Parameters affecting partitioning of 6 PCB congeners in natural sediments

Polychlorinated biphenyls (PCBs) released by bottom sediments were determined by experiments in which the sediments were artificially resuspended using sediment contaminated with PCBs in a particle entrainment simulator (PES). Sediment cores, spikedwith PCBs, were collected from the Housatonic River in Connecticut and run in the PES at simulated shear stresses from 0 to 0.6 N m^-2. Experimental results from these simulations have shown that mean concentration of PCBs in thesolid phase for sites with high volatile organic carbon (VOC) were significantly greater than samples with low VOC; the reversewas true for the water phase. In addition, on a mass load basis,the amount of PCBs found in sediment increased when shear stresses were increased from 0 to 0.6 N m^-2, beyond which shear stress did not affect mass loads in the watercolumn. Partition coefficients (K _p) were determined from PESsediment and water data for the following congeners: PCB 28, PCB 52, PCB 101, PCB 138, PCB 153, PCB 180. K _p was determined to be inversely proportional to total suspended solids (TSS), butdirectly proportional to chlorine content of the congener. Because of the strong influence of TSS and VOC concentrations onK _p values, agitation of samples using a PES better simulatedreal environmental conditions when compared to jar studies where no agitation was employed. Therefore, a device like the PES is more appropriate in obtaining K _p that would be found underreal stream flow conditions when compared to the traditionalway of measuring K _p using the jar study technique.     

沉积物中双酚类化合物的测定

通过前处理与检测条件的全面优化,建立了一种同时实现环境沉积物中9种痕量双酚类化合物的加速溶剂萃取(ASE)-固相萃取(SPE)-高效液相色谱/三重四极杆质谱(HPLC/MSMS)检测方法。沉积物样品先采用甲醇作为溶剂,在70℃条件下进行加速溶剂萃取,萃取液约100 mL,加入甲酸调节pH约为2.5,再经Oasis型HLB固相萃取柱富集与净化,该过程可将沉积物的基质效应控制在85%～95%之间。9种目标化合物在0.05～25.0μg/L(以双酚AF计)范围内呈良好的线性关系,相关系数r>0.999,检出限为0.01～0.25μg/kg,加标回收率为62%～122%,相对标准偏差为0.9%～12.7%。     

Simulation of arsenic partitioning in tributaries to drinking water resevoirs

Arsenic released by bottom sediments was determined by experiments in which the sediments were artificially re-suspended using a particle entrainment simulator (PES) to simulate river conditions. Sediment cores were collected from various tributaries to drinking water reservoirs in Connecticut spiked with arsenic, and run in the PES at simulated bed-flow shear stresses from 0.0 to 0.6 N/m². Under equilibrium conditions, the dissolved fraction of arsenic was found to range from 8.3 to 22.1 μg/l, which in most cases exceeded EPA Maximum Contaminant Level (MCL) of 10 μg/l. Experimental results from these simulations have shown that bed-flow shear stress causes an increased concentration of dissolved arsenic, most notably at shear stresses of 0.4, 0.5, and 0.6 N/m². For the solid phase under equilibrium, the concentrations of arsenic ranged between 71 and 275 mg/kg. The average concentration of arsenic on the solid phase as well as partitioning coefficient values (K _p) were highest at initial shear stress. This was attributed to the higher fraction of colloidal material and finer organic particles in the suspended solid mixture. Particles of such nature proved to have higher affinity to arsenic. K _p values were determined from PES data and were found to range from 4,687 to 24,090 l/kg. However, on a mass load basis, the amount of arsenic found in suspended sediment increased with the increase of shear stress. Similarly, the amount of arsenic in the solid phase increased significantly for sites with high Volatile Organic Carbon (VOC) content. Because of the influence of Total Suspended Solids (TSS) and VOC concentrations on K _p, the use of the PES is more appropriate in obtaining K _p values that would be found under real stream conditions when compared to the traditional way of measuring K _p using a jar study technique.     

