气相色谱测定沉积物中多氯联苯的样品处理方法研究

通过比较密闭微波萃取、超声波萃取、索氏提取3种方法对沉积物中多氯联苯(PCBs)提取效率,对比浓硫酸和Florisil小柱两种净化方式的净化效果,在实验基础上建立了密闭微波萃取-Florisil小柱净化-气相色谱(ECD)测定沉积物中多氯联苯的分析方法,加标质量比为0.2ng/g时,其相对标准偏差(RSD)为2.19%～8.71%,回收率为77.3%～94.6%,检出限为0.027～0.064ng/g。采用该方法对威海湾养殖区沉积物中PCBs进行了监测,结果表明本方法适用于海洋沉积物样品中PCBs的测定。     

广西海域沉积物重金属、滴滴涕、多氯联苯含量及生态风险分析

在广西近岸海域采集了36个站位的表层沉积物样品,测定了沉积物样品中Cu、Pb、Cd、Zn、Cr、Hg、As共7种重金属和DDTs、PCBs共2种持久性有机污染物的含量,分析了各检测因子的含量和分布特征,对沉积物中7种重金属和DDTs、PCBs进行了综合生态风险评价。结果表明:广西海域沉积物中重金属平均含量(×10-6,干重)顺序为Zn(49.4)>Cr(41.7)> Cu(21.5)>Pb(15.6)>As(9.1)>Cd(0.07)>Hg(0.026),持久性有机污染物平均含量(×10-9,干重)为PCBs(2.97)> DDTs(0.88),重金属、DDTs、PCBs所有站位含量平均值均低于一类标准,广西海域沉积物Cu、Pb、Cd、Zn、Cr、Hg、As、DDTs、PCBs总体含量水平较低;沉积物重金属潜在生态风险程度排序为Hg>As>Cd>Cu>Pb>Cr>Zn,36个监测站位的潜在生态风险指数RI平均值为19.51,广西海域总体潜在风险程度较轻,属低潜在生态风险,位于茅尾海和廉州湾的站位潜在生态风险较高,As和Cu为主要的潜在生态风险因子;沉积物中DDTs、PCBs的残留水平生态风险较低,但部分站位DDTs含量介于其相应的ERL和ERM之间。     

东湖水体中多氯联苯的研究

于1994年6月,采用高分子多孔聚合树脂对武汉东湖水进行富集采样,样品经净化后利用毛细管柱色谱进行多氯联苯（PCBs）总量及同类物（congeners）的分离测定。结果表明,东湖水样中PCBs总含量为2．7ng／L,检出的20多个PCBs同类物其含量分别在0．002－1．12ng／L范围内。其同类物中低氯取代的PCBs相对含量明显高于工业用商品PCBs中的相应含量。     

甬江口海洋倾倒区沉积物中多氯联苯分布特征和生态风险评价

为了探讨甬江口海洋倾倒区附近海域表层沉积物中多氯联苯的污染水平及生态环境影响,对2014年1月在甬江口倾倒区及附近海域采集的8个沉积物样品用气相色谱法测定PCBs残留量,并且进行环境生态风险评价。结果显示:甬江口海洋倾倒区表层沉积物中PCBs含量为1.310~6.538 μg·kg^-1,平均值为3.413 μg·kg^-1,其分布表现为西北和东南向PCBs含量高于倾倒区;10种指示性PCBs中,主要以低氯代的PCB28、PCB118和PCB155为主,其中PCB118和PCB155在表层沉积物中的含量相对较高,其含量在各采样站位中占PCBs总量的26.1%~93.1%。甬江口海洋倾倒区沉积物中PCBs污染水平低于长江口、闽江口及珠江口,高于鸭绿江口、辽河口及黄河口。采用潜在生态危害指数法、加拿大环境质量标准ISQG法、生态风险值(EPA)法及毒性当量因子法进行评价,结果基本一致:甬江口海洋倾倒区属于较低生态风险,一般不会引起生物的负效应。     

