Metal (i.e. Ag, As, Ca, Cd, Co, Cu, Mn, Pb and Zn) and metallothionein (MT) concentrations in the soft tissue of Littorina littorea were measured along the heavily polluted Western Scheldt (WS) and relatively clean Eastern Scheldt (ES) estuary. Along the WS metal and MT levels in periwinkles reflected the known downstream decreasing pollution gradient. Surprisingly in ES animals As, Mn and Zn concentrations decreased from east to west reflecting past pollution. Compared to the WS metal concentrations of ES periwinkles were significantly lower and both estuaries were maximally discriminated from each other based on their Cd soft tissue concentration using a canonical discriminant analysis. Furthermore, no overall difference was found in MT levels among animals from both estuaries. Using previously obtained condition data (i.e. dry/wet weight ratio and lipid content) the relation between soft tissue metal concentration (i.e. Cd, Cu and Zn) and fitness indicators (i.e. MT and condition data) was examined using a canonical correlation analysis. Periwinkles with a high metal load (i.e. Cd and Zn) also had high MT levels but were in a relatively poor condition.

Vegetated drainages are an effective method for removal of pollutants associated with agricultural runoff. Leersia oryzoides, a plant common to agricultural ditches, may be particularly effective in remediation; however, research characterizing responses of L. oryzoides to flooding are limited. Soil reduction resulting from flooding can change availability of nutrients to plants via changes in chemical species (e.g., increasing solubility of Fe). Additionally, plant metabolic stresses resulting from reduced soils can decrease nutrient uptake and translocation. The objective of this study was to characterize belowground and aboveground nutrient allocation of L. oryzoides subjected to various soil moisture regimes. Treatments included: a well-watered and well-drained control; a continuously saturated treatment; a 48-h pulse-flood treatment; and a partially flooded treatment in which water level was maintained at 15 cm below the soil surface and flooded to the soil surface for 48 h once a week. Soil redox potential (Eh, mV) was measured periodically over the course of the 8-week experiment. At experiment termination, concentrations of Kjeldahl nitrogen, phosphorus (P), potassium (K), iron (Fe), and manganese (Mn) were measured in plant tissues. All flooded treatments demonstrated moderately reduced soil conditions (Eh < 350 mV). Plant Kjeldahl nitrogen concentrations demonstrated no treatment effect, whereas P and K concentrations decreased in aboveground portions of the plant. Belowground concentrations of P, Mn, and Fe were significantly higher in flooded plants, likely due to the increased solubility of these nutrients resulting from the reductive decomposition of metal–phosphate complexes in the soil and subsequent precipitation in the rhizosphere. These results indicate that wetland plants may indirectly affect P, Mn, and Fe concentrations in surface waters by altering local trends in soil oxidation–reduction chemistry.

The main objective of this study was to examine the efficacy and capacity of constructed wetlands for metal removal. Between January 2006 and December 2008, removal of Cr, Cu, Cd, Zn, Pb, B, Ni, As, Fe, Hg, and Mn was measured on a monthly basis at a hierarchical mosaic of artificial ecosystems which has been in operation since 1998. The results showed a great variety of average removal efficiencies, in the range of 55% for chromium and −73% for manganese. Four elements presented negative removal: nickel, iron, arsenic, and manganese. Seasonal removal efficiencies were also studied for each element. Moreover, a correlation assessment among metal removal efficiencies and different parameters of each basin in the hierarchical mosaic of artificial ecosystems was performed. Negative significant correlations were found among Fe, Zn, Cu, Mn, As, Ni, Cd, and Hg removal and the inlet concentrations. In general, the treatment system was not a good system for removal of metals from wastewater as, in relation to other constructed wetlands, the system was not able to provide efficient removal of metals.

