Modelling of chemical species of Al, Mn, Zn, and Pb in river body waters of industrial areas of West Rhodope Mountain, Bulgaria.

The assessment of the ecological status of natural surface water, in terms of dominant trace metals, within an area subject to various sources of pollution including a non-ferrous metal ore mining, such as the West Rhodope Mountain, Bulgaria, is significant. The present study estimates the ecological status of river body waters at industrial areas of the West Rhodope Mountain, Bulgaria, simultaneously evaluating the possibility of state forecasting, together with assessing the potential risks, through the study of scenarios focusing on (i) possible variations of physicochemical parameters such as pH, concentration levels of trace metals, sulphates, and dissolved organic carbon (DOC) of surface water and (ii) consideration of potential spontaneous precipitation reactions in the studied waters. The ecological status of river body waters was assessed through a combination of experimental field, laboratory, and computational techniques. Al, Mn, Zn, and Pb were found to be the dominant pollutants with a variety of chemical species and distribution. The most significant difference characterizing the chemical species distribution in light of total spontaneous crystallization in the systems was found for Pb, followed by Zn and Mn, with the differences being more significant at lower trace metal levels. The calculated species were discussed on the basis of HSAB (hard and soft acids and bases) principle.

Trace metals accumulation in the eco-system water - soil - vegetation (Agropyron cristatum) - common voles (Microtus arvalis) - parasites (Hymenolepis diminuta) in Radnevo region, Bulgaria.

BACKGROUND: Coal and coal processing industries provoke trace metal pollution, which has a negative effect on the water - soil - vegetation - small mammals eco-system, constituting part of the food chain and exerting a serious impact on human health. OBJECTIVES: Assessment of the environmental impact of Maritza iztok coal complex, situated east of Radnevo town, Bulgaria, by tracking the dynamics and accumulation of trace metals in the eco-system water - soil - vegetation - common voles - parasites. METHODS: Samples from surface waters, their nearby uncultivated soils, meadow uncultivated vegetation (Agropyron cristatum) and field common voles (Microtus arvalis) were collected. In situ measurements and laboratory extraction procedures and analyses were performed. Accumulation and mobility indices were calculated. The distribution of dissolved Mn, Ni, Cu, Zn and Pb chemical species in water-soil extracts was calculated using a thermodynamic approach. Two thermodynamic models were applied - the classical ion-association model for calculating the inorganic trace metal species and the Stockholm Humic Model (SHM) accounting for the complexation reactions of trace metals with organic matter. Visual Minteq computer program, Version 3.1 was used. The relationship chemical species - bioaccumulation was discussed. RESULTS: Pb and Mn, together with SO42- and PO43- were found to be the main pollutants of waters in the region. The soils studied exhibited low concentrations of trace metals, not exceeding the specified MACs. The content of Mn was the highest, followed by Zn, Pb, Cu and Ni. The highest phytoaccumulation coefficients in the studied uncultivated grass vegetation were calculated for Cu and Zn, being 1-2 orders of magnitude higher than those of Mn and Ni. The accumulation of trace metals was explained on the basis of ions mobility and chemical species distribution. In the case of the host-parasite system Microtus alvaris - Hymenolepis diminuta, Zn displays the highest accumulation coefficient, followed by those of Cu and Pb. The parasite showed a higher bioaccumulation compared to infected common voles, with the highest bioaccumulation found for Ni. CONCLUSIONS: The bioaccumulation of trace metals depends on their mobility, concentration and chemical forms in water-soil solutions. Metal-organic species stimulate the phytoaccumulation of trace metals while inorganic ones suppress it. The sequence of trace metals bioaccumulation in common voles is analogous to that of soil contamination. The parasite exhibited higher bioaccumulation levels compared to infected common voles.

Precipitation and phase transformation of dicalcium phosphate dihydrate in electrolyte solutions of simulated body fluids: Thermodynamic modeling and kinetic studies.

