Aromaticity on the fly: cyclic transition state stabilization at finite temperature.

We study the transition state of pericyclic reactions at elevated temperature with unbiased ab initio molecular dynamics. We find that the transition state of the intramolecular rearrangements for barbaralane and bullvalene remains aromatic at high temperature despite the significant thermal atomic motions. Structural, magnetic, and electronic properties of the dynamical transition state show the concertedness and aromatic character. Free-energy calculations also support the validity of the transition state theory for the present rearrangement reactions. The calculations demonstrate that cyclic delocalization represents a strong force to synchronize the thermal atomic motions even at high temperatures.

Palm frond biochar production and characterisation

Palm oil has been the world's main source of oil and fats since 2004, producing over 45 million tonnes in 2009. Malaysia alone has over 4·5 million hectares planted with oil palm and, based on common practice, ~300 palm fronds are pruned per hectare per year. This agricultural waste is currently either being used as roughage feed or, more frequently, being left between rows of palm trees to prevent soil erosion, or for nutrient recycling purposes. This paper proposes an alternative use for palm frond as a source of biochar. A traditional method commonly use by gardeners in Malaysia to improve soil fertility was used to produce the biochar. A shallow earth pit was dug in the ground for the carbonisation process. The process is described and the impact of carbonisation on the earth wall is analysed and presented. The process was later re-assessed by using TGA-FTIR. Most of the hemicelluloses had fully disintegrated, but the depolymerisation of the cellulose was still incomplete at the carbonisation temperature. Most of the lignin aromatic structure was still present in the biochar. The carbonisation process was repeated in the laboratory and biochar was characterised by using BET, SEM and FTIR. An adsorption isotherm study was conducted and the experimental data were fitted to the Langmuir model. The model predicted Pb2+ adsorption rates of 83·3 mg/g, Cu2+ 41·4 mg/g, Ni2+ 13·0 mg/g and Zn2+ 19·7 mg/g. Copyright © The Royal Society of Edinburgh 2012.

ANTHROPOGENIC ORGANIC CONTAMINANTS IN WATER AND SURFACE SEDIMENTS OF LARGE SHALLOW EUTROPHIC CHAOHU LAKE, CHINA

To characterize the contamination of anthropogenic organic contaminants in the aquatic environment of Chaohu Lake, China, 7 samples for both water and surface sediment were collected in the lake. Organic contaminants were extracted by solid phase extraction (SPE) and Soxhlet extraction from the water and surface sediment samples, respectively, and then analyzed by GC-MS. One hundred and twenty kinds of organic chemicals were detected in these samples including phenol, benzene series, benzaldehydes, ethanol, polycyclic aromatic hydrocarbons (PAHs), sulfur compounds, alcoholic halides, amines, ketones, esters, alkenes and alkanes. Among them, 13 kinds of chemicals were identified as priority pollutants listed by the U.S. Environmental Protection Agency (EPA), such as phthalate esters (PAEs) and PAHs. Besides, the concentrations of 19 of PAEs and PAHs including, priority pollutants identified were also determined. Bis(2-ethylhexyl)phthalate, the predominant component of the analyzed pollutants, was in the range from 72.34 ng g(-1) DW to 613.71 ng g(-1) DW, 14.80 ng L-1 to 47.05 ng L-1 in sediment and water, respectively. The results indicated that the northwest part of the lake was heavily polluted by domestic and industrial wastewater.

Determination of PAH, PCB, and OCP in water from the Three Gorges Reservoir accumulated by semipermeable membrane devices (SPMD)

