渤海湾潮滩不同粒径沉积物中多环芳烃的分布

利用湿筛分离的方法,将采自渤海湾潮间带的沉积物分成0.063mm 3个不同的粒径组分,测定其16种EPA规定的多环芳烃(PAHs)含量、总有机碳(TOC)和碳黑(BC)含量.结果表明,不同粒径沉积物中∑PAHs含量范围在714~4870ng/g之间.在岐口(TS3)沉积物中,∑PAHs含量最高值出现在0.063mm粒径组分中.所有站点沉积物的0.031~0.063mm粒径组分中∑PAHs含量均为最低.尽管如此,有机碳标准化∑PAHs含量则随着沉积物粒径的增大呈现增加趋势.不同粒径沉积物中∑PAHs含量与BC含量之间呈现显著正相关关系,而与有机碳(OC=TOC-BC)含量之间的相关性较差.因此,不同粒径沉积物中BC的分布很可能在其中扮演着更重要的作用.     

东海内陆架沉积物中黑碳分布及其与持久性有机污染物的相关性研究

本文采用化学热氧化法测定了25个东海内陆架表层沉积物中黑碳的含量,探讨了沉积物中黑碳与总有机碳、粒度以及持久性有机污染物之间的关系.结果表明,东海内陆架表层沉积物中黑碳的含量范围为0.21～0.88 mg.g-1.沉积物中黑碳和总有机碳之间没有显著的相关性,表明两者具有不同的来源.区域内沉积物在粒度上有明显的空间分异,黑碳的空间差异则较小,表明黑碳的沉积过程受颗粒物分选过程的影响较小.沉积物中多环芳烃和滴滴涕的含量与黑碳无显著的相关性,可能与东海内陆架环境中强烈的水动力过程和持久性有机污染物来源的复杂性有关.     

山美水库表层沉积物黑碳分布特征及其对磷形态的影响

对亚热带水库福建山美水库表层沉积物黑碳的时空分布特征及其对不同形态磷的影响进行了研究.结果表明,山美水库表层沉积物黑碳(BC)含量为2.44~5.28g/kg,与国外研究水库水平相当,显著高于国内外海岸带沉积物黑碳水平.黑碳整体分布特征为:丰水期>枯水期, 入库区>库尾>近坝区>库中.沉积物中黑碳与总有机碳呈现显著的正相关性,与沉积物粒径分布无明显相关关系.黑碳与有机碳比值平均为24.95%,表明黑碳来源复杂,是陆源生物质燃烧和化石燃料燃烧的共同结果.黑碳与有机磷和铁铝结合态磷这两种易释放磷之间显著相关,其对有机磷和铁铝结合态磷具有一定的吸附固定作用,这种吸附作用可能对沉积物内源磷释放具有一定的抑制效应.     

Experimental and molecular dynamic simulation study of perfluorooctane sulfonate adsorption on soil and sediment components

Soil and sediment play a crucial role in the fate and transport of perfluorooctane sulfonate (PFOS) in the environment. However, the molecular mechanisms of major soil/sediment components on PFOS adsorption remain unclear. This study experimentally isolated three major components in soil/sediment: humin/kerogen, humic/fulvic acid (HA/FA), and inorganic component after removing organics, and explored their contributions to PFOS adsorption using batch adsorption experiments and molecular dynamic simulations. The results suggest that the humin/kerogen component dominated the PFOS adsorption due to its aliphatic featureswhere hydrophobic effect and phase transfer are the primary adsorptionmechanism. Compared with the humin/kerogen, the HA/FA component contributed less to the PFOS adsorption because of its hydrophilic and polar characteristics. The electrostatic repulsion between the polar groups of HA/FA and PFOS anions was attributable to the reduced PFOS adsorption.When the soil organicmatterwas extracted, the inorganic component also plays a non-negligible role because PFOS molecules might form surface complexes on SiO₂ surface. The findings obtained in this study illustrate the contribution of organic matters in soils and sediments to PFOS adsorption and provided newperspective to understanding the adsorption process of PFOS on micro-interface in the environment.     

