ASsessment Of Alcohol Ethoxylate Surfactants And Fatty Alcohols Mixtures In River Sediments And Prospective Risk Assessment

A feasible and relatively readily available analytical method was adapted for the assessment of alcohol ethoxylates (AE) and fatty alcohols (FA) in sediments. This study illustrates the simultaneous measurement of 38 of 114 possible alcohol ethoxylate ethoxymers (AE) and fatty alcohols (FA) found in commercially important AE products. We predicted toxicity for all identified fractions, as well as the total mixture toxicity, relative to three exposure scenarios via sewage treatment plants (STP) for these widely used chemicals in consumer products and hence generate a preliminary environmental risk screening for AE and FA in sediments. The method is based on derivatization of solvent or solid-phase extracts with 2-fluoro-N-methylpyridinium p-toluenesulfonate (Pyr+). The derivatized extracts were analyzed with liquid chromatography/mass spectrometry (LC/MS) operating in the positive ion electrospray mode. The extraction efficiency of AE and FA in three different sediments of varying composition was evaluated with spike-recovery studies, ranging from 64% to 80%. The detection limits for individual ethoxymers typically ranged from 1 to 5ngg⁻¹on a dry weight basis. The mean limit of detection (LOD) was 6ngg⁻¹and the median LOD was 3ngg⁻¹. AE and FA in sediments were found to be stable for two weeks if preserved with 3% (v/v) formalin and stored at 4–6^∘C. Based on equilibrium partitioning, background concentrations of AE and FA were predicted to be below concentrations known to elicit chronically toxic effects. Total worst case mixture toxicities for all AE ethoxymers combined with FA were predicted to result in a risk quotient less than 0.6. Activated sludge treatment (STP) significantly reduced the release of total AE and FA by four-fold, suggesting that the total mixture risk quotient would be < 0.15 for sediment dependent organisms.     

基于风险分析的流域优先有机污染物筛查:研究与应用

应用高通量分析方法对大清河流域47个沉积物中的潜在风险有机污染物进行了分析,共筛查到104种有毒有机污染物。应用基于风险分析的筛查体系对检出率高于10%的54种污染物进行了概率风险评估,筛查出11种具有潜在风险的流域优先有机污染物,包括农药(特草克、氨磺磷、枯莠隆)、工业用品及副产物(二苯胺、9,10-蒽醌、萘、2-甲基萘)及家庭及个人护理品(咖啡因、苯乙酮、苯甲酮、联苯)等。结果表明,基于风险分析的流域污染物筛查方法体系可成功地对流域内优先污染物进行识别与筛查,为流域管理提供科学依据。     

Nutrients and Heavy Metals in Legacy Sediments: Concentrations,Comparisons with Upland Soils,and Implications for Water Quality

Concentrations of nutrients and heavy metals in streambank legacy sediments are needed to estimate watershed exports and to evaluate against upland inputs. Concentrations of nutrients and heavy metals were determined for legacy sediments in 15 streambanks across northeastern Maryland, southeastern Pennsylvania, and northern Delaware. Samples were collected from multiple bank depths from forested, agricultural, urban, and suburban sites. Analyses were performed for fine (<63 μm) and coarse sediment fractions. Nutrient and heavy metal concentrations were significantly higher in fine than coarse legacy sediments and water extractable nutrient concentrations were significantly greater for fine sediments. Nutrient and heavy metal concentrations were highest in streambank legacy sediments associated with urban land use, but few differences were found with bank depth. Total N (40–3,970 mg/kg) and P (25–1,293 mg/kg) and bioavailable P (0.25–48.8 mg/kg) concentrations for legacy sediments were lower than those for upland soils. This suggests that legacy sediments could serve as sink or source of N and P depending on the redox conditions and stream water nutrient concentrations. However, despite low concentrations, caution should be exercised since streambank erosion and legacy sediment mass loadings could be high, these sediments are in immediate proximity of aquatic ecosystems, and biogeochemical transformations could result in release of the nutrients.     

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.).     

