Fate of ah receptor agonists during biological treatment of an industrial sludge containing explosives and pharmaceutical residues

GOAL, SCOPE AND BACKGROUND: Sweden is meeting prohibition for deposition of organic waste from 2005. Since 1 million tons of sludge is produced every year in Sweden and the capacity for incineration does not fill the demands, other methods of sludge management have to be introduced to a higher degree. Two biological treatment alternatives are anaerobic digestion and composting. Different oxygen concentrations result in different microbial degradation pathways and, consequently, in a different quality of the digestion or composting residue, It is therefore necessary to study sludge treatment during different oxygen regimes in order to follow both degradation of compounds and change in toxicity. In this study, an industrial sludge containing explosives and pharmaceutical residues was treated with anaerobic digestion or composting, and the change in toxicity was studied. Nitroaromatic compounds, which are the main ingredients of both pharmaceutical and explosives, are well known to cause cytotoxicity and genotoxicity. However, little data are available concerning sludge with nitroaromatics and any associated dioxin-like activity. Therefore, we studied the sludge before and after the treatments in order to detect any changes in levels of Ah receptor (AhR) agonists using two bioassays for dioxin-like compounds. METHODS: An industrial sludge was treated with anaerobic digestion or composting in small reactors in a semi-continuous manner. The same volume as the feeding volume was taken out daily and stored at -20 degrees C. Sample preparation for the bioassays was done by extraction using organic solvents, followed by clean up with silica gel or sulphuric acid, yielding two fractions. The fractions were dissolved in DMSO and tested in the bioassays. The dioxin-like activity was measured using the DR-CALUX assay with transfected H4IIE rat hepatoma pGudluc cells and an EROD induction assay with RTL-W1 rainbow trout liver cells. RESULTS AND DISCUSSION: The bioassays showed that the sludge contained AhR agonists at levels of TCDD equivalents (TEQs) higher than other sludge types in Sweden. In addition, the TEQ values for the acid resistant fractions increased considerably after anaerobic digestion, resulting in an apparent formation of acid resistant TEQs in the anaerobic reactors. Similar results have been reported from studies of fermented household waste. There was a large difference in effects between the two bioassays, with higher TEQ levels in the RTL-W1 EROD assay than in the DR-CALUX assay. This is possibly due to a more rapid metabolism in rat hepatocytes than in trout hepatocytes or to differences in sensitivities for the AhR agonists in the sludge. It was also demonstrated by GC/FID analysis that the sludge contained high concentrations of nitroaromatics. It is suggested that nitroaromatic metabolites, such as aromatic amines and nitroanilines, are possible candidates for the observed bioassay effects. It was also found that the AhR agonists in the sludge samples were volatile. CONCLUSIONS: The sludge contained fairly high concentrations of volatile AhR agonists. The increase of acid resistant AhR agonist after anaerobic digestion warrants further investigations of the chemical and toxic properties of these compounds and of the mechanisms behind this observation. RECOMMENDATION AND OUTLOOK: This study has pointed out the benefits of using different types of mechanism-specific bioassays when evaluating the change in toxicity by sludge treatment, in which measurement of dioxin-like activity can be a valuable tool. In order to study the recalcitrant properties of the compounds in the sludge using the DR-CALUX assay, the exposure time can be varied between 6 and 24 hours. The properties of the acid-resistant AhR agonists formed in the anaerobic treatment have to be investigated in order to choose the most appropriate method for sludge management.     

Dechlorination of 1,2,4-trichlorobenzene in the sediment of Ise Bay

The relation between dechlorination activities of 1,2,4-trichlorobenzene and anaerobic microbial activity were studied in the sediment collected at three sites in Ise Bay in Japan. The degradation rate of spiked 1,2,4-trichlorobenzene (3nmol ml⁻¹) ranged from 15 to 35 pmol day⁻¹ ml⁻¹ wet sediment and about 1/3 to 1/2 of degraded the trichlorobenzene was recovered as dechlorinated products. Among the dichlorobenzenes, the 1,2-isomer had the highest and 1,3-isomer had the lowest production rate. Comparing the three sampling sites, the trichlorobenzene degradation and dichlorobenzenes production rates were related to the sulfate reducing activity for the unit number of sulfate reducing bacteria. Production rates of dichlorobenzenes were completely inhibited by adding molybdate (20 mM), nitrate (60 mM), and formaldehyde solution (4 %). These results indicated that dechlorination activity in the Ise Bay sediment was supported by sulfate reduction activity in the sediment, and not supported by any other anaerobic microbial activity.     

