Occurrence and bioaccumulation of polybrominated diphenyl ethers in sediments and paddy ecosystems of Liaohe River Basin, northeast China

Concentrations of 16 polybrominated diphenyl ether(PBDE) congeners were measured in river sediments, paddy soils and three species of paddy-field organisms(crab, loach and carp) collected from the Liaohe River Basin, northeastern China. The total contents of PBDEs(∑_(16)PBDEs) in sediments and paddy soils were in the ranges of 273.4–3246.3 pg/g dry weight(dw), and 192.1–1783.8 pg/g dw, respectively. BDE 209 was the dominant congener both in sediments and paddy soils. The concentrations of ∑_(16)PBDEs in sediments were significantly higher than those in the adjacent paddy soils, indicating a potential transport of PBDEs from river to paddy ecosystems via river water irrigation. The biota–soil accumulation factor(BSAF) was calculated as the ratio between the lipid-normalized concentration in paddyfield organisms and the total organic carbon-normalized concentration in paddy soil. The average BSAF values of ∑15PBDEs followed the sequence of crab(3.6) loach(3.3) carp(2.1). BDE 154 had the highest BSAF value, and a parabolic trend between BSAF values of individual PBDE congeners and their log KOWvalues was observed. In view of the fact that crab had the larger BSAF value and higher lipid content, the ecological risk and health risk for crab cultivation in paddy fields should be of particular concern.     

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.     

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。     

基于碳氮同位素的澜沧江水库TOC来源差异性分析

水库建设所导致的生态问题正引发前所未有的深度思考,梯级水库在时间和空间尺度上的影响效应更加值得探究.为揭示新老水库有机碳分布特征及其沉积物TOC来源的差异,于2017年11月采集了苗尾、功果桥和大朝山这3个不同时期建设的水库的水样和沉积物样柱.测定了水体的温度(T)、溶解氧(DO)、总有机碳含量(TOC)、沉积物总有机碳(TOC)、氧化还原电位(ORP)、总氮(TN)和总磷(TP)等指标,并利用15N和13C同位素,结合Iso Source软件,解析沉积物中TOC来源及其来源物质对相应水库沉积物中TOC的贡献量,从而探究其内在的碳循环机制和梯级水库演进模式.结果表明,苗尾、功果桥和大朝山水库水体有机碳质量浓度平均值分别为0. 95、1. 97和4. 64 mg·L-1.对应水库沉积物中有机碳含量变化范围分别为4. 41～81. 63、18. 30～28. 42和9. 16～14. 46 g·kg-1.水库的梯级建设,使得新老水库的沉积物来源,周围补给等出现差异,使得新老水库TOC出现巨大差异.对于水体TOC,水体热力学状态和溶解氧的差异从而间接影响了水体中TOC的分布趋势.沉积物中主要考虑生源要素的影响,即沉积环境对有机质的保存能力是造成DCS、MV和GGQ沉积物垂向分布有差异的主要原因.而梯级水库的演进模式中,MV时空尺度上处于第一级段,是以累积上游来流TOC为主; GGQ处于第二级段,是以主要消耗分解上游来流TOC; DCS处于第三级段,是以主要积累水库周边TOC来源.     

沱江沉积物中有机氯农药分布特征及其与藻类有机质的关系和生态风险评估

使用气相色谱-质谱联用仪分析了长江支流沱江流域48个表层沉积物中有机氯农药（organochlorine pesticides,OCPs）的残留水平,探讨了其分布和组成特征及其与总有机碳（total organic carbon,TOC）、藻类有机质之间的关系,以及评估其生态风险.结果表明沱江流域表层沉积物中OCPs的总含量为3.17~127 ng·g^-1,其中六六六（hexachlorocyclohexane,HCHs）类农药的含量为2.83~86.0 ng·g^-1,滴滴涕（dichlorodiphenyltrichloroethane,DDTs）类农药的含量为0.340~40.9 ng·g^-1.OCPs空间分布特点为：上游 < 中游 < 下游 < 支流.HCHs和DDTs的组成成分分析表明,沱江流域存在林丹输入的现象,主要来自于历史残留,这与绝大多数流域的DDTs的输入状况相似.OCPs含量与TOC、藻类有机质含量之间存在着极显著的正相关性关系,表明藻类有机质在TOC对沉积物中的OCPs分配中起更为重要的作用.生态风险评估表明,沱江流域表层沉积物的有机氯农药存在较大的生态风险,可能对河流的底栖生物及生态环境造成明显的影响.     

