Homogeneity and stability study of the candidate reference material Adamussium colbecki for trace elements

The preparation of a new candidate certified reference material (CRM) for trace elements based on the antarctic bivalve Adamussium colbecki(IRMM 813) was carried out by the Istituto Superiore di Sanità(ISS, Rome, Italy) in cooperation with the Institute for Reference Materials and Measurements, Joint Research Centre of the European Commission (EC-JRC-IRMM), in the frame of the Italian National Programme of Research in Antarctica (Programma Nazionale di Ricerca in Antartide, PNRA). Samples were collected at Terra Nova Bay (Ross Sea) during the 2000-2001 expedition in Antarctica. The preparation of a material suitable for certification was performed by the EC-JRC-IRMM. Measurements for homogeneity and short-term stability tests were carried out by ISS. The elements selected for the certification project were As, Cd, Cu, Cr, Fe, Mn, Ni and Zn. For the above-mentioned tests, the determination of the elements of interest was performed on samples mineralised by microwave-assisted acid digestion. The analytical techniques employed to this end were inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma dynamic reaction cell quadrupole mass spectrometry (ICP-DRC-Q-MS). The candidate material was shown to be fit for purpose with regard to homogeneity and short-term stability, thus allowing the following phases of the certification project to be undertaken, in the first place the selection of expert laboratories for the accomplishment of the certification campaign.     

Behaviour and fluxes of trace and toxic elements in creek sediment near Mumbai,India

Studies on marine sediments are extremely important since they act as ultimate sink of anthropogenic pollutants. The present study was conducted near Mumbai city of India to understand andassess the behaviour and fluxes of trace and toxic elements increek sediment. Seven sediment core samples were collected andanalysed for trace and toxic elements such as Fe, Cu, Pb, Zn, Rb and Sr in different sections of the core using EDXRF technique. The fluxes of the elements in each section of the core were calculated using the mass sedimentation rates derivedfrom ²¹⁰Pb dating technique and the sediment density at each location. The estimated depositional fluxes of Fe, Rb and Sr in Zone-1 and Zone-3 are in the ranges of 0.4–0.5% cm^-2yr^-1; 4–6 g cm^-2 yr^-1 and 10–20 g cm^-2 yr^-1 respectively, where as they were about 3–4 times higher in zone-2 for the same elements. The depositionalfluxes of elements Cu (40–60 g cm^-2 yr^-1), Zn (35–43 g cm^-2 yr^-1) and Pb (6–12 g cm^-2 yr^-1) were also found to be higher in zone-2 compared tozone-1 and zone-3 which can be attributed to the release from thenewly developed chemical zone of Thane-Belapur industrial belt.     

Distribution and baseline values of trace elements in the sediment of Var River catchment,southeast France

This study reports on the determination of trace element (TE)—Li, As, Co, Cs, Cu, Pb, U, and Zn—and major element (ME)—Si, Al, Fe, Mg, Ca, Mn, Na, and K—concentrations in 18 riverbed sediments and a sediment core from the Var River catchment using inductively coupled plasma mass spectrometry (ICP-MS). The results were compared with those of a reference sediment core, and the contribution of clay and organic carbon contents in the distribution of TE and ME in the sediment samples was investigated. The mean concentrations of the ME were comparable in both core and riverbed samples and were within the natural averages. In the case of TE, the concentrations were lower in riverbed sediment samples than those found in the sediment core. High mean concentration of As was observed (7.6 μg g^?1) in both core and riverbed sediments, relatively higher than the worldwide reported values. The obtained data indicated that the natural high level of arsenic might be originated from the parent rocks, especially metamorphic rocks surrounding granites and from Permian sediments. Statistical approach, viz., Pearson correlation matrix, was applied to better understand the correlation among TE in both riverbed and sediment core samples. No significant metallic contamination was detected in the low Var valley despite of the localization of several industrial facilities. Therefore, results confirm that the concentrations of the TE obtained in the riverbed sediments could be considered as a baseline guide for future pollution monitoring program.     