春夏季黄东海溶解态丙烯酸的分布研究

为了解海洋中溶解态丙烯酸(AAd)的浓度分布及影响因素,本研究于2017年3～4月和2018年6～7月对黄东海海水中AAd进行了调查。结果表明:夏季黄东海表层海水中AAd的平均浓度((18.89±15.23) nmol·L~(-1))高于春季((13.94±9.89) nmol·L~(-1)),AAd存在明显的季节性差异。垂直分布上,P断面受长江冲淡水影响,陆源AAd的输入导致AAd含量高于B断面。春季黄东海表层海水及B断面的AAd与溶解态β-二甲基巯基丙酸内盐呈正相关性,这与AAd是β-二甲基巯基丙酸内盐的裂解产物有关。春季AAd的周日变化浓度范围是4.72～29.42 nmol·L~(-1),在18点出现最大值,与浮游动物摄食、光化学氧化及生源控制有关。春、夏季间隙水中AAd的浓度分别为30.89～131.57(平均:86.21±30.61)和5.75～84.86(平均:38.78±31.73)μmol·L~(-1),溶解有机碳(DOC)则为3.59～7.67和3.79～11.82 mg·L~(-1)。间隙水中AAd与二甲基硫(DMS)在春季存在负相关性,说明除了DMSPd的裂解,AAd还有其他的来源。研究海域沉积物间隙水中AAd的浓度比底层海水高出至少三个数量级,表明沉积物间隙水可能是底层海水中AAd的重要来源。     

三沙湾表层沉积物中有机污染物的含量及风险评价

利用气相色谱/质谱方法对三沙湾表层沉积物中多氯联苯(PCBs)、多环芳烃(PAHs)和有机氯农药(OCPs)进行测定,结果表明,PCBs、PAHs和OCPs的含量均值分别为1.28、61.76和1.18ng/g。与早期研究结果相比,PCBs含量浓度明显降低,表明其污染已得到有效控制;PAHs中高分子量组分普遍存在,通过分析菲/蒽和荧蒽/芘比值,判断其主要来源为燃料的高温燃烧;HCHs和DDTs是主要的有机氯农药污染物,二者的残留特征表明其主要来源为早期历史残留,且表层沉积物受到厌氧微生物降解。总体而言,三沙湾表层沉积物中PCBs、PAHs和OCPs的污染程度及生态风险均处于较低水平。     

赤道东北太平洋沉积物间隙水中溶解有机碳的分布特征

沉积物间隙水中的溶解有机碳(DOC)是沉积物有机质矿化过程中的中间产物[1],沉积物中的有机质通过微生物水解和(厌氧)发酵等方式溶解成各类具有不同分子量的有机化合物,通常总称为溶解有机碳,并释放到沉积物间隙水中.而溶解有机碳又进一步被细菌等微生物所利用,最终被氧化为溶解无机碳,完成有机质的矿化过程.因此,沉积物间隙水中DOC的浓度是消耗和生成之间平衡的结果[1].已有的研究表明,沉积物间隙水中DOC的含量显著高于底层水体中DOC的含量,导致其向底层水体的扩散;近期的研究也表明,来自海底沉积物的DOC通量是底层水体中DOC的重要来源,是海洋有机碳储库中的重要组成之一[2~4].     

南黄海中部海水、间隙水和沉积物中多环芳烃的分布及源分析

利用液液萃取、固相微萃取及快速溶剂萃取法对2007年9月南黄海中部海洋环境调查采集的31个调查站位的表层、30 m层、底层海水及表层沉积物样品进行前处理,并采用气相色谱-质谱检测其中的多环芳烃(PAHs).结果显示:站位表层、30 m层和底层海水中总PAHs的质量浓度分别为37.77～233.39 ng·L-1,39.45～213.27 ng·L-1,15.76～202.55 ng·L-1;表层沉积物(干重)总PAHs的质量比为16.33～229.58 ng·g-1,间隙水和上覆水中总PAHs的质量浓度为11.98～386.66 ng·L-1.间隙水的总PAHs普遍高于上覆水的,而沉积物和间隙水中的大于表层、30 m层及底层海水中的.经特征PAHs组分分析判定南黄海中部海水中PAHs的来源主要为石油及其产品,而表层沉积物中PAHs的主要来源可能为高温燃烧后的矿物燃料残余物.     

