Distribution and relationships between selected chemical elements in green alga Enteromorpha sp. from the southern Baltic

The concentrations of heavy metals (Cd, Cu, Ni, Pb, Zn and Mn) and macroelements (K, Na, Ca and Mg) were determined in green alga Enteromorpha sp. from the coastal zone of the southern Baltic including Gulf of Gdańsk and Vistula Lagoon in 2000-2003. In order to estimate the degree of accumulation of each element by the green alga, concentration and discrimination factors (CFs) with respect to seawater were calculated. The results of factor analysis (FA) and ANOVA clearly indicate geographical differences between concentrations of chemical elements. Enteromorpha sp. from Vistula Lagoon and the southern Baltic exhibited higher levels of Mn and Ni, and Na and K, respectively. Anthropogenic impact of Cu, Pb and Zn, possibly originated from municipal sewage, was identified in alga samples collected in the Gulf of Gdańsk, especially in the vicinity of Gdynia. From comparison our data with those published earlier results that Pb content in Enteromorpha sp. from the Gulf of Gdańsk decreased within 1978-2003 reflecting reducing use of leaded petrol in Baltic countries in this period. The alga Enteromorpha sp. can be used for biomonitoring surveys of metal contaminants in coastal areas of the Baltic Sea.     

High contents of rare earth elements (REEs) in stream waters of a Cu-Pb-Zn mining area

Stream waters draining an old mining area present very high rare earth element (REE) contents, reaching 928 microg/l as the maximum total value (sigmaREE). The middle rare earth elements (MREEs) are usually enriched with respect to both the light (LREEs) and heavy (HREEs) elements of this group, producing a characteristic "roof-shaped" pattern of the shale Post-Archean Australian Shales-normalized concentrations. At the Fenice Capanne Mine (FCM), the most important base metal mine of the study area, the REE source coincides with the mine tailings, mostly the oldest ones composed of iron-rich materials. The geochemical history of the REEs released into Noni stream from wastes in the FCM area is strictly determined by the pH, which controls the REE speciation and in-stream processes. The formation of Al-rich and mainly Fe-rich flocs effectively scavenges the REEs, which are readily and drastically removed from the solution when the pH approaches neutrality. Leaching experiments performed on flocs and waste materials demonstrate that Fe-oxides/oxyhydroxides play a key role in the release of lanthanide elements into stream waters. The origin of the "roof-shaped" REE distribution pattern as well as the peculiar geochemical behavior of some lanthanide elements in the aqueous system are discussed.     

Effects of organic ligands on fractionation of rare earth elements (REEs) in hydroponic plants: an application to the determination of binding capacities by humic acid for modeling

Previous studies have revealed the fractionation processes of rare earth elements (REEs) in hydroponic plants, with a heavy REE (HREE, the elements from Gd to Lu) enrichment in leaves. In this study, effects on the HREE enrichment in soybean leaves with additions of carboxylic acids (acetate, malate, citrate, NTA, EDTA and DTPA) and two soil humic acids (HAs) were investigated. REE speciation in carboxylic acid and HA solutions was simulated using Visual MINTEQ and Model V, respectively. The results showed that the effects caused by carboxylic acids were strongly dependent on the differences between their binding strengths for light REEs (LREEs, the elements from La to Eu) and those for HREEs. A good correlation existed between these effects and the changes of free REE ions in solutions. This relationship was also observed for the HA treatments, provided that the intrinsic equilibrium constants of REEs for cation–proton exchange with HA (i.e., pK_MHA) in Model V were estimated using a free-energy relationship with the stability constants for REE complexation with lactic acid. It is suggested that this set of pK_MHA values is more suitable for use in Model V for the simulation of REE complexation with HA.     

