Indications of Recovery from Hypoxia in the Inner Stockholm Archipelago

Improved benthic conditions compared to the 1990s were found during benthic investigations, including sediment and benthic macrofauna in the inner Stockholm archipelago during 2008. In the 1990s, these areas were dominated by black and laminated surface sediments and very sparse fauna. A clear relationship was found when comparing sediment status with the benthic macrofauna. Reduced surface sediment and impoverished macroinvertebrate community was only found at one sampling station representing an enclosed part of the inner archipelago, whereas the other seven stations, with depths ranging from 20 to 50 m, had oxidized surface sediments and considerable biomasses of benthic macrofauna (6–65 g m⁻²) dominated by the invading polychaete Marenzelleria neglecta. An extrapolation of the results shows that, within the investigated area, the coverage of reduced surface sediments had decreased from approximately 17% in the late 1990s to 4% in 2008.     

成都市河流表层沉积物重金属污染及潜在生态风险评价

根据流经成都市内的三条河流（府河、南河、沙河）表层沉积物重金属数据，采用Hakanson潜在生态危害指数法对重金属的潜在生态风险进行了评价。结果表明（1）重金属潜在的生态危害因子（Er^i）说明大多属于轻微生态危害范畴，产牛生态危害的主要重金属是Hg、Cd，Cu、Pb次之，As影响最小；（2）多种重金属的生态系统的潜在生态风险指数（RI）表明河流重金属污染属于轻微生态危害和接近中等生态危害，其受危害程度由强至弱的次序为：府河，南河，沙河。     

Species of copper and zinc in sediments collected from the antarctic ocean and the Taiwan Erhjin Chi coastal area

The species of copper and zinc, such as bioexchangeable, skeletal, easily reducible (Fe and Mn oxides), moderately reducible (crystalline Mn oxide), organic combined with sulfides, and detritus with minerals, in mud and sand, separated from the surface Antarctic Ocean and the Taiwan Erhjin Chi coastal (including river and estuarine) sediments, have been analyzed by sequential leaching methods. Results show that in the Antarctic Ocean sediments, high concentrations of total copper (128 mg/kg) and zinc (458 mg/kg) were found in the high mud (99.09%) content samples compared with the low concentrations of total copper (83.8 mg/kg) and zinc (288 mg/kg) in low mud (51.69%) content samples. High concentrations of copper, zinc, manganese and iron are possibly due to the characteristics of manganese nodules, in which the species of copper and zinc are mainly contained in the crystalline Mn oxide phase. In the Taiwan Erhjin Chi coastal sediments, the total copper and zinc concentrations in mud and sand vary with season and location. High values were generally observed in the river sediments during the dry season, and low values were in the estuarine and coastal sediments during the heavy rainy season. High percentages of copper (as high as 49.4%) and zinc (as high as 76.7%) in mud and sand were in the bioexchangeable phase including the skeletal phase. This result might be correlated with the problems arising from human impact on copper and zinc as well as sewage pollution in Taiwan. In the organic combined phase, biogenic particulate matter related to higher primary productivity in the Antarctic Ocean is also discussed.     

天然沸石和方解石复合覆盖技术抑制底泥磷释放的影响因素研究

提出了天然沸石和方解石复合覆盖控制底泥氮磷释放的新技术,并对该技术抑制底泥磷释放的能力及影响因素进行了研究.结果表明,天然沸石和方解石复合覆盖层不仅可以有效抑制底泥氨氮释放,也可以有效抑制磷的释放.复合覆盖层抑制底泥磷释放的效率受天然沸石投加量、方解石投加量、天然沸石粒径、沸石与方解石组合方式等因素的影响.随天然沸石和方解石投加量的增加,复合覆盖层抑制底泥磷释放的效率明显提高;随天然沸石粒径的减小,复合覆盖层抑制底泥磷释放的效果略微增强.沸石和方解石的组合方式对复合覆盖层抑制底泥磷释放的规律为：先覆盖沸石后覆盖方解石对底泥磷释放的抑制效果明显强于先覆盖方解石再覆盖沸石条件下的情况,与沸石方解石混合均匀覆盖情况相比,先覆盖沸石后覆盖方解石对底泥磷释放的效果也略有提高.     