Experimental and molecular dynamic simulation study of perfluorooctane sulfonate adsorption on soil and sediment components

Soil and sediment play a crucial role in the fate and transport of perfluorooctane sulfonate(PFOS) in the environment. However, the molecular mechanisms of major soil/sediment components on PFOS adsorption remain unclear. This study experimentally isolated three major components in soil/sediment: humin/kerogen, humic/fulvic acid(HA/FA), and inorganic component after removing organics, and explored their contributions to PFOS adsorption using batch adsorption experiments and molecular dynamic simulations. The results suggest that the humin/kerogen component dominated the PFOS adsorption due to its aliphatic features where hydrophobic effect and phase transfer are the primary adsorption mechanism.Compared with the humin/kerogen, the HA/FA component contributed less to the PFOS adsorption because of its hydrophilic and polar characteristics. The electrostatic repulsion between the polar groups of HA/FA and PFOS anions was attributable to the reduced PFOS adsorption. When the soil organic matter was extracted, the inorganic component also plays a non-negligible role because PFOS molecules might form surface complexes on SiO 2surface.The findings obtained in this study illustrate the contribution of organic matters in soils and sediments to PFOS adsorption and provided new perspective to understanding the adsorption process of PFOS on micro-interface in the environment.     

松花江水中天然有机物的提取分离与特性表征

将反渗透与XAD大孔树脂吸附技术相结合,对松花江水中天然有机物(NOM)进行了浓缩和分离,并采用紫外光谱、红外光谱、液相凝胶色谱、官能团滴定1、HNMR核磁共振等分析手段,对松花江水中NOM及其各分离组分和一种商用腐殖酸CHA的特性进行了比较和表征.结果表明,利用反渗透进行NOM浓缩对水中有机物具有很高的回收率;松花江水中NOM组成为:富里酸>腐殖酸>亲水部分;各组分芳香性为:腐殖酸>憎水部分>富里酸>亲水部分,E₄/E₆与芳香性之间缺乏必然的联系;腐殖酸和商用腐殖酸具有较高的不饱和性,NOM和亲水部分次之,憎水部分和富里酸中饱和烃含量较多;紫外吸收较弱的有机成分对NOM分子量的贡献较大;NOM及其分离组分的总酸度为9.84～12.15meq/g,羧酸含量为CHA>亲水>憎水>NOM>富里酸>腐殖酸;NOM及其各分离组分的溶解性有机物构成以脂肪烃为主.     

四海龙湾表层沉积物中有机质的组成特征及其源解析

为研究玛珥湖四海龙湾表层沉积物中有机质的组成特征及来源,采集四海龙湾表层沉积物样品,并对其中的有机质进行了分析. 结果表明,四海龙湾表层沉积物中w(TOC)(TOC为总有机碳)为6.7%、w(TN)为0.6%、δ13C_org(TOC同位素丰度)为-28.0‰、δ15N_total(TN同位素丰度)为2.2‰. 可溶性有机质主要包括脂肪烃、脂肪醇、脂肪酸和GDGTs(甘油二烷基甘油四醚脂)等,其中脂肪酸是可溶性有机质的主要组分,约占可溶性有机质总量的68.8%,主要来源于内源性的藻类和厌氧菌; 脂肪烃主要来源于陆源的C3木本植物;结合态脂肪醇具有明显的内源来源特征,而游离态脂肪醇却呈现陆源来源特征. 四海龙湾沉积物中含有丰富的GDGTs,主要来源于陆源土壤,包括支链类GDGTs和类异戊二烯类GDGTs,其中类异戊二烯类GDGTs以GDGTⅣ和GDGTⅤ为主,但其在四海龙湾沉积物中的含量相对较小. 研究显示,四海龙湾流域陆源是沉积物中可溶性有机质的主要来源,陆源有机质的大量流入改变了四海龙湾的营养水平;不同种类可溶性有机质表现出不同的来源特征,这主要是由于微生物对不同种类有机质降解速率的不同所致,并且导致降解所产生的二次有机质数量也不同.      

渤海及邻近海域表层沉积物中烃类物质的分布特征及其指示意义

本文对渤海及其邻近海域表层沉积物中有机碳（TOC）、正构烷烃（n-Alks）、石油烃（TPH）的含量、分布特征及其指示意义进行了初步的研究。结果表明,TOC含量介于0.12%~1.13%,平均值为0.44%,n-Alks含量介于0.9×10-6~5.1×10-6,平均值为2.25×10-6。C/N、δ13C结合正构烷烃的分析表明,有机质为海、陆混合来源。TPH含量介于15.2×10-6~65.3×10-6,平均值为30.1×10-6,渤海湾含量最高,受人类活动影响显著。n-Alks比值分析结果表明,正构烷烃的陆源贡献大于海洋源,沉积物普遍受到了石油污染。     

