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。     

镇江市金山湖沉积物磷元素分布特征研究

以镇江市金山湖为研究区域,于2019年1月（冬季）和2019年7月（夏季）采集了10个点位的表层沉积物样品,参照欧洲标准测试测量组织建立的沉积物磷形态分析方法（SMT）测定沉积物总磷（TP）、无机磷（IP）、有机磷（OP）、铁/铝-磷（Fe/Al-P）和钙-磷（Ca-P）质量分数,研究金山湖表层沉积物磷元素及其赋存形态的季节分布特征。结果表明,金山湖表层沉积物中TP质量分数在冬、夏季分别为727.39~1 073.70 mg/kg和700.90~1 002.17 mg/kg,处于中等污染水平;金山湖表层沉积物磷以IP为主,IP在TP中的占比在冬、夏季分别为68.58%~88.86%,73.09%~87.21%;除了Fe/Al-P以外,OP作为生物有效磷源,其冬、夏季质量分数分别为69.37~190.93 mg/kg和108.45~210.42 mg/kg;其平均值分别为129.01,160.15 mg/kg。金山湖冬、夏季沉积物各形态磷质量分数所占比例均表现为Ca-P>Fe/Al-P>OP,表明该研究区域沉积物以Ca-P占优势。金山湖表层沉积物pH值呈现弱碱性,通过Ca-P直接释放到上覆水中的磷较少,故金山湖沉积物磷元素的潜在风险较小。各形态磷的相关性分析结果发现,冬季沉积物TP与Fe/Al-P、IP呈极显著正相关（P<0.01）。夏季沉积物TP与IP、Fe/Al-P之间呈极显著正相关（P<0.01）,与Ca-P呈显著正相关（P<0.05）。此外,金山湖沉积物OP、Fe/Al-P以及Ca-P的来源不一致。pH值对沉积物IP会产生一定影响,而其余磷形态则受pH值的影响程度较小。     

洪泽湖沉积物中磷的形态研究

采用改进的七步连续提取法对洪泽湖9个采样点沉积物中的各形态磷进行了分析,结果表明,所测洪泽湖沉积物中总磷(TP)含量范围为580.7～1 447.7 mg/kg,无机磷(IP)是TP的主要部分,占TP含量的64.32％～88.60％;有机磷(0P)占TP的11.40％～35.68％.受河流注入和人为活动的影响,TP、I...     

漳河上游流域沉积物中磷的空间分布特征及其影响因素

漳河上游地区众多的水利工程改变了流域水循环,同时也影响了河流泥沙和生源物质的循环过程。为揭示人类活动干扰下的沉积物中磷的赋存特征,采用改进后的连续化学萃取法分析了漳河上游沉积物中总磷(TP)和磷形态的空间分布特征及其影响因素。研究结果表明,漳河上游沉积物中的TP含量为405.94~899.98 mg/kg,低于我国其他主要河流,接近我国东部平原湖泊含量水平。漳河上游的TP富集指数(PEI)均值为1.15,表明漳河上游富营养化风险较高。可交换态磷(Ex-P)、铁锰螯合态磷(BD-P)、铁铝氧化态磷(NaOH-P)、钙结合态磷(HCl-P)分别占沉积物中TP含量的1.13%、33.96%、12.99%、35.05%。BD-P和HCl-P是沉积物中主要的磷形态,Ex-P的含量最低,NaOH-P的含量波动最大。漳河上游沉积物中,生物可利用磷(BAP)的含量约占TP含量的38.36%~52.04%,其中,清漳干流的BAP含量明显低于其他河段。清漳源头的水土流失及浊漳河的磷输入对漳河上游BAP含量的贡献较大。统计分析显示,漳河上游表层沉积物中,TP和磷形态的空间分布无显著差异,表明以水利工程建设为代表的强烈人类活动对漳河上游沉积物中磷的空间分布的影响不显著。相关性分析和冗余分析表明,沉积物中的NaOH-P含量与沉积物中黏土和粉土的占比有较高的相关性,BD-P和NaOH-P是控制沉积物中BAP构成的重要因素,Fe含量是沉积物中TP含量的主控因子。     

