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.     

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.     

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.     

Selection and evaluation of sequential extraction procedures for the determination of phosphorus forms in lake sediment

In order to achieve comparable measurements in the determination of phosphate forms in freshwater sediments, the Standards, Measurements and Testing Programme (formerly BCR) of the European Commission has launched a project the first step of which was to select and evaluate collaboratively existing extraction procedures. This was carried out through expert consultations and a literature survey, and was followed by the organisation of a first interlaboratory study for the evaluation of four sequential extraction schemes, one of which was selected as the most promising method for achieving comparability. This scheme, a modified version of the Williams protocol, was further tested in a second interlaboratory study. The so-called SMT extraction scheme seems promising and will provide, in the near future, a valuable tool for water managers in the field of lake restoration. It will be particularly helpful in estimating the stock of P potentially available, hence the risk of eutrophication due to internal P release.     

An ultrasound accelerated sequential extraction method and its application for element partitioning studies in compost from mixed waste streams

A rapid ultrasound accelerated sequential extraction procedure is presented which is modified from the standard BCR protocol and validated using the BCR 601 reference material. The method is accelerated at the extraction steps: for example, in the standard method each extraction step takes 16 h whereas with the ultrasonic extraction method developed in this work each step took 15 min. This means a further step can be included in the protocol without greatly increasing the experimental time. An extraction with pyrophosphate solution was therefore included to provide more information about the interaction between the elements and humic substances during the composting process. The new method has been applied to monitoring the metal partitioning behaviours in a composting process involving mixed waste streams. The metal partitioning profiles obtained from this new method show that in many cases composting tends to redistribute the metals from more labile forms to combined forms, especially to forms combined with humic substances.     

SMT法测定沉积物标准样品有机磷形态分析方法探究

目前水体沉积物中磷的分级提取没有统一的方法,不同的提取方法分析沉积物中的磷形态结果可能会有很大差异。SMT法因操作简单、重复性好而被广泛应用于沉积物磷形态分析,但是在实际操作中连续提取过程比较复杂,尤其是有机磷(OP)提取步骤比较繁琐,中间转移过程较多,分析人员人为操作等因素都会导致实验出现较大误差,通过多次实验研究发现,在此基础上还存在另外一种改进的OP提取方法。为了验证改进法是否具有合理可行性,以水系沉积物标准样品GSD-9和GSD-12为标样,同时以野外采集的沉积物样品为实际样品,采用标准SMT法和改进法重复测定(n=30)沉积物中OP含量。结果表明:标准SMT法提取沉积物标准样品GSD-9和GSD-12测得的OP含量分别占其总磷(TP)含量的9.33%和23.03%;改进法测得的OP含量分别占其TP含量的10.44%和23.13%,两种OP提取方法测得结果有着极高的相似性。结果表明,改进的OP提取方法具有可行性,对于沉积物OP分析提取方法的合理选择具有指导意义。     

不同水体沉积物中磷的形态分析

磷是生态系统中必不可少的营养元素,其含量与水体的营养程度密切相关,过剩的磷会导致水体富营养化,使生态平衡遭到破坏.就不同水体沉积物中磷的形态进行了分类综述,归纳总结了不同水体沉积物中磷的形态以及分布特征,并且进一步概述了影响沉积物中磷向水体释放的因素.     

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。     

Kinetic and isotherms studies of phosphorus adsorption onto natural riparian wetland sediments: linear and non-linear methods

Riparian wetlands provide critical functions for the improvement of surface water quality and storage of nutrients. Correspondingly, investigation of the adsorption characteristic and capacity of nutrients onto its sediments is benefit for utilizing and protecting the ecosystem services provided by riparian areas. The Langmuir and Freundlich isotherms and pseudo-second-order kinetic model were applied by using both linear least-squares and trial-and-error non-linear regression methods based on the batch experiments data. The results indicated that the transformations of non-linear isotherms to linear forms would affect the determination process significantly, but the non-linear regression method could prevent such errors. Non-linear Langmuir and Freundlich isotherms both fitted well with the phosphorus adsorption process (r ²?>?0.94). Moreover, the influences of temperature and ionic strength on the adsorption of phosphorus onto natural riparian wetland sediments were also studied. Higher temperatures were suitable for phosphorus uptake from aqueous solution using the present riparian wetland sediments. The adsorption capacity increased with the enhancement of ionic strength in agreement with the formation of inner-sphere complexes. The quick adsorption of phosphorus by the sediments mainly occurred within 10 min. The adsorption kinetic was well-fitted by pseudo-second-order kinetic model (r ²?>?0.99). The scanning electron microscopy (SEM) and Fourier transformation infrared (FT-IR) spectra analyses before and after phosphorus adsorption revealed the main adsorption mechanisms in the present system.     