Historical pollution of seldom monitored trace elements in Sweden--Part B: sediment analysis of silver, antimony, thallium and indium

Sediment cores from four boreal and remote lakes in a south to north transect in central Sweden were analysed for acid leachable silver, antimony, thallium and indium in the solid sediment phase and the corresponding porewater. Dating of the cores was made by their content of acid leachable lead and the (206)Pb/(207)Pb ratio, in one lake also by (210)Pb. The impact of diagenesis on element redistribution in the sediments was included and found to be minor except for thallium. The results show lowered concentrations towards the north and most intense accumulation after the Second World War, which is taken as evidence for atmospheric deposition being the primary source. Indium has declining concentrations in recent strata while silver and antimony increase. Thallium has lowered acid-leachable concentrations in recent strata. For all metals the impact of domestic industrialisation as well as the early industrialisation of central Europe is discernible. Only thallium appears to reach a geological background at depths that correspond to the late 18th century. For the other metals elevated levels are concluded.     

Historical pollution of seldom monitored trace elements in Sweden--Part A: sediment properties and chronological indicators

Sediment cores from four small oligotrophic boreal lakes, with minor acidification, in remote regions of central Sweden were used for historical interpretation of their metal content, with focus on Cu, Cd, Pb and Zn in Lake Stensj?n, which has the longest sediment record (at least two centuries according to (210)Pb dating). Comparison is made with the other three lakes. Major and trace elements in lake water, porewater and the acid-leached (HNO(3)) solid sediment phase was analysed with ICP-MS. In addition, general lake water chemistry, TOC and principal anions were measured in the aqueous phases. Redistribution processes were interpreted from geochemical modelling. The solid/solution distribution of pe/pH sensitive elements, indicates a minor diagenetic redistribution and the concentration profiles are therefore suitable for chronological evaluation. The ratios of Al, Ti, Sc and V, indicated a qualitative shift of sedimenting material a century ago, which did not have any impact on the retention of trace elements. Lead had a concentration profile, supported by the (206)Pb/(207)Pb ratio, where it was possible to distinguish preindustrial conditions, early industrialisation in Europe, industrialisation in Sweden, and the use of leaded petrol after the Second World War. Cadmium showed a similar concentration pattern. The zinc profile resembled that of cadmium, but with less enrichment. Local lithogenic sources are believed to be quantitatively important. The solid/solution distribution (K(d)) was independent of depth for all four elements. The sediment concentrations of copper and zinc are not related to early industrialisation but its concentration has doubled since the Second World War.     

Copper and other trace elements strongly bound to humic acids along sediment cores in the Ross Sea, Antarctica

Marine sediment cores sampled in three different areas, during the 1997/98 Italian Antarctic Expedition, were studied. The cores (40 cm) were immediately subdivided into 13 or 14 layers (2-4 cm) in order to obtain a high-depth resolution in the metal content and humic substance analyses. The results obtained for the amount of metals strongly bound to humic acids showed the following order: Cu > Zn > Co > As >or= Mn. The fraction of Cu, Zn and As bound to humic acid (microg g(-1) of HA) increases in the first 10-12 cm of cores, then a decrease is observed. This observation could be related both to the presence of a mobile fraction of metals in sediments successively bound to humic acids and to different structural features showed by humic acids along the cores, due to transformation processes. For the other metals a variable pattern along the cores was found.     

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.     

