热解条件对茶叶渣生物炭特性及镉污染土壤钝化效果的影响

以泡饮过的废弃茶叶为实验原料,通过不同热解温度(300、400、500和600℃)和热解时间(1 h和2 h)制备生物炭,探讨不同热解条件对茶叶渣生物炭(TSBC)的特性及其对镉(Cd)污染土壤钝化效果的影响。结果表明:热解温度的升高可明显增加TSBC的p H和比表面积,降低生物炭的产率、电导率和表面官能团的数量,使TSBC具有弱碱性、较大比表面积和较强的稳定性,对改良酸性土壤和吸附重金属存在一定潜力;而热解时间对其特性没有明显差异,与对照组相比,添加TSBC明显增加了Cd污染土壤的p H、有机碳(SOC)和可溶性有机碳(DOC)含量,但随着制备温度的升高,Cd污染土壤中SOC和DOC增加幅度逐渐降低。添加TSBC显著降低Cd污染土壤中可交换态镉的比例,当热解温度为500~600℃时降幅最显著,其下降比例与对照相比最高可达25.56%;残渣态镉比对照增加了0.88~1.18倍。因此,TSBC对镉污染土壤有较好的钝化效果,这为重金属污染土壤的修复和生活废弃物的资源化利用提供了理论依据。     

牛粪生物炭对Cd~(2+)的吸附影响因素及特性

为了考察以牛粪为原料制备的生物炭对水溶液中Cd2+的吸附效果,进行了吸附影响因素、吸附等温线和动力学研究。结果表明,当热解温度为700℃、投加量为20 g/L、溶液初始pH为5、水溶液Cd2+初始浓度为10 mg/L、吸附平衡时间为60 min和溶液温度为25℃时,对Cd2+的吸附效果最佳,Cd2+去除率可达99%以上。提高溶液温度有利于吸附。降低生物炭热解温度和投加量对吸附效果影响不大。Langmuir方程能更好地拟合生物炭对Cd2+的吸附等温过程,吸附过程符合准二级动力学方程。牛粪生物炭是性能优良、价格经济的水溶液中Cd2+的吸附剂。     

不同热解温度下污泥基生物炭的性质及对Cd~(2+)的吸附特性

以市政污泥为原料,在300、500和700℃无氧气氛下热解制备污泥基生物炭,探讨不同热解温度对污泥基生物炭性质的影响,研究污泥基生物炭对水溶液中重金属Cd~(2+)的吸附特性。结果表明,随着热解温度升高,污泥基生物炭的产率降低,pH值增大,碳、氢、氧和氮含量降低,芳香化程度增强,亲水性和极性降低,稳定性增强;随热解温度的升高,比表面积不断增大,生物炭表面变得粗糙并且出现明显的孔隙,但平均孔径呈现先增大后减小。在700℃下制备的污泥基生物炭对水溶液中Cd~(2+)的吸附效果优于其他制备温度下获得的生物炭,温度为298.15 K时,最大吸附容量为27.47 mg·g~(-1)。污泥基生物炭对Cd~(2+)的吸附动力学符合准二级动力学方程模型,吸附速率主要由化学吸附控制。污泥基生物炭对Cd~(2+)的吸附表现为快速吸附过程,生物炭前10 min的吸附量超过饱和吸附量的80%。Langmuir吸附等温模型能很好的描述污泥基生物炭对Cd~(2+)的吸附行为,吸附容量随热解温度升高而增大。     

污泥基生物炭吸附重金属Cd的动力学和热力学

炭化是污泥资资源化利用的重要途径。研究了污泥基生物炭对Cd的吸附过程,探讨了污泥基生物炭吸附重金属Cd的动力学和热力学特征。结果显示污泥基生物炭对Cd的吸附符合准二级动力学方程。Freundlich方程能较好的模拟吸附等温线。随着温度增加,吸附呈现逐渐增强趋势。吸附热力学结果显示35℃时吸附并非自发进行,随着温度增加,吸附转为吸热并自发进行。污泥基生物炭对Cd的吸附主要以化学吸附为主,同时存在多种机制共同作用。研究结果表明污泥基生物炭有作为重金属Cd污染废水修复剂的潜力。     