Topics of water sciences and technology

In the preceding series of contributions to ESPR typical examples from actual fields of water chemistry were presented on various topics: integrated water quality management, diagnosis of water bodies, therapy of aquatic systems, and fitness for aquatic systems. These contributions clearly showed the need and importance of more intensive research. In the principle committee III 'Basic Research' of the Water Chemical Society, various expert groups work on scientific backgrounds in these fields. Some relevant topics are selected in this outlook, mainly on interactions of solids with water, the role of environmental colloids, the development of modern biochemical methods for diagnosis, the impact of chemical speciation on bioavailability and water technology, and the development of advanced methods in water treatment technology. Innovative approaches to understand the interactions between pollutants, water and solids are crucial for assessment of contaminants with biochemical and analytical methods, for the development of new efficient technologies and for application of treatment methods with little or no waste and by-product formation.     

吹脱-捕集气相色谱法测定底质中易挥发性有机物

研究并建立了利用吹脱－捕集气相色谱法测定底质中易挥发性有机物的分析方法。该方法对底质中２５种易挥发性有机物进行测定。方法回收率在９６％－１０５％,最低检出浓度在０．３－１４．５μｇ／ｋｇ,变异系数在２．７％－５．３％。     

Environmental release of dioxins from reservoir sources during beach nourishment programs

In late 1990s, USEPA/FDA made an important connection regarding the presence of elevated levels of dioxins (e.g., 1500 ng kg⁻¹ TEQ) in ball clays mined in Mississippi (USA) from a geological deposit dated to ∼40 million years (Mississippi Embayment) that stretches over several states (northern part of Mississippi to Kentucky) and levels of dioxins in selected animal food sources. Following a recent beach nourishment program along the mid-Atlantic coast of the US, a number of dark gray, blue tinted nuggets of varying sizes were found on beach strands and near the shoreline. Using the presence of these balls of clay (shape, color, and knowledge regarding their use in pottery) on the beach, together with our direct experience analyzing ball clays for dioxins, we made a possible association between these clays and elevated dioxins. Concerns regarding the potential of nourishment programs to cause severe damage to our beaches drove us to test the dioxin content of nourishment exposed clays. A number of the nuggets, along with freshly dredged and deposited sand (collected the morning after nourishment) with the same coloration, and others (sun-bleached), collected approximately 2 weeks after the completion of the nourishment efforts, were analyzed for the presence of PCDD/Fs, PCBs, and selected semi-volatile chlorinated organics. The clay PCDD/F WHO2005-TEQs (dry weight; ND = DL; EMPC = EMPC) ranged from 0.41 to 5.78 ng kg⁻¹ with an average of 2.64 ng kg⁻¹, whereas the sand sample’s TEQs ranged from 0.18 to 0.31 ng kg⁻¹ PCDD/F WHO-2005, with an average of 0.22 ng kg⁻¹. The average total tetra- through octachlorinated dibenzo-p-dioxin concentration was 2700 ng kg⁻¹ (with a maximum of 5800 ng kg⁻¹) for the clays and 8.5 ng kg⁻¹ (with a maximum of 16.8 ng kg⁻¹) for the sand samples. The congener 2,3,7,8-TCDD (TEF = 1) was detected in half of the clay samples (0.11-0.77 ng kg⁻¹). All of the clay and sand samples displayed an unambiguous and dominating 1,4,6,9-chlorination pattern across homolog groups. No other chlorinated aromatics were detected above background levels. The observations, along with the absence or an extremely low level of polychlorinated dibenzofurans, together with the mineralogical analysis, supports the conclusion that off-shore dredging activities are reaching reservoir sources containing dioxin-tainted, smectic/kaolinite clay minerals. Subsequent beach erosion provides additional environmental releases over time, as buried balls of clay from previous nourishment efforts become exposed.     

