东海大气气溶胶中二元羧酸的分布特征及来源

大气气溶胶中的二元羧酸因其在全球气候变化中的潜在作用而受到广泛关注.利用2011年5月12日-6月6日在东海采集的气溶胶样品,分析其中水溶性二元羧酸及常量离子浓度,探讨东海气溶胶中二元羧酸的时空分布特征及来源.结果显示东海大气气溶胶中乙二酸、丙二酸和丁二酸的浓度分别为26.0～1475.5 ng·m-3、0.1 ～61.4 ng·m-3和0.1～132.4 ng·m-3,乙二酸在这3种二元羧酸中的贡献最大,为88.3％.东海气溶胶中二元羧酸浓度的昼夜变化不显著.空间分布整体呈现近海高、远海低的趋势.气团的来源和迁移路径以及气象因素影响气溶胶中二元羧酸的分布,气团来自污染较重的陆源时气溶胶中二元羧酸的浓度较高,气团来自清洁的海洋源时,二元羧酸的浓度则较低;阴雾天气时气溶胶中二元羧酸浓度相对较高,降雨发生时二元羧酸的浓度较低.二元羧酸与常量离子的相关性分析表明,自然源和人为源释放的挥发性有机物质在液相中氧化生成二元羧酸是东海大气气溶胶中二元羧酸的主要源,而汽车尾气和生物质燃烧的一次排放、海洋源以及碱性粗颗粒吸收气体二元羧酸不是主要源.液相中乙醛酸氧化形成的乙二酸和长链二元羧酸氧化形成的乙二酸对东海气溶胶中乙二酸的贡献分别为41％和59％.     

海河流域重污染河流表层沉积物氨基酸组成特征

为探明子牙河水系沉积物氮的主要形态,采用柱前衍生反相高效液相色谱-同位素内标法研究了表层沉积物中20种氨基酸的形态及组成特征.结果表明:子牙河水系沉积物中有机氮是氮的主要存在形态,沉积物有机氮(SON)平均浓度为3114 mg·kg^-1,总水解氨基酸氮(THAAs-N)占SON的45.53%;蛋白类氨基酸氮是THAAs-N的主体,占THAAs-N的90.24%,为沉积物潜在释放氮及矿化氮的主体;子牙河水系表层沉积物氨基酸以甘氨酸(Gly)、脯氨酸(Pro)摩尔含量最高,分别占THAAs的14.70%、10.00 %;根据官能团类型分类,蛋白类氨基酸为主要类别,占THAAs的89.50%;蛋白类氨基酸以中性氨基酸为主,平均含量为THAAs的40.69%;亚氨基酸及非蛋白类氨基酸的含量差异性从侧面反映出水系河流污染物来源;采用Glu/γ-Aba及DI指数判断有机质的降解程度,结果显示子牙河水系大部分区域沉积物有机质降解程度较低.     

Investigation of low-molecular weight organic acids and their spatiotemporal variation characteristics in Hongfeng Lake, China

The identities and concentrations of low-molecular-weight organic acids (LMWOAs) were determined by ion chromatography throughout a 20-m water column in Hongfeng Lake, China. The spatiotemporal variations of LMWOAs and their contributions to dissolved organic matter (DOM) in a research period of 24 hr were also investigated. The results demonstrated that five LMWOAs (lactic, acetic, pyruvic, sorbic, oxalic acid) were detected, and their total concentration and proportion in DOC were 6.55 μmol/L and 7.47%. Their average levels were 2.50, 0.65, 2.35, 0.96 and 0.09 μmol/L, respectively. LMWOAs were higher during daytime (10:00-18:00 on Jun 13, 2008) than nighttime (21:00-6:00 the next morning), in particular 4.99 μmol/L high in the epilimnion ( 1 m water depth), reflecting the fact that direct import from terrigenous sources and photochemical production from humic materials were dominant during LMWOAs’ origin and accumulation. The same factors caused LMWOAs to be 0.63 μmol/L in the epilimnion higher than in the hypolimnion. The rapid decrease of total organic acid (TOA) up until 18:00 mainly resulted from bio-uptake and mineralization in the hypolimnion (>1 m water depth). Pyruvic acid increased with time in the epilimnion and decreased in the hypolimnion, largely related to the two contrary processes of continuous degradation and synthesis of macromolecular organic matter during life materials’ cycle mediated by organisms. Simultaneously, plankton behavior and thermal stratification played a pivotal role in LMWOAs’ behavior in the water column, causing decreasing and increasing profiles. The distribution of LMWOAs represents an interesting resource for biogeochemical research of DOM in aquatic ecosystems.     