徐州九里湖沉水植物对富营养化湖泊的生态改善作用

为探究沉水植物对富营养化湖泊的生态改善作用，于2021年9月—2022年8月对徐州九里湖有、无沉水植物区的水质、沉积物磷形态、浮游植物群落分别进行监测。结果表明，九里湖沉水植物能够增加水体的透明度（SD）和溶解氧（DO），对总氮（TN）有一定程度的削减作用，对总磷（TP）、氨氮（NH₃-N）和浊度（TUB）的改善效果最明显，能够有效降低九里湖的富营养化水平。九里湖沉积物中无机磷（IP）对TP含量的贡献最大，占比为64.2%～93.2%。IP当中的盐酸提取磷（HCl-P）占绝对优势。有沉水植物区沉积物中TP和有机磷（OP）含量整体略高于无沉水植物区，说明沉水植物对上覆水中的磷元素沉降有一定的促进作用。九里湖全年共监测到浮游植物7门63属93种，群落密度为2.94×10⁶～7.0×10⁷个/L。除水温较低的1—4月外，蓝藻门中的假鱼腥藻（Pseudanahaena sp.）是其中的优势种。低温情况下，浮游植物密度整体大幅降低，但是绿藻门和硅藻门占比明显提升。沉水植物对浮游植物生长具有很好的抑制作用。香农-维纳（Shannon Wiener）多样性指数结果表明，沉水植物对浮游植物多样性有降低作用。     

超高效液相色谱-串联质谱法分析土壤及沉积物中氨基甲酸酯农药

利用超高效液相色谱-串联质谱,建立土壤和沉积物中痕量氨基甲酸酯农药的分析方法。该方法用体积比1:1的二氯甲烷/甲醇对土壤和沉积物样品进行加速溶剂萃取,GCB/PSA固相萃取小柱对萃取液进行净化,内标法定量,用超高效液相色谱-串联质谱法分析土壤和沉积物中20种氨基甲酸酯农药。20种氨基甲酸酯农药在0.02~1.0 μg/mL范围内线性良好(r≥0.99),检测限为0.20~0.60 ng/g。沉积物加标样品(20ng/g)和土壤加标样品(20ng/g)的回收率分别为33.2%~101.9%、38.8%~120.5%,相对标准偏差为6.1%~28.0%、2.3%~16.0%。沉积物加标样品(2.0 ng/g)回收率为43.0%~100.0%,相对标准偏差为2.1%~11.3%。     

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。     

偏振能量色散X-射线荧光光谱法测定土壤中Ni、Cu、Zn、Pb四种重金属元素

以土壤和水系沉积物标准物质为校准样品,采用粉末样品压片制样,建立了偏振能量色散X-射线荧光光谱仪测定土壤中Ni、Cu、Zn、Pb四种重金属元素的方法。该方法分别采用Ge,Zn,Zr等3个不同二次靶对被分析元素进行选择性激发和测定,利用经验系数和康普顿散射线作内标校正基体效应,优化了元素校准曲线方程,实验结果表明,土壤和水系沉积物标准物质准确度实验结果符合定值要求,方法精密度RSD在1.12%~6.09%之间(n=10),Ni、Cu、Zn、Pb四种重金属元素的检出限分别达到2.54、0.93、0.96、0.98 mg/kg。土壤样品测定值与原子吸收法测定结果一致,该方法准确度、精密度、检出限均能满足土壤检测的需要。     

千岛湖沉积物中碳、氮、磷的分布特征及污染评价

通过测定千岛湖柱状沉积物中有机质（OM）、总氮（TN）和总磷（TP）含量,分析其污染分布特征,并评价污染水平。结果表明,千岛湖沉积物中OM、TN、TP平均值分别为1.44%、1.86mg/g、0.89mg/g。空间分布差异明显,城区库湾、新安江干流沿线污染相对较重;垂直分布,OM、TN、TP整体上均从湖底由下而上呈逐步上升变化过程。相关性分析表明,该湖沉积物中OM、TN、TP具有较高的同源性,氮、磷多以有机形式存在。C/N值表明,该湖沉积物中有机质主要来自内源的水生生物分解。评价结果显示,综合污染指数范围为1.1～4.2,该湖整体上处于重度污染水平,TP污染重于TN;有机指数范围为0.04～0.52,整体上属于轻度污染水平。     

