加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱测定土壤和沉积物中8种多溴联苯醚

建立了土壤和沉积物中8种多溴联苯醚(PBDEs,BDE-28、BDE-47、BDE-99、BDE-100、BDE-153、BDE-154、BDE-183和BDE-209)加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱(ASE-GC-MS-MS)的分析方法。通过优化加速溶剂萃取与弗罗里硅土在线净化和串联质谱多反应监测模式的条件,较好地去除基质干扰,并提高了三重四极杆串联质谱定性的准确性及定量的灵敏性。该方法采用改进的色谱柱能同时分析包括高溴代联苯醚BDE-209在内的8种PBDEs,其浓度范围为1～100 ng/mL(BDE-209为10～1 000 ng/mL),线性良好,线性回归系数均大于0.997。方法检出限为0.004～0.1 ng/g,方法回收率为75%～110%,方法精密度为2.4%～15.6%。适于批量处理土壤和沉积物中含有多组分痕量PBDEs的样品。     

The Metallic Composition of Aerosols at Three Monitoring Sites in Korea During Winter 2002

In the present study, the distribution patterns of various metals were analyzed and compared using PM samples collected concurrently from three monitoring sites located in Korea (Seoul, Busan, and Jeju island) in December 2002. As these sites can represent metal pollution with different degrees of anthropogenic activities, their concentration levels were distinguished in a systematic manner in the order of Jeju, Busan, and Seoul. By comparing the present data sets with those measured previously from other locations in Korea and around the world, we attempted to diagnose the general status of elemental pollution on the Korean peninsula. Through an application of different statistical approaches, the major processes controlling elemental levels were assessed for each of the three study sites. The results indicated the importance of both crustal and anthropogenic sources in all sites with their relative roles varying significantly from each other. The results of the metal analysis data, when examined in relation to back trajectory analysis, confirmed that their concentration changes are affected quite sensitively with air mass movement patterns. The overall results of this study consistently indicated the contribution of a strong anthropogenic source area (e.g., China) to the observed metal concentration levels in the study area, but the strengths of such signals vary considerably across the Korean peninsula.     

河口切变锋引起的滩槽泥沙交换效应

切变锋是河口湾锋系中最为常见和最易观察到的锋面类型。本文对长江口的切变锋进行现场观察和滩，槽同步水文资料分析，简述了长江口切变锋发生的部分和基本特性，提出了切变锋引起的滩，槽泥沙呈现螺旋形交换形式等论点。     

Tropic attributes of the mudskipper, Periophthalmus barbarus (Gobiidae: Oxudercinae) in the mangrove swamps of Imo River estuary, Nigeria

Aspects of the trophic attributes of the mudskipper,Periophthalmus barbarus occurring in the mangrove swamps of ImoRiver estuary, Nigeria, were investigated during a 12-month period(April, 1992-March, 1993). Feeding intensity increased with size;it was higher in the dry season (November-April) than in the wetseason (May-October); monthly changes in the indices of feedingintensity were significantly correlated. Major food objectscomprised detritus and benthic algae; crustaceans, insects,macrophyte matter and sand grains were minor food objects whilefish, molluscs, Chilopoda, nematodes and fungi were unconsciouslydevoured objects. Diet varied seasonally; algae and sesarmid crabswere generally more in the dry season than during the rains whereasFPOM and fish increased in the wet over dry season. The mudskipperdisplay a high degree of euryphagy and can be considered as ageneralist and an omnivore. The lower trophic status of P. barbarusqualifies it as a good aquaculture candidate. Food richness washigher in big-sized class (BSC) than small-sized class (SSC).Size-based and seasonal variations were not apparent in foodrichness. Diet breadth was higher in the BSC than the SSC; therewas dry season increase in diet breadth.     

Acid Deposition in the Tuscan Appennines During the Dry Period 1988-89

The typical parameters of acid precipitation are evaluated in the forest of Vallombrosa (Tuscan Appennines) during the dry period 1988-89. Individual rain events (dry and wet deposition) were sampled in a clearing of the forest and below the canopy of an evergreen tree as well as a deciduous broadleaf tree.

