Determination of organochlorinated compounds and petroleum hydrocarbons in sediment sample IAEA-408. Results from a world-wide intercalibration exercise

A sediment sample from the intertidal mudflats of the Tagus estuary was prepared, homogenised and distributed globally to laboratories as the IAEA-408 intercomparison material for the analyses of organochlorinated pesticides, PCBs and petroleum hydrocarbons (PHs). A total of 48 laboratories from 36 countries reported their results. The data from participants show that there still remain some difficulties with the accurate determination of organic contaminants such as pesticides and polycyclic aromatic hydrocarbons (PAHs). More consistent interlaboratory results were obtained for PCBs congeners. The final results of this intercomparison exercise enable individual participants to assess their performance and, where necessary, to introduce appropriate modifications in their analytical procedures. Furthermore, as a series of statistical criteria was fulfilled for a number of compounds, the sample IAEA-408 can now be used as a reference material for quality control in the determination of some persistant organic pollutants (POPs) in marine sediment samples.     

Interlaboratory variability of amphipod sediment toxicity tests in a cooperative regional monitoring program

Marine sediment toxicity tests are widely applied in monitoring programs, yet relatively little is known about the comparability of data from different laboratories. The need for comparability information is increased in cooperative monitoring programs, where multiple laboratories (often with variable skill levels) perform toxicity tests. An interlaboratory comparison exercise was conducted among seven laboratories in order to document the comparability of sediment toxicity measurements during the Bight'98 regional sediment survey in southern California. Sediments from four stations in Los Angeles and Long Beach Harbors were tested using a 10-day survival test of the amphipod Eohaustorius estuarius. All laboratories successfully performed the sediment test and associated reference toxicant test. Statistically significant differences were found in mean amphipod survival rates among some laboratories for the field-collected sediments, but there was little evidence of a consistent bias among laboratories. Although the reference toxicant test indicated a five-fold variation in test sensitivity among laboratories, these results were not accurate predictors of interlaboratory performance for the sediment tests. The laboratories demonstrated excellent concordance (Kendall's W = 0.91) in ranking the field-collected sediments by toxicity. Agreement on classifying the sediments into categories (nontoxic, moderately toxic, and highly toxic) based upon the percent of survival was best for highly toxic sediments. An analysis of test precision based upon the variance among replicates within a test indicated that the measured survival rate for a sample may vary by up to 12 percentage points from the actual response.     

The application of ICP-SMS, GF-AAS and HG-AFS to the analysis of water and sediment samples from a temperate stratified estuary

Three atomic spectrometry techniques, namely sector field inductively coupled plasma mass spectroscopy, graphite furnace atomic absorption spectrometry and hydride generation atomic fluorescence spectroscopy (ICP-SMS, GF-AAS and HG-AFS, respectively), housed at separate independent laboratories, were used to analyse water and sediment samples collected from the Huon River Estuary, SE Tasmania (Australia) in the Austral spring 1998. A dithiocarbamate-chelation/back-extraction technique was used to separate and preconcentrate Co, Ni, Cu, Zn, Cd and Pb from eight collected water samples prior to analysis by ICP-SMS and GF-AAS. A number of other elements in the waters were analysed directly (Mn, Fe and Zn by GF-AAS; As by HG-AFS), or following sample dilution (1 + 19: V, Mn, Fe, As, Mo, Ba and U by ICP-SMS). Where possible, previously corroborated GF-AAS and HG-AFS techniques were used to verify obtained ICP-SMS results. From the analysis of four reference waters (SLEW-1 and -2, SLRS-3 and NASS-5), good agreement, to within +/- 10-20%, was typically found between certified (or information only values) and measured results (irrespective of analytical technique). Exceptions included Zn (and sometimes Fe) that could not be quantified by ICP-SMS due to elevated blank signals, and As which was found to lie below ICP-SMS detection limits. For Huon Estuary water samples, inter-method agreement was within +/- 10-20% (for those elements amenable to analysis by more than one technique). Nitric acid extracts of two certified reference materials (Buffalo River Sediment and BCSS-1) and six Huon Estuary sediments were analysed by ICP-SMS (for Al, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Cd and Pb) and HG-AFS (for As). Results from the certified reference materials indicated extraction efficiencies of 60 70% (for most elements). A close correlation between ICP-SMS and HG-AFS was obtained for leachable As in the sediments. In terms of potential inorganic contaminants, the Huon Estuary was found to be a relatively 'clean' water system. The elemental concentrations measured in water and sediment samples from this region were found to lie within current Australian guidelines for estuaries. In general, no one analytical technique was able to accurately determine all elements in all samples from this relatively pristine estuarine environment. A combination of all three analytical techniques was necessary for the successful analysis of the elements considered in this study.     