太湖氮磷大气干湿沉降时空特征

为了探索太湖氮磷营养盐干湿沉降特征及对太湖营养盐输入的贡献，于2011年不同季节采集太湖不同位点的大气干湿沉降样品，分析干湿沉降中氮（N）和磷（P）的形态和沉降量。研究结果表明，输入太湖的磷以干沉降为主，而氮以湿沉降为主。在太湖干沉降中总无机氮（TIN）占总氮（TN）的77.1%，溶解性磷（DIP）占总磷（TP）的77.9%。干沉降中TIN主要以NH+4-N为主。西太湖是TN与TP通过大气干湿沉降输入太湖的最高湖区。太湖全年大气TN沉降总量为20 978 t，TP沉降总量为1 268 t，因此，氮磷大气干湿沉降是太湖营养盐输入的重要来源之一。     

An investigation of the origin and mobility of phosphorus in freshwater sediments from Bort-Les-Orgues Reservoir, France

In order to assess the origin and the potential mobility of phosphorus (P) in the sediment of the Bort-Les-Orgues Reservoir, France, two sequential extraction schemes, i.e., the SMT (modified Williams method) and the Golterman schemes, were compared. Finally, the potential mobility of P in this sediment was estimated from results of sequential extraction. The SMT method appeared to be more satisfactory than the Golterman method, which is in accordance with results from a study currently carried out in the framework of the European programme Standards, Measurements and Testing. Iron-bound P and organic P were the dominant forms of P in the sediment; these forms are likely to be released at the sediment/water interface in case of anoxia and could diffuse into the water column, thus increasing the risk of eutrophication in this sensitive reservoir. The P stock (330 +/- 66 t) is not negligible and should be taken into account in any restoration project of the reservoir. The SMT procedure seems promising and will provide, in the near future, a valuable tool for water managers in the field of lake restoration.     

Analytical approaches to the determination of phosphorus partitioning patterns in sediments

Three methods for phosphorus fractionation in sediments based on chemical extractions have been applied to fourteen aquatic sediment samples of different origin and characteristics. Two of the methods used different approaches to obtain the inorganic fractions. The Hieltjes and Lijklema procedure (HL) uses strong acids or bases, whereas the Golterman procedure (G) uses chelating reagents. The third one, the Standards, Measurements and Testing (SMT) protocol, was proposed in the frame of the SMT Programme (European Commission) which aimed to provide harmonisation and the validation of such methodologies. This harmonised procedure was also used for the certification of the extractable phosphorus contents in a sediment certified reference material (CRM BCR 684). Principal component analysis (PCA) was used to group sediments according to their composition and the three extraction methods were applied to the samples including CRM BCR 684. The data obtained show that there is some correlation between the results from the three methods when considering the organic and the residual fractions together. The SMT and the HL methods are the most comparable, whereas the G method, using a different type of reagent, yields different distribution patterns depending on sample composition. In relation to the inorganic phosphorus, the three methods give similar information, although the distribution between non-apatite and apatite fractions can be different.     

两种消解法测定沉积物总磷的对比

通过过硫酸钾消解法与HClO₄-H₂SO₄消解法对土壤和水系沉积物的标准物质,以及三峡水库沉积物未知样品中的总磷含量进行测定,并对检测结果进行对比,分析过硫酸钾消解法测定沉积物总磷的可行性。结果表明,在标准样品中,HClO₄-H₂SO₄消解法的检测结果是标准值的83%~100%,并且所有结果均在其不确定度范围之内;过硫酸钾消解法的检测结果仅达到标准值的19%~42%,超出其不确定度范围,不能作为有效数据。在未知样品中,过硫酸钾消解法检测结果也远低于HClO₄-H₂SO₄消解法检测结果,只达到后者的32%~52%。由此可见,过硫酸钾消解法测定沉积物或土壤中总磷,仍需要进一步的研究,以达到符合实际的检测结果。     

Characterisation of road sediments near Bordeaux with emphasis on phosphorus

Road sediments from the region of Bordeaux (France) were analysed for trace metals, hydrocarbons (including Polycyclic Aromatic Hydrocarbons, PAHs) and phosphorus. The aim of the study was to assess their potential risk for the environment. The sediments were collected by means of a sweeper. The particles are mostly sandy clay loam and silty clay loam with 5.6-8.3% CaO. Heavy metal concentrations are generally below the French and Dutch standards for polluted soils, but a few samples have higher concentrations, e.g., 547 mg kg(-1) for Zn, and 222 mg kg(-1) for Pb. PAH concentrations are above the Dutch target value for polluted soils, and could be a threat to the environment: pyrene (2600 microg kg(-1)) and fluoranthene (1400 microg kg(-1)) have the highest concentrations, whereas chrysene (340 microg kg(-1)) has the lowest. Consequently, these sediments must be considered as waste according to the French circular no 2001-39 from 18 June 2001 and cannot be disposed of anywhere. The Standards Measurements and Testing (SMT) protocol for sequential extraction of phosphorus in sediments was used to determine the forms of phosphorus in the samples. Total phosphorus concentration is 620 mg kg(-1) on average, with a maximum of 933 mg kg(-1); organic phosphorus content is low (36 mg kg(-1) on average). The protocol could be slightly amended, especially with regards to organic phosphorus at low concentrations and could then be used for the determination of phosphorus in other materials such as sludge from detention ponds.     

