半透膜被动采样装置(SPMDs)对PAHs 和壬基酚类的静态富集

半透膜采样装置(SPMDs)是一种被动采样装置,它能模拟有机污染物穿过生物膜从水相到生物有机相的分配平衡过程,使得结果能显示出污染物的生物可利用性。它能对环境中有机污染物进行长时间连续监测,所得的是污染物被SPMD富集后的时间权重浓度。本实验测定了温度为18℃时标准SPMD对7种PAHs和3种NPnEO(n=0～2)的静态富集过程,通过测定污染物达到平衡时在SPMD内的浓度和在水相中浓度的比值,求解了各自的SPMD/水分配平衡常数KSPMD。表明了有机污染物在SPMD和水相之间达到分配平衡所需要的时间是随着其Kow值的增高而逐渐增长的,还与其各自的分子极性有关,并且几种达到富集平衡的PAHs在SPMD内的浓度也是随着其Kow值的增高而逐渐变大。比较KSPMD的理论值和实测值可以发现,对于PAHs而言,其实测值都高于理论值,而NPnEO都是实测值低于其理论值。但是KSPMD实测值和理论值随污染物Kow值变化的趋势相同。     

Elevated CO2 facilitates C and N accumulation in a rice paddy ecosystem

Elevated CO₂ can stimulate wetland carbon (C) and nitrogen (N) exports through gaseous and dissolved pathways, however, the consequent influences on the C and N pools are still not fully known. Therefore, we set up a free-air CO₂ enrichment experiment in a paddy field in Eastern China. After five year fumigation, we studied C and N in the plant–water–soil system. The results showed: (1) elevated CO₂ stimulated rice aboveground biomass and N accumulations by 19.1% and 12.5%, respectively. (2) Elevated CO₂ significantly increased paddy soil TOC and TN contents by 12.5% and 15.5%, respectively in the 0–15 cm layer, and 22.7% and 26.0% in the 15–30 cm soil layer. (3) Averaged across the rice growing period, elevated CO₂ greatly increased TOC and TN contents in the surface water by 7.6% and 11.4%, respectively. (4) The TOC/TN ratio and natural δ¹⁵N value in the surface soil showed a decreasing trend under elevated CO₂. The above results indicate that elevated CO₂ can benefit C and N accumulation in paddy fields. Given the similarity between the paddies and natural wetlands, our results also suggest a great potential for long-term C and N accumulation in natural wetlands under future climate patterns.     

上海市冬季PM_(2.5)无机元素污染特征及来源分析

为了解高污染季节上海市细颗粒物PM2.5及其无机元素的污染特征和来源,于2013年1月4日至2月1日在上海3个点位采集PM2.5样品,并采用电感耦合等离子光谱仪(ICP-OES)测定样品中19种元素含量.结果表明,采样期间PM2.5污染水平较高,均值达(90.5±41.2)μg·m-3,且郊区明显高于市区和背景参照点.所测无机元素的空间分布规律与PM2.5一致,但背景参照点元素Zn的浓度较高.采样期间Cd、As、Zn、Pb、S和Cu等人为污染元素的富集因子较高.因子分析结果表明冬季上海市PM2.5具有多源性,主要来源于燃煤、自然尘、燃油以及机动车.     

宣威街道尘中重金属的分布特征及其健康风险评估

云南肺癌高发区(宣威)的环境污染与人群健康之间的关系一直是环境科学研究领域的热点之一.本研究采集了宣威市电厂及其上风向地区和下风向地区的街道灰尘,利用ICP-MS对样品中的重金属元素进行了分析;利用富集因子法对样品中的重金属污染及来源进行探究;并运用美国环境保护署(US EPA)发布的人体暴露风险评价方法对样品中重金属元素的健康风险进行了评估.结果表明,宣威街道尘土中Al、V、Ni、Co、Zn和Cd等金属元素的质量浓度明显呈"电厂来宾倘塘"的特征;V、Cd、Cr、Cu、Mn、Co、Ni、Pb、As和Zn等10种重金属的含量明显高于云南省土壤背景值,显示宣威市地表灰尘重金属污染较为严重;宣威街道中Cr、Cu、Zn、Pb、As和Cd等重金属主要来源于电厂排放的燃煤颗粒物.健康风险评估的结果表明,宣威街道灰尘中10种重金属元素对儿童的非致癌风险大于成人,手-口摄入是灰尘重金属暴露的主要途径;宣威街道尘土中Cd、Cr、Ni、Co和As等5种致癌重金属存在潜在的致癌风险;Cr是威胁儿童健康的主要污染因子.     