Single-particle analysis of short-term aerosol samplings can provide unique information on the rapid evolution of size distribution and chemical composition of industrial aerosols. In this work, the potential of scanning electron microscopy equipped with energy-dispersive X-ray spectrometry (SEM-EDX) for the time-resolved description of physicochemical properties of individual aerosol particles is investigated. Two sampling campaigns were carried out at a densely populated and industrialised coastal site. The first sampling campaign corresponded to low and stable atmospheric particle loads. Low temporal variations in PM₁₀ and PM₂.₅ mass concentrations during the preceding hours and during samplings were observed. In these conditions suitable to evaluate the accuracy of our sampling and analytical methodologies, very low temporal variation of physicochemical characteristics of atmospheric particles were observed, as expected. During the second sampling campaign, the ability of automated SEM-EDX to describe short temporal variation in PM₁₀ and PM₂.₅ chemical composition was demonstrated. We report the tracking of a steelworks emission plume transported over an urban area by means of short-term aerosol samplings and explore how this transient industrial emission contributed to ambient particulates. Steelworks are important point-source emitters of metallic pollutants such as iron, manganese, and zinc species. Detailed assessment of the microphysical and chemical properties of aerosols collected in the vicinity of steelworks enables to precisely describe how industrial aerosols affect the composition of urban particulate matter. The studied pollution event caused dramatic changes in the composition of urban aerosols by an input of fine metallic particles containing Fe, Mn or Zn oxides and mixed particles (Mn-Fe, Zn-Mn, Zn-Fe oxides). Metal-rich particles were often found internally mixed with marine and/or continental compounds, demonstrating how industrial aerosols efficiently coagulate with particles from other sources, thereby acting as carriers of heavy metals.

Background, aim and scope The paper presents concentrations of trace elements in blood of homebred animals (cows and sheep) from Southern Serbia (Bujanovac) and the contents of natural and anthropogenic radionuclides and some heavy metals in feed. The region of Southern Serbia was exposed to contamination by depleted uranium ammunition during NATO attacks in 1999 and therefore, is of great concern to environmental pollution and human and animal health. Materials and methods Conventional instrumental and epithermal neutron activation analyses are used to measure trace elements in cow and sheep blood samples collected randomly at six locations in the region of Bujanovac (village of Borovac) in the spring of 2005. Samples of feed (grass and crops: corn, wheat and oats), collected on the same locations (households), are analysed for the contents of radionuclides on an HPGe detector (Ortec, relative efficiency 23%) by standard gamma spectrometry. The content of Hg, Pb and Cd in feed is determined by standard atomic absorption spectrometry on the VarianSpectra220/ThermoSolar GFS97 spectrometer. Results Concentrations of 29 elements (Na, Al (P), Cl, K, Sc, Cr, Mn, Ni, Fe, Co, Zn, Se, As, Br, Sr, Rb, Sb, In, I, Ba, Cs, La, Nd, Eu, Sm, Tb, Hf, Ta and Th) are determined in blood of the examined animals. In feeds, natural ⁴⁰K is found in all of the samples, cosmogenic ⁷Be and fission product ¹³⁷Cs are detected only in the grass samples, while heavy metals Hg, Cd and Pb are found in the range of 0.01-0.02, 0.84-1.15 and 0.74-7.34 mg/kg, respectively. Calculated soil-to-blood transfer factors are in a wide range of 8·10⁻⁶ to 64, as a result of varying significance of the elements in animal metabolism and feeding habits. Discussion The results of trace elements' concentrations in animal blood are in good agreement with available data for K, Ni, Zn, Se and Rb. Higher Br concentrations in animal blood are most probably caused by large biomass burning events during blood sampling. Very low concentration of Fe in cows and sheep confirms the results of previous biochemical studies on animal anaemia in the region. High concentration of As correlates with geochemical peculiarities of the Balkans and is also likely influenced by the use of pesticides in the agricultural production. For some of the elements (La, Nd, Eu, Sm, Tb, Sb, Hf, Ta, Th, In, Ba, Sr, Sc and Cs), there are few or no literature data. Therefore, some of the presented data are significant not only for the country and the region, but on a wider scale. Activities of natural radionuclides in feeds are within the average values reported for the region, while the activities of ²¹⁰Pb and ²³⁵/²³⁸U are below the limit of detection. This is in accordance with previous investigations showing no widespread contamination by depleted uranium in the area. Contents of Hg and Pb in feeds are below the nationally permissible levels, unlike the content of Cd which exceeds it, probably caused by the use of phosphate fertilisers and fossil fuel combustion in the area. Conclusions In general, the concentrations of trace elements in blood of homebred cows and sheep are in good agreement with reference materials, available literature data and the results of previous studies in the area. The exceptions are Fe, As and Br. The contents of natural and anthropogenic radionuclides in feeds are within the expected levels, and there are no signs of contamination by depleted uranium or other fission products. Apart from Cd, there are no signs of pollution by heavy metals in feeds. The highly sensitive method of instrumental neutron activation analysis provides data on the concentration of some elements in animal blood not previously reported for the region and elsewhere. Recommendations and perspectives The presented study is a part of the long term ongoing project on the health risk assessment on animals and humans in the region. The collected data is intended to provide a base for the animal and human risk assessment as well as an estimate of the general pollution status of the environment in the region. Since some of the investigated elements are classified as important trace elements for livestock, the results could also be used to balance and improve the animal diet and thus, improve the growth and reproduction rate.