Regional assessment of marine and estuarine sediment toxicity in Southern California, USA

Sediment toxicity was investigated at 222 stations in the Southern California Bight (SCB) during 2008. This represented the first time that assessment methods established by California's new Sediment Quality Objectives program were employed in a survey of this scale. The goal was to determine the extent and magnitude of sediment toxicity in the SCB, how toxicity compared among specific environments, and whether toxicity has changed over the last decade. Two toxicity tests were used: the 10-day amphipod whole sediment survival test with Eohaustorius estuarius and a 48-h embryo development test with the mussel Mytilus galloprovincialis exposed at the sediment–water interface. Less than 1 % of the area of the SCB was found to be toxic to the amphipod test. No toxicity was found in offshore stations, but 14 % of embayment areas were toxic to the amphipods. The mussel test identified 13 % of the embayment areas to be toxic. Estuary and marina locations had the greatest areal extent of toxicity for both tests. The two toxicity methods agreed that sediments were not toxic at over half of the stations tested. The mussel test showed a greater magnitude of response than the amphipod. Sediment toxicity was shown to have declined in both extent and magnitude from levels measured in 1998 and 2003.     

Feasibility study prior to the certification of trace elements in urban and industrial wastewater reference materials

Reliable results for the determination of trace elements in urban and industrial wastewaters are of paramount importance for both checking the performance of sewage treatment and for detecting possible urban or industrial contamination sources. The quality control of measurements should in principle rely on external tools such as certified reference materials (CRM), which should represent, as closely as possible, the matrix of samples currently analysed, e.g., in the frame of environmental monitoring. To date, however, no CRM representatives of wastewater composition are available, which limits the possibility for control laboratories to check their QC externally. To fill this gap, the European Commission's Standards, Measurements and Testing Programme (formerly BCR) has started a European collaborative project of which the aim is to test the feasibility of preparation of wastewater reference materials and the analytical state-of-the-art to enable the certification of trace elements in such matrices. This paper presents the results of the first phase of this project, namely the feasibility study and the results of an interlaboratory trial.     

Atmospheric deposition of major and trace elements in Amman, Jordan

Wet and dry deposition samples were collected in the capital of Jordan, Amman. Concentrations of Al, Ba, Bi, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, V, Zn, Fe, Sr, Mg²⁺, Ca²⁺, Na⁺, K⁺, Cl⁻, NO₃ ⁻ and SO₄ ²⁻, along with pH were determined in collected samples. Mean trace metal concentrations were similar or less than those reported for other urban regions worldwide, while concentrations of Ca²⁺ and SO₄ ²⁻ were among the highest. High Ca²⁺ concentrations were attributed to the calcareous nature of the local soil and to the influence of the Saharan dust. However, high SO₄ ²⁻ concentrations were attributed to the influence of both anthropogenic and natural sources. Except for Cl⁻, NO₃ ⁻, SO₄ ²⁻ and Cu, monthly dry deposition fluxes of all measured species were higher than wet deposition fluxes. The annual wet deposition fluxes of trace metals were much lower than those reported for other urban areas worldwide.     

Using watershed characteristics,sediment, and tissue of resident mollusks to identify potential sources of trace elements to streams in a complex agricultural landscape

Trace elements used in animal feed additives can be introduced to aquatic environments through application of manures from animal feeding operations to agricultural land as fertilizer. The use of poultry feed additives containing arsenic (As) is of particular concern in the Shenandoah River watershed (Virginia, USA), an agricultural landscape with a high density of poultry operations. This study investigated the relationship between watershed characteristics of Shenandoah River tributaries and trace element concentrations in streambed sediment and tissue of resident mollusks, including: Asian clams (Corbicula fluminea), which are commonly used biomonitors, and pleurocerid snails (Leptoxis carinata), which are generally understudied. Results failed to support the primary hypothesis of a predictive relationship between watershed densities of poultry operations and As concentrations in sediment and mollusk tissue. However, there were statistical relationships between land use in tributary watersheds and other trace elements in sediment (Cu, Mn, Pb, Zn) and tissue (Cd, Hg, Pb). Principal components analysis of the sediment data suggested a possible geologic source of As at some sites. Tissue concentrations of As were significantly higher in snails than in clams, but clams accumulated higher concentrations of other trace elements (Cd, Cr, Hg, Pb, Se). Snails may be useful biomonitors of environmental As, but appear to be less suitable than clams for studies of landscape sources of other trace elements.     