PT-GC-CVAFS法测定沉积物中甲基汞的影响因素及应用

研究了碱提取吹扫捕集气相色谱冷原子荧光光谱法测定沉积物中甲基汞的影响因素,包括载气流速、柱温、衍生化试剂、样品称取量、前处理时碱性提取液加入量和反应瓶中提取液加入量的影响,分析了提取液加入量对Tenax管的影响、提取液保存的影响因素、沉积物样品保存的影响因素以及样品中Hg²⁺的干扰影响。根据影响情况确定最佳测定条件,应用于广西龙江河流域上9个代表性监测断面的底泥样品中甲基汞的测定,采用污染指数法对该流域甲基汞的污染现状进行评价。结果表明,最佳载气流速范围为22～27 mL/min,最佳柱温为46℃。衍生化试剂选择四乙基硼化钠和四丙基硼化钠均能达到较好的回收率。样品称取量选择0.50 g时回收率好。前处理时碱性提取液的加入量对甲基汞的提取效率没有显著影响。为保证水相衍生反应体系最终pH在5左右,乙酸-乙酸钠缓冲溶液的加入量随提取液加入量的增加而增加。当缓冲溶液为300μL时,提取液小于150μL不会影响Tenax管性能。避光与否对提取液的保存和样品的保存影响都不大,提取液保存3 d后、样品保存15 d后,甲基汞回收率将低于80%。衍生化前定量体积提取液中Hg     

Distribution of Chlorinated Organic Pollutants in Harbor Sediments of Livorno (Italy): A Multivariate Approach to Evaluate Dredging Sediments

Dredging is a very important procedure for harbor management. InItaly the guidelines for the offshore dumping of dredged materials are issued by the Ministry of Environment. Theydescribed a few steps of dredging activities, such as thesampling strategy, but do not deal with limits or guide-valuesfor the chemical, physical and biological composition of theresulting sediments. The quality of dredged materials is mainlydependent on the presence of inorganic and organic pollutants.In particular, polychlorinated biphenyls (PCBs) and organo-chlorinated pesticides are seen as a high priority inmarine environment by international organizations because oftheir persistence, toxicity and bioaccumulation capacity.In this article the presence of some PCBs and organo-chlorinatedpesticides in sediment samples collected from the harbor ofLivorno (Northern Tyrrhenian Sea) was investigated. Theconcentration of HCHs, Aldrin, Chlordanes, DDEs, DDTs, and PCBsin 12 representative sites ranged between <1 g kg^–1and 95, 19, 32, 35, 107, and 111 g kg^–1, respectively.The application of univariate and multivariate statisticaltechniques, such as linear regression analysis and principalcomponent analysis, to the experimental data showed a differentdistribution of PCBs in the two sediment layers. On thecontrary, the vertical distribution of the other investigatedpollutants was more homogeneous and affected by randomvariability. The multivariate approach was an important tool to establish more rational criteria for the management of dredged materials.     

往复流河道沉积物重金属的污染特征和风险评估

在往复流现象明显的蕰藻浜中下游河道选择16个采样点,分析研究沉积物性状以及Cr、Cu、Zn、Cd、Ni、Pb、Mn的含量以及分布情况。结果表明:蕰藻浜总体污染程度为中等,其中陈行桥、江杨北路桥以及淞港码头污染较严重。Cr、Cd、Pb、Ni、Cu、Zn和Mn的含量分别为24.0~357.0、0.06~0.69、20.0~85.4、18.2~132、14.2~136、84.6~685、472~1 086 mg/kg。通过分析发现,Pb、Ni、Cu、Zn和Cr总量都具有显著的相关性,很有可能来自同一外源污染,而中游河段的Mn主要来自于沉积物母质。河道两岸以往的工业与生活排污以及往复水流使得重金属污染物在沉积物中聚集是造成重金属污染的潜在原因。运用地累积指数法、潜在生态危害指数法、污染负荷指数3种风险评价法对沉积物重金属进行风险评估,总体来说,3种评价方法都表明Cu的污染程度较严重,Mn的污染较轻。其中地累积指数法结果显示,各重金属的污染顺序为CuZn≥CdPb≥CrNiMn,然而由于Cd本身生物毒性较高,对沉积物生态环境危害贡献率可达到60%;污染负荷指数评价结果发现蕰藻浜下游河段部分断面沉积物达到了极强污染程度,应当受到重视。     

