TiO2@palygorskite composite for the efficient remediation of oil spills via a dispersion-photodegradation synergy

• A novel and multi-functional clay-based oil spill remediation system was constructed. • TiO₂@PAL functions as a particulate dispersant to break oil slick into tiny droplets. • Effective dispersion leads to the direct contact of TiO₂ with oil pollutes directly. • TiO₂ loaded on PAL exhibits efficient photodegradation for oil pollutants. • TiO₂@PAL shows a typical dispersion-photocatalysis synergistic remediation. Removing spilled oil from the water surface is critically important given that oil spill accidents are a common occurrence. In this study, TiO₂@Palygorskite composite prepared by a simple coprecipitation method was used for oil spill remediation via a dispersion-photodegradation synergy. Diesel could be efficiently dispersed into small oil droplets by TiO₂@Palygorskite. These dispersed droplets had an average diameter of 20–30 mm and exhibited good time stability. The tight adsorption of TiO₂@Palygorskite on the surface of the droplets was observed in fluorescence and SEM images. As a particulate dispersant, the direct contact of TiO₂@Palygorskite with oil pollutants effectively enhanced the photodegradation efficiency of TiO₂ for oil. During the photodegradation process, •O₂⁻and •OH were detected by ESR and radical trapping experiments. The photodegradation efficiency of diesel by TiO₂@Palygorskite was enhanced by about 5 times compared with pure TiO₂ under simulated sunlight irradiation. The establishment of this new dispersion-photodegradation synergistic remediation system provides a new direction for the development of marine oil spill remediation.     

Baseline soil levels of PCDD/Fs established prior to the construction of municipal solid waste incinerators in China

In order to determine the baseline contamination by polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in different areas in China, prior to the construction of municipal solid waste incinerators (MSWIs), a total of 32 representative soil samples was collected near 16 incinerators and analyzed for their PCDD/F concentrations. The PCDD/F baseline concentrations in the soil samples ranged from 0.32 to 11.4 ng I-TEQ kg⁻¹ (dry matter), with average and median value of 2.73 and 2.24 ng I-TEQ kg⁻¹ (dry matter), respectively, and a span between maximum and minimum recorded value of 36. The PCDD homologues predominated in 26 out of 32 soil samples, with the ratio (PCDDs)/(PCDFs) ranging from 1.1 to 164; however in the other 6 samples, PCDF homologues were larger, with the same ratio varying from 0.04 to 0.8. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were used to examine PCDD/F amount and profile in these soil samples, and their possible associations with known emission sources: in this process 6 really distinct isomer fingerprints were identified. Background PCDD/F levels and profiles were comparable to those found in soils from China and other countries and indicate a rather low baseline PCDD/F contamination of soils. The present data provide the tools for future assessment of a possible impact of these MSWIs.     

温度及外加碳源对生物脱氮除磷过程的影响

针对污水处理厂普遍面临的进水碳源不足及冬季低温时出水氮磷不能稳定达标的问题,研究了温度(21、15和10℃)和外加碳源(乙酸)对活性污泥缺氧条件下反硝化及释磷过程的影响。结果表明,在缺氧条件下投加乙酸,释磷与反硝化反应可同时进行,且乙酸投量的增加仅延长快速碳源反硝化阶段及缺氧释磷阶段的反应时间;温度降低为15℃和10℃时,快速碳源反硝化阶段反硝化速率及缺氧释磷速率较21℃分别降低了约29.2%、42.2%和26.1%、32.3%。当硝态氮目标去除量与磷酸盐目标释放量之比超过5时,乙酸的最优投量以满足反硝化要求为准,计算得出21、15和10℃时常州某城镇污水处理厂乙酸最优投加量计算值约为30、39和46 mg/L。     

Pollution characteristics of 23 veterinary antibiotics in livestock manure and manure-amended soils in Jiangsu province,China