Background, aims, and scope Heavy metal contaminants in environment, especially in drinking water, are always of great concern due to their health impact. Due to the use of heavy metals as catalysts during plastic syntheses, particularly antimony, human exposure to metal release from plastic bottles has been a serious concern in recent years. The aim and scope of this study were to assess metal contaminations leaching out from a series of recycling plastic bottles upon treatments. Methodology In this study, leaching concentrations of 16 metal elements were determined in 21 different types of plastic bottles from five commercial brands, which were made of recycling materials ranging from no. 1 to no. 7. Several sets of experiments were conducted to study the factors that could potentially affect the metal elements leaching from plastic bottles, which include cooling with frozen water, heating with boiling water, microwave, incubating with low-pH water, outdoor sunlight irradiation, and in-car storage. Results Heating and microwave can lead to a noticeable increase of antimony leaching relative to the controls in bottle samples A to G, and some even reached to a higher level than the maximum contamination level (MCL) of the US Environmental Protection Agency (USEPA) regulations. Incubation with low-pH water, outdoor sunlight irradiation, and in-car storage had no significant effect on antimony leaching relative to controls in bottle samples A to G, and the levels of antimony leaching detected were below 6 ppb which is the MCL of USEPA regulations. Cooling had almost no effect on antimony leaching based on our results. For the other interested 15 metal elements (Al, V, Cr, Mn, Co, Ni, Cu, As, Se, Mo, Ag, Cd, Ba, Tl, Pb), no significant leaching was detected or the level was far below the MCL of USEPA regulations in all bottle samples in this study. In addition, washing procedure did contribute to the antimony leaching concentration for polyethylene terephthalate (PET) bottles. The difference of antimony leaching concentration between washing procedure involved and no washing procedure involved (AC) was larger than zero for samples A to G. This interesting result showed that higher antimony concentration was detected in experiments with no washing procedures compared with those experiments with washing procedures. Our study results indicate that partial antimony leaching from PET bottles comes from contaminations on the surface of plastic during manufacturing process, while major antimony leaching comes from conditional changes. Conclusion The results revealed that heating and microwaving enhance antimony leaching significantly in PET plastic bottles. Plastic bottle manufacturers should consider the contaminations during manufacturing process and washing bottles before first use was strongly recommended to remove those contaminants.

Concept and purpose Virtually all water treatment facilities worldwide generate an enormous amount of water treatment residual (WTR) solids for which environmentally friendly end-use options are continually being sought as opposed to their landfilling. Aluminium-based WTR (Al-WTR) can offer huge benefits particularly for phosphorus (P) removal and biofilm attachment when used as media in engineered wetlands. However, potential environmental risks that may arise from the leaching out of its constituents must be properly evaluated before such reuse can be assured. This paper presents results of an assessment carried out to monitor and examine the leachability and leaching patterns of the constituents of an Al-WTR used as media in laboratory-scale engineered wetland systems. Main features, materials and methods Al-WTR was used as media in four different configurations of laboratory-scale engineered wetland systems treating agricultural wastewater. Selected metal levels were determined in the Al-WTR prior to being used while levels of total and dissolved concentration for the metals were monitored in the influent and effluent samples. The increase or decrease of these metals in the used Al-WTR and their potential for leaching were determined. Leached metal levels in the effluents were compared with relevant environmental quality standards to ascertain if they pose considerable risks. Results Aluminium, arsenic, iron, lead and manganese were leached into the treated effluent, but aluminium exhibited the least leaching potential relative to its initial content in the fresh Al-WTR. Levels of P increased from 0.13 mg-P/g (fresh Al-WTR) to 33.9-40.6 mg-P/g (used Al-WTR). Dissolved levels of lead and arsenic (except on one instance) were below the prescribed limits for discharge. However, total and dissolved levels of aluminium were in most cases above the prescribed limits for discharge, especially at the beginning of the experiments. Conclusions, recommendations and perspectives Overall, the study indicates that leaching is observed when Al-WTR is beneficially reused for enhanced P removal in engineered wetlands. In particular, levels of aluminium in the treated effluent beyond the prescribed limits of 0.2 mg/l were observed. However, since the results obtained indicate that aluminium leached is mostly associated with solids, a post-treatment unit which can further reduce the level of aluminium in the treated effluent by filtering out the solids could serve to mitigate this. In addition, plants used in such wetland systems can uptake metals and this can also be a potential solution to ameliorating such metal releases. Periodic monitoring is thus advised. Notwithstanding, the use of Al-WTR as a media in engineered wetlands can serve to greatly enhance the removal of P from wastewaters and also serve as support material for biofilm attachment.

