生物炭质吸附剂对硝基苯的吸附

以花生壳为生物炭质(P-BC)原料,Zn Cl2为活化剂,采用化学活化法制备生物炭质吸附剂(Z-BC),并以其吸附水中的硝基苯,考察了p H值、吸附剂投加量和吸附时间等因素对Z-BC吸附硝基苯过程的影响。分别采用吸附动力学模型和吸附等温模型对吸附动力学和等温线进行了系统分析。结果表明:p H值对吸附的影响不大,吸附剂适宜投加量为2 g·L-1,吸附平衡时间为120 min;Z-BC对硝基苯的吸附动力学过程用准一级动力学模型能很好地描述,其计算平衡吸附量与实验值相符;颗粒内扩散模型表明,吸附过程受液膜扩散与颗粒内扩散联合控制,并以颗粒内扩散为主要速率控制步骤;Langmuir吸附等温模型能更好地描述硝基苯在Z-BC上的吸附平衡;吸附热力学方程计算得到吸附焓变(ΔH)0、吸附自由能变(ΔG)0和吸附熵变(ΔS)0,表明Z-BC对水中硝基苯的吸附为放热和熵值增加的自发过程。     

改性活性氧化镁的除氟效能及机制

通过静态吸附实验,研究了改性活性氧化镁的除氟效能,通过比表面积、孔容、孔径和表面元素及化合物含量分析,初步探讨了改性机制。结果表明,改性后的活性氧化镁吸附行为更符合Langmuir等温线的拟合,即吸附为单分子层吸附,饱吸附容量为88.50 mg/g,吸附平衡常数为0.3681 L/mg,吸附速率可用拟二级动力学方程描述;改性活性氧化镁的吸附除氟效果基本不受溶液中共存的Cl-、NO-3、SO2-4和HCO-3的影响,但HPO2-4对改性活性氧化镁等除氟效果影响较大,尤其当其浓度大于100 mg/L时,显著降低改性活性氧化镁的吸附容量。温度升高改性活性氧化镁的吸附容量增大,在实际饮用水处理中p H基本不会影响除氟效果。改性活性氧化镁吸附除氟的最佳温度为30℃,最适p H为6~9.5。比表面积和孔容的增大可能是改性活性氧化镁吸附容量提高的主要原因之一。     

海带对镉的吸附动力学与热力学研究

采用批量平衡法研究了海带对镉的吸附的动力学与热力学,并采用Lagrange假一级动力学方程、假二级动力学方程、Langmuir等温线方程、Freundlich等温线方程以及Dubimim-Radushkevich等温线方程对实验数据进行了拟合.结果表明,在4种温度下海带对镉的吸附率均随吸附反应时间增加而增大,在60 min时达到最大,此后基本保持不变,随着温度由20℃升高至50℃,其最大吸附率呈下降趋势,由90.2%降至77.5%;海带对镉的吸附动力学符合Lagrange假二级动力学方程;海带对镉的吸附热力学符合Langmuir等温线方程和Dubimim-Radushkevich等温线方程,表明吸附主要发生在海带表面的活性区位,属于单分子层吸附,其吸附平均活化自由能E为11.4 kJ/mol,表明该吸附过程为化学吸附,在4种温度下吉布斯自由能变化量△AG°均为负值,吸附焓变△H°也为负值,表明海带对镉的吸附为放热反应,能自发进行.     

葛根去除水溶液中亚甲基蓝的生物吸附机理和特性

对农副产品葛根吸附水溶液中亚甲基蓝的特性和机理进行了一系列的研究。考察了不同条件对吸附效果的影响;采用2种等温线模型和3种动力学模型对吸附机理和动力学特性进行了模拟分析,并计算了相关的热力学函数。结果发现,溶液pH值等实验条件对吸附效果有较大的影响;Langmuir方程能很好地描述其吸附等温线,吸附是一个符合二级动力学过程的物理吸附;热力学函数计算结果显示,此吸附是一个自发的放热过程。在3种不同温度下,由Langmuir方程计算的最大吸附量为98.23、91.04和87.28 mg/g,表明葛根是一种良好的,具有一定发展潜力的染料吸附剂。     

聚甲亚胺酰胺树脂对水中Cu~(2+)的吸附

制备了聚甲亚胺酰胺树脂,对其进行傅里叶变换红外光谱分析。采用批处理方法实验了pH、铜离子初始浓度、吸附时间、吸附剂用量对吸附量的影响,研究了等温吸附模型和吸附动力学模型。优化后的吸附条件为:在铜离子溶液体积50 mL、初始浓度为300 mg/L、pH为6.0时,吸附剂投放量50 mg、吸附时间60 min,此时吸附量达到269.1 mg/g,去除率达89.7%。25℃时在研究浓度范围内,铜离子吸附过程用Langmuir等温线模型和Freundlich等温线模型描述均可;与准一级动力学方程、Elovich方程及内扩散方程相比,准二级动力学方程能更好地描述其吸附动力学过程。     

