Trace metals in aerosol at Terra Nova Bay, Antarctica

Atmospheric particulate with an aerodynamic diameter <10 microm (PM10) was sampled continuously during the austral summers of 2000-2001 and 2001-2002 at a coastal site near to the Italian base of Terra Nova, Antarctica. Li, Pb, Cd, U, Ba, Bi, Cs, Rb, Tl, Sr, Al, V, Fe, Cu, Mn, Zn, Co, Ag were determined by inductively coupled sector field mass spectroscopy (ICP-SFMS) after sample digestion by a combination of HF, HNO3, and H2O2 in ultraclean conditions. Quality control of the analytical procedure was carried out by blank control, by evaluating the limits of detection, recoveries and repeatability. Concentrations found are extremely low for most metals, confirming the high purity of Antarctic aerosol. Principal Component Analysis (PCA) highlights high correlations among Pb, Cr, Bi, Cu and Zn concentration values and among Li, U, Ba, Cs, Rb, Al, V, Fe, Mn, Co concentration values permitting the identification of two principal source groups, namely crustal dust and human emission activities. Elements of anthropogenic origins (Pb, Cr, Cu, Zn) were highly enriched with respect to their crustal composition.     

Trace metals and radionuclides in macroalgae from Moroccan coastal waters

Macroalgae species Codium sp, Bangia atropurpurea, Membranoptera alata, Plocamium cartilagineum, Dictyota dichotoma, Fucus spiralis and Stypocaulon scoparia were collected from seven stations along the north coast of Morocco. Samples were analysed to determine activities of naturally occurring radionuclides ((210)Pb, U isotopes and (40)K) and concentrations of metals (Zn, Fe, Co, Cu, Ni, Mn, Pb, Cd, As and Cr) using radiometric and ICP-OES techniques, respectively. Metal concentrations were within ranges reported in the scientific literature, and concentrations of bio-essential elements were in the order Mn>Fe> Zn>Cu in all samples. Brown algae had the highest concentrations of almost all metals, and concentrations decreased in the order brown>red>green algae. With respect to radionuclides, the red alga P. cartilagineum had the highest activities of (210)Pb, in most cases an order of magnitude higher than for the green alga Codium sp. (234)U and (238)U activities in all algae samples were in the range 0.96- 7.61 and 1.16-6.14 Bq/kg dry weight, respectively. Our analyses of radionuclide activities and metal concentrations in marine macroalgae showed large differences among taxa. These results provide insights into which algal species should be used for biomonitoring programmes.     

Carbon speciation in airborne particulate matter with C (1s) NEXAFS spectroscopy

Recent and current research activities on the chemical characterization of carbon in airborne carbonaceous particulate matter with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy are reviewed. NEXAFS spectroscopy uses soft X-rays from synchrotron radiation facilities and allows for the bulk and surface speciation of particulates smaller than 2.5 micrometres (PM 2.5). This relatively novel technique is often superior to TEM-EELS and FTIR spectroscopy. In the extreme case, one single PM particle is sufficient for characterization. Liquids, extracts, solid core and surface functional groups can be quantified. Preliminary data on combustion derived PM such as diesel soot, wood smoke and tobacco smoke are compared with ambient samples.     

Characterisation of particulate matter for toxic metals in ambient air of Kochi City, India

Measurement of respirable suspended particulate matter (RSPM) and analysis of toxic metals in air of Kochi city was carried out for a period of one year, 1997. Seasonal variations of RSPM and toxic metals are analysed to identify the influence of meteorological parameters. The air pollution problem with respect to RSPM and lead is moderately significant especially in winter season. The profile of other toxic metals in RSPM is not much significant. Domestic fuel used mainly coal/wood and petrol/diesel fueled motor vehicles are the major contributors to the RSPM and toxic metals. Various control strategies are delineated for reduction of ambient RSPM and toxic metals in air of Kochi city.     

