沈阳地区水环境和生物样品中全氟化合物的污染分布特征

采用高效液相色谱/电喷雾负电离源串联质谱法对沈阳市各类水环境和生物样品中全氟化合物(PFCs)进行测定,研究了PFCs的河流分布及季节分布特征.同时,对通过饮用水及家禽和鱼摄入全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)的人体健康风险进行了评价.结果表明,沈阳市各类水环境样品中总PFCs浓度范围为nd～6.01ng·L-1,平均浓度为5.23ng·L-1.PFOS和PFOA是沈阳地区所有水环境样品中最主要的PFCs污染物,浓度范围分别为nd～2.83ng·L-1和nd～5.71ng·L-1,平均浓度分别为1.11和2.13ng·L-1.细河的PFOS含量最高,约为浑河PFOS含量的2倍,蒲河PFOS含量的3倍.一些PFCs化合物之间呈正相关关系,说明其可能具有相同的来源.PFOS与PFOA之间无相关关系,由此推断沈阳水体中二者具有不同来源.浑河流经沈阳市时,PFOS和PFOA浓度升高.流经沈阳市区后,PFOS和全氟己烷磺酸钾(PFHxS)浓度明显升高.细河中PFHxS也有检出,表明沈阳市是周边水体中PFOS及PFHxS的主要污染来源.丰水期地表水中PFOS和PFOA浓度与枯水期相比没有明显差异,但丰水期水中PFCs组成更为丰富,出现了大量全氟庚酸(PFHpA).沈阳地区自来水中PFOS和PFOA浓度平均值分别为0.39和0.85ng·L-1,最高浓度分别为1.16和2.55ng·L-1,均低于美国饮用水健康参考值.沈阳生物样品中PFOS和全氟十一酸(PFUnDA)是最普遍的化合物.总PFCs平均含量在鱼样品中为6.59ng.g-1(以干重计),鸡和鸭血清样品中分别为1.65和0.69ng·mL-1,鸡和鸭肝脏样品中分别为0.41和1.68ng.g-1(以干重计),与文献报道相比处于较低水平.     

Organic matter extracted from activated sludge with ammonium hydroxide and its characterization

In order to characterize the organic properties of waste activated sludge in a wastewater treatment plant,organic matter within sludge was extracted with NH 3 ·H 2 O preferentially,and subsequently fractionated into five fractions using XAD-8/XAD-4 resins.Up to a 63.8%-71.1% of organic matter within the sludge could be efficiently extracted by NH 3 ·H 2 O.Fractionation results showed that hydrophobic acid and hydrophilic fraction were two main components among the sludge organic matter (accounting for 32.2% and 48.0% of the bulk organic matter,respectively),whereas transphilic acid,hydrophobic neutral and transphilic neutral were quite low (accounting for 9.2%,5.8% and 4.8%,respectively).Despite that the extractant of NH 3 ·H 2 O showed a relatively higher extraction efficiency of the aromatic components,the relatively low aromaticity of the organic fractions implied that those non-aromatic components could also be effectively extracted,especially for neutral and hydrophilic fractions.In addition,acidic fractions contained more aromatic humic-like components,whereas the neutral fractions had a greater content of aromatic proteins and soluble microbial byproduct-like components.Extraction of sludge organics with NH 3 ·H 2 O and subsequential fractionation using XAD resins could be a novel method for further characterization of sludge organics.     

Co-transport of dissolved organic matter and heavy metals in soils induced by excessive phosphorus applications

To evaluate the e ects of long-term applications of phosphorus fertilizers on mobility of dissolved organic matter (DOM) and heavy metals in agricultural soils, a sandy soil and a loamy soil were spiked with ammonium phosphate at application rates of 0, 25, 50, 100, 250, and 500 mg P per kilogram of soil. A series of 15-cm long soil columns were constructed by packing incubated soils of varying concentrations of P. The soil columns were consecutively leached by simulated rainfalls for six cycles. The contents of water extractable organic carbon in both sandy and loamy soils increased significantly with increasing rates of P applications. Relatively high rates of P applications could induce a marked increase in DOM concentrations in the leachates, the e ects were larger with the sandy soil rather than with the loamy soil. Applications of P changed the partitioning of trace metals in the soil solids and the soil solutions. The increased P application rates also seemed to elevate the leaching of Cu, Cd, and Zn from soils. The concentrations of Cu, Cd, and Zn in the leachates were positively correlated with DOM, probably due to the formation of metal-DOM complexes. In contrast, Pb concentrations in the leachates were negatively correlated with DOM, and decreased with increasing rates of P applications. The boosted leaching of DOM induced by high rates of P applications was probably due to the added phosphate ions competing for adsorption sites in the soil solids with the indigenous DOM.     