液化和压缩气体半球形扩散模型集的构建和应用

国内外液化和压缩气体的泄漏爆炸事故屡见不鲜,针对其性质和短时间近地面扩散的特点,总结、修正和扩展了瞬时泄漏下的平均半球形扩散模型。对于连续泄漏,利用数学积分理论建立了静风下的半球形扩散模型。接着对有风时的情况进行建模推导,将风速和气体自身扩散速度进行矢量合成,得到了半椭球形扩散和半椭圆锥与1/4椭球体组合扩散下气体的质量浓度和质量浓度变化趋势。最后用实例验证了该模型的先进性。该模型集能较好地反映液化和压缩气体泄漏后不同泄漏情况、时间、近地面区域和风速下的扩散浓度空间分布及其动态变化过程,为事故后果预估和应急救援决策提供参考。     

海藻酸钠包埋活性炭与细菌的条件优化及其对Pb~(2+)的吸附特征研究

利用海藻酸钠固定化包埋活性炭与多黏类芽孢杆菌GA1,通过正交试验研究海藻酸钠溶液浓度、包炭量及包菌量吸附Pb2+的最佳配比,并研究了这种新型的固定化小球对Pb2+的吸附特征.结果表明,固定化活性炭与多黏类芽孢杆菌GA1小球最佳制备条件为海藻酸钠质量分数2.5%、包炭量1:20和包菌量1:2,在该制备条件下吸附率达到93.74%.固定化小球的最佳吸附条件为pH5、温度30℃和Pb2+初始浓度300mg·L-1,活性炭与GA1经固定后对pH、温度和Pb2+初始浓度适应范围扩大.吸附平衡曲线表明,对Pb2+的吸附在30min内是一个快速的过程,在2h时基本趋于平衡,且平衡曲线能较好地用Langmuir模型和Freundlich模型来描述,其吸附过程主要为单分子层吸附,最大单分子层吸附量为370.37mg·g-1.解吸结果表明固定化小球能有效地循环利用.     

Isolation of Cr(VI) reducing bacteria from industrial e uents and their potential use in bioremediation of chromium containing wastewater

The present study is aimed at assessing the ability of Bacillus sp.JDM-2-1 and Staphylococcus capitis to reduce hexavalent chromium into its trivalent form.Bacillus sp.JDM-2-1 could tolerate Cr(Ⅵ) (4800 μg/mL) and S.capitis could tolerate Cr(Ⅵ) (2800 μg/mL).Both organisms were able to resist Cd2+ (50 μg/mL),Cu2+ (200 μg/mL),Pb2+ (800 μg/mL),Hg2+ (50 μg/mL) and Ni2+ (4000 μg/mL).S.capitis resisted Zn2+ at 700 μg/mL while Bacillus sp.JDM-2-1 only showed resistance up to 50 μg/mL.Bacillus sp.JDM-2-1 and S.capitis showed optimum growth at pH 6 and 7,respectively,while both bacteria showed optimum growth at 37℃.Bacillus sp.JDM-2-1 and S.capitis could reduce 85% and 81% of hexavalent chromium from the medium after 96 h and were also capable of reducing hexavalent chromium 86% and 89%,respectively,from the industrial effluents after 144 h.Cell free extracts of Bacillus sp.JDM-2-1 and S.capitis showed reduction of 83% and 70% at concentration of 10 μg Cr(Ⅵ)/mL,respectively.The presence of an induced protein having molecular weight around 25 kDa in the presence of chromium points out a possible role of this protein in chromium reduction.The bacterial isolates can be exploited for bioremediation of hexavalent chromium containing wastes,since they seem to have the potential to reduce the toxic hexavalent form to its nontoxic trivalent form.     

植物角质层的蜡质组分对甲萘酚的吸附作用

采用批量平衡法,比较研究了苹果角质结合蜡质、分离蜡质和重建蜡质对极性有机污染物甲萘酚的吸附作用,并探讨了不同负载量的重建蜡质的吸附性能,以期为准确预测有机污染物在不同状态蜡质组分上的吸附行为提供依据.结果表明,甲萘酚在苹果角质层、脱蜡角质层、分离蜡质(IW)、重建蜡质(BW)上的等温吸附线呈非线性,符合Freundlich方程.植物蜡质对甲萘酚的吸附作用与蜡质所处状态密切相关,吸附能力(Koc)大小顺序为:重建蜡质(321.2) > 分离蜡质(190.4) > 角质结合蜡质(128.4),表明植物角质层进入土壤后发生演化过程中,其中不易降解的蜡质的吸附能力逐渐增大.重建蜡质(BW)的吸附系数(Kd)与甲萘酚的浓度呈负相关,与蜡质的负载量呈正有关.在低浓度时,甲萘酚的有机碳标化吸附系数Koc值随有机碳含量(foc)增大先增大后减小,存在一些强的特殊作用;而高浓度时, Koc-基本为一常数,不随蜡质负载量而变化,主要吸附机理为分配作用.角质结合蜡质(CW)对角质层的总吸附作用的贡献较小,但随甲萘酚平衡浓度的增大而逐渐增大,并于高浓度时, CW的吸附能力与IW相当.     