Effective monitoring of pollution by toxic trace elements in waters,sediment and biota of the Derwent River Estuary,Tasmania, through long-term retention of analytical facilities

This study considers the effectiveness of the monitoring of toxic trace elements in various media from a polluted river estuary over a period of 15 years, using the same analytical techniques, facilities and, in some cases, the same operators. It shows that reliable comparisons can be made for monitoring waters, sediment and biota from the Derwent River Estuary between 1975 data and that from 1990. Rigorous studies were undertaken before and during 1975 to ensure that reliable data was achieved at that time. Such studies are reviewed and included the evaluation of digestion techniques for a range of heavy metals, specific attention to the reliability of mercury determination in sediments between laboratories, a comparison of direct calibration and standard addition techniques for metals in seawater, recoveries of an organomercury compound from fish, and sources of error arising from sample preparation of biota for subsequent metal analysis. Comparative results for standard reference materials in both 1975 and 1990 show good agreement and are considered reliable except for lead at low concentrations. The long-term retention of the analytical facilities permits a direct comparison of data from 2 monitoring programmes over the space of 15 years.     

Natural attenuation of coal combustion waste in river sediments

The weathering of coal combustion products (CCPs) in a lotic environment was assessed following the Tennessee Valley Authority (Kingston, TN) fly ash release of 2008 into surrounding rivers. Sampled materials included stockpiled ash and sediment collected from 180 to 880 days following the release. Total recoverable concentrations of heavy metals and metalloids in sediment were measured, and percent ash was estimated visually or quantified by particle counts. Arsenic and selenium in sediment were positively correlated with percent ash. For samples collected 180 days after the release, total concentrations of trace elements downstream of the release were greater than reference levels but less than concentrations measured in stockpiled ash. Total concentrations of trace elements remained elevated in ash-laden sediment after almost 2.5 years. A sequential extraction procedure (SEP) was used to speciate selected fractions of arsenic, copper, lead, nickel, and selenium in decreasing order of bioavailability. Concentrations of trace elements in sequentially extracted fractions were one to two orders of magnitude lower than total recoverable trace elements. The bulk of sequentially extractable trace elements was associated with iron-manganese oxides, the least bioavailable fraction of those measured. By 780 days, trace element concentrations in the SEP fractions approached reference concentrations in the more bioavailable water soluble, ion exchangeable, and carbonate-bound fractions. For each trace element, the percentage composition of the bioavailable fractions relative to the total concentration was calculated. These SEP indices were summed and shown to significantly decrease over time. These results document the natural attenuation of leachable trace elements in CCPs in river sediment as a result of the loss of bioavailable trace elements over time.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

Determination of arsenic species in fish, crustacean and sediment samples from Thailand using high performance liquid chromatography (HPLC) coupled with inductively coupled plasma mass spectrometry (ICP-MS)