贵州乌江渡水库沉积速率及碳氮埋藏通量估算

我国西南地区峡谷型梯级水库沉积物的碳汇效应对全球碳循环有着重要意义。为了探明该区域水库的碳汇强度,本研究选择乌江流域的乌江渡水库作为研究对象,于2015年5月对水库沉积物进行采样,并利用210Pbex核素计年技术,结合沉积物碳氮分析,估算乌江渡水库的碳埋藏量。结果表明:乌江渡水库沉积物平均沉积速率为0.155g/(cm~2·a),TOC沉降通量为70.85g/(m~2·a),堆积通量为29.14g/(m~2·a);TN沉降通量为8.22g/(m~2·a),堆积通量为2.79g/(m~2·a)。乌江渡水库沉积物年均TOC总埋藏通量为1.39×10~9g/a,其中82%来自水库内部光合作用形成的有机质。因此,依据保守的估算,乌江渡水库沉积物的净碳汇通量为23.9g/(m~2·a),保存的净碳汇量为1.1×10~9g/a。研究结果表明水库沉积物是一个重要的碳汇。     

Export of dissolved carbonaceous and nitrogenous substances in rivers of the “Water Tower of Asia”

Rivers are critical links in the carbon and nitrogen cycle in aquatic,terrestrial,and atmospheric environments.Here riverine carbon and nitrogen exports in nine large rivers on the Tibetan Plateau—the"Water Tower of Asia"—were investigated in the monsoon season from 2013 to 2015.Compared with the world average,concentrations of dissolved inorganic carbon(DIC,30.7 mg/L)were high in river basins of the plateau due to extensive topographic relief and intensive water erosion.Low concentrations of dissolved organic carbon(DOC,1.16 mg/L)were likely due to the low temperature and unproductive land vegetation environments.Average concentrations of riverine DIN(0.32 mg/L)and DON(0.35 mg/L)on the Tibetan Plateau were close to the world average.However,despite its predominantly pristine environment,discharge from agricultural activities and urban areas of the plateau has raised riverine N export.In addition,DOC/DON ratio(C/N,~6.5)in rivers of the Tibetan Plateau was much lower than the global average,indicating that dissolved organic carbon in the rivers of this region might be more bioavailable.Therefore,along with global warming and anthropogenic activities,increasing export of bioavailable riverine carbon and nitrogen from rivers of the Tibetan Plateau can be expected in the future,which will possibly influence the regional carbon and nitrogen cycle.     

Source apportionment of perfluoroalkyl substances in surface sediments from lakes in Jiangsu Province, China: Comparison of three receptor models

Receptor models have been proved as useful tools to identify source categories and quantitatively calculate the contributions of extracted sources.In this study,sixty surface sediment samples were collected from fourteen lakes in Jiangsu Province,China.The total concentrations of C_4–C_(14)-perfluoroalkyl carboxylic acids and perfluorooctane sulfonic acid(∑_(12)PFASs) in sediments ranged from 0.264 to 4.44 ng/g dw(dry weight),with an average of 1.76 ng/g dw.Three commonly-applied receptor models,namely principal component analysis-multiple linear regression(PCA-MLR),positive matrix factorization(PMF) and Unmix models,were employed to apportion PFAS sources in sediments.Overall,these three models all could well track the ∑_(12) PFASs concentrations as well as the concentrations explained in sediments.These three models identified consistently four PFAS sources:the textile treatment sources,the fluoropolymer processing aid/fluororesin coating sources,the textile treatment/metal plating sources and the precious metal sources,contributing 28.1%,37.0%,29.7% and 5.3% by PCA-MLR model,30.60%,39.3%,22.4% and 7.7% by PMF model,and 20.6%,52.4%,20.2% and 6.8% by Unmix model to the ∑_(12) PFASs,respectively.Comparative statistics of multiple analytical methods could minimize individual-method weaknesses and provide convergent results to enhance the persuasiveness of the conclusions.The findings could give us a better knowledge of PFAS sources in aquatic environments.     

Quantification, morphology and source of humic acid, kerogen and black carbon in offshore marine sediments from Xiamen Gulf, China

Three types of macromolecular organic matters (MOMs), i.e. humic acid (HA), kerogen+black carbon (KB), and black carbon (BC) were extracted from marine sediments of Xiamen Gulf, southeast of China. The chemical composition, morphological property and source of the three extractions were characterized by elemental analyzer/isotope ratio mass spectrometry (EA/IRMS) and scanning electron microscope (SEM). The results showed that KB was the predominant fraction in MOMs, which accounted for 61.79%-89.15% of the total organic content (TOC), while HA consisted less than 5%. The relative high contents of kerogen and BC, and low contents of HA in the samples indicated that anthropogenic input might be the major source of organic matter in marine sediments near the industrial regions. The characterization of SEM, not only revealed morphological properties of the three fractions, but also allowed a better understanding of the source of MOMs. The δ 13 C values of the three fractions suggested that materials from terrestrial C 3 plants were predominant. Furthermore, the anthropogenic activities, such as the discharge of sewage, coal and biomass combustion from industry nearby and agricultural practices within drainage basin of the Jiulong River, were remarkably contributed to the variations in δ 13 C values of MOMs in the offshore marine sediments.     