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP) were measured in the water column from Three Gorges Reservoir (TGR) collected in May 2008 using semipermeable membrane devices (SPMDs). The sampling sites spanned the whole reservoir from the upstream Chongqing to the great dam covering more than 600 km long distance with water flow velocities ranging from <0.05 to 1.5 m s(-1). This is the first experience of SPMD application in the biggest reservoir in the world. The results of water sampling rates based on performance reference compounds (PRC) were tested to be significantly correlated with water flow velocities in the big river. Results of back-calculated aqueous concentrations based on PRC showed obvious regional variations of PAH, PCB and OCP levels in the reservoir. Total PAH ranged from 13.8 to 97.2 ng L-1, with the higher concentrations occurring in the region of upstream and near the dam. Phenanthrene, fluoranthene, pyrene and chrysene were the predominant PAH compounds in TGR water. Total PCB ranged from 0.08 to 0.51 ng L-1, with the highest one occurring in the region near the dam. PCB 28, 52, 101, 138, 153, 180, 118 were the most abundant PCB congeners in the water. The total OCP ranged from 2.33 to 3.60 ng L-1 and the levels showed homogenous distribution in the whole reservoir. HCH, DDT and HCB, PeCB were the major compounds of OCP fingerprints. Based on water quality criteria, the TGR water could be designated as being polluted by HCB and PAH. Data on PAH, PCB and OCP concentrations found in this survey can be used as reference levels for future POP monitoring programmes in TGR. (C) 2009 Elsevier Ltd. All rights reserved.

How polluted is the Yangtze River? Water quality downstream from the Three Gorges Dam

The concentrations of major anions and cations, nitrogen and phosphorus, dissolved and particulate trace elements, and organic pollutants were determined for the middle and lower reaches of the Yangtze River (Changjiang) from below the Three Gorges Dam (TGD) to the mouth at Shanghai in November 2006. The concentration of dissolved inorganic phosphate (DIP) was constant at a low level of 6-8 mu gP/L, but the concentration of nitrate (NO3-) approximately doubled downstream and was closely correlated with K+. This translated to a daily load of well over 1000 It of dissolved inorganic nitrogen (DIN) at Datong. The average concentrations of dissolved Pb (0.078 +/- 0.023 mu g/L), Cd (0.024 +/- 0.009 mu g/L), Cr(0.57 +/- 0.09 mu g/L), Cu (1.9 +/- 0.7 mu g/L), and Ni (0.50 +/- 0.49 mu g/L) were comparable with those in other major world rivers, while As (3.3 +/- 1.3 mu g/L) and Zn (1.5 +/- 0.6 mu g/L) were higher by factors of 5.5 and 2.5, respectively. The trace element contents of suspended particles of As (31 +/- 28 mu g/g), Pb (83 +/- 34 mu g/g), and Ni (52 +/- 16 mu g/g) were close to maximum concentrations recommended for rivers by the European Community (EC). The average concentrations of Cd (2.6 +/- 1.6 mu g/g), Cr (185 +/- 102 mu g/g), Cu (115 +/- 106 mu g/g), and Zn (500 +/- 300 mu g/g) exceeded the EC standards by a factor of two, and Hg (4.4 +/- 4.7 mu g/g) by a factor of 4 to 5. Locally occurring peak concentrations exceed these values up to fourfold, among them the notorious elements As, Hg, and Tl. All dissolved and particulate trace element concentrations were higher than estimates made twenty years ago [Zhang, J., Geochemistry of trace metals from Chinese river/estuary systems: an overview. Estuar Coast Shelf Sci 1995; 41: 631-658.]. The enormous loads of anthropogenic pollutants disposed to the river were diluted by the large water discharge of the Yangtze even during the lowest flow resulting in the relatively low concentration levels of trace elements and organic pollutants observed. We estimated loads of e.g. As, Pb and Ni to the East China Sea to be about 4600 kg As d(-1), 3000 kg Pb d(-1), and 2000 kg Ni d(-1). About 6000 t d(-1) of dissolved organic carbon (DOC) was delivered into the sea at the time of our cruise. We tested for 236 organic pollutants, and only the most infamous were found to be barely above detection limits. We estimated that the load of chlorinated compounds, aromatic hydrocarbons, phenols, and PAHs were between 500 and 3500 kg d(-1). We also detected eight herbicides entering the estuary with loads of 5-350 kg d(-1). The pollutant load, even when at low concentrations, are considerable and pose an increasing threat to the health of the East China Sea ecosystem. (c) 2008 Elsevier B.V. All rights reserved.