Suitable techniques have been developed for the extraction of arsenic species in a variety of biological and environmental samples from the Pak Pa-Nang Estuary and catchment, located in Southern Thailand, and for their determination using HPLC directly coupled with ICP-MS. The estuary catchment comprises a tin mining area and inhabitants of the region can suffer from various stages of arsenic poisoning. The important arsenic species, AsB, DMA, MMA, and inorganic arsenic (As III and V) have been determined in fish and crustacean samples to provide toxicological information on those fauna which contribute to the local diet. A Hamilton PRP-X100 anion-exchange HPLC system employing a step elution has been used successfully to achieve separation of the arsenic species. A nitric acid microwave digestion procedure, followed by carrier gas nitrogen addition- (N2)-ICP-MS analysis was used to measure total arsenic in sample digests and extracts. The arsenic speciation of the biological samples was preserved using a Trypsin enzymatic extraction procedure. Extraction efficiencies were high, with values of 82-102%(As) for fish and crustacean samples. Validation for these procedures was carried out using certified reference materials. Fish and crustacean samples from the Pak Pa-Nang Estuary showed a range for total arsenic concentration, up to 17 microg g(-1) dry mass. The major species of arsenic in all fauna samples taken was AsB, together with smaller quantities of DMA and, more importantly, inorganic As. For sediment samples, arsenic species were determined following phosphoric acid (1 M H3PO4) extraction in an open focused microwave system. A phosphate-based eluant, pH 6-7.5, with anion exchange HPLC coupled with ICP-MS was used for separation and detection of AsIII, AsV, MMA and DMA. The optimum conditions, identified using an estuarine sediment reference material (LGC), were achieved using 45 W power and a 20 minute heating period for extraction of 0.5 g sediment. The stability and recovery of arsenic species under the extraction conditions were also determined by a spiking procedure which included the estuarine sediment reference material. The results show good stability for all species after extraction with a variability of less than 10%. Total concentrations of arsenic in the sediments from the Pak Pa-Nang river catchment and the estuary covered the ranges 7-269 microg g(-1)and 4-20 [micro sign]g g(-1)(dry weight), respectively. AsV was the major species found in all the sediment samples with smaller quantities of AsIII. The presence of the more toxic inorganic forms of arsenic in both sediments and biota samples has implications for human health, particularly as they are readily 'available'.     

Certification of the extractable contents of Cd, Cr, Cu, Ni, Pb and Zn in a freshwater sediment following a collaboratively tested and optimised three-step sequential extraction procedure

Sequential extraction procedures have been used during the last decades to study and determine trace element mobility in aquatic sediments. However, the results obtained are operationally defined and, therefore, the significance of the analytical results is related to the extraction scheme used. So, there is a need for suitable reference materials for this type of study to enable the validation of the methodologies and to control the quality of the measurements. This paper describes the preparation of a sediment reference material, BCR-701, the homogeneity and stability studies and the analytical work performed for the certification of the extractable contents of some trace elements, following a collaboratively tested and optimised sequential (three-step) extraction procedure. The paper contains all the results and gives the methods used to certify the extractable contents (mass fractions expressed as mg kg-1 on a dry matter basis) of Cd, Cr, Cu, Ni, Pb and Zn in all steps. Moreover, indicative values are given for the aqua regia extractable contents of the six elements in the sediment and the residue obtained after sequential extraction.     

Soils and sediments of the Thua Thien-Hue Province (central Vietnam): recognizing trace element sources and the likely influence of natural events

Trace element concentrations have been measured in soil and sediment samples taken from the Thua Thien Hue (TT-H) Province and the Tam Giang-Cau Hai (TG-CH) Lagoon in 2002 and 2004. Results show that the lagoon is only slightly contaminated by elements such as Ag, Cd, Cr, Cu, Ni, Pb and Zn, whereas As, probably naturally enriched in this Asian region, reaches values above the lowest internationally accepted sediment quality guidelines. Concentrations in soils are ascribable to natural sources and distributions in the TG-CH Lagoon are mainly influenced by river inputs, with Ag and Cd undergoing estuarine desorption processes. However, concentration-depth profiles of most trace elements in sediments show a recent increasing trend that might be linked to the economic development of the area. The comparison of porosity and (210)Pb depth profiles (confirmed also by Cd and As) from repeated samplings of the same core locations in the TG-CH Lagoon seems to account for a loss of 5-10 cm of surficial sediment that took place during the time interval between the two samplings. It is hypothesized that extreme meteorological events (e.g. a major typhoon that hit the area in November 2003) could be responsible for such sediment displacement.     

微波消解电感耦合等离子体质谱法测定土壤中稀土金属元素

建立了一种电感耦合等离子体质谱测定土壤中微量稀土金属的方法.分析了土壤标准样品中的微量稀土元素,结果与标准值一致.土壤实际样品分析也得到可靠结果.该方法样品采用微波溶样,灵敏度高,是一种比较可靠的微量稀土元素分析新方法.     

Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.     

Interpretation of standard leaching test BS EN 12457-2: is your sample hazardous or inert?