莱州湾表层沉积物中多氯联苯分布特征及生态风险评价

为探明莱州湾海域多氯联苯(PCBs)的分布及污染状况,本文利用2017年春夏季13个站位表层沉积物采样结果进行研究分析。结果表明,春季、夏季PCBs含量分别为1.27～4.10μg/kg和1.07～2.80μg/kg,均以低氯代为主。春季含量高于夏季,莱州湾西部浓度高于东部。本文分别用EPA法、环境质量标准法、潜在生态危害指数法、毒性当量因子法等对莱州湾表层沉积物中PCBs的潜在生态风险进行评价,均表明莱州湾海域PCBs潜在生态风险较低。     

海底水－沉积物界面系统中稀土元素的变化及配分特征

本文利用”大洋多金属结核调查“期间”海洋4“号调查船HY₄-871、881航次在东太平洋海盆取得的底层水、沉积物、间隙水及多金属结核样品,对比研究了稀土元素(REE)在海底水-沉积物界面系统不同物质相中的分布变化及配分特征。结果表明,在大洋氧化性沉积物间隙水中REE相对于底层水亏损。除Ce外,沉积物与多金属结核REE含量较为接近。底层水、沉积物、间隙水REE配分特征极为相似,都表现出中稀土相对于轻、重稀土的轻度分离和富集,Ce表现为负异常。多金属结核中中稀土也有类似的富集倾向,但Ce主要表现为正异常。随深度的增加,沉积物REE含量增加,但其配分模式不变。     

Contrasting chemical and isotopic compositions of organic matter in Changjiang (Yangtze River) estuarine and East China Sea shelf sediments

To examine the source and preservation of organic matter in the shelf sediments of the East China Sea (ECS), we measured bulk C/N and isotopes, organic biomarkers (n-alkanes and fatty acids) and compound-specific (fatty acids) stable carbon isotope ratios in three sediment cores collected from two sites near the Changjiang Estuary and one in the ECS shelf. Contrasting chemical and isotopic compositions of organic matter were observed between the estuarine and shelf sediments. The concentrations of total n-alkanes and fatty acids in the shelf surface sediments (0–2 cm) were 5–10 times higher than those in estuarine surface sediments but they all decreased rapidly to comparable levels below the surface layer. The compositions of n-alkanes in the estuarine sediments were dominated by C₂₆-C₃₃ long-chain n-alkanes with a strong odd-to-even carbon number predominance. In contrast, the composition of n-alkanes in the shelf sediment was dominated by nC₁₅ to nC₂₂ compounds. Long-chain (>C₂₀) fatty acids (terrestrial biomarkers) accounted for a significantly higher fraction in the estuarine sediments compared to that in the shelf sediment, while short-chain (<C₂₀) saturated and unsaturated fatty acids were more abundant in the shelf surface sediments than in the estuarine sediments. Stable carbon isotopic ratios of individual fatty acids showed a general positive shift from estuarine to shelf sediments, consistent with the variations in bulk δ ¹³C_TOCTOC. These contrasts between the estuarine and shelf sediments indicate that terrestrial organic matter was mainly deposited within the Changjiang Estuary and inner shelf of ECS. Post-depositional diagenetic processes in the surface sediments rapidly altered the chemical compositions and control the preservation of organic matter in the region.     

云贵高原湖泊沉积物─水界面碱度扩散通量研究

于１９９１－１９９５年间５次在云贵高原泸沽湖，洱海湖和贵州阿哈湖，百花湖的湖心采集沉积物柱芯，界面水和湖水样品，通过其ｐＨ值和ＨＣＯ３浓度剖面及界面碱度扩散通量的研究，首次定量评估高原湖泊界面扩散作用上不体碱度的影响程度，研究结果表明，云贵高原某些湖水寄宿时间对较长，湖水深度相对小的湖泊，界面扩散作用是水体碱度的重要来源之一，湖水寄宿时间较短，深度较小的湖泊，界面扩散对上覆水体的影响可以忽略不地。     

Dissolved silica concentrations and reactions in pore waters from continental slope sediments offshore from Cape Hatteras, North Carolina, USA

