湖北农村降水中SO_4~(2-)浓度变化研究

在湖北农村 10个地点 ,利用澳大利亚集雨器自 1996年 1月至 1998年 6月 ,按季度采集大气降水样品测定SO2 - 4浓度 ,并对数据进行统计分析。研究结果表明 ,各地 1997年降水中SO2 - 4浓度年均值比 1996年显著升高 ;大多数地点 1996、1997、1998年 1季度和 2季度降水中SO2 - 4浓度呈逐年升高趋势 ;大多数地点每年 1、4季度降水中SO2 - 4浓度高 ,2、3季度降水中SO2 - 4浓度低 ,说明湖北农村降水中的硫对秋冬作物影响比对春夏作物影响大 ;湖北农村降水中SO2 - 4浓度近两年不仅有时间变化规律 ,而且同一季度内的地区差异也很明显 ,在 1996年和 1997年 8个季度 10个点的降水SO2 - 4浓度最大值中 ,有 4个最大值出现在襄樊 ,它是目前湖北继宜昌市区、恩施市区之后又一个酸雨发展较快的地区     

絮凝剂PAN-DCD与甲基橙相互作用中的热力学研究

用平衡渗析法研究了有机高分子絮凝剂ＰＡＮ－ＤＣＤ与甲基橙（ＭＯ）在２０,２５,３０,３５℃下相互作用的热力学,求得结合常数Ｋ和热力学参数△Ｇ,△Ｈ,△Ｓ,在对不同絮凝剂结构进行表征的基础上,探讨了不同ＰＡＮ,ＤＣＤ配比对合成的絮凝剂与ＭＯ相互作用的影响,结果表明：ＰＡＮ－ＤＣＤ与ＭＯ的相互作用中能量作用是主要的：随ＰＡＮ与ＤＣＤ的比值增大,合成的絮凝剂ＰＤ１,ＰＤ２,ＰＤ３在常温下与ＭＯ的结合程试     

长江重庆段表层水体中多环芳烃的分布及来源分析

采集了长江重庆段干流以及重要支流共7个断面的表层水样,采用液相色谱法分析15种优先控制的多环芳烃(PAHs).结果表明,水体中总PAHs浓度范围为6.44—109.39 ng·L-1,平均值为41.83 ng·L-1.在5个断面水体中检出苯并(a)芘,浓度为0.05—1.32 ng·L-1,低于我国地表水标准限值(2.8 ng·L-1).长江重庆段的PAHs浓度水平低于大部分国内其他河流,与国外一些河流的浓度水平相当.PAHs组成以中低环PAHs(3环和4环)为主,平均比例分别为55.7%和38.8%,高环PAHs(5环和6环)含量较低,分别占3.6%和1.9%.示踪PAHs比值法结果显示长江重庆段表层水体PAHs主要来源于石化产品的泄漏污染.     

Nationwide monitoring of atmospheric PCDD/Fs and dioxin-like PCBs in South Korea

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) were measured in ambient air samples collected from different parts of South Korea in 2008, and the measured levels were used for assessing the spatial and temporal distribution of atmospheric PCDDFs and DL-PCBs in South Korea. The average concentrations of atmospheric PCDD/Fs and DL-PCBs among the 37 sites were 28 fg I-TEQ m⁻³ (ND ∼ 617) and 1 fg WHO-TEQ m⁻³ (ND ∼ 0.016). Elevated atmospheric levels of PCDD/Fs and DL-PCBs observed at residential/industrial sites and in the north-west of Korea, indicated a potential contribution and impacts of anthropogenic sources of PCDD/Fs and DL-PCBs. These levels were similar or lower than those previously reported in other ambient air surveys. Average concentrations of PCDD/Fs showed small seasonal variations (ANOVA analysis, p = 0.144). The highest concentrations of PCDD/Fs were observed during winter, followed by spring, autumn and summer. Atmospheric PCDD/Fs and DL-PCBs in South Korea rapidly decreased during the last 10 years (1998-2008), demonstrating the efficiency of stricter regulations and the application of best available technologies/best environmental practices at emission sources. Comparison of the congener profiles and principal component analysis showed that current atmospheric PCDD/Fs are mostly influenced by industrial sources and PCBs from old commercial PCB uses. Nationwide POPs monitoring will continue and allows an effective evaluation of the implementation of the Stockholm Convention on POPs.     