Influence of Indian mustard （Brassicajuncea） on rhizosphere soil solution chemistry in long-term contaminated soils： A rhizobox study

This study investigated the influence of Indian mustard (Brassica juncea) root exudation on soil solution properties (pH, dissolved organic carbon (DOC), metal solubility) in the rhizosphere using a rhizobox. Measurement was conducted following the cultivation of Indian mustard in the rhizobox filled four di erent types of heavy metal contaminated soils (two alkaline soils and two acidic soils). The growth of Indian mustard resulted in a significant increase (by 0.6 pH units) in rhizosphere soil solution pH of acidic soils and only a slight increase (< 0.1 pH units) in alkaline soils. Furthermore, the DOC concentration increased by 17–156 mg/L in the rhizosphere regardless of soil type and the extent of contamination, demonstrating the exudation of DOC from root. Ion chromatographic determination showed a marked increase in the total dissolved organic acids (OAs) in rhizosphere. While root exudates were observed in all soils, the amount of DOC and OAs in soil solution varied considerably amongst di erent soils, resulting in significant changes to soil solution metals in the rhizosphere. For example, the soil solution Cd, Cu, Pb, and Zn concentrations increased in the rhizosphere of alkaline soils compared to bulk soil following plant cultivation. In contrast, the soluble concentrations of Cd, Pb, and Zn in acidic soils decreased in rhizosphere soil when compared to bulk soils. Besides the influence of pH and DOC on metal solubility, the increase of heavy metal concentration having high stability constant such as Cu and Pb resulted in a release of Cd and Zn from solid phase to liquid phase.     

Interaction mechanisms of organic contaminants with burned straw ash charcoal

Black carbons(e.g.,charcoal) have a great impact on the transport of organic contaminants in soil and water because of its strong affnity and ubiquity in the environment.To further elucidate their interaction mechanism,sorption of polar(p-nitrotoluene,m-dinitrobenzene and nitrobenzene) and nonpolar(naphthalene) aromatic contaminants to burned straw ash charcoal under different de-ashed treatments were investigated.The sorption isotherms fitted well with Freundlich equation,and the Freundlich N values were all around 0.31-0.38,being independent of the sorbate properties and sorbent types.After sequential removal of ashes by acid treatments(HCl and HCl-HF) ,both adsorption and partition were enhanced due to the enrichment of charcoal component.The separated contribution of adsorption and partition to total sorption were quantified.The effective carbon content in ash charcoal functioned as adsorption sites,partition phases,and hybrid regions with adsorption and partition were conceptualized and calculated.The hybrid regions increased obviously after de-ashed treatment.The linear relationships of Freundlich N values with the charring-temperature of charcoal or biochar(the charred byproduct in biomass pyrolysis) were observed based on the current study and the cited publications which included 15 different temperatures(100-850°C) ,10 kinds of precursors of charcoal/biochar,and 10 organic sorbates.     

Ambient levels of atmospheric carbonyls in Beijing during the 2008 Olympic Games

The measurements of atmospheric carbonyls concentrations in Beijing were conducted from 12 July to 8 October, 2008, covering the periods of the 2008 Olympic Games and Paralympic Games. Six carbonyls, including formaldehyde, acetaldehyde, acetone, butyraldehyde, valeraldehyde, and hexaldehyde, were identified in all air samples. The total average concentrations of these carbonyls before, during, and after traffic restriction were (48.1 ± 15.2), (36.6 ± 14.5) and (23.4 ± 12.3) μg/m3, respectively. Compared with the period after traffic restriction, the distinct high concentrations of the carbonyls before and during traffic restriction were primarily ascribed to the remarkable contribution of photochemical reactions. With respect to our previous investigation in the summer of 2005, the reductions of formaldehyde, acetaldehyde and acetone during traffic restriction period were about 64%, 47% and 27%, respectively, indicating that the air cleaning actions adopted by the Chinese government for the two games were efficient. The lowest levels of atmospheric carbonyls and the extremely high composition proportion of acetone after the traffic restriction were mainly attributed to the long-term effect of the control measures for the two games.     