In atmospheric precipitation the pH values usually vary around 4.4, with neutralization in the hot season due to calcareous material from distant sources. Relatively large concentrations of Pb and Cd are found in rain, but only in a small amount in canopy leachate. Aluminium, manganese and iron are more significantly washed off than Pb and Cd.     

Levels of tin in core sediments along the Alexandria Coast, Egypt

Tin concentrations were determined in surface and core sediments from three hot spots along the Alexandria coast, namely: Abu-Qir Bay, Eastern Harbour, and Western Harbour. The mean concentrations in surface sediment were 2.434, 3.212, and 5.572 μg/g dry weight for Abu-Qir Bay, Eastern Harbour, and Western Harbour, respectively. A sharp decrease in tin level in core sediments with depth was observed in almost all locations except for core 4 in Abu-Qir Bay and core 17 in the Eastern Harbour, where the sub-sample at the 5 cm level recorded the highest tin concentrations.     

The Influence of Chironomus plumosus Larvae on Nutrient Fluxes and Phosphorus Fractions in Aluminum Treated Lake Sediment

One of the methods to diminish the internal phosphorus (P) loading is inactivation of P by aluminum (Al). After addition of Al to lake water an Al(OH)₃ floc is formed, which settles to the bottom and initially form a lid on the sediment surface. The effects of Chironomus plumosus larvae on sediment nutrient fluxes and P binding-sites in the sediment after addition of Al were tested. C. plumosus larvae were added to sediment cores in which sediment–water fluxes of nutrients were measured four times. After one month, the sediment was sectioned with depth and P fractions were measured by sequential chemical extraction. The chironomids created burrows through the Al layer which caused a significantly increased efflux of P from the Al treated sediment, because the P had only limited contact to the added Al. The chironomids also affected the P fractions in the sediment by their bioturbating activity. Thus, they caused increased Al concentrations in the upper part of the Al treated sediment. This created an enhanced contact between Al and P in the upper 7 cm of the sediment and, as a result, an increased binding of P to Al and a lowered porewater P. The DIP efflux is therefore expected to be lowered after the initial phase. Al had no effects on the nitrogen fluxes, but the chironomids enhanced the release, and decreased the release or increased the uptake by the sediments.     

Extension of the EUROS Integrated Air Quality Model to Fine Particulate Matter by Coupling to CACM/MADRID 2

The European Operational Smog (EUROS) integrated air quality modelling system has been extended to model fine particulate matter (PM). From an extended literature study, the Caltech Atmospheric Chemistry Mechanism and the Model of Aerosol Dynamics, Reaction, Ionisation and Dissolution were selected and recently coupled to EUROS. Currently, modelling of mass and chemical composition of aerosols in two size fractions (PM_2.5 and PM_10–2.5) is possible. The chemical composition is expressed in terms of seven components: ammonium, nitrate, sulphate, elementary carbon, primary inorganic compounds, primary organic compounds and secondary organic compounds. Calculated PM₁₀ concentrations and chemical composition are presented for two summer months of the year 2003 (1 July to 31 August).     

Biological Activity in a Heavily Organohalogen-Contaminated River Sediment (8 pp)