污泥生物炭对土壤中Pb和Cd的生物有效性的影响

以污泥为原料,在500℃缺氧条件下制备污泥生物炭,结合X射线能谱(EDS)、环境扫描电镜(SEM)和红外光谱(FTIR)等表征手段,分析添加污泥生物炭后污染土壤pH和Pb与Cd化学形态的变化来探究污泥生物炭对土壤中Pb、Cd的固定效果,并用盆栽方式评估添加污泥生物炭对小青菜生物量及体内重金属含量的影响。结果表明:添加污泥生物炭后,污染土壤的pH随平衡时间的延长显著升高;对于单一污染土壤和复合污染土壤,污泥生物炭对Pb和Cd均有较强的固定作用,而污泥生物炭在复合污染土壤中对Pb的固定效果优于在单一污染土壤中;添加污泥生物炭能提高小青菜的生物量,且能有效降低小青菜对污染土壤中Pb和Cd的吸收。     

新制备生物炭的特性表征及其对石油烃污染土壤的吸附效果

生物炭作为一种绿色环保的功能材料因其在污水处理和污染土壤修复方面具有显著效果而受到极大关注.采用红外光谱、元素分析仪及微孔分析对不同温度(200、300、400、500和600℃)条件下制备的木屑和麦秆生物炭进行特性表征,并采用制备的生物炭净化石油污染土壤,分别考察了污染物性质、生物质原料和热解温度对其净化效果的影响.结果表明,随着热解温度的增高,生物炭芳香化程度增加,极性降低,微孔结构逐渐发育,表面积增大.加入生物炭33 d后,污染土壤中总石油烃及其组分烷烃的浓度比对照略有降低,而PAHs浓度下降显著.随着热解温度升高,2种生物炭对PAHs的吸附强度均逐渐增大,芳香度增高、表面积增大是强吸附的主要原因.2种生物炭在400℃及以下温度制备时对PAHs的吸附强度为:木屑生物炭＞麦秆生物炭;而400℃以上温度制备的生物炭吸附强度则相反,即麦秆生物炭＞木屑生物炭,说明生物炭原料对其吸附强度也具有显著影响.     

生物炭对土壤吸附邻苯二甲酸二乙酯的影响

选择花生壳为原材料,采用限氧升温法在450、700℃温度下分别热解2、4、6 h制备6种生物炭,在对其表面性质和元素组成进行分析的基础上,重点考察生物炭对土壤吸附邻苯二甲酸二乙酯(diethyl phthalate,DEP)的影响。结果表明:生物炭的比表面积和总孔体积随着热解温度的升高而增加,热解时间的延长也会提高比表面积和总孔体积,而4 h是较为适宜的热解时间;生物炭中元素组成主要受热解温度的影响,热解时间的作用很小,热解温度的升高使生物炭的芳香性增强,极性降低;添加生物炭能显著提高土壤对DEP的吸附能力;Langmuir模型和Freundlich模型均能较好地拟合添加生物炭土壤对DEP的吸附特征;在不同的平衡浓度条件下,生物炭对土壤吸附DEP的贡献率介于82.07%~99.49%之间,表明生物炭对土壤中DEP的吸附发挥着主导作用。相关分析发现,吸附参数ΔKoc与生物炭的比表面积和总孔体积具有显著相关性,提高比表面积和改善孔隙结构可以增强生物炭对DEP的吸附能力。     

