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 $\rm{MeSO}_{4}^{\kern3pt{0}}$ (Me = Mn, Zn, Cd and Pb), $\rm{PbCO}_{3}^{\kern3pt{0}}$ and $\rm{PbHCO}_{3}^{\kern3pt{+}}$ species as well as $\rm{Fe(OH)}_{2}^{\kern3pt{+}}$ , $\rm{Al(OH)}_{4}^{\kern3pt{-}}$ , $\rm{Al(OH)}_{2}^{\kern3pt{+}}$ , $\rm{Al(OH)}_{3}^{\kern3pt{0}}$ were prevailing in the system. $\rm{MeSO}_{4}^{\kern3pt{+}}$ and $\rm{Me(SO}_{4})_{2}^{\kern3pt{-}}$ (Me = Fe, Al), $\rm{Me(SO}_{4})_{2}^{\kern3pt{2-}}$ (Me = Zn, Cd and Pb), $\rm{Me(SO}_{4})_{3}^{\kern3pt{4-}}$ (Me = Zn, Cd) and $\rm{Cd(SO}_{4})_{4}^{\kern3pt{6-}}$ species polluted and affected waters. The major elements K and Na were mainly Me^?+? species, whereas Ca and Mg were Me^2?+? and $\rm{MeSO}_{4}^{\kern3pt{0}}$ species in different ratios. The concentration of concentration of $\rm{NO}_{2}^{\kern3pt{-}}$ , $\rm{NO}_{3}^{\kern3pt{-}}$ and $\rm{NH}_{4}^{\kern3pt{+}}$ species as well as complex phosphorous species such as H₂ $\rm{PO}_{4}^{\kern3pt{-}}$ , $\rm{FeHPO}_{4}^{\kern3pt{+}}$ , $\rm{HPO}_{4}^{\kern4pt{2-}}$ , $\rm{CaPO}_{4}^{\kern3pt{-}}$ , $\rm{CaHPO}_{4}^{\kern3pt{0}}$ and $\rm{MgHPO}_{4}^{\kern3pt{0}}$ 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.     

Environmental and economic impacts of water scarcity and market reform on the Mooki catchment

Over-allocation of irrigation water has led to widespread environmental degradation in the Murray-Darling Basin (MDB) in Australia, prompting discussions of the water efficiency performance of irrigated industries. There is increasing pressure for irrigators to adopt water efficient practices in line with ecologically sustainable principles, especially with current drought conditions. However, there is great uncertainty surrounding the available practices to improve irrigation efficiency from both ecological and economic standpoints. This paper examines the economic and environmental impact of several possible water efficient practices and government policies, using an interdisciplinary approach combining biophysical modelling and economic modelling. This is done for the case-study of the Mooki catchment in the MDB, located in northern New South Wales, Australia.     

Fullerol C<Subscript>60</Subscript>(OH)<Subscript>24</Subscript> nanoparticles and mycotoxigenic fungi: a preliminary investigation into modulation of mycotoxin production

Increased use of fullerols in various fields and expected increase of their environmental spread impose the necessity for testing fullerol nanoparticles (FNP) effects on microbiota. There is little information available on the interaction of mycotoxigenic fungi and FNP, despite FNP having a great potential of modifying mycotoxin production. Namely, FNP exhibit both ROS-quenching and ROS-producing properties, while oxidative stress stimulates mycotoxin synthesis in the fungi. In order to shed some light on the extent of interaction between FNP and mycotoxigenic fungi, the effects of fullerol C₆₀(OH)₂₄ nanoparticles (10, 100, 1000 ng/mL) on mycelial growth, aflatoxin production and oxidative stress modulation in an aflatoxigenic strain of Aspergillus flavus (NRRL 3251) during 168 h of incubation in a liquid culture medium were examined. FNP slightly reduced mycelial biomass weight, but significantly decreased aflatoxin concentration in media. Lipid peroxide content, superoxide dismutase, catalase and glutathione peroxidase activities suggest that FNP treatments hormetically reduced oxidative stress within fungal cells in turn suppressing aflatoxin production. These findings contribute to the assessment of environmental risk and application potential of fullerols.     

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 AlPO $_{4}^{0}$ and Al₂(OH)₂PO $_{4}^{+}$ ; (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 MeSO $_{4}^{0}$ , MeCO $_{3}^{0}$ species, and of MeCl $_{2}^{0}$ (Me = Zn, Cd) species were also calculated. In the wastewaters, two more species [Me(SO $_{4})_{2}^{2-}$ and Me(SO $_{4})_{3}^{4-}$ ] of the softer Zn and Cd metals were also calculated; (3) Cu^2?+? and Pb^2?+?, as “soft” acids with CFSE $\ne $ 0 preferentially coordinated with softer CO $_{3}^{2-}$ ions and in natural waters existed mainly as MeCO $_{3}^{0}$ and PbHCO $_{3}^{+}$ , followed by free Me^2?+?ions and MeOH^?+?. In the wastewaters, MeSO $_{4}^{0}$ and Pb(SO $_{4})_{2}^{2-}$ 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 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?? (81.8%), PbCO?? (77.2%) and hydroxy species Fe(OH) ??(55.2%) and Fe(OH)+?(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)?? for Fe was calculated for sea and hyper-saline water.     

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.     

On the influence of soil properties on the transfer of 137Cs from two soils (Chromic Luvisol and Eutric Fluvisol) to wheat and cabbage

Two types of soils (Eutric Fluvisol and Chromic Luvisol) and two crops (wheat and cabbage) were investigated for determination of the transfer of 137Cs from soil to plant. Measurements were performed using gamma-spectrometry. Results for the soil characteristics, transfer factors of the radionuclides (TF), and conversion factors (CF) (cabbage/wheat) were obtained. The transfer of 137Cs was higher for Chromic Luvisol for both the plants. Statistically significant dependence of TF of 137Cs on its concentration in soil was established for cabbage. Dependence between K content in the soil and the transfer factor of 137Cs was not found due to the high concentrations of available K. Use of bioconcentration factor (BCF) (ratio between the activity concentration of a radionuclide in a reference plant to its concentration in another plant) is demonstrated and proposed for risk assessment studies.