The metastable and stable equilibria of a precipitation in the biomimetic system Simulated Body Fluid (SBF)-CaCl2 -K2 HPO4 -KOH-H2 O were modeled in the pH region 3-7 at a Ca/P molar ratio of 1 using a thermodynamic approach. Saturation indices (SI) of the solid phases were calculated and used to prognose the salt precipitation/dissolution processes. At рН < 4, the solutions are undersaturated (SI < 0) in respect of all solid phases; co-precipitation of dicalcium phosphate dihydrate (DCPD) and hydroxyapatite (HA) occurs at рН 4 while at рН > 4 the stable phase is DCPD but the number of other co-precipitated solid phases increases. This result is associated with the increase in HPO42- , CaHPO40 , and KНРО4- species in the studied solution. The phase transformations of five model DCPD-based calcium phosphate precursors in three simulated body fluids differing in their composition, to more stable octacalcium phosphate and hydroxyapatite was thermodynamically prognosed and experimentally confirmed by kinetic studies, as well as by chemical, XRD, SEM, and IR methods.

Dynamics of trace metals in the system water - soil - plant - wild rats - tapeworms (Hymenolepis diminuta) in Maglizh area, Bulgaria.

BACKGROUND: The impact of chemical elements on the biosphere is a function of their concentration and chemical form. Elucidation and prognosing of the latters in water basins and soil extracts is of particular significance for the assessment of their bioaccumulation in plants and animals. OBJECTIVES: Trace metals dynamics in the system water - soil-plant-wild rats - Hymenolepis diminuta in two agro-industrial zones (East and West) around Maglizh city, Bulgaria were investigated through experimental studies and thermodynamic modelling of the chemical species. METHODS: Samples from surface waters of rivers, their nearby uncultivated soils, meadow uncultivated vegetation (Ranunculus acris and Gramineae) and field rats were collected. In situ measurements and laboratory analyses were performed for the determination of the physico-chemical characteristics and total concentrations of Al, Fe, Mn, Ni, Cu, Zn and Pb. The distribution of their dissolved chemical species in water samples and in the aqueous soil extracts was calculated using a thermodynamic approach. The relationship chemical species - bioaccumulation was discussed. RESULTS: Waters and soils in the East zone of Maglizh area were found to be more polluted compared to those in the West one, regarding Ni, Mn, Zn, Pb and Cu, while Mn and Cu displayed the highest mobility in West zone soils. Trace metals contents in Ranunculus acris exceed that in Gramineae, since the highest accumulation factors were calculated for Cu and Zn. The highest accumulation in rats was found for Zn followed by Cu, being higher in the West zone. Thermodynamic modelling shows that Mn2+ free ions are dominant in both waters and aqueous soil extracts. Ni2+ and Zn2+ ions followed by metal-organic complexes are dominant in waters of East zone while metal-organic complexes followed by free ions are dominant in waters of West zone and both soil extracts. Metal-organic complexes are dominant for Fe, Cu and Pb in all samples studied, while mainly hydroxy forms (Al(OH)4-) followed by metal-organic complexes are typically for Al depending on pH. CONCLUSIONS: Experimentally established bioaccumulation of trace metals in the studied vegetation and rats is a consequence of the total concentration of trace metals in waters and soils, their mobility and chemical species. The dominance of organic complexes of trace metals is a prerequisite for their bioaccumulation in plants. Rats are in direct contact with the soil solution and therefore, of importance is the content of free ions of Mn2+, Ni2+, Zn2+, which are easily absorbed through the skin. The host-helminth system wild rat/H. diminuta could be used as a bioindicator for trace metals pollution.

Trace metals pollution of waters and soils in Kardjali region, Bulgaria.