The metabolism of neonicotinoid insecticide thiamethoxam by soil enrichment cultures,and the bacterial diversity and plant growth‐promoting properties of the cultured isolates

A soil enrichment culture (SEC) rapidly degraded 96% of 200 mg L^?1 neonicotinoid insecticide thiamethoxam (TMX) in MSM broth within 30 d; therefore, its metabolic pathway of TMX, bacterial diversity and plant growth‐promoting rhizobacteria (PGPR) activities of the cultured isolates were studied. The SEC transformed TMX via the nitro reduction pathway to form nitrso, urea metabolites and via cleavage of the oxadiazine cycle to form a new metabolite, hydroxyl CLO‐tri. In addition, 16S rRNA gene‐denaturing gradient gel electrophoresis analysis revealed that uncultured rhizobacteria are predominant in the SEC broth and that 77.8% of the identified bacteria belonged to uncultured bacteria. A total of 31 cultured bacterial strains including six genera (Achromobacter, Agromyces, Ensifer, Mesorhizobium, Microbacterium and Pseudoxanthomonas) were isolated from the SEC broth. The 12 strains of Ensifer adhaerens have the ability to degrade TMX. All six selected bacteria showed PGPR activities. E. adhaerens TMX‐23 and Agromyces mediolanus TMX‐25 produced indole‐3‐acetic acid, whereas E. adhaerens TMX‐23 and Mesorhizobium alhagi TMX‐36 are N₂‐fixing bacteria. The six‐isolated microbes were tolerant to 200 mg L^?1 TMX, and the growth of E. adhaerens was significantly enhanced by TMX, whereas that of Achromobacter sp. TMX‐5 and Microbacterium sp.TMX‐6 were enhanced slightly. The present study will help to explain the fate of TMX in the environment and its microbial degradation mechanism, as well as to facilitate future investigations of the mechanism through which TMX enhances plant vigor.     

Dissecting the spatial scales of mercury accumulation in Ontario lake sediment

Total mercury concentration was analyzed in 171 lakes from pre-industrial (>30 cm depth; Hg_{pre-industrial}) and present-day sediments (0.5–1 cm; Hg_present-day). Numerous hot or cold spots of sediment mercury enrichment (Hg EF; Hg_{pre-industrial}/Hg_present-day) were evident as determined by local tests of autocorrelation, although in most cases, the maximum correlation among sites was not the nearest neighbor, indicating a strong influence of watershed characteristics. Hg EF was correlated with the area of open water (ha) (r = 0.91, p = 0.035), mine tailings (r = 0.94, p = 0.019), and organic deposits in surficial geology of the watershed (r = −0.91, p = 0.034). Through use of local rather than global regression coefficients, R² increased from 0.20 (p = 0.005) to 0.60 (p = 0.013). A broad spatial pattern (>500 km) observed only in Hg_{pre-industrial} was best explained by mean annual precipitation (shared variance = 3.5%), while finer spatial patterns only observed in Hg_present-day and Hg EF were best explained by pH (average shared variance = 10.8%).     

Effects of macronutrient additions on nickel uptake and distribution in the dinoflagellate Prorocentrum donghaiense Lu

The influences of macronutrient additions on nickel (Ni) uptake and distribution in the subcellular structures and macromolecular components of the dinoflagellate Prorocentrum donghaiense Lu were examined using a radioisotope tracer method. The results showed that nitrate addition enhanced the uptake of Ni by P. donghaiense, whereas phosphate addition inhibited Ni uptake at high-Ni concentration. Nitrate or phosphate addition significantly affected Ni distribution in the subcellular structures and components. The majority of Ni was found in the soluble substances (>70%) and in the proteins (55.0-79.6%) of the algal cells. Urea reduced the Ni content in the amino acid-carbohydrate but elevated its content in proteins, and shown significantly correlated with the protein content of the algal cells. Thus, nutrient enrichment could influence both metal uptake and its distribution in the subcellular structures and components of the phytoplankton, as well as its subsequent transfer in marine food chains.     