Predicting the bioavailability of sediment-associated polybrominated diphenyl ethers using a 45-d sequential Tenax extraction

A 45-d Tenax extraction was used to evaluate the bioavailability of polybrominated diphenyl ethers (PBDEs) in three spiked sediments. The effect of aging on desorption kinetics of PBDEs was investigated by incubating one of the sediments for 7, 14, 30 and 60 d at room temperature. Desorption kinetics were well described by a three-compartment model. The fraction of very slow desorption (Fvs) contributed the most of the desorbed PBDEs from sediments. The total desorption amount of PBDEs decreased with the increase of total organic carbon in the sediments, suggesting that organic matter is an important factor controlling the partition of PBDEs in sediments. The total desorption amount of PBDEs decreased while log [(Fslow+Fvs)/Frap] increased with logKow of PBDE congeners, indicating that the bioavailability of PBDEs in sediment decreases with logKow of the congeners. As the residential time of PBDEs in the sediment increased from 7 to 60 d, Frap of individual PBDE congeners decreased gradually with simultaneous increase of Fvs. There was a good positive correlation between Frap and F6/F24, indicating that either 6 h or 24 h Tenax extraction could be a proxy for Frap and bioavailability. In general, the results in present study suggest that the bioavailability of nona- and deca-BDEs in sediment is very low due to their strong hydrophobicity and large molecular size.     

基于单颗粒质谱技术的石家庄冬春季气溶胶成分特征及混合状态研究

利用位于石家庄市大气梯度监测站(20 m)的单颗粒气溶胶质谱仪分析了冬、春季大气环境中气溶胶的化学组成及混合状态,并采用ART-2a分类法对气溶胶分类。结果表明,石家庄市大气中主要存在8类颗粒物,即元素碳(EC)、有机碳(OC,相对分子质量小于150)、高分子有机碳(HOC,相对分子质量大于150)、混合碳(元素-有机碳混合,ECOC)、重金属、左旋葡聚糖碎片(LEV)、矿物质和富钾颗粒。8类颗粒中绝大部分包含SO_4~-、NO_2~-和NO_3~-等二次离子组分,表明采集到的颗粒物大都经历了不同的老化,或与二次组分进行了不同程度的混合。冬季气溶胶的主要成分是OC(数浓度36.1%),谱图含有C2H+3、C_2H_3O~+、C_5H_3~+、C_6H_5~+等离子,主要来自化石燃料、生物质等燃烧产生的一次排放颗粒,以及由挥发性有机物光化学氧化而成的二次有机颗粒;春季气溶胶的主要成分是EC(数浓度43.6%)和矿物质(数浓度15.4%)。EC中含有一系列单质碳峰,来自化石燃料或木材等生物质不完全燃烧的一次排放;矿物质颗粒中含有Mg~+、Al~+、Ca~+、Fe~+及SiO_3~-,主要来自扬尘。发生灰霾时,冬季OC和ECOC颗粒占比增大,EC颗粒占比减小;春季矿物质和ECOC颗粒占比变大,OC颗粒占比变小。随着灰霾天气发生,冬、春季碳气溶胶与二次无机气溶胶颗粒的混合加剧,而NH_4~+与碳气溶胶的混合加剧最为明显。冬季气溶胶的数浓度与气象因素的相关性高于春季,而低风速、高湿度和低气压易导致灰霾出现。石家庄市春季和冬季气溶胶污染应分别从机动车尾气、扬尘及燃煤、制药企业加以管控。     

巢湖周边表土中有机质、全氮和全磷空间分布及其相关性

测定了巢湖周边3 528 km2范围内60个混合土样中的有机质(organic matter,OM)、全氮(total nitrogen,TN)和全磷(total phosphorus,TP)含量,通过GS 7.0+地统计学分析软件、Surfer 8.0及Mapinfo 8.5软件研究了这3种营养盐的空间分布,并使用SPSS 17.0软件对各指标间的相关性进行了分析.结果表明:①巢湖周边表土中ω(OM)、ω(TN)和ω(TP)平均值依次为19 500、1 027和483 mg.kg-1,东巢湖表土中ω(OM)和ω(TN)均值高于西巢湖,而磷矿的存在导致了ω(TP)均值西高东低;②位于巢湖西南的杭埠-丰乐河和白石天河周边表土中(TP)本底值较高,且水土流失十分严重,巢湖面源污染管理必须高度重视该两河的TP控制;③在线性模型下,巢湖周边表土中ω(OM)、ω(TN)和ω(TP)的块金值/基台值依次为0.015、0.202和0.128.巢湖周边表土中ω(OM)、ω(TN)和ω(TP)具有极强的空间自相关性,三者Pearson检验为两两显著相关,巢湖周边表土中ω(TN)和ω(TP)可由ω(OM)通过文中所得的公式估算,精度能满足日常管理需要.     