A slag sample from a lead refiner has been obtained and given to two analytical laboratories to determine the release of trace elements from the sample according to BS EN 12457-2. Samples analysed by one laboratory passed waste acceptance criteria, leading it to be classified as an inert material; samples of the same material analysed by the other laboratory failed waste acceptance criteria and were classified as hazardous. It was found that the sample preparation procedure is the critical step in the leaching analysis and that the effects of particle size on leachability should be taken into account when using this standard. The purpose of this paper is to open a debate on designing a better defined standard leaching test and making current waste acceptance criteria more flexible.     

Preparation and evaluation of candidate certified reference materials (CRMs) for nutrients in seawater

Certified reference materials (CRMs) are an essential part of the quality assurance (QA) necessary for the reliable analytical measurement of nutrients in seawater. The CRMs currently available for these analyses are not matrix matched to marine samples. QUASIMEME routinely produces test materials for the nutrients in seawater and nutrients in estuarine water and low-salinity open water Laboratory Performance Studies (LPS) that are both homogeneous and stable. QUASIMEME, in conjunction with Eurofins Scientific, Denmark have produced two reference materials (RMs). The homogeneity testing and preliminary stability studies were carried out by QUASIMEME, and the results are presented in this article. Participants of the QUASIMEME LPS who demonstrated satisfactory long-term performance for the analysis of nutrients in seawater and nutrients in estuarine water and low-salinity open water were invited to take part in the certification exercise. Twenty laboratories returned data, a summary of which is also presented. The certification and long-term stability testing and additional data analysis were carried out by Eurofins Scientific, Denmark, and are outwith the scope of this article and not reported here. Eurofins Scientific, Denmark have marketed these RMs as part of their range of VKI Reference Materials (further information is available from eurofins@eurofins.dk).     

土壤重金属元素检测国际实验室比对研究

IERM和CNAS合作组织开展了亚太实验室合作组织(APLAC)能力验证计划"APLAC T066土壤重金属元素检测",其目的是评价参加实验室定量分析土壤重金属元素总量的能力。研究所用的能力验证样品为IERM研制的土壤标准样品。结果表明,参加实验室检测土壤砷、铜、汞、镍、铅和锌的结果满意率分别为85.7%、95.8%、77.1%、83.3%、93.5%和91.7%。样品消解过程加入氢氟酸时,铅和锌的检测结果与标准值更加接近,说明检测土壤重金属元素总量时氢氟酸的加入非常关键。文章还对比对实验室结果评价的统计方法进行了探讨。     

Fraction distribution and risk assessment of heavy metals and trace elements in sediments of Lake Uluabat

To examine the status and risk of heavy metal pollution, the distribution of As, Cd, Cr, Ni, and Pb in the sediment of Lake Uluabat was characterized. The present study used a four-stage method to assess the ecotoxicological effects of the heavy metal and trace elements fractions in the sediment of Lake Uluabat. Total Cr and Ni concentrations in the sediment were determined to have exceeded the severe effect level (SEL) limit values. The percentages of the variable fractions of Cr and Ni were below 10%. Because of this reason, they were not defined to have a high risk. The relationships among the physicochemical parameters, heavy metals and trace elements in water and sediment were determined statistically. Pb, Cd, and As in the water were found in relation with some of the fractions. Moreover, it was thought that the amounts of the elements of As releasing into the water might be increased due to their relations with the physicochemical parameters.     

Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials

The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission proposed a three-step sequential extraction procedure for sediment analysis, following extensive expert consultations and two interlaboratory studies. This scheme was recently used to certify the extractable trace element contents of a sediment reference material (CRM 601). Although this procedure offers a means to ensure the comparability of data in this field, some difficulties concerning the interlaboratory reproducibility still remain, and a new project is currently being conducted to determine the causes of poor reproducibility in the extraction scheme. The final objective of the project is the certification of new sediment and soil reference materials for their extractable contents of Cd, Cr, Cu, Ni, Pb and Zn. This paper presents the results of a small-scale interlaboratory study, which aimed to test a revised version of the extraction schemes by comparing the original and the modified protocols using the CRM 601 sample. This work offers an improvement to the BCR sequential extraction procedure through intercomparison exercises. This improved procedure will allow the obtaining of CRMs to validate analytical data in the analysis of soils and sediments, and it will also facilitate comparability of data in the European Union.     