Distribution and fractionation of heavy metals in the Tisa (Tisza) River sediments

Introduction In this work, sediments of the River Tisa (Tisza) are studied to assess their environmental pollution levels for some major heavy metals, as well as to predict the investigated elements’ mobility on the basis of their association type with the substrate. The Tisa River catchments area is a subbasin of the River Danube. Part of this river, 166 km long, belongs to the Serbian province of Vojvodina, before it flows into the Danube. It has been chosen for our investigation, because it has been exposed to intense pollution in the last decades. Materials and Methods The river sediment samples were collected at 32 locations. The proportions of sand, silt and clay fractions were determined. The sequential extraction procedure following a modified Tessier method was applied for speciation of the metal forms in the collected samples. The metal concentrations of Zn, Cd, Pb, Ni, Cu, Cr, Fe and Mn in extracts were determined by atomic absorption spectroscopy. Results and Discussion Granulometric analysis showed that some 50% of the Tisa River sediments were silt and clay, while the rest was sand with quartz, as the main constituent. The average metal content of the surface river sediment samples for every fraction of sequential extraction was presented and discussed in relation to pH, Eh and metal fractionation. The average metal content from the Tisa River sediments, obtained as an average of the metal’s concentration released in all five sequential extraction fractions was compared with: average metal contents of the Tisa River sediments in Hungary, metal content in soils formed on the Tisa River alluvium of Vojvodina, average metal content in soils of Vojvodina, and average metal content in soils of Hungary. An assessment of metal pollution levels in Tisa River sediments was made by comparing mean values for obtained results for the Tisa River sediments with the freshwater sediment’s Quality Guidelines as published by US EPA, Environment Canada and soil standards for Serbia. Conclusion According to US EPA and Canadian Quality Guidelines for freshwater sediments, the concentration of heavy metals in Tisa sediments were: (a) much higher than defined concentrations below which harmful effects on river biota are unlikely to be observed, (b) below defined concentrations above which harmful effects on river biota are likely to be observed. The concentration levels of Pb, Ni, Cu and Cr in Tisa River sediments are safe when compared with Serbian MAQ (Maximum Allowed Quantity) standards for soils, but they are unsafe in the case of Zn and Cd. Recommendations and Outlook The quality of sediments in the Tisa River was on the border line between potentially polluted and polluted. This line could very easily be exceeded since the quality of sediments in the Tisa River in Hungary was already worse than in Serbia. These results indicated the need for further monitoring of heavy metals in that locality.     

成渝经济区主要河流沉积物重金属赋存形态及生态风险评估

以成渝经济区主要水系水体沉积物为研究对象,利用Eri（单一金属潜在生态风险因子）和RI（多金属潜在风险指数）等定量诊断工具分析沉积物中的重金属的潜在生态风险,为成渝经济区战略环评提供数据支撑。根据风险指标评价结果和重金属空间分布规律,将区域水系分为3种生态风险功能区。结合沉积物中重金属赋存形态,得出区域Cd的生态风险较...     

太湖湖滨湿地沉积物氮磷与2种挺水植物氮磷的关系

在无锡太湖湖滨带布设3条样带、36个样点进行了调查,分析了表层沉积物（0~15 cm）和芦苇（Phragmites australis（Cav.）Trin.）、茭白（Zizania latifolia（Griseb.）Turcz.）2种挺水植物w（N）、w（P）的变化,揭示了沉积物N、P的空间分布以及与2种挺水植物N、P的关系。结果表明：（1）表层沉积物w（N）自上而下分别为7.89~4.24 mg.g-1（0~5 cm）、7.56~3.81 mg.g-1（0~10 cm）、7.61~3.77 mg.g-1（0~15 cm）,w（P）分别为1.293~0.532 mg.g-1（0~5 cm）、1.112~0.497 mg.g-1（0~10 cm）、0.952~0.471 mg.g-1（0~15 cm）。（2）生态修复区表层沉积物N、P的水平变化规律一致,按陆向辐射区-水位变幅区-水向辐射区依次递减,而从垂直变化来看,w（N）、w（P）均以表层最高,并依次向下层递减;硬质护坡区P的变化与之一致,但N的水平分布却按陆向辐射区-水位变幅区-水向辐射区依次递增,垂直分布呈现表层最低,并依次向下层递增变化。（3）2种挺水植物w（N）、w（P）不同,芦苇对N、P的吸收明显高于茭白（芦苇地上部分w（N）31.75~42.61 mg.g-1,地下部分w（N）13.57~18.21 mg.g-1;茭白地上w（N）14.78~23.57 mg.g-1,地下部分w（N）13.57~18.21 mg.g-1,而芦苇地上部分w（P）3.62~5.08 mg.g-1,茭白地上部分w（P）1.42~1.93 mg.g-1,地下部分w（P）0.35~0.57 mg.g-1）。2种挺水植物地上部分N、P吸收量远远大于地下部分吸收量。（4）相关分析表明,2种植物地下部分w（TP）与沉积物w（TP）呈正相关,而芦苇地下部分w（TP）与沉积物w（TP）相关性显著（P〈0.05）,说明芦苇根系对沉积物中的P具有强烈吸附作用。（5）2种植物对太湖中沉积物N、P分配有显著影响,生态恢复区沉积物中w（N）显著高于硬质护坡,而w（P）较硬质护坡显著降低,适度恢复水生植被可有效缓解湖泊水体的富营养化。     