磷改性生物炭对Pb、Cd复合污染土壤的钝化效果

中国存在着较大面积受重金属污染土壤,尤其是Pb、Cd两种重金属的复合污染较常见。利用磷改性生物炭对Pb、Cd复合污染土壤展开修复研究。结果表明:(1)磷改性生物炭可使土壤中Pb、Cd由弱酸提取态向可氧化态、残渣态转变,Pb的可氧化态和残渣态分别增加了19.4、16.9百分点,Cd的可氧化态、残渣态分别增加了17.4、9.9百分点;(2)磷改性生物炭可提高土壤有效磷,有效磷最终稳定在39 mg/kg左右;(3)磷改性生物炭能显著增加土壤阳离子交换量至19.3 cmol/kg。磷改性生物炭不仅能有效钝化重金属,还能有效改善土壤质量。     

有机肥料联合东南景天修复重金属污染土壤的研究

将两种有机肥料黄腐酸钾和紫云英(Astragalus sinensis)分别与重金属超积累植物东南景天(Sedum alfredii)联用修复重金属污染土壤,研究有机肥料对污染土壤重金属生物有效性、形态以及东南景天重金属积累量的影响。结果显示,修复0～4个月,施加有机肥料对土壤重金属生物有效性均有一定的促进作用;而修复4～8个月,土壤重金属向可氧化态和残渣态转化,生物有效性受到抑制。从东南景天地上部重金属积累量看,修复0～4个月,施加0.3%(质量分数)黄腐酸钾促进东南景天对锌、镉的吸收积累,锌、镉积累量分别比对照提高了280.37%、265.44%;而修复4～8个月,东南景天地上部重金属积累量相较对照均下降。由此可见,提升重金属污染土壤的植物修复效果,还需考虑修复周期的影响。     

热解温度对污泥生物炭的表面特性及重金属安全性的影响

以一套中试干燥热解一体化处理设备,采用热解工艺,在300~600℃范围内对污水处理厂产生的剩余污泥进行了批处理,得到了系列污泥生物炭产品,并对其表面电荷、FT-IR图谱等进行了测试,对污泥及生物炭的重金属总量和DTPA可提取态进行了比较分析。研究表明,热解温度会影响生物炭表面电荷分布,而且在400℃时表面电荷分布最均匀。经热解反应后,污泥中的重金属总量虽然得到了一定程度的富集,但Pb,Zn,Cu,Fe和Mn 5种重金属的DTPA-可提取态的含量大幅度降低,因此,污泥生物炭中的重金属被惰性化,降低了环境风险。     

Sources and fate of PCDD and PCDF

PCDD and PCDF were found in urban air particulates from St. Louis and Washington, D.C., and in sediments from the Great Lakes and Siskiwit Lake, Isle Royale. The similarity between the PCDD and PCDF found in air particulates and sediment samples and the presence of PCDD and PCDF in sediment from Siskiwit Lake (a location which can receive only atmospheric inputs) suggest that these compounds are emitted to the atmosphere from combustion sources. The historical input of PCDD and PCDF to dated sediment cores shows a strong increase since 1940, and this suggests that the incineration of chlorinated organic compounds is an important source of PCDD and PCDF to the environment.     

Meta-analysis of time-series studies of air pollution and mortality: effects of gases and particles and the influence of cause of death,age, and season

A comprehensive, systematic synthesis was conducted of daily time-series studies of air pollution and mortality from around the world. Estimates of effect sizes were extracted from 109 studies, from single- and multipollutant models, and by cause of death, age, and season. Random effects pooled estimates of excess all-cause mortality (single-pollutant models) associated with a change in pollutant concentration equal to the mean value among a representative group of cities were 2.0% (95% CI 1.5-2.4%) per 31.3 microg/m3 particulate matter (PM) of median diameter < or = 10 microm (PM10); 1.7% (1.2-2.2%) per 1.1 ppm CO; 2.8% (2.1-3.5%) per 24.0 ppb NO2; 1.6% (1.1-2.0%) per 31.2 ppb O3; and 0.9% (0.7-1.2%) per 9.4 ppb SO2 (daily maximum concentration for O3, daily average for others). Effect sizes were generally reduced in multipollutant models, but remained significantly different from zero for PM10 and SO2. Larger effect sizes were observed for respiratory mortality for all pollutants except O3. Heterogeneity among studies was partially accounted for by differences in variability of pollutant concentrations, and results were robust to alternative approaches to selecting estimates from the pool of available candidates. This synthesis leaves little doubt that acute air pollution exposure is a significant contributor to mortality.     