Sulfur organic compounds in bottom sediments of the eastern Gulf of Finland

Background, Aims and Scope Despite the large number of studies on the forms of sulfur in marine deposits, investigations on sulfur organic compounds are still rare. It is known that the processes leading to formation of intermediate and final sulfur compounds (including organic ones) in modern deposits are the results of microbiological transformation of sulfur containing proteins, as well as the microbiological reduction of sulfate ions. The latter are finally reduced by anaerobic sulfate-reducing bacteria to H₂S, HS⁻ and S²⁻; the total sum of these is referred to as ‘hydrogen sulfide’ in chemical oceanography. Further, the formation of reduced sulfur organic derivatives (sulfides and polysulfides) is the result of interaction of the organic substance destruction products with the sulfide ions. In such cases, the main source of organic substances, as well as sulfates for the sulfur reducing processes, is the pore water in the sediments. The choice of the target of our study is based on the fact that the eastern part of the Gulf of Finland water area receives the bulk of the anthropogenic load of the St. Petersburg region. Low vertical intermixing of the water thickness is observed there (thus creating a deficiency of oxygen near the bottom), and the bottom sea current transfers the polluted salty water of the Baltic Sea into the Neva Bay. The whole of the above are the preconditions for the formation of sulfur-bearing organic compounds. A great number of bottom sediment samples for analytical surveys were collected in the Eastern Gulf of Finland during research expeditions in the years of 1997 and 2001. These were screened for structures of sulfur organic microcontaminants, including organic forms of sulfur, using advanced instrumentation and experienced personnel in our two, cooperating laboratories. This work is a part of the research being carried out on organic micro-admixtures present in bottom sediments, and is the summary of our findings on previously unstudied sulfur organic substances there. Materials and Methods A number of sulfur organic compounds present in nineteen bottom sediment samples from the Eastern Gulf of Finland (EGF) were characterized by high performance gas chromatography connected to low and high resolution mass spectrometers (GC/LRMS and GC/HRMS). The structure screening was carried out as compared with literature and library mass spectra, and taking the GC retention times into account. In the cases of an absence of mass spectra not in the literature, interpretation of the most probable structures was performed with the help of high resolution mass-spectrometric data, fragmentation rules for sulfur-bearing organic substances and ICLU simulation of spectra. These data were registered to form a conclusive ‘fingerprint’ for identification and confirmation of the structure of each novel compound found, e.g. by later syntheses of authentic model compounds. The relative contents of sulfur organic compounds were determined from MS response ratios of each compound to 2-fluorine naphthalene (internal standard). Results This paper is a completion of work, which has been published in part as three papers in the European Journal of Mass Spectrometry. As the total study result, 43 sulfur-bearing compounds were characterized. The mass spectra of 20 of them were found in the literature. The most probable structures for the 23 compounds whose mass-spectra were not available in the literature data were proposed. All of those 23 compounds were detected in bottom sediments for the first time, and 5 of them were described as originating from plants or being generated by chemical synthesis products, while the remaining 18 substances were previously unknown. The structures of these were deduced to be most probably the following (in order of their GC retention): dichloromethyl thiylsulfenylchloride, chloromethyl dichloromethyl disulfide, 3,4-dithiacyclohexene, 1,2,4-trithiacycloheptane, 1,2,3-trithiacyclohexane, tetrathiacyclopentane, 3,4,5-trithiacyclohexene, 1,2,4-trithiacyclohexane, cyclopropylhydrotrisulfide, 1,2-dithiane-3-thiol, 1,3-dithiane-2-thiol, bis(trichloromethyl)-tri-sulfide, 1,2,4,5-tetrathiacyclohexane, 1,2,3,4-tetrathiacycloheptane, 1,2,3,4-tetrathiacycloheptane, 1,2,3,4-tetrathia-cyclo-hexane, pentathiacyclohexane, and 1,2,4,6-tetrathiacyclooctane. The highest amounts of sulfur organic compounds were found in the deepest, bottom areas in the open part of the sea, where the salinity was highest, and oxygen deficiency occurred as well. Also, some coastal places with a high solid matter deposition rate had elevated contents of sulfur organic compounds. Discussion From the 43 sulfur organic compounds found, the HRMS data provided the atomic composition of the molecular ions for 16 compounds with a high confidence (see Table 3). The LRMS spectra could be identified with catalogue or literature spectra in 29 cases. The MS information obtained was insufficient in two cases: 1) The obvious molecular ion (at m/z 110) of compound 1 was not visible in LRMS. 2) For compound 43, the HRMS measurement, due to the low intensity (2%) of the molecular ion (m/z 210), could not exclude the presence of 2 oxygen atoms (instead of one sulfur atom) in the molecule. Major fragments, however, of our 43, certainly contained no oxygen atoms according to HRMS. The limited LRMS data in the literature, for an isomer of 43, had m/z values of all fragments different from those of the compound found by us. The retention times (RT) formed one more evidence for identity between compounds in different samples. The use of different non-polar columns in GC and similar, but not identical, temperature programs produced eluted peaks of novel and known compounds in each sample (mixture) in GC/HRMS and GC/LRMS. These gave sets of RTs which were in a very significant linear correlation (measured example R = 0.999866, p = 1.85E-06, N = 5). Therefore, the RTs in the HRMS analysis systems could be converted to values comparable with those from the LRMS device. The RT values, HRMS m/z values, LRMS spectra, and ICLU simulation results for each organic sulfur compound form an identification ‘fingerprint’. The interpretation of these experimental data, with supporting use of fragmentation rules, allow the giving of a provisional name and structure to the ‘suspect’. In this study and in environmental surveys of micropollutants in general, the compounds suspected of anthropogenic or natural origin occur at low levels in complex mixtures. Therefore, no bulk amount of an authentic, pure model substance for the suspect is available quite often. The most probable name and structure from the fingerprint data are very useful in guiding the preparation of the model substance for a conclusive identification. Similarly, the unknown criminal can be identified in advance by forensic science and his fingerprint, DNA, etc. as registered before the arrest. The analogy can be found in the literature and CAS register of organic polysulfides, which in great part consists of the results of sensitive mixture analysis methods. Conclusions Sediment of the Eastern Gulf of Finland is over large areas anaerobic, as indicated by the existence of novel, non-oxygenated sulfur organic microcontaminants. These substances were most abundant in anoxic and saline, deep bottom regions, and, in addition, in one coastal area near industrial discharges. This occurrence, and also the limited information about sulfur organic compounds in scientific literature, is considered evidence for the dominantly natural processes in their formation. Recommendations and Perspectives The importance and necessity of investigating the sulfur organic compounds in the bottom sediments, result from the fact that their presence can be an indicator of stable anaerobic processes. Similarly, the oxygen disappearance (anoxia) in the marine water, due to a high concentration of the sulfate ions and relatively high content of organic matter, is practically always connected with the appearance of hydrogen sulfide and sulfides. The generation of sulfur organic compounds precedes the formation of the new, or expansion of the existing anaerobic (‘hydrogen sulfide’) zones, which lead to such environmental disasters as mass destruction of hydrobionts. Many organic compounds of sulfur, including sulfides and polysulfides, are toxic to the aquatic organisms. Therefore, in addition to the danger of mass wholesale deaths of marine fauna in the bottom sediments region, there exists a probability of secondary pollution of the water thickness as well, due to the entry of those substances from bottom sediments in the water when the environmental conditions are changed (stormy weather, floods, geological activity of the earth’s crust, etc.).     