鄱阳湖沉积物有机磷累积特征及其与流域发展间的响应关系

选取了鄱阳湖4个柱状沉积物,应用改进的Hedley磷形态连续提取法和有机磷(OP)酶水解技术,研究了其OP累积特征、生物有效性变化及其与流域发展间的响应关系.结果表明:1自1972年以来,鄱阳湖沉积物OP含量呈持续增长趋势,其中南部湖区和"五河"尾闾区较北部和中部湖区增长趋势明显;不同阶段沉积物OP中H2O-Po和HCl-Po含量呈先下降,而近十年又有所增加趋势;Na OH-EDTA-Po含量则呈持续增长趋势,即鄱阳湖沉积物OP增加主要是由于Na OH-EDTA-Po的增加所致.2鄱阳湖沉积物各形态OP组成各异,其中H2O-Po含量较低,以类植酸磷为主,生物有效性较低;Na OH-EDTA-Po含量较高,以活性单酯磷为主,生物有效性较高.鄱阳湖沉积物OP增加主要来源于活性单酯磷,其生物有效性也呈增长趋势,二酯磷和类植酸磷则在1972—2002年间为下降趋势,2002年以来有所增加.3鄱阳湖沉积物OP,特别是Na OHEDTA-Po的累积主要受流域农业面源污染影响,其中沉积物OP和Na OH-EDTA-Po含量与流域单位面积磷肥施用量显著正相关,表明流域农业面源污染是导致鄱阳湖沉积物OP含量增加的重要原因之一.     

摇蚊幼虫与霍普水丝蚓扰动对河流沉积物中氮、磷、氧释放的影响

定量研究河床沉积物中的生物扰动对污染物的影响效应,对于维护河流健康具有重要的理论指导作用.基于室内实验模拟摇蚊和霍普水丝蚓对河床沉积物的扰动过程,研究两种生物扰动作用对沉积物中氮、磷释放以及生物扰动对上覆水中溶解氧的影响.在相同的沉积物环境中分别放入单一物种,实验结果显示,相对于空白组,摇蚊幼虫组的上覆水中氨氮、总氮、总磷平均净增量分别为2.32、0.787、0.105 mg · L^-1,霍普水丝蚓组的氨氮、总氮、总磷平均净增量分别为0.72、0.462、0.063 mg · L^-1,表明摇蚊幼虫和霍普水丝蚓的扰动作用均能促进沉积物中氨氮、总氮、总磷向上覆水中的释放,且摇蚊幼虫对污染物释放的作用效果比水丝蚓更明显;当摇蚊幼虫和水丝蚓混合放入后,摇蚊幼虫对沉积物中氨氮、总氮、总磷释放起主要促进作用;在混合实验组(摇蚊23条,霍普水丝蚓47条)中,氨氮、总氮、总磷的平均净增量均低于单一物种的摇蚊组和水丝蚓组,表明在该组中,摇蚊幼虫和霍普水丝蚓在沉积物中共同扰动作用对氮、磷释放的促进效果减弱;对上覆水中溶解氧浓度而言,摇蚊所占比例越高,溶解氧浓度就越低,且上覆水中的溶解氧浓度变化,会影响生物扰动对沉积物氮、磷释放的效果.     

长江中游沉积物中多溴联苯醚的污染特征及风险评价

多溴联苯醚(PBDEs)具有高毒性和生物累积性,进入水体后易与有机质相结合,成为PBDEs污染物的重要归宿,对人类健康和水生生态系统造成潜在的危险.为揭示多溴联苯醚(PBDEs)在长江中游流域的污染现状,通过采集该地区流域内13个表层沉积物样品,采用高分辨气相色谱/高分辨质谱法(HRGC/HRMS)对沉积物中9种PBDEs同类物进行分析.结果表明该地区沉积物中9种PBDEs的含量范围(干重)约为46.1~326 pg·g~(-1),而BDE-99是其中最主要的贡献单体,平均贡献率约为51.6%;其次是BDE-47,约为19.6%.与国内外其他海域的研究相比,长江中游沉积物中PBDEs残留量处于较低水平.通过测定沉积物中总有机碳(TOC),研究结果发现PBDEs含量与TOC无明显的正相关关系.结合商值法对PBDEs的健康风险进行初步评估,结果表明,本研究中PBDEs对人体产生的健康风险较小.