到97.4%、95.6%和91.2%。通过计算得到培养7d后广玉兰、龙爪槐和黄杨的50%抑制效应质量浓度(EC50)分别为0.52、1.04、5.87g/L,而90%抑制效应质量浓度(EC90)分别为3.79、6.45、9.09g/L。首次发现此3种植物浸提液中富含能抑制铜绿微囊藻细胞增殖的化学物质,可以作为抑藻化感物质的一个重要来源。根据EC50和EC90对培养时间的拟合方程判断,广玉兰和龙爪槐浸提液对铜绿微囊藻的抑制效果较黄杨浸提液更为长效,且由于其抑制效果优于农作物秸秆,具有进一步研究的价值。     

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.