Monitoring bioaccumulation and toxic effects of hexachlorobenzene using the polyurethane foam unit method in the microbial communities of the Fuhe River, Wuhan

Hexachlorobenzene (HCB) is a chlorinated aromatic hydrocarbon that was widely used for seed dressing in prevention of fungal growth on crops, and also as a component of fireworks, ammunition, and synthetic rubbers. Because of its resistance to degradation and mobility, HCB is widely distributed throughout the environment and is accumulated through food chains in different ecosystems. In this study, a preliminary investigation was carried out on the bioaccumulation and the toxic effects of HCB in the microbial (protozoan in particular) communities in the Fuhe River, Wuhan, a water body receiving industrial wastewaters containing HCB and other pollutants, using the standardized polyurethane foam units (PFU) method. Field samples were taken from eight stations established along the Fuhe River in January and August 2006. The concentration ratios of HCB in microbial communities and in water were 9.66-18.64, and the microbial communities accumulated 13.29-56.88 mu g/L of HCB in January and 0.82-10.25 mu g/L HCB in August. Correlation analysis showed a negative correlation between the HCB contents in the microbial assemblage, and the number of species and the diversity index of the protozoan communities. This study demonstrated the applicability of the PFU method in monitoring the effects of HCB on the level of microbial communities.

A screening study on persistent bioaccumulation toxins (PBT) in fuel combustion soot

Persistent bioaccumulative toxins (PBTs) are organic substances that are persistent, bioaccumulative and can cause severe toxic effects (e.g. potential oncogens, mutagenic, endocrine disrupters) to human health or environment which are the ones that need special attention. PBT chemicals could be released to the environment from several types of sources and are ubiquitous in environment. However, fast and efficiency monitoring and assessment methods to investigate PBTs in environment are still lacking. In this study, a cleaning-up procedure of analyzing PBTs in fuels combustion soot was developed and its performance was assessed through comparing the chromatograms of crude extracts with their cleaned extracts after the cleaning-up procedure. The results showed that polycyclic aromatic compounds (PACs) were the main components in fuel combustion soot and the clean-up procedure developed in this paper can be well used as the method of analyzing PBTs in fuels combustion soot.

Evaluation of soot particles of biomass fuels with endocrine-modulating activity in yeast-based bioassay

Exposure to indoor air pollution (IAP) from the combustion of biomass fuels is an important cause of morbidity and mortality in developing countries. In the work discussed in this paper we evaluated the endocrine activity of soot particles from biomass fuels by using yeast bioassay. These pollutants could have beta-galactosidase activity with a relative potency (RP) about 10(-7)-10(-9) that of estradiol. Soot particles from wood and straw combustion only partially induced beta-galactosidase activity whereas others produced fully inductive activity in the yeast assay system. These pollutants did not have estrogen antagonist and progesterone agonist activity within the defined concentration range. However, these pollutants require 2-4 orders of magnitude higher IC50 to inhibit the activity of progesterone in a similar dose-response manner to mifepristone. We therefore propose that the endocrine activity of some environmental pollutants may be because of inhibition of the progesterone receptor (hPR). GC-MS results showed that substituted polycyclic aromatic hydrocarbon (PAH) compounds, substituted phenolic compounds and derivatives, aromatic carbonyl compounds, and phytosteroids in these soot particles may be mimicking endogenous hormones.

Presence of estrogenic activity from emission of fossil fuel combustion as detected by a recombinant yeast bioassay