Rare earth elements in naturally grown fern Dicranopteris linearis in relation to their variation in soils in south-Jiangxi region (southern China)

Ferns (Dicranopteris linearis) and soils, sampled from four rare earth mining areas and one non-mining area locating in South-Jiangxi region, were chosen for analysis of 15 rare earth elements (REEs) by inductively coupled plasma-mass spectrometry (ICP-MS). The fern samples were divided into 4 parts: root, stem, petiole, and lamina. The soils of the same sites were also sampled, and 4 soil layers were observed at the profile: A (0-20 cm depth), B (20-150 cm depth), C (150-400 cm depth), and D (rock). The distribution patterns and transportation characteristics of REEs of different soil layers and of different parts of D. linearis were studied. The results showed that in the soil layers, the sigma REE (the sum of the concentrations of 15 REEs) of A layer, as well as B layer were lower than that of C layer, but Ce was relatively concentrated in A layer. The sigma REE of different parts of D. linearis were lamina, root > stem > petiole. The REE distribution patterns of D. linearis root were similar to the total REE distribution patterns of the A layer of their host soils, especially to the soluble REE distribution patterns of the A layer of their host soils. The REEs were fractionated in their transportation in D. linearis. The abundances of heavy rare earth elements (HREEs, Gd to Lu and Y) in the stem, petiole, lamina are lower than those in the root.     

Scandium,yttrium, and lanthanide contents in soil from Serbia and their accumulation in the mushroom Macrolepiota procera (Scop.) Singer

The mobility (fractionation) of rare earth elements (REEs) and their possible impacts on ecosystems are still relatively unknown. Soil samples were collected from two sites in central Serbia, an unpolluted mountain region (site 1) and a forest near a city (site 2). In order to investigate REE fractions (acid-soluble/exchangeable, reducible, oxidizable, and residual) in soils, BCR sequential extraction was performed. Additionally, the content of REEs was also determined in stipes and caps of the mushroom Macrolepiota procera, growing in the observed sites. Sc, Y, and lanthanide contents were determined by inductively coupled plasma mass spectrometry (ICP-MS), and results were subjected to multivariate data analysis. Application of pattern recognition technique revealed the existence of two distinguished clusters belonging to different geographical sites and determined by greater levels of Sc, Y, and lanthanides in Go? soil compared to Trstenik soil. Additionally, PCA analysis showed that REEs in soil were concentrated in two groups: the first consisted of elements belonging to light REEs and the second contained heavy REEs. These results suggest that the distribution of REEs in soils could indicate the geographical origin and type of soil. The bioconcentration factors and translocation factors for each REE were also calculated. This study provides baseline data on the rare earth element levels in the wild edible mushroom M. procera, growing in Serbia. In terms of bioconcentration and bioexclusion concept, Sc, Y, and REEs were bioexcluded in M. procera for both studied sites.

     

Organotin compounds in surface sediments of the Southern Baltic coastal zone: a study on the main factors for their accumulation and degradation

Sediment samples were collected in the Gulf of Gdańsk, and the Vistula and Szczecin Lagoons—all located in the coastal zone of the Southern Baltic Sea—just after the total ban on using harmful organotins in antifouling paints on ships came into force, to assess their butyltin and phenyltin contamination extent. Altogether, 26 sampling stations were chosen to account for different potential exposure to organotin pollution and environmental conditions: from shallow and well-oxygenated waters, shipping routes and river mouths, to deep and anoxic sites. Additionally, the organic carbon content, pigment content, and grain size of all the sediment samples were determined, and some parameters of the near-bottom water (oxygen content, salinity, temperature) were measured as well. Total concentrations of butyltin compounds ranged between 2 and 182 ng Sn g^?1 d.w., whereas phenyltins were below the detection limit. Sediments from the Gulf of Gdańsk and Vistula Lagoon were found moderately contaminated with tributyltin, whereas those from the Szczecin Lagoon were ranked as highly contaminated. Butyltin degradation indices prove a recent tributyltin input into the sediments adjacent to sites used for dumping for dredged harbor materials and for anchorage in the Gulf of Gdańsk (where two big international ports are located), and into those collected in the Szczecin Lagoon. Essential factors affecting the degradation and distribution of organotins, based on significant correlations between butyltins and environmental variables, were found in the study area.     