Introduction From the metallurgic industry zone of Dambovita County, we harvested and analyzed seven herbaceous plants species (Lolium perenne, Festuca pratensis, Stipa capillata, Agrostis alba, Cynodon dactylon, Luzula campestris, and Agrostis tenuis) to establish the heavy metal accumulation levels in these species. Materials and method The heavy metal contents (for Cr, Mn, Zn, Sr, Cu, Ba, and Sn) were determined by analyzing the dry matter with an inductively coupled plasma-atomic emission spectrometer. This method has detection limits of 0.4-0.6 mg/kg for the analyzed metals. The heavy metal concentrations in plants harvested from the industrial area are in milligram per kilogram of dry matter and ranged from 10.03 to 191.98 mg/kg of dry matter for Cr, 165.89 to 1,103.92 mg/kg of dry matter for Mn, 62.09 to 921.67 mg/kg of dry matter for Zn, 29.21 to 50.12 mg/kg of dry matter for Sr, 0.99 to 113.83 mg/kg of dry matter for Cu, 58.66 to 133.51 mg/kg of dry matter for Ba, and 8.38 to 276.44 mg/kg of dry matter for Sn. The heavy metal accumulation levels in the studied species of plants were calculated by the rapport between the concentration level of the metal in plant samples and the level of the same metal in the soil, near the radicular system for each species of plants. Results The highest accumulation levels were found in A. alba for Cr (267.69%); in L. perenne for Mn (51.45%), Sr (114.35%), and Ba (60.81%); and in C. dactylon for Zn (136.62%), Cu (97.65%), and F. pratensis for Sn (704.00%).

Background, aim, and scope High mountain soils constitute a long-term cumulative record of atmospherically deposited trace elements from both natural and anthropogenic sources. The main aims of this study were to determine the level of major and trace metals (Al, Ti, Mn, Fe, and Zr) of lithologic origin and airborne contaminating trace elements (Ni, Cu, Zn, As, Cd, and Pb) in soils in the Central Pyrenees as an indication of background contamination over SW Europe, to establish whether there is a spatial pattern of accumulation of trace elements in soils as a function of altitude, and to examine whether altitude-related physicochemical properties of soils affect the accumulation of major metals and trace elements. Methods Major metals and trace elements were measured in “top” (i.e., first 10 cm) and “bottom” (i.e., below 10 cm) soil samples along an altitudinal transect (1,520-2,880 m a.s.l.) in the Central Pyrenees. Total concentrations were determined by X-ray fluorescense spectrometry. Total major metal concentrations were analysed by conventional X-ray fluorescence spectrometry (XRF) with a Siemens SRS 303 instrument. Total trace element concentrations were determined with an energy-dispersive multielement miniprobe XRF analyser. Acid-extractable concentrations were measured by inductively coupled plasma after previous extraction with nitric acid and hydrogen peroxide in closed beakers. Acid-extractable major metal concentrations were measured by inductively coupled plasma (ICP)-Optic Emission Spectrometry with a Perkin Elmer 3200 RL Instrument. Acid-extractable trace element concentrations were determined by ICP-Mass Spectrometry with a Perkin Elmer ELAN 6000. Results Trace element concentration ranges were (in mg kg⁻¹, inventories in g m⁻² between parenthesis) <2-58 (0.5-6.6) for Ni, 6-30 (0.2-3.4) for Cu, 38-236 (1.6-32.4) for Zn, 6-209 (0.2-12.8) for As, 0.02-0.64 (<0.04) for Cd, and 28-94 (0.6-13.0) for Pb. These concentrations were, in general, comparable to those recorded in soils from other European mountainous areas and were in many cases above the threshold recommended for ecosystem protection by regional and European environmental authorities. The highest concentrations were found at lower altitudes, indicating an effect of local contamination up to ∼2,300 m a.s.l. Only above this altitude can trace elements in soils be considered representative of a background, long-range atmospheric contamination. Conclusions None of the storage capacity properties of soils examined were determinant of the differences in elemental concentrations along the altitudinal transect. At the upper altitude range, Ni, Cu, and Pb showed a approximately two- to fivefold increase over the average concentration of the local dominant lithology, reflecting the regional and global background of atmospheric contamination in the area.