Sorbed metals fractionation and risk assessment of release in river sediment and particulate matter

Fractionation of metals in natural sediment and suspended particulate matter (SPM) of Tadjan River is investigated. Competitive sorption, sorption capacities of sediment and SPM as well as fractionation of metal-loaded sediment and SPM are also examined. A risk assessment code (RAC) is applied to estimate the risk of heavy metals release into the environment during the sorption process. Results revealed that sediments and SPM containing more than 25 % of clay minerals and higher amounts of calcite have great capacity of metal sorption, particularly for Cu, Ni, and Mn. Assessing the risk of metals release prior to and following sorption tests indicates that RAC of metals would significantly increase from the level of no or low risk in natural sediment and SPM to high or very high risk after sorption. The Langmuir model reveals that the highest affinity for Cu, Mn, and Ni in sediment is the organic fraction. The classic isotherm models of Freundlich and Langmuir can fit the data from chemical extraction studies of adsorbed metals, indicating that although sorption was apparently a physical and chemical process in the river, isotherm models can be used to simulate the sorption and accumulation in different geochemical phases within the particulate matter.     

Arsenic concentration and speciation of the marine hyperaccumulator whelk Buccinum undatum collected in coastal waters of Northern Britain

European whelks (Buccinum undatum) have shown to accumulate high levels of arsenic. Since the accumulation process is not well understood it is necessary to gain information about the geographical variability of the arsenic concentration in them. Here we show that the mean arsenic concentrations of the whelks are site specific and vary by a factor of 3.5 in ten different geographical locations. At fishing grounds where whelks exhibited low arsenic concentrations the arsenic concentration increased linearly with size, whereas the whelks with high arsenic levels from a different location showed no correlation. Although the overall arsenic concentration in the whelks differed between 45 and 655 mg kg(-1) d.w., the inorganic arsenic concentration did not exceed 0.4 mg kg(-1) d.w. The main arsenic compound is arsenobetaine, which is widely considered as non-toxic. The exposure to toxic inorganic arsenic when eating whelks cannot be estimated from their size or their total arsenic concentration.     

Development of monitoring technology for airborne particulate matter

Particulate matter suspended in the air has adverse effects onhuman health. Its level of concentration is an important parameter in evaluating the degree of hazard it poses to the atmosphere. Conventional methods used in measuring particulatematter are often filter-based, which indicates some disadvantagesbecause such a base requires labor and time. In this study, to achieve real-time measurements, a new electrical method was developed for measuring PM10 and PM2.5 concentrations. The basicprinciple is to electrically charge particles passing through thePM inlet using a corona charger and measure the currents createdby charged particles to obtain the number concentration of particulate matter. A new type inlet based on the particle cupimpactor configuration was designed and its performance was evaluated. A unipolar diffusion charger was developed and thecharger's efficiency was determined experimentally in terms ofPn, which represents the penetration through the charger,P, times the average charge number acquired by a particle,n, for different particle sizes. The correlation was constructed between the PM10 (or the PM2.5) mass concentrationsand the electrical currents due to particles, which were chargedby the diffusion charger.     

Heavy metals concentrations in zooplankton and suspended particulate matter in a southwestern Atlantic temperate estuary (Argentina)

The present work includes part of the first studies of metals concentrations in the zooplankton from a heavily industrialized estuary of Argentina, the Bahía Blanca estuary. Cd, Cu, and Pb concentrations in the zooplankton (macro- and mesozooplankton) and the suspended particulate matter were measured at stations with different degree of pollution. Physicochemical variables and zooplankton composition and abundance were also analyzed. Thus, the aim of the present work was to analyze the spatial and temporal distribution of heavy metals in these two different fractions, and the possible relation among them due to their importance in the biogeochemical cycles of marine environments. Samplings were carried out during a year, from March 2005 to April 2006, every 2 months, at stations located near chemical and petrochemical industries, stations far from these points and one station in an intermediate location. In the mesozooplankton, the mean concentrations of Cd, Cu, and Pb were 3.63?±?1.46, 34.46?±?5.40, and 11.54?±?3.04 μg?g^?1 dry weight (d.w.) respectively, while in the macrozooplankton, 3.20?±?2.28, 21.86?±?4.79, and 8.36?±?1.85 μg?g^?1 d.w. On the other hand, particulate Cd, Cu, and Pb presented a mean concentration of 3.33?±?1.22, 12.75?±?2.67, and 12.53?±?3.20 μg?g^?1 d.w., respectively. Metals’ levels in both the SPM and zooplankton fluctuated throughout the study time and were relatively high in the particulate phase especially for Cu and Pb. Moreover, zooplankton accumulated important concentrations of the three metals. The sources of them are probably the discharges of the industries and domestic sewages located near the estuary.     