The pore water concentrations of dissolved silica in sediment cores from the continental slope offshore from Cape Hatteras, North Carolina, varied from 150 to almost 700 μ,M with depth in the top 40 cm of sediment. Sediment cores from 630 to 2010 m depth had very similar profiles of dissolved silica in their pore waters, even though these cores came from regions greatly different in slope, topography, sedimentation rate, and abundance of benthic macrofauna. Cores from 474 to 525 m were more variable, both with respect to pore water dissolved silica profiles, and with respect to sediment texture. Experiments indicate that both the rate of dissolution of silica and the saturation concentration decrease as sediment depth below the sediment-seawater interface increases. These data are consistent with depletion of a reactive silica phase in surface sediment, which may be radiolarian tests, or the alteration of biogenic silica to a less reactive form over time. Experimental results suggest that the pore water dissolved silica concentration in sediments below the top few centimeters may be higher than the sediments could now achieve. The flux of dissolved silica out of these sediments is estimated to be 15 μmoles cm⁻² yr⁻¹.     

Sources and distribution of organic matter in a river-dominated estuary (Winyah Bay, SC, USA)

The sources and distribution of organic matter (OM) in surface waters and sediments from Winyah Bay (South Carolina, USA) were investigated using a variety of analytical techniques, including elemental, stable isotope and organic biomarker analyses. Several locations along the estuary salinity gradient were sampled during four different periods of contrasting river discharge and tidal range. The dissolved organic carbon (DOC) concentrations of surface waters ranged from 7 mg l⁻¹ in the lower bay stations closest to the ocean to 20 mg l⁻¹ in the river and upper bay samples. There was a general linear relationship between DOC concentrations and salinity in three of the four sampling periods. In contrast, particulate organic carbon (POC) concentrations were significantly lower (0.1–3 mg l⁻¹) and showed no relationship with salinity. The high molecular weight dissolved OM (HMW DOM) isolated from selected water samples collected along the bay displayed atomic carbon:nitrogen ratios ([C/N]a) and stable carbon isotopic compositions of organic carbon (δ¹³C_OC) that ranged from 10 to 30 and from −28 to −25‰, respectively. Combined, such compositions indicate that in most HMW DOM samples, the majority of the OM originates from terrigenous sources, with smaller contributions from riverine and estuarine phytoplankton. In contrast, the [C/N]a ratios of particulate OM (POM) samples varied significantly among the collection periods, ranging from low values of 5 to high values of >20. Overall, the trends in [C/N]a ratios indicated that algal sources of POM were most important during the early and late summer, whereas terrigenous sources dominated in the winter and early spring.In Winyah Bay bottom sediments, the concentrations of the mineral-associated OM were positively correlated with sediment surface area. The [C/N]a ratios and δ¹³C_OC compositions of the bulk sedimentary OM ranged from 5 to 45 and from −28 to −23‰, respectively. These compositions were consistent with predominant contributions of terrigenous sources and lesser (but significant) inputs of freshwater, estuarine and marine phytoplankton. The highest terrigenous contents were found in sediments from the river and upper bay sites, with smaller contributions to the lower parts of the estuary. The yields of lignin-derived CuO oxidation products from Winyah Bay sediments indicated that the terrigenous OM in these samples was composed of variable mixtures of relatively fresh vascular plant detritus and moderately altered soil OM. Based on the lignin phenol compositions, most of this material appeared to be derived from angiosperm and gymnosperm vascular plant sources similar to those found in the upland coastal forests in this region. A few samples displayed lignin compositions that suggested a more significant contribution from marsh C₃ grasses. However, there was no evidence of inputs of Spartina alterniflora (a C₄ grass) remains from the salt marshes that surround the lower sections of Winyah Bay.     