黄河不同粒径悬浮物中POC含量及输运特征研究

悬浮物(TSS)粒径与颗粒有机碳(POC)含量关系的研究,是河流POC形态变化及输送过程和输运通量研究的基础.本研究在沉降分级法基础上,结合激光粒度仪粒度测定和多元线性回归分析的数据处理方法,对2005-06-29黄河利津站、2005-09-27黄河口低盐度区以及2006年11月兰州、潼关、花园口各站TSS样品分析发现：黄河TSS中POC与其对应的中值粒径存在良好的负指数关系,POC的极限值为0.56%,普遍低于世界其它河流;黄河不同区段站位TSS性质不同使各样品相同粒级间POC存在明显的差异,黄河口站>花园口站>兰州站>潼关站>利津站,如<8 μm粒级TSS中POC依次是0.661%、 0.627%、 0.550%、 0.505%、 0.493%;黄河各粒级TSS所承载的POC量占样品POC总量的比例在不同区段各样品间极其相近,POC随TSS粒径增大显著递减, 80%以上的POC集中在<16 μm的TSS中,而粒径<32 μm的TSS承载了95%以上的POC.可见虽然黄河自西向东横跨5　000　km之多,落差达4　000　m以上,但POC的输运规律具有一致性,TSS粒径是控制POC输运特性的主要因素.     

Runoff and dissolved organic carbon loss from a paired-watershed study of three adjacent agricultural Watersheds

Organic matter plays several important roles in the biogeochemistry of terrestrial and aquatic ecosystems including the mobilization and transport of nutrients and pollutants. Cropping, tillage practices and vegetative buffer strip installation affect losses of dissolved organic carbon (DOC). While many studies show reductions in pollutant export from agroecosystems where vegetative buffers have been implemented, buffer strips may be a source of DOC and contribute to surface water pollution. Using a paired-watershed approach, the objectives of this study were to determine the effect of grass and agroforestry buffers on runoff and DOC loss, compare runoff and DOC losses between the growing and fallow seasons, and investigate crop effects on runoff and DOC losses. The study design consisted of three small agricultural Watersheds in a no-till, maize-soybean rotation located in the claypan region of northeast Missouri, USA; one watershed was planted with grass buffer strips, one with agroforestry buffer strips, and one unaltered watershed served as the control. Runoff and DOC loss were measured during a six-year calibration period (1991–1997) prior to buffer installation and for a nine-year treatment period (1997–2006). The grass buffer strips significantly decreased runoff by 8.4% (p = 0.015) during the treatment period while the agroforestry buffer system exhibited no significant change in runoff (p = 0.207). Loss of DOC was not significantly affected by grass or agroforestry buffer installation (p = 0.535 and p = 0.246, respectively). Additionally, no significant difference in runoff or DOC loss was found between crops (maize and soybean) or between seasons (growing and fallow). Overall, this study indicates that grass buffer systems are effective at reducing runoff and that DOC contamination of surface waters is not exacerbated by either type of vegetative buffer strip.     

Simulated dynamics of carbon stocks driven by changes in land use, management and climate in a tropical moist ecosystem of Ghana

Sub-Saharan Africa is large and diverse with regions of food insecurity and high vulnerability to climate change. This project quantifies carbon stocks and fluxes in the humid forest zone of Ghana, as a part of an assessment in West Africa. The General Ensemble biogeochemical Modeling System (GEMS) was used to simulate the responses of natural and managed systems to projected scenarios of changes in climate, land use and cover, and nitrogen fertilization in the Assin district of Ghana. Model inputs included historical land use and cover data, historical climate records and projected climate changes, and national management inventories. Our results show that deforestation for crop production led to a loss of soil organic carbon (SOC) by 33% from 1900 to 2000. The results also show that the trend of carbon emissions from cropland in the 20th century will continue through the 21st century and will be increased under the projected warming and drying scenarios. Nitrogen (N) fertilization in agricultural systems could offset SOC loss by 6% with 30 kg N ha⁻¹ year⁻¹ and by 11% with 60 kg N ha⁻¹ year⁻¹. To increase N fertilizer input would be one of the vital adaptive measures to ensure food security and maintain agricultural sustainability through the 21st century.     

紫外光降解反应器去除氯苯气体模型的建立与应用

从光化学反应过程出发,基于线性光源球面辐射能量分布（LSSE）,以反应器内部空间的辐射能吸收密度、空塔停留时间、进口浓度等为主要参数,建立了气相环境中紫外光化学反应器去除氯苯的数学模型.结果表明,建立的模型能很好地模拟和预测紫外光化学反应器对氯苯气体的去除性能.氯苯气体的紫外光化学反应表现出一级反应动力学的特征.该模型包含了紫外光降解反应器设计的主要参数,同时被用于预测了反应器在不同进口浓度和不同空塔停留时间条件下的出口氯苯浓度,进而获得不同进口浓度达标排放所需要的最小空塔停留时间,为气相污染物的紫外光降解反应器的设计与运行提供了重要的理论指导.