Distribution of rare earth elements in an alluvial aquifer affected by acid mine drainage: the Guadiamar aquifer (SW Spain)

This work analyses the spatial distribution, the origin, and the shale-normalised fractionation patterns of the rare earth elements (REE) in the alluvial aquifer of the Guadiamar River (south-western Spain). This river received notoriety in April 1998 for a spill that spread a great amount of slurry (mainly pyrites) and acid waters in a narrow strip along the river course. Groundwaters and surface waters were sampled to analyse, among other elements, the REEs. Their spatial distribution shows a peak close to the mining region, in an area with low values of pH and high concentrations of sulphates and other metals such as Zn, Cu, Co, Ni, Pb, and Cd. The patterns of shale-normalised fractionation at the most-contaminated points show an enrichment in the middle rare earth elements (MREE) with respect to the light (LREE) and heavy (HREE) ones, typical of acid waters. The Ce-anomaly becomes more negative as pH increases, due to the preferential fractionation of Ce in oxyhydroxides of Fe.     

Bioaccumulation of the rare earth elements lanthanum, gadolinium and yttrium in carp (Cyprinus carpio)

Widespread use of the rare earth elements (REEs) in China for agricultural purposes, together with many other applications, has resulted in a remarkable increase of REE concentrations in the environment. The comparative bioaccumulations of representative light, medium and heavy REEs in a variety of tissues of carp (Cyprinus carpio L.) were investigated for an evaluation of their impacts on aquatic animals. The fish were exposed continuously to solutions containing 0.50 mg litre(-1) of each element for 45 days at pH 6.0 and sacrificed at time intervals. Skeleton, muscle, gills and internal organs were analysed for REE contents. A method using cation-exchange resin separation and ICP-AES determination was developed for the quatification of individual REEs. The results show that carp has low ability to take up the REEs under the experimental conditions. The order of REEs under the experimental conditions. The order of maximum bioconcentration factors was mostly internal organs > gills > skeleton > muscle. Neither synergistic nor antagonistic effects of the mixed REE solutions for carp were observed. The relative distributions of different REEs in the investigated tissues exhibited similar patterns. Among the selected tissues studied, the concentration of a heavy REE (Y) was the smallest, while concentrations of a medium (Gd) and a light REE (La) showed only a slight difference.     

Chemical speciation and bioavailability of rare earth elements (REEs) in the ecosystem: a review

Rare earths (RE), chemically uniform group of elements due to similar physicochemical behavior, are termed as lanthanides. Natural occurrence depends on the geological circumstances and has been of long interest for geologist as tools for further scientific research into the region of ores, rocks, and oceanic water. The review paper mainly focuses to provide scientific literature about rare earth elements (REEs) with potential environmental and health effects in understanding the research. This is the initial review of RE speciation and bioavailability with current initiative toward development needs and research perceptive. In this paper, we have also discussed mineralogy, extraction, geochemistry, analytical methods of rare earth elements. In this study, REEs with their transformation and vertical distribution in different environments such as fresh and seawater, sediments, soil, weathering, transport, and solubility have been reported with most recent literature along key methods of findings. Speciation and bioavailability have been discussed in detail with special emphasis on soil, plant, and aquatic ecosystems and their impacts on the environment. This review shows that REE gained more importance in last few years due to their detrimental effects on living organisms, so their speciation, bioavailability, and composition are much more important to evaluate their health risks and are discussed thoroughly as well.     