Effects of Cu（Ⅱ） and humic acid on atrazine photodegradation

This work was designed to explore the characteristics of photodegradation of herbicides in the copper-polluted water body. The results showed that Cu(II) alone could induce a photo Fenton-like reaction to enhance the degradation of atrazine, in which hydroxyl radical ( OH) was a main active species. Humic acids restrained atrazine degradation, nevertheless, when introducing Cu(II), the photodegradation was accelerated, in which singlet oxygen (1O2) replaced OH acting as the prevailing species. A feasible mechanism for the photochemical process was also proposed, which is helpful for better understanding the environmental photochemistry of atrazine in the copper-polluted water.     

Evaluation of adsorption capacities of humic acids extracted from Algerian soil on polyaniline for application to remove pollutants such as Cd(Ⅱ), Zn(Ⅱ) and Ni(Ⅱ) and characterization with cavity microelectrode

The adsorption capacities of new humic acids isolated from Yakouren forest (YHA) and Sahara (Tamenrasset: THA) soils (Algeria) and commercial humic acid (PFHA) on polyaniline emeraldine base (PEB) were studied at pH 6.6. Also the adsorption of heavy metals such as Cd2+, Zn2+ and Ni2+ on humic acid-polyaniline systems (HA-PEB) was investigated at the same conditions. HA-PEB compounds were characterized by scanning electron microscopy (SEM), infrared spectrometry and cavity microelectrode. In addition, batch adsorption and cavity microelectrode were used in the adsorption study of Cd2+, Zn2+ and Ni2+ on HA-PEB. To develop biocaptors of polluting metals using a cavity microelectrode modified by HA-PEB systems, the adsorption kinetic and adsorption capacity were investigated. The SEM analysis showed that the presence of humic acid affected the PEB surface and caused the formation of a granular morphology. The maximum adsorption capacities (qmax) of PFHA, THA and YHA determined by adsorption isotherms were 91.31, 132.1 and 151.0 mg/g, respectively. Batch adsorption results showed that qmax of Cd2+, Zn2+ and Ni2+ on HA-PEB followed the order: THA-PEB > YHA-PEB > PFHA-PEB. The voltammograms obtained with HA-PEB modified cavity microelectrode showed the appearance of new redox couples reflecting the adsorption of HA on PEB. Metal-humic acid-polyaniline voltammograms were characterized by appearance of oxidation-reduction couples or reduction wave corresponding to metal. Finally, the result may be exploited to develop a biocaptor based on the cavity microelectrode amended by THA-PEB and YHA-PEB.     

Compositions and sources of organic acids in fine particles (PM2.5) over the Pearl River Delta region, south China

Organic acids as important constituents of organic aerosols not only influence the aerosols' hygroscopic property, but also enhance the formation of new particles and secondary organic aerosols. This study reported organic acids including C14–C32fatty acids, C4–C9dicarboxylic acids and aromatic acids in PM2.5collected during winter 2009 at six typical urban, suburban and rural sites in the Pearl River Delta region. Averaged concentrations of C14–C32fatty acids, aromatic acids and C4– C9 dicarboxylic acids were 157, 72.5 and 50.7 ng/m3, respectively. They totally accounted for 1.7% of measured organic carbon. C20–C32fatty acids mainly deriving from higher plant wax showed the highest concentration at the upwind rural site with more vegetation around, while C14–C18fatty acids were more abundant at urban and suburban sites, and dicarboxylic acids and aromatic acids except 1,4-phthalic acid peaked at the downwind rural site. Succinic and azelaic acid were the most abundant among C4–C9dicarboxylic acids, and 1,2-phthalic and 1,4-phthalic acid were dominant aromatic acids. Dicarboxylic acids and aromatic acids exhibited significant mutual correlations except for 1,4-phthalic acid, which was probably primarily emitted from combustion of solid wastes containing polyethylene terephthalate plastics. Spatial patterns and correlations with typical source tracers suggested that C14–C32fatty acids were mainly primary while dicarboxylic and aromatic acids were largely secondary. Principal component analysis resolved six sources including biomass burning, natural higher plant wax, two mixed anthropogenic and two secondary sources; further multiple linear regression revealed their contributions to individual organic acids. It turned out that more than 70% of C14–C18fatty acids were attributed to anthropogenic sources, about 50%–85% of the C20–C32fatty acids were attributed to natural sources, 80%–95% of dicarboxylic acids and 1,2-phthalic acid were secondary in contrast with that 81% of 1,4-phthalic acid was primary.     