玄武湖沉积物中磷的形态分布特征

利用分级提取法分析了玄武湖的沉积磷形态,在玄武湖沉积物中,铝结合态磷的含量较低,平均值为64 mg/kg,其余形态磷中,铁结合态磷为241 mg/kg,有机磷为335 mg/kg,钙结合态磷为394 mg/kg.在环境变化的条件下,铁结合态磷可以释放到间隙水和上层水体中,是湖泊产生富营养化的重要因素;铝结合态磷由于含量少,对湖泊富营养化影响很小;钙结合态磷相对稳定且很难被生物利用,对湖泊富营养化影响不大;有机磷对水体有机负荷影响较大,并影响水体富营养化程度.     

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.     

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...     

Metal levels in sediments from the Minho estuary salt marsh: a metal clean area?

Total-recoverable metals (Al, Cr, Cu, Fe, Mn, Ni, Pb and Zn) in sediments from Minho estuary salt marsh were determined to evaluate possible increase in anthropogenic contamination by metals and to evaluate the possibility of this area to be considered a pristine area in terms of metals, which can be used as a reference site for other metal-contaminated national and international estuaries/salt marshes. This study revealed that the spatial distribution of metals in the salt marsh sediments was not homogeneous and that two sampling sites (sites 5 and 7) had indications of anthropogenic contamination. However, metal levels in these salt marsh sediments were lower than those observed in the wetlands of the main Portuguese estuaries. Comparison with Portuguese and international reference values used in the evaluation of the ecological quality of sediments, indicated that the sediments can be classified as “clean sediment” and that metal levels were lower or similar (only for Cu and Ni) to the values of ERL, which are the values that define the concentrations ranges that are rarely associated to adverse biologic effects in organisms. In addition, metal levels in the sediments were in chemical forms that were not easily available to organisms, indicating that these sediments probably will not have negative influences in the organisms living in the salt marsh, although no life-form ecological safety tests have been carried out. Therefore, the Minho estuary salt marsh area can probably be considered a pristine area in terms of metals and can be used as a reference for other metal-contaminated estuaries/salt marshes.     

Implication of two in-stream processes in the fate of nutrients discharged by sewage system into a temporary river

The aim of this study was to better understand the fate of nutrients discharged by sewage treatment plants into an intermittent Mediterranean river, during a low-flow period. Many pollutants stored in the riverbed during the low-flow period can be transferred to the downstream environments during flood events. The study focused on two processes that affect the fate and the transport of nutrients, a physical process (retention in the riverbed sediments) and a biological process (denitrification). A spatial campaign was carried out during a low-flow period to characterize the nutrient contents of both water and sediments in the Vène River. The results showed high nutrient concentrations in the water column downstream of the treated wastewater disposal (up to 13,315 μg N/L for ammonium and 2,901 μg P/L for total phosphorus). Nutrient concentrations decreased rapidly downstream of the disposal whereas nutrient contents in the sediments increased (up to 1,898 and 784 μg/g for total phosphorus and Kjeldahl nitrogen, respectively). According to an in situ experiment using sediment boxes placed in the riverbed for 85 days, we estimated that the proportion of nutrients trapped in the sediments represents 25% (respectively 10%) of phosphorus (respectively nitrogen) loads lost from the water column. In parallel, laboratory tests indicated that denitrification occurred in the Vène River, and we estimated that denitrification likely coupled to nitrification processes during the 85 days of the experiment was significantly involved in the removal of nitrogen loads (up to 38%) from the water column and was greater than accumulation processes.     

Evaluation of analytical strategies for the determination of metal concentrations to assess landfill leachate contamination

Due to the complex nature of landfill leachates, metal and metalloid analyses prove to be tricky and suffer from a lack of standard protocols. A complete approach has been adopted to investigate the influence of the different steps during the sample processing of French landfill leachates. The validation of the entire protocol has been achieved using a laboratory reference material. This material, which is a real landfill leachate, is representative of real samples. Its evaluation has allowed a quality control for metal and metalloid analyses in landfill leachates. Precautions concerning storage temperature, aeration and filtration are proposed to perform accurate metal analyses in these complex matrices. The sample processing has been applied to the seasonal monitoring of a French landfill. The assessment of major leachate metallic contaminants such as As, Cr, Sb, Sn, has been performed by evaluating the relative enrichment of metals and metalloids in comparison with rain water and groundwater. In addition, hydrological data are useful and complementary information for pointing out the main factors affecting metal concentrations and thus their potential remobilisation pathways.     

湖泊底泥挖掘可能导致水体氮磷平衡破坏的研究

挖掘底泥是减少富营养化湖泊内源性氮、磷元素的主要手段 ,但若挖掘不当 ,则一段时间内可能会导致水体氮、磷平衡破坏 ,富营养化加剧。从底泥挖掘可能导致水体营养元素平衡破坏的成因入手 ,探讨避免水体富营养化加剧的对策。     

Development of a Standardised Approach to River Habitat Assessment in Australia

Despite the demonstrated utility of the Australian River Assessment Scheme (AUSRIVAS) to provide national-scale information on the biological condition of rivers, there is no commensurate scheme that can provide standardised information on physical habitat. Existing habitat assessment methods are not suitable for implementation on a national scale, so we present a new habitat assessment protocol that incorporates favorable elements of existing methods. Habitat Predictive Modelling forms the basis for the protocol because it can predict the occurrence of local-scale features from large-scale data, uses the reference condition concept, can be modified to incorporate a range of biologically and geomorphologically relevant variables, and employs a rapid survey approach. However, the protocol has been augmented with geomorphological variables and incorporates principles of hierarchy and geomorphological river zonation. There are four sequential components to the implementation of the protocol: reference site selection, data collection, predictive model construction and assessment of test sites using the predictive models. Once implemented, the habitat assessment protocol will provide a standardised tool for the assessment of river habitat condition at a variety of governance levels.     