Concentrations and profiles of PCDD/Fs in sediments of major Polish rivers and the Gdansk Basin--Baltic Sea

The present state of contamination of bottom sediments in southern part of the Baltic Sea with PCDD/Fs was compared to the findings made for the north-western and eastern Baltic Sea coastal areas of Finland, Sweden and Denmark. The extent of the study area--from marine the Gdańsk Basin, the lower Oder and Vistula Rivers up till W?oc?awek reservoir--allowed to obtain the sediment samples with diversified properties. Dioxin's concentrations in sediments examined in the Polish costal area allows us to evaluate this zone as relatively less contaminated. Higher dioxin concentration has been found in Wloclawek Dam Reservoir. Differences in congener patterns and temporal changes in marine sediment profiles were examined. The highest concentrations of tetra- and penta-congeners still remain in the surface layer of Gdansk Deep, whereas the decline in concentrations of these most toxic congeners, have been observed in the sediments from some other parts of the Baltic coast. Excess concentration of dioxins in sediments has a great impact on human being due to special ability of accumulation in the trophic chain as well as in water (fishes) and land (milk, meat).     

Poland’s environment - past,present and future state of the environment in the vistula and odra river basins

In the middle of the last century in the case of many river basins, it became obvious that the targets of the Helsinki-Commission (HELCOM) concerning a 50% reduction of nitrogen and phosphorus inputs to the Baltic Sea had not been reached. Such conclusions could be derived from the observed loads. But the measurements regarding the analysis were not sufficient to determine what the reasons for this report were, what has to be done to fulfil this agreement and to evaluate the time at which the targets can be reached. This contribution presents the current state of Polish surface water quality as well as results of modelling nutrient and heavy metal emissions into the two biggest Polish river basins: Vistula and Odra, which both cover approximately 90% of Poland's territory.     

Heavy metals in zooplankton from the Southern Baltic

Samples of zooplankton and suspended matter were collected using a Bongo net (0.33/0.50 mm mesh net), and Nucleopore filters, respectively, from the Southern Baltic off Poland. Major classes of zooplankton, and selected heavy metals (Fe, Co, Ni, Mn, Pb, Cd, Cu, Zn, Cr) were determined in the collected samples. Concentrations of heavy metals in zooplankton were corrected for metals contributed by particulate matter adhering to zooplankton organisms. Heavy metals levels measured in nearshore samples (Bay of Gdańsk, Pomeranian Bay) were higher than those in the samples from the open sea. The only exception was cadmium exhibiting larger concentrations in the offshore as compared to the nearshore samples (0.8 vs. 1.3 microg/g d.w.). This was attributed to decreased concentrations, of both dissolved and particulate cadmium, caused by algal bloom. Larger concentrations of heavy metals in the Bay of Gdańsk in comparison with the Pomeranian Bay (e.g. Cd-1.3 vs. 0.8 microg/g, Cu-20.5 vs. 8.3 microg/g, Pb-12.9 vs. 1.2 microg/g, Cr-12.4 vs. 1.4 microg/g) were attributed to the direct discharge of the Vistula river to the Bay of Gdańsk, while the Pomeranian Bay receives the Odra river runoff indirectly, via the Szczecin Lagoon. The nonlinear estimation of the data set was used to evaluate concentrations of heavy metals in Copepoda and Cladocera. Copepoda proved to be enriched with heavy metals in comparison with Cladocera.     

Speciation of rare earth elements in soil and accumulation by wheat with rare earth fertilizer application

A greenhouse study was conducted to investigate the accumulation of rare earth elements (REEs), La, Ce, Pr and Nd, in winter wheat (Triticum aestivum L.), and the speciation of these elements in soil following the application of REE-based fertilizers. Improved crop yield was confirmed by the experiment. The accumulation behavior of La, Ce, Pr and Nd in wheat varied depending on the concentration of REE fertilizer application, i.e. increased with increasing REE concentration at low fertilization application, constant over the medium REE range, and decreased with increasing REE concentration at high fertilizer application. Significant negative correlation was obtained between REE contents in roots and soil pH (r = -0.5787 to -0.8442 for La). REEs in both the fertilized and unfertilized soils were fractionated by a three-stage sequential extraction procedure into three chemically distinct fractions: water soluble, exchangeable and carbonate bound (B1), Fe-Mn oxide bound (B2), and organic and sulfide bound (B3). REEs in fertilized soils were found mainly in the B2 and B3 fractions, with only a small amount in the B1 fraction. REEs in B1 and B2 fractions were negatively correlated with soil pH (r = -0.6892 to -0.8927 and -0.7462 to -0.9482). Significant correlation was obtained between REEs in B1 fraction and REE contents in root. The correlation coefficients ranged from 0.6159 to 0.7410 when fertilizer application was lower than 20.0 mg/kg soil. No acceptable relationship was observed between REE contents in shoot and any of the extractable fractions in soils.     