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。     

滇池流域宝象河水库沉积物中多环芳烃的垂直分布特征及来源解析

采用GC-MS检测了滇池宝象河水库沉积物中16种美国环保署(US EPA)优先控制的多环芳烃(PAHs)的含量,并对其垂直分布特征及来源进行分析,以此了解宝象河水库近年来PAHs的变化.结果表明,水库沉积物中16种PAHs均有检出,其含量范围为162.26~762.24ng·g~(-1),平均值为423.30 ng·g~(-1).自底层50 cm至表层,沉积物中PAHs含量呈上升趋势.从多环芳烃环数来看,沉积物中的PAHs以2~3环为主,其含量为128.34~518.81 ng·g~(-1),平均值为279.88 ng·g~(-1),占PAHs总量的42.2%~84.1%,平均值为67.6%.FLA/(FLA+PYR)、Ba A/(Ba A+CHR)和Icd P/(Icd P+Bghi P)3组比值及PAHs各组分的分析结果表明,燃烧过程是沉积物中PAHs的主要来源,主要为煤炭、生物质的燃烧.PAHs含量与总有机碳(TOC)之间有显著正相关关系,TOC影响宝象河水库沉积物中PAHs的分布.     

兰州市表土黑碳分布特征与来源初探

为探究兰州市城市表土中黑碳(Black Carbon,简称BC)的分布特征及其来源,在兰州市主城区(城关区、七里河区、安宁区和西固区)道路沿线绿化带采集了95个表层(0~5 cm)土壤样品,并使用重铬酸钾氧化法测定其黑碳含量.结果表明:兰州市表土黑碳含量在1.02~74.27g·kg~(-1)之间,黑碳含量空间分布表现为城关区七里河区西固区安宁区,高值区域主要集中在工厂周围和交通密集区.进一步分析发现,黑碳与有机碳(Organic Carbon,简称OC)比值(BC/OC)的平均值为0.34;黑碳与有机碳含量及砷(As)、铜(Cu)、铅(Pb)、锌(Zn)等重金属元素含量显著相关.研究表明,兰州市表土中黑碳主要来源于本地交通排放和局部工业活动过程中化石燃料燃烧和工业粉尘沉积.     

抚仙湖沉积物有机碳埋藏特征及来源解析

为探讨近百年来抚仙湖不同湖区沉积物中有机碳埋藏及其来源变化特征,以抚仙湖南北部沉积柱为研究对象,分析有机碳埋藏速率时空变化特征,利用正构烷烃及其分布特征对埋藏在沉积物中的有机碳来源进行解析.结果显示,抚仙湖沉积物中有机碳含量为1.79~29.39mg/g,有机碳埋藏速率为3.07~27.71g/（m²·a）,两者均随时间的增加呈现整体上升的趋势,1980年以来增长速度明显加快;沉积物中有机碳含量北部（8.70mg/g）小于南部（12.59mg/g）,但有机碳埋藏速率北部（13.54g/（m²·a））大于南部（8.29g/（m²·a））,这与抚仙湖南北部有机质来源类型及人类活动的加剧造成的流域环境变化有关;抚仙湖沉积物中正构烷烃碳数范围为C₁₂~C₃₃,整体以高碳数组分为主,奇偶优势明显,表明沉积物中有机质主要来源于高等植物,Paq指示水生植物中以沉水植物占主导优势,2C₃₁/（C₂₇+C₂₉）与ACL_27~33指示陆生高等植物来源中,草本植物与木本植物的贡献相当,水生植物在北部湖区贡献大于南部,陆生高等植物在南部湖区的贡献大于北部.     