Field and laboratory studies of the fate and enantiomeric enrichment of venlafaxine and O-desmethylvenlafaxine under aerobic and anaerobic conditions

The stereoselectivity of R,S-venlafaxine and its metabolites R,S-O-desmethylvenlafaxine, N-desmethylvenlafaxine, O,N-didesmethylvenlafaxine, N,N-didesmethylvenlafaxine and tridesmethylvenlafaxine was studied in three processes: (i) anaerobic and aerobic laboratory scale tests; (ii) six wastewater treatment plants (WWTPs) operating under different conditions; and (iii) a variety of wastewater treatments including conventional activated sludge, natural attenuation along a receiving river stream and storage in operational and seasonal reservoirs. In the laboratory and field studies, the degradation of the venlafaxine yielded O-desmethylvenalfaxine as the dominant metabolite under aerobic and anaerobic conditions. Venlafaxine was almost exclusively converted to O-desmethylvenlafaxine under anaerobic conditions, but only a fraction of the drug was transformed to O-desmethylvenlafaxine under aerobic conditions. Degradation of venlafaxine involved only small stereoisomeric selectivity. In contrast, the degradation of O-desmethylvenlafaxine yielded remarkable S to R enrichment under aerobic conditions but none under anaerobic conditions. Determination of venlafaxine and its metabolites in the WWTPs agreed well with the stereoselectivity observed in the laboratory studies. Our results suggest that the levels of the drug and its metabolites and the stereoisomeric enrichment of the metabolite and its parent drug can be used for source tracking and for discrimination between domestic and nondomestic wastewater pollution. This was indeed demonstrated in the investigations carried out at the Jerusalem WWTP.     

Meta-Analysis of Time-Series Studies of Air Pollution and Mortality: Effects of Gases and Particles and the Influence of Cause of Death,Age, and Season

Abstract

A comprehensive, systematic synthesis was conducted of daily time-series studies of air pollution and mortality from around the world. Estimates of effect sizes were extracted from 109 studies, from single- and multipollutant models, and by cause of death, age, and season. Random effects pooled estimates of excess all-cause mortality (single-pollutant models) associated with a change in pollutant concentration equal to the mean value among a representative group of cities were 2.0% (95% CI 1.5-2.4%) per 31.3 μg/m³ particulate matter (PM) of median diameter <10 μm (PM₁₀); 1.7% (1.2-2.2%) per 1.1 ppm CO; 2.8% (2.1-3.5%) per 24.0 ppb NO₂; 1.6% (1.1-2.0%) per 31.2 ppb O₃; and 0.9% (0.7-1.2%) per 9.4 ppb SO₂ (daily maximum concentration for O₃, daily average for others). Effect sizes were generally reduced in multipollutant models, but remained significantly different from zero for PM₁₀ and SO₂. Larger effect sizes were observed for respiratory mortality for all pollutants except O₃. Heterogeneity among studies was partially accounted for by differences in variability of pollutant concentrations, and results were robust to alternative approaches to selecting estimates from the pool of available candidates. This synthesis leaves little doubt that acute air pollution exposure is a significant contributor to mortality.     