The aim of this study was to investigate the pollution characteristics of typical veterinary antibiotics in manure and soil of livestock farms in Jiangsu province. This investigation employed solid-phase extraction (SPE) coupled with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). A total of 53 manure and 50 amended soil samples from 16 livestock farms in Jiangsu province were collected for analysis. In the manure samples, the highest detected frequencies and concentrations were those of tetracyclines (TCs, 54.1 ± 5775.6 μgkg^?1), followed by fluoroquinolones (FQs, 8.4 ± 435.6 μgkg^?1), sulphonamides (SAs, 3.2 ± 5.2 μgkg^?1) and macrolides (MACs, 0.4 ± 110.5 μgkg^?1). Statistical analysis was used to illuminate the pollution characteristics of 23 veterinary antibiotics for various animal types and different regions in Jiangsu province. The results showed that the pollution level in cow manure was relatively lower compared with pig and chicken manure due to the relative restriction of medication. Furthermore, contamination was serious in amended soil from chicken farms. The pollution level in manure among different regions was higher to the south and north compared with the centre of the region. The same outcome was found for soil. Antibiotic residues in organic fertilizer were also investigated in this study. We found that although the detected concentration was lower in organic fertilizer than in fresh manure, detection frequencies (10–90%) were high, especially for roxithromycin (90%) in MACs (30–90%). This finding suggests attention should be paid to the pollution levels in organic fertilizer. This study is the first extensive investigation of the occurrence and distribution of many kinds of typical veterinary antibiotics in manure and soil from livestock farms of Jiangsu province. This investigation systematically assesses veterinary antibiotics usage and related emissions in southeast China.     

复合填料热传导过程数值模拟

复合填料由废铸砂、粉煤灰、聚苯乙烯(EPS)颗粒、水泥和水按一定质量比例混合制成,具有低导热性、抗冻胀和轻质特性。根据热阻力法则和比等效导热系数相等法则,将材料视为由大量正方形单元体组成,其中心为一个球形EPS颗粒,这种单元体与总体的导热系数相等。运用AN SY S软件对复合填料单元体的传热过程进行了有限元模拟,根据瞬态法导热系数测试原理,推求不同EPS掺入比情况下的复合填料导热系数,分析EPS颗粒与导热系数的关系,发现材料导热系数随着EPS掺入比的增加而快速降低。将材料导热系数数值模拟与实测结果作比较,发现有限元模拟值与实测值接近,说明采用有限元方法可以实现对材料传热过程的模拟。     

Thermogravimetric analysis and kinetic study on pyrolysis of representative medical waste composition

To obtain detailed information on the pyrolysis characteristics, a thermogravimetric study on the pyrolysis of 14 typical medical waste compositions was carried out in thermogravimetric analysis (TGA) equipment using dynamic techniques in a stream of N(2). An index representing pyrolysis reactivity of waste was presented. Kinetic parameters were obtained by Coats-Redfern method and used to model the TG curve. The results showed that: (a) Plastic, protein, cellulosic material, synthetic fibre, and rubber entered pyrolysis process in succession. (b) There was one decomposition stage in the pyrolysis of one-off medical glove, operating glove, cellulosic waste, absorbable catgut suture and adhesive plaster, while other components had two obvious weight loss stages. (c) The obtained apparent activation energy for second stage pyrolysis was comparably higher than that for first stage. (d) Each stage was controlled by only one kinetic mechanism, in which kinetic parameters were constant. (e) The degradation kinetics of medical waste may be affected by special physical and chemical treatment in the product manufacturing process. (f) Among 13 waste samples, the pyrolysis index of cellulosic matter was the highest, which indicated cellulosic matter had strong pyrolysis reactivity. (g) With increasing heating rate, TG curve and DTG peak shifted to high temperatures and main reaction interval of the sample became longer.     