超声波-气相色谱法测定鱼肉样品中硝基苯类化合物

以鱼肉样品为研究对象,采用超声波法提取鱼肉中的硝基苯类化合物,并通过凝胶色谱进行净化、浓缩,最后用气相色谱定量分析,得到生物样品中硝基苯类化合物的检出限,同时与传统的索氏提取法进行加标回收试验比较。结果表明:用超声波提取鱼肉样品中的硝基苯类化合物方法可行,回收率稳定,并且得到检出限为0.13~2.72 ng/g,加标回收率在60%~78%,RSD在0.04%~3.2%。     

Development of a harmonised phosphorus extraction procedure and certification of a sediment reference material

A harmonised procedure for the determination of the forms of phosphorus in freshwater sediments, developed in the frame of the European Programme, Standards, Measurements and Testing (SMT) has been used for a certification campaign for a reference material. This operationally defined scheme is a good compromise between method performance and reproducibility. Furthermore, the method is rather simple to implement and could be used by water managers on a routine basis. A homogeneous and stable sediment reference material has been prepared and will be available before mid 2001. The so-called SMT protocol, together with the reference material, are useful tools in the field of water management, especially at a time when quality assurance is of paramount importance in laboratory analyses. Knowledge of the bioavailable forms of phosphorus is important not only for analysis of sediments but also for sludge and soils. Therefore, the SMT protocol could be extended to these materials.     

铋磷钼蓝分光光度法测定土壤中磷含量

土壤中磷含量的分析是土壤环境监测的主要项目之一.建立了铋磷钼蓝分光光度法测定土壤中磷含量的新方法,与现有的《土壤全磷测定方法》(GB 9837-88)和土壤总磷快速检测仪方法进行了比较讨论.方法的检出限为5.0 mg/kg,对磷含量为475 mg/kg和292 mg/kg的标准土壤样品进行测定,结果与标准值吻合,其相对...     

Optimization of the Microwave-Assisted Solvent Extraction of Petroleum Hydrocarbons in Marine Sediment and Soil

A microwave-assisted solvent extraction (MASE) technique was developed for the quantitative extraction of gasoline- and diesel-range petroleum hydrocarbons (PHs) from soil and marine sediment samples. The influence of different extracting solvents, extraction temperature and duration of extraction on the recoveries of PHs was evaluated using a two-level orthogonal array design (OAD) with a OA8(27) matrix. Gas chromatographic-mass spectrometry (GC-MS) in multiple selective ion monitoring (MSIM) mode was used for the analysis of the PHs in environmental samples. The spiking range of the PHs in the environmental samples was between 1 to 1000 g/g. Good recoveries (>80%) could be obtained for most of the PHs using the optimum MASE conditions. The limit of detection (LOD) achieved by the GC-MS-MSIM was 0.02 g/g. A preliminary survey for the levels of PHs in marine sediment and soil samples from different parts of Singapore was carried out using the method.     

The effect of humic acids on the sequential extraction of metals in soils and sediments using ICP-AES and chemometric analysis

The effect of humic acids on the sequential extraction of metals from various soils and sediments has been studied. A new multi-element extraction method optimised via experimental design has been employed. The method uses centrifugation to pass the extractant solution, at varying pH, through the sediment sample. The sequential leaches were collected and analysed by ICP-AES. Chemometric data processing was utilised to identify the composition of the physico-chemical components in order to characterise the sample. A sediment sample collected from Carnon River (Cornwall, UK) and a reference material (NIST 2711 agricultural soil) were spiked with humic acids and the sequential extraction scheme was used to monitor the changes in metal distribution. The method has proved a quick and reliable way to evaluate different sediment samples, and has potential as a new tool for environmental geochemistry analysis.