Evaluation of resin and fatty acid concentration levels by online sample enrichment followed by atmospheric pressure chemical ionization-mass spectrometry (APCI-MS)

Background, aim, and scope  In papermaking, there is a continuous interest both to minimize fresh water consumption and to reduce discharges into the environment. These general trends mean an increase in the amounts of detrimental substances, such as resin and fatty acids, in papermaking process waters. Resin acids, in particular, are responsible for much of the toxicity typically present in paper mill effluents and, for this reason, the routine and rapid monitoring of these compounds in various process streams is necessary. This also means that there is a continuous need to develop straightforward offline and online techniques to clarify problems occurring, for example, as a result of the introduction of more intensively closed systems of water circulation. In the present study, we describe the use of a novel, online, sample enrichment technique followed by atmospheric pressure chemical ionization–mass spectrometry (APCI-MS) suitable for monitoring the concentration levels of common resin and fatty acids in papermaking process waters. Materials and methods  The representative process water samples were taken from the grinding zone of a thermomechanical pulping mill. The samples were first preconcentrated in a precolumn C18, and the analytes were transferred online to MS. The high intensive [M–H]⁻ ion was used for the identification of each analyte since, according to the present ionization method, no other fragmentation was observed. Laboratory-scale, online measurements with an online sample feed were carried out by connecting a centrifugal pump and a ceramic filter to the APCI-MS. Results  Quality parameters, such as repeatability, linearity, and limit of detection (LOD), were determined by using dehydroabietic acid (DHAA) in order to evaluate the suitability of the method for the rapid screening of concentration levels. This method provided satisfactory linearity and a good correlation between analyte concentration and peak area. The suitability of the system for the continuous analysis of the same acids was evaluated in laboratory-scale, online experiments. In all cases, the response to changes in the analyte concentration was linear, and the repeatability of the system was also satisfactory. Discussion  Only a few studies have been published on the analysis of resin and fatty acids with MS techniques. The present method was applied to the monitoring of dehydroabietic, oleic, and stearic acids. The quality parameters were highly comparable with those reported earlier, and the LOD values of the DHAA were below the levels usually encountered in process waters. The quality parameters were only slightly higher than those obtained by the traditional methods of analysis, probably due to the absence of an effective sample clean-up before analysis. Conclusions  The results of the laboratory-scale, online experiments indicated that the online enrichment APCI-MS system is a suitable alternative for monitoring the concentration levels of selected resin and fatty acids in papermaking process waters. The method can be used, for example, to provide useful information about the concentration levels of these acids in different stages of the process, thus signaling possibly impending problems. In general, faster and simpler measurements are needed to meet the requirements for a reduction in fresh water usage in papermaking. Recommendations and perspectives  Compared to the conventional methods used for this purpose, the main benefits of the method are rapidity of measurement, simplicity of use, and absence of the need for multistage sample treatments (short analysis time). For this reason, this online method is more suitable for the control of papermaking by analyzing the concentration levels of interfering substances (i.e., selected resin and fatty acids) than an offline analysis detailing all the individual extractives-based compounds in process streams. It is also obvious that the technique can easily be modified for other environmental pollutants as well.     

北方某市环境空气颗粒物中重金属污染状况研究

对我国北方某市大气颗粒物的污染状况进行了研究。在主导风向上设置采样点,于冬季、夏季分别采集TSP、PM₁₀、PM_2.5 3种不同动力学直径的大气颗粒物。采用ICP-MS对TSP、PM₁₀、PM_2.5中的元素浓度进行分析,并对3种不同粒径颗粒物中的10种重金属采用富集因子法进行评价。结果表明,北方某市环境空气颗粒物中富集程度最严重的为Cd、Pb;在采暖期,随着颗粒物粒径变小,Pb、Cd的富集指数呈现逐渐增大的趋势;非采暖期则无此趋势。     

常州市春季大气PM2.5中金属元素的分析及污染特征

建立了微波消解-电感耦合等离子体质谱(ICP-MS)法,同时测定大气PM2.5中K、Na、Ca、Mg、Fe、Al、Zn、Si、Ti、V、Cr、Mn、Co、Ni、Cu、As、Cd和Pb等18种金属元素的分析方法.样品用HNO3+H2O2(5∶1)经微波消解系统进行前处理.该方法操作方便,酸用量少,由于是密闭消解,对环境污染也少.经过反复调试,确定了仪器最佳操作条件.结果表明,各种元素标准曲线的线性相关系数均在0.9990以上,方法检出限在0.07 μg/L ～1.16 mg/L之间,精密度实验中各元素的RSD均小于7.53％,回收率在91.38％～117.53％之间.该方法能够快速有效地实现多元素同时测定,检测线性范围宽,测试结果准确可靠,可以应用于大气颗粒物中多种金属元素的测定.采用富集因子分析法对常州市大气中PM25做来源分析表明,常州市大气PM25中,大部元素的富集因子都大于10,其中,Ni、Cu、Zn、As、Cd、Co和Pb在各个采样点的富集因子都非常高,表明主要来自于人为污染.