温带典型草原土壤总有机碳及溶解性有机碳对模拟氮沉降的响应

2008年5月～2011年10月,以内蒙古温带典型草原为研究对象,利用小区模拟控制试验,设置对照[0 g·(m2·a)-1]、低氮[5 g·(m2·a)-1]、中氮[10 g·(m2·a)-1]、高氮[20 g·(m2·a)-1]这4个净氮输入量处理,模拟研究了大气氮沉降水平变化对土壤总有机碳(TOC)以及溶解性有机碳(DOC)含量、年际变化及其垂直分布格局的影响,并分析了两者之间的关系.结果表明,除个别年份外,土壤TOC与DOC含量均随土壤深度增加而递减,4 a的连续施氮并未改变土壤TOC与DOC的垂直分布规律,但施氮降低了土壤TOC的垂直变异,增加了土壤DOC的垂直变异;施氮4 a对于草地表层0～20 cm土壤TOC与DOC含量的变化并未表现出显著影响(P>0.05).不同氮输入水平处理0～20 cm土层有机碳密度在3.9～5.6 kg·m-2之间变动,试验前两年不同氮处理0～20 cm土壤有机碳密度均低于对照或与对照接近,试验后两年,施氮对土壤总有机碳密度逐渐呈现出一定的促进作用,但与对照的差异仍不显著(P>0.05);不同处理0～20 cm土层DOC/TOC约为0.32%～1.09%,氮输入增加普遍降低了DOC在整个TOC中所占的比例;草地土壤TOC与DOC的变化呈显著正相关(P<0.01).不同处理草地土壤DOC随时间的变异均远大于TOC,与TOC相比,草地土壤DOC的变化更为迅速,是研究草地土壤碳库对氮沉降变化响应的重要敏感性指标.     

Entry and toxicity of organic pesticides and copper in vineyard streams: Erosion rills jeopardise the efficiency of riparian buffer strips

The present study was performed to characterise in-stream pesticide exposure within the Palatinate vineyard region in south-west Germany, evaluate the influence of buffer strip widths and identify mitigation measures for the relevant entry pathways. In-stream water and sediment samples that were taken at nine sampling sites of different buffer widths following intense rainfall, and edge-of-field runoff that were sampled in erosion rills were analysed regarding 28 active ingredients of pesticides including copper. In-stream samples contained a mix of 8 ± 4 pesticide compounds, resulting in total pesticide concentrations of 1.4-8.9 μg l⁻¹ for water and 16-670 μg kg⁻¹ dw for sediment. Following an exceptional rainfall event with a previous 34-day drought period, pesticide concentrations reached 7.0-83.4 μg l⁻¹. Fungicides were the most important pesticides found and were significantly correlated with the pesticide application frequency and rate. The calculated toxicity values per sample (TU_max) indicated that both organic pesticides and copper concentrations likely cause ecotoxicological effects in the field. The buffer strip width was of little importance for pesticide in-stream concentrations because pesticide entry occurred mainly via the field path network and erosion rills. Pesticide in-stream concentrations were significantly and positively correlated with the concentrations detected in erosion rills (R² = 0.56). As possible risk mitigation measures, we suggest the implementation of grassed field paths and vegetated ditches or wetlands.     

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.     

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.     

珠三角表层沉积物的有机碳及其与卤系阻燃剂的关系

测定了珠江三角洲130个表层沉积物中总有机碳(TOC)和10类卤系阻燃剂(HFRs)的含量,并探讨了TOC与HFRs之间的关系.结果表明:珠三角表层沉积物TOC范围为0.16％～5.76％,平均值为1.25％,呈现明显的空间变化.在工业化程度较高的东莞和广州,沉积物中HFRs与TOC有显著的相关性,而西江和珠江口沉积物中HFRs与TOC的相关性较差,可能与珠江三角洲水动力过程、电子垃圾拆解活动和HFRs不同的来源有关.     

Physico-chemical characterization and source tracking of black carbon at a suburban site in Beijing

Particles from ambient air and combustion sources including vehicle emission, coal combustion and biomass burning were collected and chemically pretreated with the purpose of obtaining isolated BC (black carbon) samples. TEM (transmission electron microscopy) results indicate that BC from combustion sources shows various patterns, and airborne BC appears spherical and about 50 nm in diameter with a homogeneous surface and turbostratic structure. The BET (Barrett–Emmett–Teller) results suggest that the surface areas of these BC particles fall in the range of 3–23 m²/g, with a total pore volume of 0.03–0.05 cm³/g and a mean pore diameter of 7–53 nm. The nitrogen adsorption–desorption isotherms are indicative of the accumulation mode and uniform pore size. O₂-TPO (temperature programmed oxidation) profiles suggest that the airborne BC oxidation could be classified as the oxidation of amorphous carbon, which falls in the range of 406–490°C with peaks at 418, 423 and 475°C, respectively. Generally, the BC characteristics and source analysis suggest that airborne BC most likely comes from diesel vehicle emission at this site.     

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。