Trace metals pollution of surface waters and their nearby soils in the metallurgically polluted Kardjali region, Bulgaria, were studied. Thermodynamic modeling including the dissolved organic carbon (DOC) was carried out for evaluating the distribution of metal species in waters and soil solutions. Zn was found to be the most widespread pollutant in the water samples, followed by Cu, Mn, and Cd. Geoaccumulation indices of trace metals for the tested soils were calculated, indicating that regarding Al, Fe, Co, Ni, and Cu all soils are "uncontaminated". The most significant soil pollutant was found to be Cd, with all soils being either "extremely contaminated" by this metal or close to the limit, followed by Pb and Zn. The dynamics of trace metal chemical species distribution in surface waters and in the water-soluble soil fractions, as a result of possible spontaneous precipitations, was calculated by applying different thermodynamic models. Regarding Mn, Co, Ni, and Cd in waters and aqueous soil extracts and Zn in aqueous soil extracts, their free ion species prevailed, being more labile and hence toxic for the ecosystem. In the case of Al, Fe, Cu, Cd, and Pb in the waters and aqueous soil extracts and of Zn in waters, stable organic complexes with bidentate bonds, Me(OH)4- or Me(OH)02 prevailed.

Chemical speciation in natural and brine sea waters.

A combined approach consisting of monitoring and thermodynamic modeling was used in order to calculate the concentration of trace element species in water samples of a broad salinity range and to explain their chemical behaviour. The study was performed on water samples (fresh, marine, hyper-saline) taken from the area of Burgas Bay, Bulgaria. The ion association model based on Debye-Hückel theory using the sst2008.dat database and the ion interaction model based on Pitzer theory using a new pit2010.dat database were compared and combined for the purposes of this study. The new pit2010.dat database combines the sst2008.dat database and the pitzer.dat database of the PHREEQCI computer program as well as the thermodynamic data for the elements Fe, Mn, Cu, Zn, Cd and Pb and their Pitzer ion interaction parameters. The results showed that: (1) the predominant species in fresh waters were free ions of Mn(2+) (73.6%), Zn(2+) (58.0%) and Cd(2+) ions (78.3%) as well as carbonate species CuCO°3 (81.8%), PbCO°3 (77.2%) and hydroxy species Fe(OH) °3(55.2%) and Fe(OH)+2(35.6%); (2) an increase in chloride species MeCl²(n)-(n)(n = 1-4, Me = Mn, Zn, Cu, Pb and Cd) and of the hydroxy species Fe(OH)⁺2 for Fe was calculated for sea and hyper-saline water.

Chemical speciation in waters influenced by lead-zinc metallurgical industry.

The Lead-Zinc Company region, Kardjali city, Bulgaria, is known to be highly polluted with heavy metals from its pyrometallurgical activities. The polluted levels and the chemical speciation in surface natural waters in the region as well as in the wastewaters of the factory were investigated in January 2008 by application of monitoring studies, thermodynamic modeling, and interpretation in terms of the "softness-hardness" factor. It was found that the levels of trace metals pollution of surface waters were lower than the legislation limits for the regions with Pb and Zn production. The wastewater treatment facilities of the company were found to operate properly, and the quality of the cleaned waters in station Kar4 was comparable to the other surface waters studied (e.g., station Kar5). The trace metals were divided into three groups: (1) Fe(3+) and Al(3+), being "hard" acids, existed in all the studied waters as hydroxy species Fe(OH)2(+), AlOH(2+), and Al(OH)2(+), followed by the phosphate species AlPO4(0) and Al(2)(OH)(2)PO4(0); (2) Mn(2+), Zn(2+), and Cd(2+) being "soft" acids with crystal field stabilization energy (CFSE) = 0 were present in natural waters mainly as free Me(2+) ions. Small concentrations of their MeSO4(0), MeCO3(0) species, and of MeCl2(0) (Me = Zn, Cd) species were also calculated. In the wastewaters, two more species [Me(SO4)2(2-) and Me(SO4)3(4-)] of the softer Zn and Cd metals were also calculated; (3) Cu(2+) and Pb(2+), as "soft" acids with CFSE not equal to 0 preferentially coordinated with softer CO3(2-) ions and in natural waters existed mainly as MeCO3(0) and PbHCO3(+), followed by free Me(2+)ions and MeOH(+). In the wastewaters, MeSO4(0) and Pb(SO4)2(2-) species increased at the expense of the free Me(2+) ions. The highest self-cleaning capability of natural waters was found with respect to Al and Fe, followed by Mn and Cd. The lowest corresponded to Pb, Cu, and Zn.