An assessment of trace element contamination in intertidal sediment cores of Sunderban mangrove wetland, India for evaluating sediment quality guidelines

This paper presents a comprehensive account regarding concentration, distribution and possible sources of trace elements (Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn) in 20-30 cm sediment cores (<63 microm particle size) collected at the confluence of the Ganges River and Bay of Bengal (Sunderban wetland, India). This work aims to evaluate the fluvio-marine and geochemical processes influencing the metal distribution. The most interesting features are the downward increase of concentrations of majority of the elements reaching overall maximum values at a depth of 10-15 cm observed in station Lot No.8 located along the main stream of the Ganges estuary as well as an overall elevated concentration of all the elements in the lower littoral zone. The interelemental relationship revealed the identical behaviour of elements during its transport in the estuarine environment. The overall variation in concentration can be attributed to differential discharge of effluents originating from industrial and agricultural as well as from domestic sewage. Arsenic exceeded effects range - low (ER - L) concentrations, implying occasional or frequent adverse biological effects. For Cu, Ni and Cr a smaller proportion of samples had exceeded the ER - L values indicating that the dataset would be suitable for future use in evaluating predictive abilities of SQGs.     

Seasonal and spatial distribution of trace elements in the water and sediments of the Tsurumi River in Japan

The Tsurumi, a class-one Japanese river, has a significant metal loading originating from urban environment. Water and sediment samples were collected from 20 sites in winter and summer, 2009 and were analyzed to determine and compare the extent of different trace element enrichment. A widely used five-step sequential extraction procedure was also employed for the fractionation of the trace elements. Concentrations of zinc, copper, lead, chromium, and cadmium were three to four times higher than that of reference values and downstream sediments are much more polluted than the upstream sites. Geochemical partitioning results suggest that the potential trace metal mobility in aquatic environment was in the order of: cadmium > zinc > lead > copper > cobalt > chromium > molybdenum > nickel. About 80.2% zinc, 77.9% molybdenum, 75.3% cobalt, 63.7% lead, 60.9% copper, 55.1% chromium, and 39.8% nickel in the sediment were contributed anthropogenically. According to intensity of pollution, Tsurumi river sediments are moderately to heavily contaminated by zinc, lead, and cobalt. Enrichment factor values demonstrated that zinc, lead, and molybdenum have minor enrichment in both the season. The pollution load index (PLI) has been used to access the pollution load of different sampling sites. The area load index and average PLI values of the river were 7.77 and 4.93 in winter and 7.72 and 4.89 in summer, respectively. If the magnitude of pollution with trace metal in the river system increases continuously, it may have a severe impact on the river’s aquatic ecology.     

Comparative assessment of essential and heavy metals in fruits from different geographical origins

The aim of this investigation was to estimate and compare essential and heavy metals contents in 98 commercially available fresh fruits from different geographic regions using multivariate techniques. The concentrations of 12 elements (calcium, magnesium, potassium, sodium, phophorus, cobalt (Co), manganese, iron, chromium (Cr), nickel (Ni), zinc and copper) were determined using flame atomic absorption spectrometry with deuterium-background correction. Phosphorus was determined in the form of phosphomolybdate by a spectrophotometric method. Reliability of the procedure was checked by analysis of the certified reference materials tea (NCS DC 73351), cabbage (IAEA-359) and spinach leaves (NIST-1570). Recoveries of the elements analysed varied between 85.5 and 103 %, and precisions for the reference materials were 0.13–6.08 %. Based on recommended dietary allowance and adequate intake estimated for essential elements, it was concluded that accessory fruits such as pineapples, raspberries and strawberries supply organism with the highest amounts of bioelements. Although accessory fruits were also found to be the greatest source of Ni among all the analysed fruits, in all the fruits Ni was more abundant than Cr and Co. Significant correlation coefficients (p?<?0.001, p?<?0.01 and p?<?0.05) were found between concentrations of some metals in fresh fruits. Application of ANOVA Kruskal–Wallis test and multivariate techniques such as factor analysis and cluster analysis enabled us to differentiate particular botanical families and types of fruits.