Aging activity of DDE in dissimilar rice soils in a greenhouse experiment

A green-house study was conducted in late 2005 to investigate the aging behavior of p,p'-DDE in two types of soil, Hydragric Anthrosols (An) and Hydragric Acrisols (Ac), according to the World Reference Base (WRB) [FAO/ISRIC/ISSS. 1998. World reference base for soil resources. World soil resources reports, Rome. p. 87]. Paddy rice and dry rice were grown in submerged paddy soils and non-submerged upland soils, respectively. The concentration of extractable p,p'-DDE in fresh DDE-spiked soils was 746.2ngg(-1). During the first few weeks of the experiment, the extractability of p,p'-DDE became increasingly low as the aging period prolonged. However, certain amount of p,p'-DDE that had been captured by soil minerals and organic matter (OM) could be released and became extractable in the later period. The extractability of p,p'-DDE in submerged soils was significantly lower than that in non-submerged soil, because flooding could increase the binding of pollutants to soil particles. The plantation of both dry rice and paddy rice slowed down the aging process of p,p'-DDE. After one month's growth of rice, p,p'-DDE bound to soil particles was released and became extractable. The OM and silt content of An are higher than that of Ac, resulting in more bound residues and relative lower extractability of p,p'-DDE in An. In addition, the extractability of p,p'-DDE could be reduced by the addition of rice straw to soils.     

Non-microcystin producing Microcystis wesenbergii (Komárek) Komárek (Cyanobacteria) representing a main waterbloom-forming species in Chinese waters

It is well known that several morphospecies of Microcystis, such as Microcystis aeruginosa (Kützing) Lemmermann and Microcystis viridis (A. Brown) Lemmermann can produce hepatotoxic microcystins. However, previous studies gave contradictory conclusions about microcystin production of Microcystis wesenbergii (Komárek) Komárek. In the present study, ten Microcystis morphospecies were identified in waterblooms of seven Chinese waterbodies, and Microcystis wesenbergii was shown as the dominant species in these waters. More than 250 single colonies of M. wesenbergii were chosen, under morphological identification, to examine whether M. wesenbergii produce hepatotoxic microcystin by using multiplex PCR for molecular detection of a region (mcyA) of microcystin synthesis genes, and chemical analyses of microcystin content by ELISA and HPLC for 21 isolated strains of M. wesenbergii from these waters were also performed. Both molecular and chemical methods demonstrated that M. wesenbergii from Chinese waters did not produce microcystin.     

Sorption of polar and nonpolar aromatic compounds to four surface soils of eastern China

Improved predictions on the fate of organic pollutants in surface environments require a better understanding of the underlying sorption mechanisms that control their uptake by soils. In this study, we monitored sorption of nine aromatic compounds with varying physicochemical properties (hydrophobicity, electron-donor/acceptor ability and polarity), including two polycyclic aromatic hydrocarbons, two chlorobenzenes, two nitroaromatic compounds, dichlobenil, carbaryl and 2,4-dichlorophenol in aqueous suspension of four surface soils of eastern China. The tested soils were characterized with respect to organic carbon (OC) content, black carbon content, mineralogy, morphology and size fraction to assess the role of the diverse soil characteristics in sorption. The results of this study show that not only the solute hydrophobicity and the OC content of soil are important to the retention of organic pollutants, but also the solute molecular structure and the soil nature.     

MnFe/海泡石后置协同低温等离子体降解甲苯的研究

低温等离子体(NTP)净化法是去除挥发性有机物(VOCs)的常用方法之一。利用NTP协同催化剂处理VOCs时可降低能耗,减少副产物,提升CO₂选择性和VOCs的去除效率。以盐酸改性海泡石(SEP)纤维为载体,利用浸渍法制备了不同Mn、Fe负载量的MnFe/SEP催化剂,采用BET、SEM、TEM、XRD、XPS等方法对催化剂进行了微观结构表征和组分分析,并利用介质阻挡放电等离子体结合后置的MnFe/SEP催化剂,开展了等离子体协同催化剂催化降解甲苯的试验研究。结果表明：海泡石纤维是性能优良的催化剂载体,可以很好地分散MnO₂和Fe₂O₃等活性组分,并保持较高的比表面积;锰铁氧化物可以提升甲苯去除率、碳平衡、CO₂选择性,减少O₃残留浓度;当负载的Mn含量为6wt%时,锰铁氧化物高度分散在海泡石纤维表面,催化活性高,性价比较高。