Distribution of heavy metals in water, particulate matter and sediments of Gediz River (Eastern Aegean)

The present paper is the first document of heavy metal levels in surficial sediment, water and particulate matter of the Gediz River collected from five different sites in August, October 1998, February, June 1999. The present work attempts to establish the status of distribution and environmental implications of metals in the sediment, water and particulate matter and their possible sources of derivation. The concentrations of mercury ranged 0.037–0.81, 120–430; lead 0.59–1.5, 190–8,100; copper 0.24–1.6, 30–180; zinc 0.19–2.9, 10–80; manganese 30–170, 20–490; nickel 0.39–9.0, 100–510; iron 1.3–687, 100–6,200 μg/l in water and particulate matter, respectively. The maximum values in water were generally obtained in summer periods due to industrial and agricultural activities at Muradiye. The particulate metal concentrations also generally showed increased levels from the upper Gediz to the mouth of the river. Calculation of metal partition coefficients shows that the relative importance of the particulate and the water phases varies in response to water hydrochemistry and suspended solid content, but that most elements achieve a conditional equilibrium in the Gediz River. The metals ranged between Hg: 0.25–0.49, Cr: 59–814, Pb: 38–198, Cu: 15–148, Zn: 34–196, Mn: 235–1,371, Ni: 35–175, and Fe: 10,629–72,387 mg/kg in sediment. The significant increase of metals found in Muradiye suggested a pollution effect, related to anthropogenic wastes. Also, relatively high concentrations of Ni and Mn occurred in sampling site upstream, due to geochemical composition of the sediments. Maximum values of contamination factor for metals were noticed for sediment of Muradiye. The sampling stations have very high degree of contamination indicating serious anthropogenic pollution.     

Ensuring quality in long term environmental monitoring for chemical speciation

The awareness regarding quality assurance (QA) and quality control (QC) for environmental monitoring has considerably increased in the past few years, especially with respect to the determination of chemical species, since errors occurring at various levels may considerably affect the interpretation of results (e.g. studies of toxic impact, geochemical pathways, etc.). QA for environmental analysis covers a broad range of activities from sample collection to laboratory work and the approach for ensuring quality data should be considered in a global context. However, whereas great emphasis has been placed on QA within the laboratory, there have been few systematic attempts to evaluate risks of discrepancies related, for example, to field manipulations. The situation is even worse when monitoring is applied to relatively new fields such as chemical speciation. This paper outlines some of the main aspects of quality control of environmental analysis, including the validation of methods, sampling and sample handling, storage, etc., with special emphasis on the monitoring of chemical forms of elements (e.g. species of tin, mercury, lead and selenium).     

Trace metal speciation and contamination in an intertidal estuary

An analysis of the geochemical distribution of selected trace metals among various geochemical phases of the sediments in the Tees estuary was carried out using a sequential extraction technique and Differential Stripping Voltammetry. The sediments of the estuary are mainly organic rich clay silts and metal concentrations exceed those in the water column. Speciation results show that contamination of the estuary is mainly from anthropogenic sources. Pb and Zn are associated with the reducible, residual and oxidisable fractions. The speciation pattern of Cd was similar to those of lead and zinc. However there were also some exchangeable and bound to carbonate fractions although these were less significant. Cu is largely associated with the oxidisable and residual fractions, with insignificant bound to carbonate, exchangeable and reducible fractions. The most bioavailable forms of the metals are the free inorganic ions. Total metal concentrations in the estuary display a downward trend since the 1970s.     

