Variability of dust iron solubility in atmospheric waters: Investigation of the role of oxalate organic complexation

Atmospheric dust deposition is a major external iron source for remote surface ocean waters. Organic complexation is known to play a role in the dissolution of iron-containing minerals. In this paper, we present our study on the effect of oxalate on dust iron solubility in simulated rainwater. Our results reveal that the solubility of iron carried by analogs of different African dusts varies with the dust source. Our experiments indicate a positive linear correlation between iron solubility and oxalate concentration. Soluble iron (SFe) increases from 0.0025(±0.0005)% to 0.26(±0.01)% of total iron, considering all dust sources and with oxalate concentrations ranging from 0 to 8 μM. These results show that the observed variability of iron solubility in aerosols collected over the Atlantic Ocean is, at least partly, due to an increase in dust iron solubility, with the presence of oxalate complexation, rather than to the presence of more soluble anthropogenic iron. Considering the mineralogical composition of those particles, experiments with pure minerals (hematite, goethite and illite) were performed to study the dissolution process. We found that oxalate promotes the solubility of iron contained in clay and hence confirmed that more than 95% of SFe from soil dust is provided by clay (illite). This experimental work enables us to establish a parameterization of iron solubility in dust as a function of oxalate concentration and based on the individual iron solubility of pure iron-bearing minerals usually present in dust particles. Finally, our results emphasize that oxalate contributes to iron solubility on the same order of magnitude as the acid processes. Organic complexation appears to be a process that increases iron solubility and likely enhances the bioavailability of iron from dust.     

Salting-out phenomenon and 1-octanol/water partition coefficient of metalaxyl pesticide

In this paper, we present the effect of inorganic cations such as Na⁺, K⁺, Ca²⁺, Mg²⁺ on the salting-out phenomenon of metalaxyl from pure water to aqueous salt solutions. Moreover the 1-octanol/water partition coefficient in pure water is presented. To accomplish this, aqueous solubility of metalaxyl was determined in pure water, in different salt solution (NaCl, KCl, CaCl₂ and MgCl₂), and at different concentration level ranging from 0.01 to 1.5 M. The 1-octanol/water partition coefficient was determined using the static shake-flask method. Solubility was determined using dynamic saturation method for pure water in the range of 298.15-325.15 K and at 298.15 K for different salt solutions. The solubility value in pure water for studied interval was found constant (m = 3.118 × 10⁻² mol kg⁻¹).Solubility values were used to calculate the standard molar Gibbs free energy of dissolution (Δ_solG°) and transfer (Δ_trG°) at 298.15 K. The values of Δ_trG° from pure to all studied aqueous salt solutions did not exceed 2 kJ mol⁻¹, the value of Δ_solG° of dissolution is 18.5 ±0.72 kJ mol⁻¹. The 1-octanol/water partition coefficient in pure water log K_o/w is equal to 1.69. The obtained results confirm the classification of the neutral metalaxyl as a slightly hydrophobic molecule.     

Experimental and theoretical studies on physico-chemical parameters affecting the solubility of phosphogypsum

Phosphogypsum is a waste by-product of the phosphate fertilizer industry, which is usually disposed in the environment because of its restricted use in industrial applications. Physico-chemical conditions existing in stack fluids and leachates are of major importance and determine solubility and redox stability of phosphogypsum, as well as radionuclide release from stacks to terrestrial environments. The aim of this study is to assess the effect of key parameters (e.g. ionic strength, temperature, pH) on the solubility of phosphogypsum. Phosphogypsum sampling and in-situ measurements were carried out at a coastal stack in Cyprus, solubility experiments were performed in simulated laboratory systems and thermodynamic calculations by means of MINTEQA2, an equilibrium speciation model. Generally, increasing ionic strength and temperature leads to increased phosphogypsum solubility, with the former being much more effective. The increased solubility of phosphogypsum in saline solutions is attributed solely to ionic strength effects on the activity of ionic species in solution and no solid phase transformations could be observed. The effect of pH on phosphogypsum solubility seems to be insignificant at least in a pH range between 4 and 8. Regarding uranium levels, there is a strong correlation between salinity and uranium concentration and linear correlation between phosphogypsum solubility and uranium levels in stack solutions, indicating the incorporation of uranium into the gypsum lattice and the formation of a solid solution.     