Sorption and desorption of Cu and Cd by macroalgae and microalgae

The sorption and desorption of Cu and Cd by two species of brown macroalgae and five species of microalgae were studied. The two brown macroalgae, Laminaria japonica and Sargassum kjellmanianum, were found to have high capacities at pHs between 4.0 and 5.0 while for microalgae, optimum pH lay at 6.7. The presence of other cations in solution was found to reduce the sorption of the target cation, suggesting a competition for sorption sites on organisms. Sorption isotherms obeyed the Freundlich equation, suggesting involvement of a multiplicity of mechanisms and sorption sites. For the microalgae tested, Spirulina platensis had the highest capacity for Cd, followed by Nannochloropsis oculata, Phaeodactylum tricornutum, Platymonas cordifolia and Chaetoceros minutissimus. The reversibility of metal sorption by macroalgae was examined and the results show that both HCl and EDTA solutions were very effective in desorbing sorbed metal ions from macroalgae, with up to 99.5% of metals being recovered. The regenerated biomass showed undiminished sorption performance for the two metals studied, suggesting the potential of such material for use in water and wastewater treatment.     

剩余污泥浓缩脱水投药量优化和模型建立

应用高分子阳离子絮凝剂（CPF-100）和聚丙烯酰胺（PAM）对污水厂剩余污泥进行浓缩脱水实验，研究表明：CPF-100的浓缩脱水效果优于PAM；当CPF-00投加量为1．16‰时，污泥沉降性能改善程度为37．51％；且在CPF-100投加量逐渐增大的初始阶段，污泥沉降性能改善程度随投加量的增加而增大，但CPF-100投加量也不宜过大，当CPF-100投加量超过1．16‰后，反而会使浓缩脱水效果变差。同时，建立了污泥沉降性能改善程度与絮凝剂CPF-100投加量、沉降时间之间的数学模型，其能较好地反映污水厂剩余污泥的浓缩脱水效果。     

骆马湖富营养化和生态状况调查与评价

为了了解骆马湖水质状况，在2005年对骆马湖富营养化状态和生态特性进行了调查，并结合“十五”期间的监测资料进行了分析。2005年骆马湖水体中总氮和总磷的平均值超《地表水环境质量标准》（GB3838-2002）中Ⅲ类，超标情况分别为0．78倍和0．54倍，达到湖库特定项目Ⅳ类水标准，骆马湖处于轻度富营养化状态。对骆马湖生态特征分析表明，由于该湖泊的形态以及“藻型浊水状态”和“泥沙型浊水状态”交替出现，遏制了湖水从高营养盐含量向全面富营养化状态演变，保障了底栖动物的良好生长环境，从而形成了骆马湖独特的环境生态平衡。     

Experimental and statistical validation of SPME-GC-MS analysis of phenol and chlorophenols in raw and treated water

A procedure based on solid-phase microextraction (SPME) and gas chromatography coupled with mass spectrometry (GC-MS) was developed and validated in order to analyse 10 phenols in water samples. The optimised conditions were obtained using polyacrylate fibre (PA), 20ml of sample volume, 10% NaCl, pH 4.0 and direct extraction at 35 degrees C and 1000rpm, for 40min. The linear range and quantification limits for these compounds by SPME-GC-MS were defined. An evaluation of the main uncertainty sources of this method is included, which allows expanded uncertainties in the 9.4-35% range for the majority of the compounds. The main source of uncertainty is associated with matrix effects. The validated method is suitable for monitoring the production and distribution of potable water and was used, in field trials, for the analysis of samples from main intakes of water (surface or underground) and from water supply system of a large area (Lisbon and neighbour municipalities).     

Copper-catalyzed chlorination and condensation of acetylene and dichloroacetylene

The chlorination and condensation of acetylene at low temperatures is demonstrated using copper chlorides as chlorinated agents coated to model borosilicate surfaces. Experiments with and without both a chlorine source and borosilicate surfaces indicate the absence of gas-phase and gas-surface reactions. Chlorination and condensation occur only in the presence of the copper catalyst. C₂ through C₈ organic products were observed in the effluent; PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed that is consistent with the observed product distributions. Similar experiments with dichloroacetylene indicate greater reactivity in the absence of the copper catalyst. Reaction is observed in the gas-phase and in the presence of borosilicate surfaces at low temperatures. The formation of hexachlorobenzene is only observed in the presence of a copper catalyst. PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed for the formation of hexachlorobenzene from dichloroacetylene.