北京夏季大气主要含氮无机化合物的变化规律与相互作用

利用SJAC-MOBIC/FIA在2006年8月16日—9月9日在线测量了北京城市大气细颗粒物中主要水溶性含氮离子组分(NO₃^-和 NH₄⁺),与重要含氮气态污染物(HNO₃、HNO₂和 NH₃),以追踪细颗粒物中含氮二次无机组分和含氮气态污染物的变化规律及其相互作用。观测期间,NO₃^- 和 NH₄⁺的平均浓度分别为13.08和11.93 μg/m³,它们与SO₄^2-浓度之和在细颗粒物(PM_2.5)中的平均比例为55%,明显高于其他季节;污染过程中,积聚模态颗粒物体积浓度及其与爱根核模态颗粒物体积浓度比值逐渐增加,说明二次转化是北京夏季细颗粒物的重要来源。白天HONO迅速光解产生OH自由基,而OH自由基是生成HNO₃的重要物种,因此HONO和HNO₃具有相反的日变化规律。在温度较高的白天,大气环境不利于NH₄NO₃的生成与存在;夜间低温高湿的条件下硝酸铵理论平衡系数Ke与气态氨和硝酸的乘积Km相当或低于后者,较有利于NH₄NO₃的生成。北京夏季大气具有足量气态NH₃以中和硫酸盐;但在NO₃^-与阳离子的电荷平衡中,金属阳离子也非常重要。     

重点流域水系沉积物中多环芳烃标准样品制备

环境标准样品是监测过程中重要的质量控制手段,中国受天然基体标准样品制备技术的制约,尚未拥有自己的沉积物中多环芳烃标准样品。为制备符合中国重点流域沉积物类型及多环芳烃浓度水平的沉积物标准样品,对中国6个重点流域的沉积物进行了采样,获得了制备多环芳烃标准样品的原料。分析常温及冷冻2种干燥方式对多环芳烃的影响,为制备大批量多环芳烃标准样品提供数据支持。对11个点位样品采用气相色谱质谱法测定16种优控多环芳烃化合物浓度,结果表明,样品均匀性良好,样品中多环芳烃检出率在99%以上,江河沉积物样品中多环芳烃浓度区间为664~2.91×103μg/kg,湖泊样品最高值达到1.25×105μg/kg,其主要污染源是化学燃料的燃烧。为中国制备水系沉积物中多环芳烃标准样品积累了技术基础。     

灌河口海域沉积物中PAHs的垂直分布及生态危害研究

2011年4月通过GC-MS检测和210Pb测年对灌河口海域沉积物(GHES)中的PAHs进行了分析,柱状沉积物中21种PAHs总浓度为21.0~209.0 ng/g,均值为88.1 ng/g,7种致癌PAHs浓度为7.0~90.0 ng/g,其中致癌剂苯并[a]芘浓度为ND~2.0 ng/g。PAHs浓度与沉积物中有机质含量呈低度正相关,与p H无明显相关性。源解析表明,近50年来GHES中的PAHs大部分来自煤和生物质燃烧。近50年来,总PAHs和16种优控PAHs浓度在波动中升高;近年来苊、苊烯、苯并[b]荧蒽、荧蒽、茚并[1,2,3-cd]芘的浓度增高,需查明来源。生态风险评价表明,GHES中以芴为主的负面生物毒性效应会偶尔发生。芴、苯并[b]荧蒽、苯并[k]荧蒽的浓度介于临界与偶然效应浓度值之间,应尽量减少对该海域沉积物的搅动,防止污染物再悬浮导致水体的二次污染。     

Trace Element Concentrations in Fish, Surficial Sediments and Water from Northern Part of the Persian Gulf