An investigation of the sources and seasonal variations of highly branched isoprenoid hydrocarbons in intertidal sediments of the Tamar Estuary, UK

The concentrations and distributions of highly branched isoprenoid (HBI) hydrocarbons in the surficial sediments of an intertidal mudflat in the Tamar Estuary, UK, were examined at monthly intervals throughout 1990. C₂₀ and C₂₅ HBIs were present all the year round and their concentrations covaried, maximising at several times in the year, notably in April–June. Since C₂₅ HBIs are known to be produced by a species of diatom (Haslea ostrearia) in culture, it seemed likely that the sedimentary maxima were also due to production from sediment diatoms. It was interesting therefore that the April–June HBI maximum did not coincide with the (August) maximum concentration of the common diatom hydrocarbon n-heneicosa-hexaene (HE), even though HE is also produced by the diatom species which produces C₂₅ HBIs in culture. Diatoms isolated from the sediments in August produced abundant HE and only a small proportion of C₂₅ HBIs. These results suggest that HBI and HE production maximise at different diatom growth stages, or that the major sources of HBIs in the sediments are as yet unidentified diatom species. The diatoms isolated from the sediment did not produce C₂₀ HBIs and to date no organism has produced these in culture. Nonetheless, the δ¹³C values of the sedimentary C₂₀ HBIs were consistent with an algal source.     

Sources and preservation of organic matter in Plum Island salt marsh sediments (MA, USA): long-chain n-alkanes and stable carbon isotope compositions

Elemental (TOC, TN, C/N) and stable carbon isotopic (δ¹³C) compositions and n-alkane (nC_16–38) concentrations were measured for Spartina alterniflora, a C₄ marsh grass, Typha latifolia, a C₃ marsh grass, and three sediment cores collected from middle and upper estuarine sites from the Plum Island salt marshes. Our results indicated that the organic matter preserved in the sediments was highly affected by the marsh plants that dominated the sampling sites. δ¹³C values of organic matter preserved in the upper fresh water site sediment were more negative (−23.0±0.3‰) as affected by the C₃ plants than the values of organic matter preserved in the sediments of middle (−18.9±0.8‰) and mud flat sites (−19.4±0.1‰) as influenced mainly by the C₄ marsh plants. The distribution of n-alkanes measured in all sediments showed similar patterns as those determined in the marsh grasses S. alterniflora and T. latifolia, and nC₂₁ to nC₃₃ long-chain n-alkanes were the major compounds determined in all sediment samples. The strong odd-to-even carbon numbered n-alkane predominance was found in all three sediments and nC₂₉ was the most abundant homologue in all samples measured. Both δ¹³C compositions of organic matter and n-alkane distributions in these sediments indicate that the marsh plants could contribute significant amount of organic matter preserved in Plum Island salt marsh sediments. This suggests that salt marshes play an important role in the cycling of nutrients and organic carbon in the estuary and adjacent coastal waters.     

海水中微量元素无机离子交换动力学研究 Ⅳ.海水中铀(Ⅵ)与水合氧化钛离子交换反应的级数和活化能的测定

关于海水中铀(Ⅵ)与水合氧化钛的作用、国内外已有许多报导,内容包括水合氧化钛制备方法的不同对交换铀量的影响,水合氧化钛和海水中铀的基本物理—化学性质的研究及它们在反应过程中物理—化学性质变化规律的研究,海水中铀与水合氧化钛作用机理的研究等等。但对这一反应的动力学研究文献上报导极少,除了在本研究Ⅰ、Ⅱ和Ⅲ中报导的反应机理的研究[1,2]证明反应过程的速率由液膜扩散所控制之外,关于这一离子交换过程的反应级数和活化能的研究却至今未见有文献报导。     

Higher plant n-alkane average chain length as an indicator of petrogenic hydrocarbon contamination in marine sediments

The n-alkane average chain length (ACL) is the weight-averaged number of carbon atoms of the higher plant C₂₅–C₃₃ n-alkanes. The abundance of individual n-alkanes from higher plant sources generally increases with increasing carbon number in coastal marine sediments around Taiwan, but this trend is reversed for petrogenic hydrocarbons. The ACL would potentially be lowered if petrogenic hydrocarbons were added to sediments containing biogenic hydrocarbons alone. To test this idea, a marine environment off southwestern Taiwan known to contain both biogenic and petrogenic hydrocarbons and two nearby rivers were selected for investigating possible difference in ACL values between their sediments. The average CPI of C₂₅–C₃₃ n-alkanes was 4.08 ± 2.04 (range 1.90–8.96, n = 15) for the river sediments and 1.70 ± 0.16 (range 1.43–1.97, n = 15) for the marine sediments. The ACL of C₂₅–C₃₃ n-alkanes for river sediments ranged from 29.2 to 30.5 (average 29.9 ± 0.4), and for marine sediments from 28.4 to 29.3 (average 28.9 ± 0.3). The ACL difference between marine and river sediments was significant (Student's t test at 99% confidence) although it appeared small. It is suggested that the ACL can be an additional indicator for detection of petrogenic hydrocarbons in coastal marine sediments.     