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.     

Concentration of trace elements in feathers of waterfowl,Korea

Cadmium (Cd), lead (Pb), chromium (Cr), copper (Cu), manganese (Mn), zinc (Zn), and iron (Fe) were analyzed in the breast feather of white-fronted geese (Anser albifrons, n?=?15), mallards (Anas platyrhynchos, n?=?4), and spot-billed ducks (Anas poecilorhyncha, n?=?13) found dead in Gimpo, Korea. All of the mallards and eight of the 13 spot-billed ducks had embedded shot. Concentrations of Pb, Cr, Cu, Mn, Zn, and Fe were significantly different among waterfowl species. Mallards with embedded shot had relatively higher Pb, Cr, Mn, and Fe concentrations than the other species. Cd and Cr in feathers of waterfowl species were within the range reported for other birds, and no specimen exceeded the tentative threshold effect levels of Cd (2 μg/g dry weight (dw)) and Cr (2.8 μg/g dw) for birds. However, Pb in feathers of all four mallards and two spot-billed ducks exceeded the threshold for deleterious effects (>4 μg/g dw). Essential elements such as Cu, Mn, Zn, and Fe in the feather of waterfowl species were not at toxic levels and within the background or normal range for the homeostatic mechanisms.     

Reactivity, interactions and transport of trace elements, organic carbon and particulate material in a mountain range river system (Adour River, France)

The background levels, variability, partitioning and transport of eleven trace elements-Ag, Al, As, Cd, Co, Cr, Cu, Mn, Pb, Zn and U-were investigated in a mountain range river system (Adour River, France). This particular river system displayed a turbulent hydrodynamic regime, characterized by flash-transient discharge conditions leading to fast shifts in suspended particulate matter (SPM) concentrations as high as two orders of magnitude (12 to 600 mg l(-1)). The distribution of SPM was accurately predicted with a "hysteresis" transport model, indicating that about 75% of the annual solids load was exported within 20 to 40 days. Dissolved and particulate concentrations of most trace elements were low compared to their concentrations in other reference river systems expect for Pb and Cr, associated with historical anthropogenic activities. Although dissolved and particulate metal concentrations were steady for most elements during low and average discharge conditions, significant changes were observed with increasing river discharge. The changes in trace element concentrations in the two compartments was found to induce a partitioning anomaly referred to as the particulate concentration effect. This anomaly was significant for Cr, Mn, Pb, Zn, Cu and organic carbon (p < 0.03). The processes driving this anomaly were possibly linked to the modification and/or increase of colloidal organic and inorganic vectors, suggested by the significant increase of DOC (p < 0.001) and dissolved Al concentrations (p < 0.05) during flood conditions. A complementary process linked to the influence of coarse particles of low complexation capacity and transported mainly during high discharge may also effect trace element concentrations. Annual metal fluxes transported by this river system were estimated using the hysteresis SPM model with consideration of these fate processes. Metals in the Adour River system are primarily exported into the Bay of Biscay (Atlantic Ocean).     

Air quality and deposition of trace elements in Didouche Mourad, Algeria

Total suspended particulate matter and deposition fluxes of particles were investigated in the town of Didouche Mourad which is located 13 km north of Constantine. Samples of air particulate matter were collected at one site located in the heart of the town and situated 3 km north of a cement plant. Samples were collected from 2 November 2002 to 28 April 2003 every 3 days using a high volume air sampler. Sampling intervals were 24 h in all cases. During the same period, samples of dust fallout were collected at the same site. Samples were collected at 30-day intervals. Lead, chromium, manganese, nickel, copper, cobalt and cadmium deposition fluxes were measured and both the soluble and insoluble fractions were determined. Furthermore, the information gathered by this study was correlated with the corresponding hourly weather data provided by a weather station installed at the study station. The possible sources for dust and trace metals were analyzed by comparing average contributions of wind aspects to the concentrations and depositions of mass and chemical species with the average frequencies of wind direction. The mean concentration was 300 μg/m³. The average dust deposition rate through the period of study was 221 mg/(m².day). Results indicate that anthropogenic sources contribute greatly to trace elements. An exposure assessment to the heavy metals taking into account the inhalation route and soil dust ingestion was carried out and allowed direct comparison of trace metal intakes via these routes.     