麦秸及其烟尘中正构脂肪酸的组成

在不同燃烧条件下对6种麦草进行焚烧,并利用GC/MS对麦秸和烟尘中的正构脂肪酸进行了测定.结果表明,烟尘中含有碳数C8~C32的正构脂肪酸.在明火烟尘中,正构脂肪酸总含量分布于1 509.3~10 543.7 mg·kg-1之间,平均值为5 871.2mg·kg-1.其轻(C8~C16)、重(C17~C32)正构脂肪酸含量之比(L/H)为0.8~5.3,平均值为2.8;C14/C16、C28/C16、C30/C16等比值的平均值分别为16.5%、14.1%、11.4%.正构脂肪酸呈双峰式分布,其主峰碳数是C16,次峰碳数是C28或C30,且具有显著的偶碳数优势.其碳优势指数(CPI)和平均碳链长度(ACL)的平均值分别为19.8和18.2.在闷烧烟尘中,正构脂肪酸的总含量为5 799.3~37 244 mg·kg-1,平均值为15 838.6 mg·kg-1.其L/H值介于1.2~5.6之间,平均为4.2;C14/C16、C28/C16、C30/C16的平均值分别为12.7%、10.1%、6.0%.闷烧烟尘中正构脂肪酸的分布模式与明火烟尘的类似,其CPI和ACL的平均值分别为24.7和17.7.总之,虽然两类烟尘和麦秸中的正构脂肪酸均具有类似的分布模式和偶碳数优势,但三者在组成上仍然存在明显的差别.这有助于识别大气气溶胶中麦秸及其燃烧排放的正构脂肪酸.     

紫外辐射对小分子有机酸化学凝聚性作用途径探讨

通过烧杯实验系统考察了紫外辐射对脂肪羧酸类和酚酸类小分子有机酸的化学凝聚性的作用途径.结果表明,溶液pH对柠檬酸、草酸、酒石酸和丁二酸等脂肪羧酸类有机物的混凝性能影响较小.紫外辐射处理后,脂肪羧酸类小分子有机物的混凝去除率均高于未经紫外辐射处理的水样.进一步研究表明,紫外辐射过程中发生了光化学反应,使得脂肪羧酸的表面负电性降低,进而提高了其化学凝聚性.与脂肪类小分子有机酸不同,苯酚、水杨酸和苯甲酸的化学凝聚性较差,且受紫外辐射过程的影响小.单宁酸的混凝性能较好,pH=6时的去除率最高可达90%以上,这可能与其分子中脂肪酸碳链结构的存在以及单宁酸分子较大,易与PACl的水解产物发生吸附电中和反应有关.     

不同碳源在污水处理过程中的变化规律研究

通过对A2/O污水处理工艺长期的分析监测,探明了城市污水处理厂原水中有机物不同生物降解性及碳源赋存形态比例.原水中大部分有机物以颗粒态存在,占进水有机物的61%.原水中快速、慢速、难生物降解有机物比例分别为15.8%、54.2%和30%,快速生物降解有机物主要以溶解态存在,慢速生物降解有机物则主要以颗粒态存在.通过快速、慢速生物降解有机物的沿程监测分析,明确了两种碳源在污水处理过程中的变化规律,厌氧池与缺氧池内均存在微生物水解发酵引起的慢速生物降解有机物的转化作用,其中厌氧反应池的转化效率最高.分析计算了污水处理过程中不同碳源的转化,明确了快慢速有机物在各单元的转化和利用情况,结果指出,2 h内慢速生物降解有机物在厌氧池与好氧池转化率分别为33%和20%.从脂肪酸的种类及含量来说,厌氧池与缺氧池的脂肪酸的种类及含量均高于原水.     

餐厨垃圾固态发酵过程中挥发性脂肪酸与产气的变化关系研究

为了研究餐厨垃圾固态发酵过程中挥发性脂肪酸(VFAs)与产气的变化关系,采用中温(37.0±0.2)℃连续式发酵,在完全混合CSTR反应器中连续运行100 d,分析餐厨垃圾固态发酵过程的启动、运行、失衡、失衡后恢复及实现固态发酵全过程各参数的变化趋势,重点研究VFAs各成分与产气、pH等的关系.结果表明,餐厨垃圾固态发酵实验过程可划分为4个时期:适应期(0~13 d)、启动期(14~30 d)、抑制期(31~50d)、恢复及稳定期(51~100 d).不同时期的容积产气率、VFAs及各参数均表现出不同的阶段性变化.在餐厨垃圾固态发酵全过程中,pH保持在5~7之间,正丁酸比例一直处于较高水平;VFAs与pH和容积产气率在初期基本保持反比关系,最终在稳定期达到平衡,均稳定在一定范围内波动.在恢复及稳定阶段以NaOH稀碱液调节当日回流渗滤液的pH值,在第63 d时pH值上升至6.76,VFAs含量稳定在20~22 g·L~(-1)之间,产气量明显提高;在81 d时TS达到20%以上,系统容积产气量和生物降解率均保持相对稳定.