湖泊沉积物有机质的连续提取与荧光光谱特征分析

采用化学连续提取与三维荧光光谱相结合的方法研究了蠡湖沉积物中可提取有机质的组成、结构和空间分布特征,并探讨了可提取态有机质组分与可交换态氮和弱吸附态磷之间的相关关系.结果表明,蠡湖沉积物中有机质含量为5.59~22.11 g·kg~(-1)(以C计),均值为12.28g·kg~(-1),其中水可提取态有机质(WSOM)、富里酸(FA)、胡敏酸(HA)和胡敏素(HM)的比例分别为5.14%、11.81%、9.63%和73.42%,空间上呈现由西向东逐渐递增,湖岸大于湖心的分布趋势.WSOM鉴别出3个荧光组分,以类氨基酸荧光峰(W-C1)占优势,占总荧光强度的比例为42.49%;FA鉴别出2个荧光组分,以富里酸荧光峰(F-C2)为主,比例为67.63%;HA的3个荧光峰中,以类胡敏酸荧光峰(H-C1和H-C3)为主,两者之和的比例为71.55%.多元回归统计表明,可提取有机质组分与游离态氮和易解析态磷含量之间均显著正相关,且与氮的相关性系数大于与磷,反映了可提取有机质与可交换态氮的关系更为密切,可用于指示沉积物生物可利用性氮磷的污染状况.     

Phenanthrene sorption to environmental black carbon in sediments from the Song-Liao watershed (China)

Black carbon (BC) in ten contaminated sediments from the Song-Liao watershed, NE China, was isolated upon treatments using a combustion method at 375°C, and the isolates’ sorption isotherms for phenanthrene (Phen) were determined. All sorption isotherms were nonlinear and fitted well by the Freundlich model. A negative relation was found between Freundlich sorption nonlinearity parameter (n values) and BC/total organic carbon (TOC) content of the original sediments (r ² = 0.687, p<0.01), indicating the dominance of BC in Phen sorption nonlinearity. The BC isolates from this industrialized region had n values of 0.342 to 0.505 and logK _FOC values of 6.02 to 6.42 (μg·kg⁻¹·OC⁻¹)/(μg·L⁻¹) ⁿ for Phen. At a given C _e, the BC had higher K _oc value than the original sediments, revealing a higher sorption capacity for BC. BC was responsible for 50.0% to 87.3% of the total sorption at C _e= 0.05 S _w, clearly indicating the dominance of BC particles in overall sorption of Phen by sediments.     

黄河口附近海域沉积物中碳氮元素地球化学特征及有机质来源研究

本文调查分析了黄河口附近海域沉积物中碳氮元素地球化学特征及有机质来源研究。发现黄河口附近海域沉积物TOC、TN含量、C/N、δ13C以及δ15N分别为（0.40±0.19）%、（0.049±0.018）%、7.92±1.48、（-23.94±0.69）‰、（7.06±0.72）‰。其中TOC随着输送距离增加显著下降（P < 0.05）,δ13C沿着输送距离增加极显著上升（P < 0.01）。黄河口附近海域沉积物有机质来源可分为陆源、河口源、海源3种来源。其含量分别为（44.6±6.5）%、（6.5±5.5）%、（48.9±6.1）%。陆源有机质含量随着输送距离增加显著下降,海源有机质含量随着输送距离增加显著上升（P < 0.05）。研究区域陆源有机碳埋藏速率为171~214 t/（km2·a）,约20%左右黄河输送陆源有机碳埋藏在黄河口附近海域。黄河输送不仅影响了河口及周边海域有机质来源组成,还促进了陆源有机质在河口区域的埋藏。     

菲在渤海湾潮滩不同粒径沉积物上的吸附行为

采用批量试验的方法,研究了菲(PHE)在渤海湾潮间带不同粒径沉积物上的吸附行为,探讨了吸附等温式参数与有机质含最和性质之间的相关关系.结果表明:(1)不同粒径沉积物中总有机碳(TOC)含量(0.86～10.67 mg/g)表现为:粘粒＞砂粒＞粉砂粒;岐口不同粒径沉积物中碳黑(BC)含量(0.25～1.46mg/g)与T...     