In situ hydrocarbon concentrations from pressurized cores in surface sediments, Northern Gulf of Mexico

Two newly developed coring devices, the Multi-Autoclave-Corer and the Dynamic Autoclave Piston Corer were deployed in shallow gas hydrate-bearing sediments in the northern Gulf of Mexico during research cruise SO174 (Oct–Nov 2003). For the first time, they enable the retrieval of near-surface sediment cores under ambient pressure. This enables the determination of in situ methane concentrations and amounts of gas hydrate in sediment depths where bottom water temperature and pressure changes most strongly influence gas/hydrate relationships. At seep sites of GC185 (Bush Hill) and the newly discovered sites at GC415, we determined the volume of low-weight hydrocarbons (C₁ through C₅) from nine pressurized cores via controlled degassing. The resulting in situ methane concentrations vary by two orders of magnitudes between 0.031 and 0.985 mol kg^− 1 pore water below the zone of sulfate depletion. This includes dissolved, free, and hydrate-bound CH₄. Combined with results from conventional cores, this establishes a variability of methane concentrations in close proximity to seep sites of five orders of magnitude. In total four out of nine pressure cores had CH₄ concentrations above equilibrium with gas hydrates. Two of them contain gas hydrate volumes of 15% (GC185) and 18% (GC415) of pore space. The measurements prove that the highest methane concentrations are not necessarily related to the highest advection rates. Brine advection inhibits gas hydrate stability a few centimeters below the sediment surface at the depth of anaerobic oxidation of methane and thus inhibits the storage of enhanced methane volumes. Here, computerized tomography (CT) of the pressure cores detected small amounts of free gas. This finding has major implications for methane distribution, possible consumption, and escape into the bottom water in fluid flow systems related to halokinesis.     

Effects of oxic and anoxic filtration on determined methyl mercury concentrations in sediment pore waters

Accurate determination of methyl mercury (MeHg) concentrations in sediment pore waters is crucial for an improved understanding of mercury (Hg) biogeochemistry, and for improved risk assessment of Hg contaminated sites. In the present study, effects of oxic (air) and anoxic (N₂) filtration (after centrifugation) on determined pore water MeHg concentrations were investigated in severely Hg contaminated pulp fibre sediments from two estuaries of the Bothnian Sea, Sweden. MeHg was determined in the filtrate using species-specific isotope dilution gas chromatography inductively coupled plasma mass spectrometry (SSID–GC–ICPMS), after ethylation with sodium tetraethylborate. Determined concentrations of MeHg were greater after anoxic filtration than after oxic filtration for all samples investigated, with MeHg(N₂)/MeHg(air) ratios ranging between 3.4 and 343. Adsorption to newly formed Fe(III)/Mn(III/IV)-oxy/hydroxide surfaces is proposed as the main mechanism responsible for MeHg removal during oxic filtration. This is supported by decreases in dissolved Fe and Mn concentrations during oxic filtration, and by decreases in dissolved sulphur concentrations during oxic filtration in the samples with largest effect on MeHg concentrations. The latter is explained by adsorption of SO₄²⁻ to newly formed Fe(III)/Mn(III/IV)-oxy/hydroxide surfaces. The effect of oxidation during filtration on pore water MeHg concentrations was largest in samples in which FeS(s) was not present, but with calculated pe-values below − 3. Thus, our results indicate that the largest errors with respect to pore water MeHg concentrations when filtering in air can be expected in samples with an intermediate redox potential, possibly buffered by a mixture of oxidation sensitive Fe(II/III) minerals.