改性丝瓜络纤维对水体日落黄的吸附特性

采用化学改性的方法将丝瓜络制备为阴离子吸附剂,并将其用于水体日落黄(SY)染料的吸附,分别考察了吸附剂的用量、日落黄染料的初始浓度(C0)、p H值、温度(K)、时间(T)5个因素对吸附效果的影响。通过模拟吸附等温曲线、吸附动力学以及热力学方程并通过比表面积(BET)和红外光谱(FTIR)分析改性丝瓜络吸附染料前后和丝瓜络改性前后的变化情况以此探究其吸附机理。结果表明,p H对吸附效果影响不明显;最大吸附量随温度升高而增大,在298 K温度时最大吸附量达到137 mg/g,是未改性丝瓜络的9.78倍。Langmuir方程拟合吸附过程描述最好,吸附类别为化学吸附。吸附过程符合伪二级动力学,是一个自发和吸热的过程。改性丝瓜络可以有效去除水体中的日落黄染料。     

铝锰复合氧化物负载沸石对氨氮和磷的同步吸附特性

采用氧化还原-共沉淀法将铝锰复合氧化物负载到沸石表面制成颗粒型吸附材料,探究了该吸附剂同步去除氨氮(NH_4~+-N)和磷(P)的吸附动力学和吸附等温线特征,并讨论了吸附剂投加量和溶液p H值对吸附效果的影响。结果表明:铝锰复合氧化物改性沸石(aluminum-manganese bimetal oxide coated zeolite,AMOCZ)对NH_4~+-N及P的吸附动力学曲线均符合拟二阶吸附动力学方程的特征;NH_4~+-N的吸附等温线数据可用Freundlich方程进行较好地拟合,而Langmuir方程更适用于描述P的吸附等温线特征。NH_4~+-N和P共存时,两者在AMOCZ表面的饱和吸附量分别从单独体系下的1.24和6.43mg·g~(-1)变为8.17和6.51 mg·g~(-1)。这说明P的存在可显著促进AMOCZ对NH_4~+-N的吸附,而NH_4~+-N的存在对P的吸附无显著影响。此外,复合污染条件下,P的存在在p H=3~10范围内均能促进AMOCZ对NH_4~+-N的吸附;NH_4~+-N在p H为3~8时对P的吸附起促进作用,p H大于8时则会抑制AMOCZ对P的吸附。     

MgAl型层状化合物对六价铬的吸附性能

尿素-水热法制备层状双金属氢氧化物Mg Al-LDH,系统考察了焙烧温度、p H值、初始Cr(VI)浓度、吸附时间和吸附温度对样品的吸附性能的影响。并对其吸附热力学、动力学和吸附机理进行研究。采用傅里叶红外光谱(FT-IR)对吸附Cr(VI)前后的Mg Al-LDH进行表征。Mg Al-LDH的最佳吸附条件为p H=2.5,吸附过程符合Langmuir等温模型,最大吸附容量为105.15 mg·g-1,其对Cr(VI)的吸附为放热过程,并遵守准二级动力学模型,化学吸附为主导。Mg Al-LDH对Cr(VI)的吸附主要在酸性条件下进行,吸附机理主要为静电作用和离子交换:在酸性条件下,Mg Al-LDH表面带正电荷,并通过静电作用吸附Cr(VI)阴离子,同时Mg Al-LDH的层间CO2-3和NO-3与溶液中的Cr(VI)阴离子进行离子交换。     

改性伊利石对活性艳蓝K-GR的吸附

采用十六烷基三甲基溴化铵(CTMAB)对伊利石进行改性,利用红外光谱、扫描电镜、X射线衍射及热重分析对吸附剂进行结构表征。研究了改性吸附剂对活性艳蓝K-GR的吸附性能。结果表明,最佳吸附条件为:p H 3,吸附剂用量0.3 g,CTMAB/伊利石质量比0.125。吸附过程符合准二级动力学方程,吸附等温线可以很好地用Langmuir模型描述。在热力学研究中,ΔG00,ΔH00,ΔS00,说明吸附过程是自发、吸热和熵增加的过程。     

好氧污泥对活性艳兰KN-G的吸附特性研究

实验研究了活性艳兰KN-G在好氧污泥上的吸附等温线和吸附动力学,考察了pH对好氧污泥吸附活性艳兰KN-G的影响。结果表明,好氧污泥对活性艳兰KN-G的吸附Freund lich和Langmu ir方程准确性较高,但是从模型的准确性和稳定性两方面考虑,Freund lich方程更适合描述好氧污泥吸附活性艳兰KN-G。应用伪一级、伪二级反应动力学和颗粒内扩散方程模型对实验数据进行验证,表明好氧污泥吸附活性艳兰KN-G更符合伪二级反应动力学模型。pH值对活性艳兰KN-G的吸附影响很大,pH值与吸附量呈负相关。     

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.