Airborne particulate matter and BTEX in office environments

Total suspended particulate (TSP), PM(2.5) and BTEX were collected in nine offices in the province of Antwerp, Belgium. Both indoor and outdoor aerosol samples were analysed for their weight, elemental composition, and water-soluble fraction. Indoor TSP and PM(2.5) concentrations ranged from 7-31 microg m(-3) and 5-28 microg m(-3), with an average of 18 and 11 microg m(-3), respectively. Of all the elements analysed in indoor TSP, more than 95% was represented by Al, Si, K, Ca, Fe, Cl and S, accounting for 12% of the TSP by mass. The other elements showed significant enrichment relative to the earth's crust. The water-soluble ionic fraction accounted for almost 30% of the sampled indoor TSP by weight, and was enriched by anthropogenic activities. It was shown that the indoor PM levels varied among the offices, depending on the ventilation pattern, location, and occupation density of the office. Indoor BTEX levels ranged together from 5-47 microg m(-3) and were considerably higher than the corresponding outdoor levels. It was observed that some recently constructed and renovated buildings were clearly burdened with elevated levels for toluene, ethyl benzene, and xylenes, while outdoor air was found to be the main source for BTEX levels at the 'older' offices.     

Designing an integrated environmental monitoring plan for land-based marine fish farms located at exposed and hard bottom coastal areas

The increase in aquaculture activities in the last few decades has not been accompanied by a corresponding increase in environmental controls and regulations. In this context, the application of environmental monitoring plans (EMPs) has become necessary to assess the environmental impact associated with fish farming wastes. The objective of this review paper is to evaluate the suitability of experimental and analytical procedures as monitoring tools for inclusion in EMPs for intensive land-based marine fish farms (LBMFFs). The strong hydrodynamics and, in particular, the lack of sediment on the rocky coasts where LBMFFs are usually located, greatly limit the monitoring tools that can be used. We propose EMPs that employ a weight-of-evidence approach to evaluate: contamination, trophic and toxic effects, and ecological integrity. Laboratory tests, in situ bioassays and field surveys of local species are presented as key tools for assessing the impact of LBMFFs on ecosystems. The δ(15)N signal along a spatial gradient is proposed for evaluating exposure to contaminants. Trophic effects can be determined by growth of transplanted macro- and microalgae. Toxic effects can be evaluated by responses at different levels of biological organization, including biochemical and histological changes, physiological alterations and survival, in species from different trophic levels. Fouling tests and analysis of community structures are recommended for assessing ecological integrity. This review contributes to the development of environmental controls for intensive LBMFFs, and for other activities that discharge wastewater to rocky shores.     

Seasonal variability of endotoxin in ambient fine particulate matter

Endotoxin is a toxic, pro-inflammatory compound that has been detected in indoor air and dust in homes and occupational settings, and also in outdoor air. Data on the outdoor sampling of endotoxin are limited. Currently, little is known about the seasonal variation and influence of temperature on outdoor endotoxin levels. In the present study, we report endotoxin levels in fine fraction particulate matter with a 50% aerodynamic cutoff diameter of 2.5 microm (PM2.5) and describe the seasonal variation of endotoxin in Munich, Germany. In 1999-2000, PM2.5 was collected at forty outdoor monitoring sites across Munich. Approximately four samples were collected at each site for a total of 158 samples. Endotoxin concentrations in the PM2.5 samples were determined using the kinetic chromogenic Limulus Amebocyte Lysate (LAL) assay. The geometric mean endotoxin concentration was 1.07 EU mg PM2.5(-1) (95% C.I.: 0.915-1.251) or 0.015 EU m(-3) of sampled air (95% C.I.: 0.013-0.018). Munich endotoxin levels were significantly related to ambient temperature (p < 0.0001) and percent relative humidity (p < 0.0001). Sampling periods with higher average temperatures yielded higher levels of endotoxin in PM2.5 (r = 0.641), whereas decreases in percent relative humidity were associated with increased endotoxin levels in PM2.5 (r = -0.388). Endotoxin levels were significantly higher during the warmer seasons of spring [means ratio (MR): 2.5-2.7] and summer (MR: 2.1-3.0) than during winter. Although temperature and relative humidity do not explain all of the variability in endotoxin levels, their effects were significant in our data set. Temperature effects and seasonal variation of endotoxin should be considered in future studies of outdoor endotoxin.     