Longitudinal heterogeneity of sediment characteristics during southwest monsoon season in hyper-eutrophic Krishnagiri reservoir,India

Krishnagiri reservoir is a hyper-eutrophicated reservoir located in Krishnagiri district which is one of the drought-prone districts in Tamil Nadu, India. The reservoir water is being used for various purposes such as irrigation, drinking, fish rearing, livestock rearing, and recreation. Since there is no an evidence of investigation on bottom sediments in Krishnagiri reservoir, the present study was carried out during southwest monsoon season in 2008. This study examined the physical and chemical characteristics of the bottom sediments such as composition, redox potential, moisture content, organic carbon, organic matter, total phosphorus, and total iron at 15 locations in the reservoir. Phosphorus fractionation study was carried out to find out different fractions such as loosely adsorbed phosphorous, iron and aluminium-bound phosphorus, calcium-bound phosphorous, and organic phosphorous. Results indicated that there was spatial variation in the composition of sediments and low values of redox potential. The significant positive correlation exists between the organic carbon and organic phosphorus concentration. The lacustrine zone of the reservoir showed high accumulation of total phosphorus and total iron when compared to riverine and transition zones. This study concludes an allogenic origin of majority of inorganic phosphorus in the reservoir during the study period and this might have been derived from the catchment during the erosion process. The high concentration of surface sediment phosphorus clearly indicates a greater threat of eutrophication in Krishnagiri reservoir.     

Fractionation and bioavailability of phosphorus in a tropical estuary, Southwest India

Phosphorus fractionation was employed to find the bioavailability of phosphorus and its seasonal variations in the Panangad region of Cochin estuary, the largest estuarine system in the southwest coast of India. Sequential extraction of the surficial sediments using chelating agents was taken as a tool for this. Phosphate in the water column showed seasonal variations, with high values during the monsoon months, suggesting external runoff. Sediment texture was found to be the main factor influencing the spatial distribution of the geochemical parameters in the study region. Similarly, total phosphorus also showed granulometric dependence and it ranged between 319.54 and 2,938.83 ??g/g. Calcium-bound fraction was the main phosphorus pool in the estuary. Significant spatial variations were observed for all bioavailable fractions; iron-bound inorganic phosphorus (5.04?C474.24 ??g/g), calcium-bound inorganic phosphorus (11.16?C826.09 ??g/g), and acid-soluble organic phosphorus (22.22?C365.86 ??g/g). Among the non-bioavailable phosphorus, alkali-soluble organic fraction was the major one (51.92?C1,002.45 ??g/g). Residual organic phosphorus was comparatively smaller fraction (3.25?C14.64% of total). The sandy and muddy stations showed distinct fractional composition and the speciation study could endorse the overall geochemical character. There could be buffering of phosphorus, suggested by the increase in the percentage of bioavailable fractions during the lean pre-monsoon period, counteracting the decreases in the external loads. Principal component analysis was employed to find the possible processes influencing the speciation of phosphorus in the study region.     

The development of a novel method for directional dust monitoring

Dust monitoring using sticky pads was popularised in the 1980s. The discolouration caused by dust adhering to white adhesive material was measured with a smoke stain reflectometer. This loss of reflectance was expressed as the percentage effective area coverage (EAC%) per day. EAC% can be used as a measure of nuisance caused by dust. EAC% may also be measured with a hand-held Sticky Pad Reader (SPR). Sticky pads can be mounted on flat or cylindrical surfaces to measure dust by deposition or in flux. An alternative method was developed in the 1990s that measured total dust coverage using computer-based scanning. DustScan used a transparent adhesive film wrapped around a vertical cylinder with magnetic north marked. The sticky pad was sealed with another transparent sheet before scanning at 50 dots per inch (dpi). Dust levels were assessed by comparing the grey-scale values of pixels in the exposed area with an unexposed reference area. Insects and other extraneous material could be ‘masked out’ from the computer analysis. Dust coverage was expressed as percentage absolute area coverage (AAC%). DustScan has subsequently been developed commercially. A limited trial indicated that monitoring periods of 7–14 days were preferred to avoid dust saturation of the sticky pad. A method for calculating EAC% has been developed and shown to have a high degree of correspondence with an SPR. A trial for the Minerals Industry Research Organisation (MIRO) made comparisons between DustScan and other dust monitoring methods. Dust nuisance limits based on AAC% and EAC% are proposed.par