Concentrations of cadmium, lead, nickel and vanadium were determined in water, surficial sediments and the muscle of three demersal fish species (Epinephelus coioides, Psettodes erumei and Solea elongate) from 15 sampling sites in the northern part of Persian Gulf. Concentrations of the elements were determined using Inductively Coupled Plasma Mass Spectrometer. There were no significant differences among the sampling sites in Cd and Pb levels in the sediments. The highest concentrations of Ni and V in sediments were found near the southern coast of Qeshm Iland and Bandar Lengeh. Concentrations of Cd, Pb and Ni in the sediments were notably higher than global baseline values. Nearly in all cases the element concentrations in the sediments were considerably greater than RSA (ROPME Sea Area) and the ERL (Effects Range Low) guidelines. Significant differences among the sampling sites could be found for concentrations of all the four metals in water. The mean Ni, Pb and Cd levels in the water samples were relatively higher than those in some other regions of the Persian Gulf. Except few cases, the mean concentrations of the elements in muscle of the selected fish species were markedly below the international guidelines for human consumption.     

Environmental Assessment of Aromatic Hydrocarbons-Contaminated Sediments of the Mexican Salina Cruz Bay

Concentrations of total aromatic hydrocarbons and extractable organic matter in the water column and sediment were determined in samples collected in the course of the last 20 years from the Salina Cruz Harbor, México, to assess the degree of organic contamination. In sediments, organic compounds accumulate in shallow areas mostly associated with extractable organic matter and fine fractions. Calculated geocumulation index and enrichment factors suggest that contamination could be derived from anthropogenic activities attributed to harbor and ship scrapping activities, as well as transboundary source. Concentration of total aromatic hydrocarbons (as chrysene equivalents) ranged from 0.01 to 534 μg l⁻¹ in water, and from 0.10 to 2,160 μg g⁻¹ in sediments. Total aromatic concentration of 5 μg g⁻¹ is proposed as background concentration.     

Determination and Assessment of HCHs and DDTs Residues in Sediments from Lake Dongting, China

The contamination of organochlorine pesticides hexachlorocyclohexane (HCH) and Dichlorodiphenyltrichloroethane (DDT) and their eco-environmental assessment in surface sediments from Lake Dongting, the second-largest freshwater lake in China, were studied. Concentrations of ∑HCH (=α-HCH + β-HCH + γ-HCH +δ-HCH) were 0.21--9.59 ng/g dry weight and those of ∑ DDT = p,p'-DDD+p,p'-DDE+o,p'-DDT+p,p'-DDT) ranged from under detectable limit to 10.15 ng/g dry weight. The ratios of α-HCH to γ-HCH were above 7 at most sampling sites while no or a small amount of β-HCH were found at all sites, suggesting the degradation of HCH used in the history and possibly current use of HCH in the region. The low ratios (below 2.0 in most cases) of (p,p'-DDE+p,p'-DDD) to p,p'-DDT and high levels of individual isomers of DDT at some sites also suggested that there have still been fresh inputs of DDT into Lake Dongting. Through the comparison between concentrations of HCH and DDT residues in sediments of Lake Dongting and those from other places in China and also from the results of our eco-environmental assessment, it can be concluded that Lake Dongting is the water body with high contamination of both HCH and DDT in its sediments in comparison with other water bodies in China.     

液相色谱-串联质谱法测定水体、沉积物及土壤中全氟化合物

建立了水、沉积物及土壤中13种全氟化合物(PFCs)的富集、净化、浓缩的前处理方法及快速液相色谱三重四级杆串联质谱的分析方法。9种全氟羧酸、2种典型全氟磺酸、2种磺酰铵衍生前体物的响应因子与质量浓度的线性关系良好。添加回收实验表明,13种全氟化合物在水、土壤和沉积物中的回收率为52.3%~119.3%,变异系数为2.3%~19.4%,方法检出限分别为0.015~0.472 ng/L、0.012~0.875 ng/g、0.004~0.743 ng/g。该法成功应用于实际样品的测定,沉积物和土壤中分别检测到3种和10种全氟化合物。     