Chemical speciation in mining affected waters: the case study of Asarel-Medet mine.

The inorganic chemical species in Maresh and Luda Yana rivers affected by the Cu- Mo Asarel-Medet mine, Bulgaria were determined during a low-flow and a high-flow period. The mining activities, the weathering and the oxidation processes strongly influenced the physicochemical processes in the whole water system. The main pollution source was a small lake receiving the acid effluents of the mining activities. High levels of SO4(2-), Cu, Mg, Al, Mn and Fe were determined at the mining polluted and affected stations. Cu(2+) and CuCO3(0) species (1:1) were present in the reference waters and Cu(2+) and CuSO4(0) species (1:1) in the polluted and affected waters; Cu(2+) species was dominating downstream. Me(2+) followed by MeSO4(0) (Me = Mn, Zn, Cd and Pb), PbCO3(0) and PbHCO3(+) species as well as Fe(OH)2(+), Al(OH)4(-), Al(OH)2(+), Al(OH)3(0) were prevailing in the system. MeSO4(+) and Me(SO4)2(-) (Me = Fe, Al), Me(SO4)2(2-) (Me = Zn, Cd and Pb), Me(SO4)3(4-) (Me = Zn, Cd) and Cd(SO4)4(6-) species polluted and affected waters. The major elements K and Na were mainly Me(+) species, whereas Ca and Mg were Me(2+) and MeSO4(0) species in different ratios. The concentration of concentration of NO2(-), NO3(-) and NO4(+) species as well as complex phosphorous species such as H2PO4(-), FeHPO4(+), HPO4(2-), CaPO4(-), CaHPO4(0) and MgHPO4(0) were also calculated. The trace element concentrations decreased downstream due to dilution, sorption processes and precipitation, but the percentage of free metal species, which are more toxic, increased. An exception was iron and aluminum of which the dominant hydroxy colloidal and sulphate species were easily incorporated into the suspended phase.

Chemical speciation of inorganic pollutants in river-estuary-sea water systems.

Monitoring studies and thermodynamic modeling were used to reveal the changes of inorganic chemical species of some water pollutants (nutrients and trace metals such as Fe, Mn, Zn, Cu, Cd and Pb) inthe river-estuary-sea water system. The case studies were two rivers, Kamchiya and Ropotamo, representing part of the Bulgarian Black Sea water catchment area, and having different flow characteristics. There were no major differences in inorganic chemical species of the two river systems. NO3(-) and NO2(-) chemical species showed no changes along the river-estuary-sea water system. Concerning phosphates six different species were calculated and differences between the three parts of the systems were established. The HPO4(2-) and H2PO4(-) species were found to be dominant in river waters. The H2PO4(-) species quickly decreased at the expense of HPO4(2-) and Ca, Mg and Na phosphate complexes in estuary and seawater. Trace metals showed a great variety of chemical species. Fe(OH)2(+) species prevailed in river waters, and Fe(OH)3(0) species--in sea waters. Me2+ and MeCO3(0) (Me = Cu, Pb) and PbHCO3(+) were dominant in river waters, while Cu(CO3)2(2-) and PbCl(-) species appear also in sea waters. Cd2+ species prevailed in river and estuary waters, and CdCln(2-n) (n = 1-3) species, in seawater. Free Zn2+ species predominated in all systems but downstream their percentage decreased at the expense of Zn phosphates, carbonates,sulfates and chlorides complexes. Only free Mn2+ species were dominant along the systems.