Estrogenic activities of emission samples generated by fossil fuel combustion were investigated with human estrogen receptor (ER) recombinant yeast bioassay. The results showed that there were weak but clear estrogenic activities in combustion emissions of fossil fuels including coal, petroleum, and diesel. The estrogenic relative potency (RP) of fossil fuel combustion was the highest in petroleum-fired car, followed by coal-fired stove, diesel-fired agrimotor, coal-fired electric power station. On the other hand, the estrogenic relative inductive efficiency (RIE) was the highest in coal-fired stove and coal-fired electric power station, followed by petroleum-fired car and diesel-fired agrimotor. The estrogenic activities in the sub-fractions from chromatographic separation of emitted materials were also determined. The results indicated that different chemical fractions in these complex systems have different estrogenic potencies. The GC/MS analysis of the emission showed that there were many aromatic carbonyls, big molecular alcohol, PAHs and derivatives, and substituted phenolic compounds and derivatives which have been reported as environmental estrogens. The existence of estrogenic substances in fossil fuel combustion demands further investigation of their potential adverse effects on human and on the ecosystem. The magnitude of pollution due to global usage of fossil fuels makes it imperative to understand the issue of fossil fuel-derived endocrine activities and the associated health risks, particularly the aggregated risks stemmed from exposure to toxicants of multiple sources. (C) 2003 Elsevier Science Ltd. All rights reserved.

含空穴传输基团PPV的合成与性能研究

该论文以提高聚苯撑乙烯（PPV）类发光聚合物的空穴传输性能为主要目的,通过将具有较高空穴传输能力的芳胺类小分子基元引入发光聚合物分子链,设计并合成了一系列含芳胺基元的PPV聚合物.另外,还通过对分子结构进行设计和控制,获得了红绿蓝三基色发光.最后还利用在共轭分子主链上引入具有三维空间位阻的侧链基团,获得了高效率的绿色发光聚合物材料.

芳香环状低聚物的合成及其开环聚合的研究

本文由聚芳脂环状低聚物入手，研究了芳香环状低聚物成环技术的规律，进而进行了用一系列新型结构单体合成环状斯聚物的探索研究。以及在目前国外仍处于研究合成环状PC及U聚合聚合的现状下，进行了合成新型高性能环状底聚物的尝试，报导了聚芳脂环状低聚物的开环聚合的研究结果。也涉及芳香环状低聚物的分离、提纯及结构表征方面采用的新技术。

芳香聚酰胺反渗透复合膜的结构、分离功能及耐氯性的研究

本工作研究了仿香聚酰胺反渗透复合膜的结构与性能，包括优化底膜结构、完善复合工艺、明确超薄功能层化学结构与耐氯耐氧化性能的关系。

微生物固定化方法修复多环芳烃污染土壤

针对传统游离微生物修复技术的缺点和弊端，提出了采用固定化微生物技术修复受多环芳烃污染的非流体介质的新课题。本文筛选出2株高效降解菌，并进行了固定化载体筛选，优化并确定了3种固定化工艺。通过实验室模拟实验，考察了固定化菌对PAHs污染非流体介质的修复能力，最后通过扫描电子显微镜（SEM）分析，对固定化微环境强化修复机制进行了初步探讨。 细菌芽孢杆菌（Bacillus sp.，SB02）和真菌毛霉（Mucor sp.，SF06）对土壤中的Pyr、BaP降解率高，降解速率快，为高效降解微生物。 碱化后的泥炭土适宜作为细菌固定化载体；玉米芯适宜作为真菌固定化载体；改性后蛭石适宜作为混合菌固定化载体。这些载体来源广泛，成本低廉，工艺简单，安全无毒。 将固定化菌应用于Pyr、BaP污染土壤的修复，考察了初始接种量、环境温度、土壤含水量对固定化菌降解Pyr、BaP的影响，固定化菌对不同系列浓度Pyr、BaP的降解，以及固定化菌在不灭菌土壤中对Pyr、BaP的降解，表明固定化菌对土壤中Pyr和BaP的降解率均高出游离菌20%，固定化混和菌降解效果最好，其次是固定化真菌，再次是固定化细菌。 SEM分析了固定化颗粒的微观结构和微生物在颗粒内部的形态变化，结果表明颗粒内部丰富的疏松多孔结构和巨大的比表面积为微生物提供了适宜的生存空间，使吸附固定化成为可能。 固定化菌对沈抚灌区PAHs污染土壤修复效果非常理想，经过6个月，土壤中总PAHs的去除率达70.3%，高于游离菌。