黄河甘宁蒙段表层沉积物中总磷3种提取方法的比较

通过微波消解法、标准测试方法(SMT)和碱熔法分别测定了水系沉积物成分分析标准物质GBW07307a(GSD-7a)中的总磷(TP)含量,并分别采用3种方法对采集于黄河流域甘宁蒙段表层沉积物样品进行TP含量和样品加标回收率的测定。结果表明:测定标准物质的相对误差绝对值:微波消解法碱熔法SMT法;变异系数:微波消解法碱熔法SMT法。同时,微波消解法提取的表层沉积物TP含量的范围为634.3~909.2μg/g;SMT法TP含量的范围为627.1~889.5μg/g;碱熔法TP含量的范围为559.1~784.8μg/g。微波消解法的测定结果相对偏高,SMT法的测定结果相对偏低。样品加标回收率平均值:微波消解法SMT法碱熔法;变异系数:微波消解法碱熔法SMT法。综合测定标准物质中TP含量以及样品加标回收率实验结果的准确度和精密度,对于黄河甘宁蒙段表层沉积物,使用SMT法提取TP较优于微波消解法和碱熔法。     

Heavy Metal Pollution Assessment in Sediments of the Izmit Bay, Turkey

Surface sediments in the fraction < 63 μm collected from eight stations along the north coastline of Izmit Bay, north-eastern Marmara Sea, Turkey, were analyzed for major (organic carbon, Al, Ba, Fe and Mg) and trace (As, Cd, Co, Cr, Cu, Mo, Ni, Pb and Zn) elements by using inductively coupled plasma atomic emission spectrometry (ICP-AES). Sediments heavily contaminated are evaluated by the Sediment Quality Guidelines (SQG) of US EPA. The results were compared with the marine sediment quality standards (SQS), as well as literature values reported to assess the pollution status of the sediments. The enrichment factors (EFs) were calculated to evaluate actual level of contamination for all the elements using the earth crust as reference matrix, based on elemental values by Mason which show a normal pattern near to unity. The analysis revealed two groups of elements: (i) Arsenic, Cd, Pb, and Zn are the most enriched elements; (ii) Barium, Co, Cr, Cu, Fe, Mg, Mo and Ni are at background levels. The results show that road traffic run-offs, paint industries and coal combustion are among the most significant sources.     

基于快速消解的海洋沉积物重金属ICP-MS测定条件优化

准确测定海洋沉积物中重金属元素的含量,是开展海洋生态环境评价与管理的基础。比较研究了当前生态环境监测领域几种主要的检测标准方法和近年热门的土壤快速消解法对海洋沉积物中重金属的检测效果。通过研究不同消解体系、消解压力、校准溶液配制方法以及内标元素、内标浓度等条件对海洋沉积物重金属测定效果的影响,优化了海洋沉积物样品的快速消解过程和测定条件。结果表明:优化后的快速消解方法针对Cr、Ni、Cu、Zn、Cd和Pb的方法检出限为0.004~0.8 mg/kg,测定下限为0.016~3.2 mg/kg,回收率为95.4%~109.2%,相对标准偏差为0%~3.22%,方法准确可靠、快速高效,满足海洋沉积物样品(尤其是大批量样品)的重金属测试需求。     

洞庭湖表层沉积物中重金属污染特征、来源与生态风险

选择洞庭湖9个有代表性的样点,研究了洞庭湖表层沉积物中重金属的空间分布特征、主要来源与生态风险。结果表明,洞庭湖Cd、Hg、As、Cu、Pb、Cr的含量分别为0.60~20.70、0.090~0.640、10.4~83.7、17.9~70.9、16.9~95.8、59.0~199.0 mg/kg,Cd、As出现超过土壤环境质量三级标准的现象,是主要重金属污染物;Cd、Hg的空间分布相似,表现为南洞庭湖区西洞庭湖区东洞庭湖区;As、Cu、Pb、Cr的空间分布相似,表现为南洞庭湖区东洞庭湖区西洞庭湖区。相关分析结果显示:As、Cd、Hg、Cu、Pb之间呈显著正相关,Cr与其它重金属之间没有显著的相关性。主成分分析结果表明,第一主成分的Hg、As、Cd主要受工矿业采冶支配,第二主成分的Cr、Pb、Cu主要与生活污水排放和农业生产有关。沉积物质量基准法初步评价结果表明,洞庭湖Cd、Hg、As、Cu、Pb、Cr等重金属均具有引起较低生态风险的可能性,部分点位Cd、As、Cr具有引起较高生态风险的可能性。受Cd、As含量较高的影响,南洞庭湖区具有较高的生态风险。     