基于灰色预测模型与一元线性回归模型的煤矿瓦斯涌出量预测比较

在介绍灰色预测模型和一元线性回归模型的基础上,结合某煤矿实际,采用两种模型对瓦斯涌出量进行了预测,并对两种模型的预测值进行比较,结果表明:对基本符合线性关系的数据,采用灰色GM(1,1)模型较一元线性回归模型的预测精度要高。     

Adverse effects of metal exposure on chemotaxis towards water-soluble attractants regulated mainly by ASE sensory neuron in nematode Caenorhabditis elegans

Chemotaxis to water-soluble attractants is mainly controlled by ASE sensory neuron whose specification is regulated by che-1 in Caenorhabditis elegans. Our data suggested that exposure to high concentrations of metals, such as Pb, Cu, Ag, and Cr, would result in severe defects of chemotaxis to water-soluble attractants of NaCl, cAMP, and biotin. Moreover, the morphology of ASE neuron structures as observed by relative fluorescent intensities and relative size of fluorescent puncta of cell bodies, relative lengths of sensory endings in ASE neurons, and the expression patterns of che-1 were obviously altered in metal exposed animals when they meanwhile exhibited obvious chemotaxis defects to water-soluble attractants. In addition, the dendrite morphology could be noticeably changed in animals exposed to 150 mol/L of Pb, Cu, and Ag. Furthermore, we observed significant decreases of chemotaxis to water-soluble attractants in Pb exposed che-1 mutant at concentrations more than 2.5 mol/L, and in Cu, Ag, and Cr exposed che-1 mutant at concentrations more than 50 mol/L. Therefore, impairment of the ASE neuron structures and functions may largely contribute to the appearance of chemotaxis defects to water-soluble attractants in metal exposed nematodes.     

“Achromobacter sp. CH-1-Cr(Ⅵ)-H2O”体系Cr(Ⅵ)还原的电化学行为

采用循环伏安法探明了"Achromobacter sp.CH-1-Cr(Ⅵ)-水"体系的电化学行为.结果表明:循环伏安曲线上-0.62V(相对于SCE)的电流峰对应的反应为Cr(Ⅵ)还原成Cr(Ⅲ)的反应,在电势为-0.82V时Cr(Ⅲ)开始还原为零价铬.体系中的电极反应为不可逆过程,阳极扫描时Cr(Ⅲ)不会被重新氧化为Cr(Ⅵ).细菌的存在使Cr(Ⅵ)的还原更容易进行,其还原峰电势正移约0.2 V,细菌对体系中的电化学反应起了催化作用.随细菌量的增加,氢气的析出、六价铬还原为三价铬及三价铬进一步还原为零价铬的电势均发生了正移,过高的细菌量主要影响三价铬还原沉积为金属铬的过程.铬浓度对细菌还原Cr(Ⅵ)溶液的循环伏安曲线的影响不大.初始pH值为10是细菌还原Cr(Ⅵ)的最佳pH值.     

Thermal hazard and decomposition kinetics of 1-butyl-2,3-dimethylimidazolium nitrate via TGA/DSC and FTIR

1-Butyl-2,3-dimethylimidazolium nitrate ([Bmmim][NO₃]), a kind of versatile and novel ionic liquids, is widely applied in the modern petrochemical industry. Nevertheless, its thermal hazard safety data at high temperature or thermal disturbance conditions are currently unavailable. Therefore, this study aimed to characterize the thermal risk of [Bmmim][NO₃] through auto-ignition temperature measurements, flash point analysis, thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC), TGA-Fourier transform infrared spectroscopy (TGA-FTIR) and thermal decomposition kinetics analysis. Additionally, [Bmmim][NO₃] was examined using isothermal thermogravimetric analysis at different temperatures (220, 230, 240, 250, 260 and 270 °C). The experimental results show that the flash point of [Bmmim][NO₃] is 305.70 ± 9.30 °C and the auto-ignition temperature is 341.00 ± 21.60 °C with an ignition delay time of 8.6 s. In addition, using the nitrogen atmosphere TGA data to calculate the activation energy according to the Friedman, Kissinger and Flynn-Wall-Ozawa methods, roughly the same results were obtained. Finally, TGA-FTIR results show that [Bmmim][NO₃] produced acetylene, butane, butanol and carbon dioxide during the thermal decomposition process. This study could provide data support and some guidance for the thermal hazard assessment and safety control of [Bmmim][NO₃] during its use and storage.