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.     

PCB congener distribution in estuarine water,sediment and fish samples: implications for monitoring programs

Traditional analyses for PCBs in environmental matrices havefocused on commercial Aroclor mixtures with detection limits inthe 100 to 1000 part per trillion range. This approach hasrecently been supplanted by analyses for specific PCB compoundscalled congeners with detection limits less than 0.5 ppt. At thenational level, total PCB determinations based upon selected PCBcongeners typically characterize analyses of surface water,sediment and tissue. These federal efforts rely on a suite of 18to 20 congeners out of a total of 209 congeners to characterizetotal PCB. The present study compares total PCB estimates basedupon this subset of congeners with estimates based upon anexpanded list of 81 congeners from water, sediment and fishtissue collected from the Delaware Estuary.Analytical data from monitoring programs conducted in theDelaware Estuary by the Delaware River Basin Commission, NOAANational Ocean Service, U.S. Army Corps of Engineers and the U.S.Environmental Protection Agency from 1996 to 1998 were evaluated. Total PCB estimates derived from the different sets of congeners,including the adjustment factor of 2.0 used by NOAA, werecompared. This evaluation indicated that differences existbetween total PCB determinations based upon these approaches, andthat these differences vary depending on the matrix analyzed. The bias associated with using a smaller set of PCB congeners,and the implications for risk assessment are discussed.     

Evaluation of the state-of-the-art of butyl- and phenyltin compound determinations in freshwater sediment prior to certification of a reference material

In order to control the quality of butyl- and phenyltin compound determinations in sediment, the Standards, Measurements and Testing Programme (formerly BCR) of the European Commission has started a project, the final aim of which is to certify a freshwater sediment for its contents of a range of organotin compounds (mono-, di- and tributyltin, and mono-, di- and triphenyltin). The first part of this project involved an interlaboratory study which aimed to test the feasibility of preparation of candidate freshwater sediment reference material and to detect and remove most of the pitfalls observed in organotin determinations. This paper presents the main results of this interlaboratory study carried out prior to the certification campaign. The agreement obtained among laboratories for the six compounds determined was considered to reflect the state-of-the-art and was encouraging enough to decide upon the organisation of a certification campaign, which will be concluded in June 1999.     

Study of trace elements in wet atmospheric precipitation in Tehran,Iran

In this study, measurements of the trace metals Zn, Cd, Cr, Ni, Pb, Cu, Fe and Al were performed on 53 wet atmospheric precipitation samples (snow and rainwater) collected at a central site of Tehran. Samples were collected using a bulk sampler equipped with a high-density polyethylene funnel from November to May in 2011 and 2012 on the roof of a building in the city centre. Trace metals in the filtered samples were measured with ICP-MS. Statistical analysis of the results revealed that Al, which is principally a crustal-derived element, was the highest mean measured concentration. The pH ranged from 4.2 to 7.1 with a mean value of 5.1. Crustal enrichment factors (EF_c) related to the relative abundance of elements in crustal material was calculated using Al as reference crustal. EF_c calculations indicated that samples were not enriched with Fe and Cr but were, fairly to extremely, enriched with Zn, Cd, Ni, Pb and Cu. Factor component analysis with varimax-normalized rotation was conducted to find the probable sources of the measured species. This resulted in two factors with eigenvalues greater than unity. Factor 1 showed an anthropogenic source, mostly industrial combustion and local traffic emissions, for Zn, Cd, Ni, Pb, and Cu while factor 2 showed a crustal contribution for Al, Fe and Cr.