污泥生物炭硼掺杂改性及其对水中1,2-二氯乙烷吸附行为和机制

以市政污泥为前驱体，采用硼酸掺杂改性共热解法，制备了污泥生物炭(BC600)和B掺杂污泥生物炭(BBC600),采用SEM、BET、FTIR、Zeta电位和静态接触角等手段对材料进行了结构表征，研究了BC600和BBC600对水中1,2-二氯乙烷(1,2-DCA)的吸附行为、机制和影响因素.结构表征结果表明，B掺杂改性后，生物炭中B元素含量、比表面积和孔容分别提高了76%、48%和30%;B掺杂改性对生物炭表面电荷及亲疏水性影响不大，BC600和BBC600表面均带有负电荷，接触角均<90°,两者均具有较好的亲水性.吸附实验结果表明，BBC600对1,2-DCA的吸附性能优于BC600,缘于BBC600更大的比表面积和强度更高的含氧官能团；准一级动力学方程可以较好描述BC600吸附1,2-DCA过程，准二级动力学方程能较好拟合BBC600吸附1,2-DCA过程，颗粒内扩散不是影响吸附速率的唯一限速步骤；碱性条件下生物炭材料更加分散和稳定，且其含氧官能团去质子化，供电子能力增强，有利于对1,2-DCA的吸附；腐殖酸(HA)对BC600吸附1,2-DCA呈现低浓度促进，高浓度抑制的作...     

长江流域沉积物中黑碳分布及其与多环芳烃的相关性研究

本文采用CTO-375法测定了长江流域主流及直流20个表层沉积物中黑碳的含量,探讨了沉积物中黑碳与粒度、总有机碳以及多环芳烃之间的关系。结果表明,长江流域沉积物中黑碳的含量范围在0.22~1.89mg/g之间,与粘土、粉砂及砂含量之间的相关性并不明显,说明粒度组成并不是控制BC分布的主要因素。BC与TOC之间的显著正相关性,表明BC与TOC有相似的来源,如人类活动、土壤流失。沉积物中BC与PAHs有较好的相关性,表明二者之间有相似的来源,同时也表明PAHs在研究区域沉积物中吸附主要由BC控制,这为研究多环芳烃在长江流域的环境归趋与影响因素等提供了新的信息。     

Characterisation of black carbon-rich samples by <Superscript>13</Superscript>C solid-state nuclear magnetic resonance

There are difficulties in quantifying and characterising the organic matter (OM) in soils that contain significant amounts of partially oxidised char or charcoal materials. The anthropogenic black carbon (BC), such as that found in the Terra Preta de índio soils of the Amazon region, is a good example of the OM that is difficult to analyse in such soils. ¹³C direct polarisation/magic angle spinning (DP/MAS) at high MAS frequency, ¹H-¹³C cross polarisation (CP)/MAS with total suppression of spinning sidebands (TOSS), and chemical shift anisotropy (CSA) filter nuclear magnetic resonance techniques have been applied successfully for quantifying the different components of OM. However, because pyrogenic materials present strong local magnetic susceptibility heterogeneities, the use of CSA-filter and TOSS make the pulse sequences very sensitive to imperfections in the π pulses. In this study, the DP/MAS pulse sequence was replaced by a CP with a radio frequency ramp—variable amplitude CP (VACP)—VACP/MAS pulse sequence, and composite π pulses were used in the CSA-filter and TOSS pulse sequences. In that way, the component functionalities in a humic acid from a BC soil were successfully determined. The spectrometer time needed was greatly decreased by employing this VACP/MAS technique. This development provides an accurate method for characterising BC-rich samples from different origins.     

热液成矿流体中的有机物质

热液流体中的主要有机质包括腐殖物质（t＜50℃）、有机羧酸（t＝80～140℃）、原油（120～180℃）和水溶性甲烷气（180～300℃）。腐殖物质在初始矿源层形成中起重要作用，在腐殖酸缩合成干酪根过程中通过去氧而导致还原的成岩环境，从而有效地防止金属元素在初始矿源石化过程中的分散。有机羧酸是干酪很早期演化的必然产物，富含有机羧酸的油田卤水可以成为MVT铅锌矿的成矿流体。在一定成熟度范围内原油可能成为汞金热液流体的重要有机组分。水溶性甲烷气是铜、铀、金等中低温热液流体的重要有机组分。有机质演化的阶段性决定了相应热液流体中有机质的类型；此外沉积建造的类型、金属元素在油／卤之间分配系数差异和构造条件差异导致了金属矿化分异。     

Carbonaceous particles in the atmosphere and precipitation of the Nam Co region, central Tibet

A continuous air and precipitation sampling for carbonaceous particles was conducted in a field observatory beside Nam Co, Central Tibetan Plateau during July of 2006 through January of 2007. Organic carbon (OC) was the dominant composition of the carbonaceous particles both in the atmosphere (1660 ng/m³) and precipitation (476 ng/g) in this area, while the average elemental carbon (BC) concentrations in the atmosphere and precipitation were only 82 ng/m³ and 8 ng/g, respectively. Very high OC/BC ratio suggested local secondary organic carbon could be a dominant contribution to OC over the Nam Co region, while BC could be mainly originated from Southern Asia, as indicated by trajectory analysis and aerosol optical depth. Comparison between the BC concentrations measured in Lhasa, those at “Nepal Climate Observatory at Pyramid (NCO-P)” site on the southern slope of the Himalayas, and Nam Co suggested BC in the Nam Co region reflected a background with weak anthropogenic disturbances and the emissions from Lhasa might have little impact on the atmospheric environment here, while the pollutants from the Indo-Gangetic Basin of Southern Asia could be transported to the Nam Co region by both the summer monsoon and the westerly.     