土壤中PAHs的光催化降解动力学及机制研究

本文以土壤为介质，以三环的菲（Phe）、四环的芘（Pyr）和五环的苯并[a]芘（BaP）为目标污染物，研究了紫外灯照射下土壤中多环芳烃（PAHs）的降解，并以半导体纳米TiO2和Fe2O3为催化剂研究了土壤中PAHs的催化降解，对光降解及光催化降解的动力学进行了研究，在室内条件下考察了土壤条件和环境因子对光降解及光催化降解PAHs的影响；研究了太阳光照条件下土壤pH值对光降解和催化降解的影响和腐殖酸对光降解的影响；初步探讨了纳米TiO2催化光降解土壤中PAHs的机制。 研究结果表明：土壤中PAHs的紫外光降解符合一级动力学模型，土壤中PAHs光降解与土壤厚度呈显著负相关，土壤粒径对紫外光解PAHs有显著影响，温度从20 ℃升高到30 ℃，光解速率逐渐增加，在PAHs污染土壤的光降解中腐殖酸起敏化作用，随着紫外辐射强度的增加，光降解速率加快。 纳米TiO2和Fe2O3均能促进土壤中PAHs的紫外光降解，PAHs光催化降解符合一级动力学模型，在酸性和碱性土壤条件下，光催化降解PAHs的速率均高于中性，在不同光质条件下，TiO2 、Fe2O3催化光降解PAHs的速率发生变化，随着紫外辐射强度的增加，光催化降解速率常数增加，半衰期减少；腐殖酸促进TiO2 、Fe2O3催化土壤中PAHs的光降解，腐殖酸在这个过程中起着敏化作用。 在太阳光照射下酸性和碱性土壤中PAHs的降解快于中性，PAHs污染土壤中在加入腐殖酸后光降解速率加快，在酸性条件下催化降解最快，在碱性和中性条件下相差不大。 土壤中PAHs存在着PAH的光致电离、电子向O2的转移的两种降解途径；在有催化剂TiO2条件下，由于催化剂在光照后形成的电子-空穴能够氧化还原污染物，PAH的光致电离、电子向O2的转移的引起的降解，共同促进了土壤中PAHs的光催化降解。

植物与微生物联合修复多环芳烃污染土壤及机理研究

本文以多环芳烃污染土壤为研究对象，以菲（Phe）、芘（Pyr）和苯并[a]芘（BaP）为目标污染物，以建立生态、经济、高效污染土壤修复技术为目标，在研究植物与微生物联合修复多环芳烃污染土壤效果的基础上，重点研究了植物与微生物联合修复污染土壤过程中多环芳烃的去除机制。 研究结果表明：种植苜蓿和黑麦草能够促进土壤中多环芳烃的去除，提高土壤中多环芳烃的去除率。植物根际土壤中多环芳烃的去除速度快于于非根际土壤。在植物与高效降解菌联合作用过程中，植物的存在强化了菌剂对土壤中多环芳烃的去除作用。苜蓿和黑麦草与高效降解菌的联合作用使菲、芘和苯并[a]芘去除率分别比对照土壤提高了26.64%、30.41%、32.04%和26.93%、27.43%、30.15%。 植物根和茎叶中菲、芘和苯并[a]芘的含量与土壤污染物浓度正相关，但其吸收积累作用对土壤中多环芳烃去除的贡献率小于0.34%。植物对土壤多环芳烃污染的修复作用主要源于植物生长显著提高了根际微生物的降解活性。 植物根际微生物的数量和土壤酶活性显著高于非根际土壤。植物根系的存在提高了土壤中微生物的数量和酶活性，从而提高了土壤中PAHs的去除率。这是根际土壤中多环芳烃去除的主要机制。 模拟根际修复，研究了添加根系分泌物对土壤中芘降解的影响。添加20mg/kg根系分泌物土壤中细菌数量为未添加根系分泌物土壤的19.43-36.29倍，真菌为3.05-6.60倍，土壤中芘的半衰期比未添加根系分泌物处理减少10.91天。植物根系分泌物是影响根际修复的一个重要原因。