Stability and storage problems in organotin speciation in environmental samples

The stability of both tributyltin (TBT) and triphenyltin (TPT) in water, sediment, oysters and cockles was studied over a period of 18 months using several storage conditions. Butyltins were stable in unacidified sea-water stored in polycarbonate bottles in the dark at 4 degrees C for 7 months, but half of the TBT concentration was lost after 540 d. A comparable preservation time was achieved for butyltins stored on C18 cartridges at room temperature. However, phenyltins extracted from sea-water were stable for only 60 d stored on cartridges and even more pronounced losses (about 90% after 540 d) occurred when they were stored in either polycarbonate or Pyrex glass bottles. Losses of organotins were observed in sediments after air drying and pasteurization treatments using a freeze-dried sediment as a comparator, whereas both butyltin and phenyltin species remained stable in sediments stored at -20 degrees C for the 18 months tested, irrespective of the treatment used for stabilization. Air drying followed by pasteurization was shown to be superior to other treatments for the stabilization of organotin compounds in sediments stored at higher temperatures, but 30% of TBT was lost after 540 d at 25 degrees C. Finally, butyltins were stable in both frozen cockles and oysters in the dark over a 7 month period and in freeze-dried samples stored at 4 degrees C for 5 months, but TBT losses of about 70% were observed after 540 d.     

Trace metal bioaccumulation in eight common coastal Australian polychaeta

Whole tissue trace metal concentrations of ten metals in eight common coastal Australian polychaete species collected from uncontaminated locations were measured. The mean concentration range for each trace metal was: Mn: 2.6-13 microg g(-1); Co: 0.8-4.6 microg g(-1); Cu: 3.4-26 microg g(-1); Zn: 47-225 microg g(-1); As: 18-101 microg g(-1); Se: 2.2-20.4 microg g(-1); Ag: 0.03-2.5 microg g(-1); Cd: 0.07-17 microg g(-1); Hg: 0.08-0.88 microg g(-1) and Pb: 0.09-3.2 microg g(-1)dry mass. Principal components analysis of trace metal signatures revealed that the habitat, i.e. exposed coast sand or rock, estuarine sand or estuarine mud substrate in which a polychaete species was found, had a significant influence on the bioaccumulation of six trace metals (Mn, Cu, Zn, Ag, Cd and Pb). However, there is no clear relationship between trace metal concentrations in substrates and polychaetes. The results of the current study contribute to a reference dataset of polychaete species-specific natural background trace metal concentrations for use in determining the extent of trace metal contamination by urban and industrial sources.     

Information needs for marine pollution studies

Information needed for the resolution of environmental problems is a commodity with an economic value. The minimum necessary information implies minimal costs. The formulation of the information is considered for the case of biocides that can disrupt marine ecosystems.     

A case study of trace metals in suspended particulate matter and biota before wastewater treatment plant from the Izmir Bay,Turkey

The concentrations of trace metals (Cu, Zn, Mn, Ni, and Fe) from suspended particulate matter (SPM) and biota in Izmir Bay (Eastern Aegean Sea) were studied in order to evaluate the environmental impact of the anthropogenic metals before building of Wastewater Treatment Plant. SPM samples were collected in wet and dry periods from Izmir Bay. Metal concentrations in SPM (Cu, 0.36–2.19; Mn, 0.07–11.3; Ni, 0.43–7.81; Zn, 7.33–269; Fe, 1.00–266 μgdm^− 3) were comparable to those reported for other moderately polluted bays. Maximum metal concentrations in SPM were observed during summer season. SPM metal concentrations displayed a clear spatial trend with values increasing with proximity to urban centers. Cu and Zn concentrations in SPM were especially high in the inner bay. SPM were found to be contaminated by Zn. The vertical profile of Mn, Zn, and Ni concentrations in SPM had a maximal value at the upper layer and decreased to minimal value at the bottom layer of the inner bay in summer, in contrast to the observed pattern of Fe and Cu. Maximum Cu concentrations were obtained in Penaeus kerathurus. Also, maximum Zn and Fe concentrations were found in Mytilus galloprovincialis. Relatively high Cu levels were found in Sardina pilcardus and Mullus barbatus than other fish species. Besides, Cu levels were lower in Diplodus annularis and Merluccius merluccius. Finally, metal levels in biota tissues were lower than the limits of European Dietary Standards and Guidelines.