长江河口水库沉积物磷形态、吸附和释放特性

为了对长江河口青草沙水库沉积物磷形态分布、磷吸附特性和磷释放特性进行分析,2011年4月~2012年1月对沉积物进行实地调查分析.磷形态分析结果表明沉积物总磷含量范围为535.07~910.9 mg·kg-1,以无机磷为主,有机磷含量相对较低.无机磷主要以钙结合态的磷存在,钙结合态磷占总磷的75.57%.磷吸附特性结果表明沉积物磷的等温吸附特征符合修正的Langmuir模型,沉积物磷的最大吸附量为9.78~39.84 mg·kg-1,沉积物-水界面平衡浓度EPC0(equilibrium phosphorus concentration)范围为0.024~0.12 mg·L-1,均高于上覆水体中相应的磷含量,因此,沉积物有向上覆水体释放磷的趋势.磷的释放特性结果表明沉积物最大释放量为11.03 mg·kg-1,在6 h左右达到最大值.沉积物磷释放量来自沉积物的铁/锰结合态的磷、钙结合态磷和有机磷,其中,铁/锰结合态磷和沉积物释放量呈相关性(P0.01).总体上,青草沙水库沉积物呈现释放状态,影响水库水体磷含量.     

北运河沙河水库沉积物营养盐分布特征及其溯源分析

通过采集沙河水库表层(0～20 cm)沉积物样品,分析了沉积物中氮、磷、有机质的分布特征,并结合排污口附近和水库典型区域沉积物中有机质(Organic Matter, OM)和溶解性有机物(Dissolved Organic Matter, DOM)的荧光光谱特征、分子量分布特征(Molecular Weight Distribution, MWD),研究了点源污染对沙河水库沉积物营养盐分布的潜在影响.结果表明,表层沉积物间隙水中氨氮(NH~+_4-N)、磷酸盐(PO■-P)平均浓度及沉积物中总氮(TN)、总磷(TP)的平均含量依次为(52.13±40.32)、(1.75±1.88) mg·L~(-1)与(2853.81±1501.93)、(1496.00±454.06) mg·kg~(-1).库区沉积物中TN、TP含量由库上游((1898.00±1047.54)、(1264.00±104.61) mg·kg~(-1))经库心区((2996.67±1405.13)、(1340.00±332.47) mg·kg~(-1))至库下游((4500.00±920.00)、(1750.00±10.00) mg·kg~(-1))依次增高.沉积物C/N比分析表明,点源污染区与库区沉积物中有机质来源于陆源与自生生物源的混合源.而三维荧光光谱和分子量分布的分析表明,点源污染区与库区沉积物中DOM的组成特性具有一致性,且主要来源于自生生物源.Pearson相关性分析表明,沉积物中营养盐(TN、TP)与有机质具有显著相关关系(p0.01).这些结果清楚地表明,点源污染区沉积物中高的营养盐、有机质含量是库区污染物累积的潜在重要来源.     

东海内陆架表层沉积物中黑碳的分布及来源

对东海内陆架表层沉积物中黑碳含量进行了分析,探讨了黑碳在东海内陆架不同区域的分布特征、影响因素及来源,并与长江口徐六径悬浮颗粒物中的黑碳进行了对比。结果显示,长江口徐六径悬浮颗粒物中黑碳的含量平均为1.68±0.51mg/g,且枯季浓度要高于洪季,这反映了燃烧活动的季节变化。黑碳在东海内陆架表层沉积物的分布具有明显的区域特征,近岸区域沉积物中的黑碳含量接近,且与粒径成负相关,并低于徐六径悬浮颗粒物中黑碳的含量,说明来自长江输入的黑碳主要以烟炱为主,并且部分粒径极小的颗粒未完全沉积下来;在123°E以东区域的表层沉积物中的黑碳含量分布较广,并与平均粒径成正相关,说明该区域主要以石墨态黑碳为主。另外,东海内陆架表层沉积物BC/TOC在0.11～0.55之间,因此在研究该区域碳循环过程中,不可忽视BC在不同区域的分布特征及类型差别。