河湖底泥污染物释放影响因素及底泥处理的研究进展

结合国内外的研究,对温度、pH值、溶解氧等环境因素影响污染物释放的机制进行了综述。其中,温度的升高会促进底泥中氮磷的释放;随着溶解氧含量的增多,污染物越发不易释放;但pH值对底泥中的氮磷以及重金属的释放影响规律则各有不同。此外,结合国内外工程案例及试验研究,对污染底泥的治理技术进行了总结,分析了物理、化学和生物处理方法的利弊。联合处理方法则综合了多种方法的优点,具有良好的应用前景。     

Current status and perspectives of accelerated carbonation processes on municipal waste combustion residues

The increasing volumes of municipal solid waste produced worldwide are encouraging the development of processes to reduce the environmental impact of this waste stream. Combustion technology can facilitate volume reduction of up to 90%, with the inorganic contaminants being captured in furnace bottom ash, and fly ash/APC residues. The disposal or reuse of these residues is however governed by the potential release of constituent contaminants into the environment. Accelerated carbonation has been shown to have a potential for improving the chemical stability and leaching behaviour of both bottom ash and fly ash/APC residues. However, the efficacy of carbonation depends on whether the method of gas application is direct or indirect. Also important are the mineralogy, chemistry and physical properties of the fresh ash, the carbonation reaction conditions such as temperature, contact time, CO₂ partial pressure and relative humidity. This paper reviews the main issues pertaining to the application of accelerated carbonation to municipal waste combustion residues to elucidate the potential benefits on the stabilization of such residues and for reducing CO₂ emissions. In particular, the modification of ash properties that occur upon carbonation and the CO₂ sequestration potential possible under different conditions are discussed. Although accelerated carbonation is a developing technology, it could be introduced in new incinerator facilities as a “finishing step” for both ash treatment and reduction of CO₂ emissions.