Extractable organic halogens (EOX) in sediments from selected Polish rivers and lakes--a measure of the quality of the inland water environment

EOX in sediments from the two main Polish rivers (the Vistula and the Oder/Odra) as well as five lakes was assayed coulometrically and its values examined with respect to the location of the sample collection points. EOX values were found to increase near industrial areas and large urban agglomerations, although mean values--comparable for rivers and lakes--were similar to those recorded elsewhere. EOX tends to rise as TOC does so. On the other hand, the EOX:TOC ratio decreases sharply in the case of lakes, since TOC values there are roughly one order of magnitude higher than in rivers. Furthermore, the contents of selected polychlorinated biphenyls and organochlorine pesticides are directly related to EOX values. These relationships constitute a basis for the application of EOX as a parameter reflecting the level of organochlorine compounds in environmental quality evaluation.     

Rare earth elements (REEs) in naturally grown plants in relation to their variation in soils

The concentrations of rare earth elements (REEs) in plant leaves, soils in which they grow, and mother rocks were determined using Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES). Concentration levels of REEs in most plants were low. However, one of the herb species, pokeweed (Phytolacca americana) and two species of ferns (Dicranopteris dichotoma and Athyrium yokoscence) revealed relatively high concentrations of REEs. In the case of pokeweed, the REE distribution pattern reflected well that of its soils. On the whole, high concentrations of REEs in plants were related to REE concentrations in the soils in which they grow. These observations are promising to evaluate the possible contamination of environment by REEs resulting from their increased usage in modern industry.     

Effect of complexation with humic substances on diffusion of metal ions in water

Most studies on diffusion of metal ions in various water-rock systems have dealt with free ions (hydrated ions). However, it is often the case that metal ions are dissolved as complexed species such as with humic substances (HS) in natural waters. Hence, we need to study the diffusion behavior of these complexes in order to understand fully the diffusion phenomenon in natural. In this study, the diffusion coefficients of free metal ions (M(z+)) and their complexes with HS (M-HS) were compared to understand the effect of complexation with HS on the diffusion of metal ions such as Co(2+), Cd(2+), and rare earth elements (REE(3+)). Although the diffusion coefficients of free metal ions depend on ionic potential, such dependence was not observed in the presence of HS. Comparing the diffusion coefficients of metal complexes with ethylenediaminetetraacetate (EDTA), fulvic acid, and humic acid showed that the molecular weight (MW), or the size of the ligand, is of primary importance for the diffusion of M-HS. As a consequence, the diffusion coefficients of all REE(3+) were similar in the presence of HS, while they were different in the absence of HS due to the different size of each REE(3+). The similarity among the diffusion coefficients of REE-HS was caused by the much larger size of HS compared with each ion. However, the distribution coefficients of M-HS were not similar among REE(3+), Cd(2+), and Co(2+). REE(3+) and Cd(2+) which have higher affinities for larger MW fraction in HS diffused slower than Co(2+) which favors smaller MW fraction. The results show that the affinity for different MW fractions among HS controls the diffusion of M-HS, which must be important to predict precisely the diffusion behavior of metal ions bound to HS in natural systems.     