区域大型环境空气综合观测中外场观测与实验室分析数据质量控制研究

环境监测的质量保证是监测数据准确性、可比性的重要保障.在区域大气联合观测项目中,完善的质量保证体系应包括管理机制和技术措施两部分,但目前我国对这类项目质量保证尚无统一标准.针对大气重污染成因与治理攻关项目（简称"大气攻关项目"）外场观测任务量大、承担单位多、监测项目复杂的特点,为保证观测数据的质量,避免出现由于监测和质控方法不统一造成的数据可比性差、结果矛盾的问题,提出了大气攻关项目质量保证体系和管理机制.其中,质量保证体系包括制定总体要求（技术文件、监测项目及质控要求）、外场观测质量保证（内部质量管理体系、项目外场观测质量保证体系）、实验室分析质量保证（实验室遴选、项目实验室分析多级质量保证体系、实验室比对和飞行检查）和数据质量控制（数据线上审核、项目实验室分析质控报告、项目数据质量评价）4个方面.管理机制为项目管理办公室、质控实验室和承担单位三级主体,两级监督的分级管理模式.通过项目实践,项目质量保证体系达到了保证观测数据准确性、可比性的预期效果,为揭示区域雾霾形成机理、突破污染控制关键技术提供了有力的技术支持,同时为区域大气联合观测项目的数据质量保证提供了借鉴.      

中国内陆流域地表水体光电化学特征研究

太阳辐射是自然界中最主要的能量来源.目前人们对自然界利用太阳能途径的认识主要集中于具有生物光采集系统(如叶绿体)的光合作用,而对于非生物光采集系统是否广泛存在于地表水体中仍不清楚.本研究通过测定全国范围内151个地表水样光生电子的能力,绘制了中国内陆流域地表水体光电化学特征图谱.通过利用XPS、XRD和EEM等手段表征水样悬浮态和溶解态物质组成,揭示了地表水体光电化学活性来源及其影响因素.结果显示,我国地表水体普遍存在光电化学活性.按生物质换算,我国地表水体光生电子每年可转化生物质当量约为1.4×10³～1.1×10⁴万t葡萄糖,相当于光合作用固碳总量的0.51%～4.02%.地表水体的光电流大小与光强和光敏物质浓度呈正相关,相关系数分别达到0.99和0.99.水体的光电化学活性主要来源于悬浮态物质,其贡献度大于60%,与含Ti或含S的半导体矿物丰度呈正相关;而溶解态物质贡献较小(<40%),其光电化学成分主要为溶解性有机质,并与腐殖酸类或富里酸类物质浓度呈正相关.本研究为自然界微生物光电能营养作用的发生提供线索,同时也为量化自然地表水...     

Characterizing the optimal operation of photocatalytic degradation of BDE-209 by nano-sized TiO2

Brominated flame retardants have been widely used in industry. There is a rapid growing public concern for their availabilities in the environment. Advanced oxidation process (AOP) is a promising and efficient technology which may be used to remove emerging chemicals such as brominated flame retardants. This project aims at investigating optimal operational conditions for the removal of BDE-209 using nano-scaled titanium(IV) oxide. The residual PBDE congeners after photocatalytical degradation of BDE-209 by TiO₂ were analysed by gas chromatography-mass spectrometry (GC-MS). It was found that the degradability of BDE-209 by TiO₂ was attributed to its photocatalytic activity but not the small size of the particles. The half-life of removing BDE-209 by TiO₂ was 3.05 days under visible light. Tetra- and penta-BDEs were the major degraded products of BDE-209. Optimum conditions for photocatalytical degradation of BDE-209 was found to be at pH 12 (93% ± 1%), 5, 10, 20 mg/L (93.0% ± 1.70%, 91.6% ± 3.21%, 91.9% ± 0.952%, respectively), respectively of humic acid and in the form of anatase/rutile TiO₂ (82% ± 3%). Hence, the efficiency of removing BDE-209 can be maximized while being cost effective at the said operating conditions.