洪泽湖湖滨带表层沉积物氮、磷、有机质分布及污染评价

洪泽湖作为中国第四大淡水湖泊,是江苏北部地区重要的水源地,同时也是南水北调东线工程的重要调蓄湖泊之一,研究其湖滨带表层沉积物氮、磷、有机质的污染情况对维持洪泽湖水安全和生物多样性具有重要现实意义。基于2020年8月于洪泽湖湖滨带采集的43个表层（0~10 cm）沉积物样品,分析了总氮（TN）、总磷（TP）和有机质（OM）含量的空间分布特征及相关性,并运用综合污染指数法和有机污染指数法评价其污染程度。结果表明,洪泽湖湖滨带表层沉积物TN、TP、OM含量范围分别为232~2 152 ,123~439,0.91~18.65 mg/kg,均值分别为985,276,10.93 mg/kg;空间分布上均表现为东部大堤、成子湖和西部区域的TN、TP、OM含量高于过水通道;Pearson相关性分析显示,表层沉积物中ω(OM)与ω(TN)（r=0.705,P<0.01）、ω(TN)与ω(TP)（r=0.504,P<0.01）呈显著正相关;洪泽湖湖滨带表层沉积物综合污染指数范围为0.45~1.88,平均值为0.93,有机污染指数范围为0.001~0.221,平均值为0.067,2种评价方法均显示洪泽湖湖滨带表层沉积物中TN、TP、OM整体处于清洁—轻度污染状态。     

重金属在贾鲁河表层沉积物中的污染特征及来源分析

采用原子吸收分光光度法、原子荧光法和电感耦合等离子体发射光谱法测定了贾鲁河表层沉积物中6种重金属的含量,用灼烧法测定贾鲁河表层沉积物中有机质含量。运用地累积指数法对贾鲁河流域表层沉积物中重金属污染状况进行评价,并且通过主成分分析法研究贾鲁河重金属污染来源。结果表明：贾鲁河表层沉积物中As、Cu、Ni、Zn的含量比2004年淮河表层沉积物中相应重金属含量明显偏高。重金属污染程度为：As〉Cu〉Zn〉Pb〉Ni〉Cr。通过主成分分析进一步对重金属来源的确定,发现前2个主成分的贡献率分别为58．85％和19．74％,污染来源主要有两类,分别是工农业、生活排污的点源污染,自然变化对沉积物的影响,岩石风化与侵蚀过程和有机质降解矿化的内源污染。     

南宁城市内河沉积物中SVOCs的分布与风险评价

采用加速溶剂萃取-气相色谱-质谱联用技术对南宁市7条城市内河表层沉积物中的64种半挥发性有机物(SVOCs)进行了分析测定,定量检出12种SVOCs,包括7种多环芳烃类(PAHs)、1种酚类和4种酯类,其中属于我国优先控制污染物的有8种,属于美国优先控制污染物的有11种。南宁市城市内河沉积物中的SVOCs总量范围为6.75~34.45 μg/g(以干质量计),均值为15.85 μg/g(以干质量计),以竹排冲的含量最高,污染程度与工业污染源的关系十分密切。特征污染物为酞酸酯,在各测点的比重均占检出总含量的83%以上。除相思湖外的6条城市内河的沉积物均检出PAHs,区域内的工业生产活动对城市内河沉积物的PAHs有重要贡献。应用效应区间低值(ERL)和效应区间中值(ERM)指标对沉积物进行的生态风险评价表明,南宁市城市内河沉积物的生态风险较小。