Screening-level ecological risk assessment of polychlorinated dibenzo-p-dioxins and dibenzofurans in sediments and aquatic biota from the Venice Lagoon, Italy

Recent monitoring data indicate that portions of Italy's Venice Lagoon ecosystem have been degraded due to biological and chemical pollution from a variety of potential sources. Using polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) data collected from sediment, fish and shellfish in the Lagoon, a screening-level ecological risk assessment (ERA) was performed to evaluate the risks to representative aquatic biota and wildlife receptors. Risks to aquatic invertebrates posed by PCDD/Fs in sediment were evaluated by comparing measured tissue concentrations in fish and shellfish to appropriate ecotoxicological reference values. For mammalian and avian receptors, risks posed by theoretical exposures to PCDD/Fs through the food chain were calculated using conservative wildlife exposure models. Results of the screening-level approach indicate that the potential for adverse effects to fish and aquatic invertebrate receptors from PCDD/Fs in surficial sediments are unlikely. Adverse effects to wildlife are possible but highly uncertain, and warrants further investigation in a more comprehensive ERA.     

Evaluation of the anthropogenic influx of metal and metalloid contaminants into the Moulay Bousselham lagoon, Morocco, using chemometric methods coupled to geographical information systems

Superficial and cored sediment samples from the Moulay Bousselham lagoon and sub-watershed were analyzed for Al, Fe, Cu, Zn, Pb, Mn, Ni, Cr, As, Hg, and Cd. The temporal and spatial distributions of the main contamination sources of heavy metals were identified and described using chemometric and geographic information system (GIS) methods. Sediments from coastal lagoons near urban and agricultural areas are commonly contaminated with heavy metals, and the concentrations found in surface sediments are significantly higher than those from 50–100 years ago. The concentrations of these elements decrease sharply with depth in the sediment column, and the elements are preferentially enriched in the <2-μm-sized fraction of the sediment. The zones of enhanced risk of heavy metals were detected by means of GIS-based geostatistical modeling. According to sediment pollution indices and statistical analysis, heavy metals (Pb, Cu, Ni, Zn, Cr, and Hg) that pose a risk have become largely enriched in the lagoon sediments during the recent period of agricultural intensification.     

Effects of rare earth elements on the distribution of mineral elements and heavy metals in horseradish

In order to investigate the effects of rare earth elements (REEs) on horseradish, the distribution of the mineral elements and heavy metals in different organs of horseradish have been studied by using inductively coupled plasma-atomic emission spectrometry (ICP-AES). Meanwhile, three variable major parameters, namely the concentration of REEs, the type of REEs, and the growth stage of plant were chosen. The results indicated that the test REEs, Ce(III) and Tb(III), could be accumulated in leaves, stems and roots of horseradish. In addition, we found that the content of mineral elements was increased in horseradish treated with 20mgl(-1) of Ce(III), but not those with the 20mgl(-1) of Tb(III). Moreover, the content of mineral elements in horseradish was decreased with the increasing concentration of REEs (100, 300mgl(-1)). Furthermore, we found that there were the opposite effects on the content of the heavy metals in horseradish treated with REEs. Finally, we found that the effect of REEs on the accumulation of REEs, and the content of mineral elements or heavy metals of horseradish during vigorous growth stage, no matter positive or negative, was more obvious than that of the other growth stages. These results demonstrated that the distribution behaviors of mineral elements and heavy metals in horseradish can be affected by the type and concentration of REEs, and the growth period of plant.     

Origin of middle rare earth element enrichment in acid mine drainage-impacted areas

The commonly observed enrichment of middle rare earth elements (MREE) in water sampled in acid mine drainage (AMD)-impacted areas was found to be the result of preferential release from the widespread mineral pyrite (FeS₂). Three different mining-impacted sites in Europe were sampled for water, and various pyrite samples were used in batch experiments with diluted sulphuric acid simulating AMD-impacted water with high sulphate concentration and high acidity. All water samples independent on their origin from groundwater, creek water or lake water as well as on the surrounding rock types showed MREE enrichment. Also the pyrite samples showed MREE enrichment in the respective acidic leachate but not always in their total contents indicating a process-controlled release. It is discussed that most probably complexation to sulphite (SO₃ ^2?) or another intermediate S-species during pyrite oxidation is the reason for the MREE enrichment in the normalized REE patterns.