Background, Aims and Scope Sediments of the Spittelwasser creek are highly polluted with organic compounds and heavy metals due to the discharge of untreated waste waters from the industrial region of Bitterfeld-Wolfen, Germany over the course of more than one century. However, relatively few data have been published about the chloroorganic contamination of the sediment. This paper reports on the content of different (chloro)organic compounds with special emphasis on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), and chlorobenzenes. Existing concepts for the remediation of Spittelwasser sediment include the investigation of natural attenuation processes, which largely depend on the presence of an intact microbial food web. In order to gain more insight in terms of biological activity, we analyzed the capacity of sediment microflora to degrade organic matter by measuring the activities of extracellular hydrolytic enzymes involved in the biogeochemical cycling of carbon, nitrogen, phosphorus and sulfur. Furthermore, the detection of physiologically active bacteria in the sediment, particularly of those known for their capability to reductively dehalogenate organochlorine compounds, illustrates the potential for intrinsic bioremediation processes. Methods PCDD/F and chlorobenzenes were analyzed by gas chromatography(GC)/mass spectrometry and GC/flame ionization detection, respectively. The activities of hydrolytic enzymes were determined from freshly sampled sediment layers using 4-methylumbelliferyl (MUF) or 7-amino-4-methylcoumarin-conjugated model compounds and kinetic fluorescence measurements. Physiologically active bacteria from different sediment layers were microscopically visualized by fluorescence in situ hybridization (FISH). Specific bacteria were identified by 16S rRNA gene amplification and sequencing. Results and Discussion The PCDD/F congener profile was dominated by dibenzofurans. In addition, the presence of specific tetra and pentachlorinated dibenzofurans supported the assumption that extensive magnesium production was one possible source for the high contamination. A range of other chloroorganic compounds, including several isomers of chlorobenzenes, hexachlorocyclohexane and 1,1,1-trichloro-2,2-bis (p-chloro-phenyl)ethane (DDT), was present in the sediment. Activities of extracellular hydrolytic enzymes showed a strong decrease in those sediment layers that were characterized by high contents of absorbable organic halogen (AOX), indicating disturbed organic matter decay. Interestingly, an abnormal increase of cellulolytic enzyme activities below the organochlorine-rich layers was observed, possibly caused by residual cellulose from discharges of sulfite pulping wastes. FISH revealed physiologically active bacteria in most sediment layers from the surface down to the depth of about 60 cm, including members of Desulfitobacterium (D.) and Sulfurospirillum. The presence of D. dehalogenans was confirmed by its partial 16S rRNA gene sequence. Conclusions Results of chemical sediment analyses demonstrated high loads of organochlorine compounds, particularly of PCDD/F. Several years after stopping the waste water discharge to Spittelwasser creek, this sediment remains a main source for pollution of the downstream river system by way of the ongoing mobilization of sediment during high floods. As indicated by our enzyme activity measurements, the decomposition potential for organic matter is low in organochlorine-rich sediment layers. In contrast, the comparably higher enzyme activities in less organochlorine-polluted sediment layers as well as the presence of physiologically active bacteria suggest a considerable potential for natural attenuation. Recommendations and Perspectives From our data we strongly recommend to explore the degradative capacity of sediment microorganisms and the limits for in situ activity towards specific sediment pollutants in more detail. This will give a sound basis for the integration of bioremediation approaches into general concepts to reduce the risk that permanently radiates from this highly contaminated sediment. Submission Editor: Dr. Henner Hollert (Henner.Hollert@urz.uniheidelberg.de)     

不同轮作模式下作物根际土壤养分及真菌群落组成特征

为研究宁夏中部干旱带不同轮作模式下土壤养分及真菌群落组成的特征,以谷子轮作大豆（MRG）、轮作籽粒苋（MRA）、轮作藜麦（MRQ）及谷子连作（CK）为对象,测定了土壤养分含量,并利用Illumina MiSeq高通量测序平台测定了土壤真菌的ITS变异区序列.结果表明,不同轮作模式对土壤养分的影响存在差异.3种轮作模式下土壤pH和电导率均有所下降,土壤全氮、全钾、全磷和有机质含量均上升,OTUs数和α多样性指数均高于连作.真菌群落组成研究结果显示,子囊菌门（Ascomycota）为4种模式下的优势菌群.聚类分析显示MRA和MRG的真菌属组成最为相似,其次是MRQ,CK与3种轮作模式相差较大.相关性分析显示,土壤养分与几种优势真菌属呈显著相关性（P<0.05或P<0.01）,土壤全氮、全钾、硝态氮和有机质含量是影响土壤真菌群落最主要的因子.主成分分析（PCA）表明,MRG轮作模式优于MRA和MRQ模式.综上所述,轮作提高了真菌群落多样性指数,改变了土壤真菌群落结构,改善了土壤肥力状况,其中以谷子与大豆轮作效果最佳,建议将谷豆轮作作为中部干旱带杂粮产业中主要的轮作模式之一进行推广.