Secondary arsenic minerals in the environment: A review

Information on arsenic (As) speciation in solid materials is critical for many environmental studies concerned with As stability and/or mobility in natural As-impacted soils and mining or industrial sites contaminated by As. The investigation of these systems has provided evidence for a number of secondary As minerals that have often played a significant role in As mobility in the solid phase–water system. This paper presents a list of environmentally important secondary As minerals in contaminated soil and waste systems, summarizes the information about their origin, occurrence, environmental stability and thermodynamics, and proposes several important avenues for further investigation.     

Solubility of toluene, benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.     

Temperature-dependent sorption of polycyclic aromatic hydrocarbons on natural and treated sediments

In aqueous environment temperature is considered to play a significant role in the sorption process of polycyclic aromatic hydrocarbons (PAHs) and its influence on the sorption equilibrium is indicative of sorption energies and mechanisms. In this study, sorptions of five PAHs on three heterogeneous sorbents including one river sediment (YHR), one estuary sediment (YRD) and one treated sediment with organic matter removed (IM) were carried out at a range of temperature from 5 °C to 35 °C. Stronger sorptions were observed at lower temperatures, with the equilibrium sorption coefficient K_d increasing 2-5 times as the temperature decreases 30 °C. The increase of K_d value was attributed primarily to the change of PAH water solubility, which predicted 40-75% of the increase of K_d in the sorption process. To provide insight into the sorption mechanism, enthalpy change (ΔH_S) for the sorption process was calculated and the values were observed to be negative for all of the interactions, suggesting that the exothermal sorption of PAHs inversely dependents on temperature. Based on the values of ΔH_S, van der Waals forces were inferred as the main sorption mechanism for the PAHs, especially on the YHR sediment which contained more organic matter. For sorption of larger size PAHs on the sorbents with low organic matter, specific interactions were deduced to contribute to the overall sorption.     

Modeling the partitioning of BTEX in water-reformulated gasoline systems containing ethanol

The objectives of this research were to quantify the extent of cosolvency for water–gasoline mixtures containing ethanol and to identify appropriate modeling tools for predicting the equilibrium partitioning of BTEX compounds and ethanol between an ethanol-bearing gasoline and water. Batch-equilibrium experiments were performed to measure ethanol and BTEX partitioning between a gasoline and aqueous phase. The experiments incorporated simple binary and multicomponent organic mixtures comprised of as many as eight compounds as well as highly complex commercial gasolines where the composition of the organic phase was not completely defined. At high ethanol volume fractions, the measured partition coefficients displayed an approximate linear relationship when plotted on semi-log scale as a function of ethanol volume fraction. At lower concentrations, however, there was a distinctly different trend which is attributed to a change in solubilization mechanisms at these concentrations. Three mathematical models were compared with or fit to the experimental results. Log-linear and UNIFAC-based models were used in a predictive capacity and were capable of representing the overall increase in partition coefficients as a function of increasing ethanol content in the aqueous phase. However, neither of these predicted the observed two-part curve. A piecewise model comprised of a linear relationship for low ethanol volume fractions and a log-linear model for higher concentrations was fit to data for a surrogate gasoline comprised of eight compounds and was then used to predict BTEX concentrations in the aqueous phase equilibrated with three different commercial gasolines. This model was superior to the UNIFAC predictions, especially at the low aqueous ethanol concentrations.     

Toxicity assessment and histopathological analysis of nano-ZnO against marine fish (Mugilogobius chulae) embryos

The toxicity of nano-materials has received increasing attention in recent years.Nevertheless,relatively few studies have focused on their oceanic distributions and toxicities.In this study,we assessed nano-ZnO toxicity in marine organisms using the yellowstriped goby(Mugilogobius chulae).The relative differences in nano-ZnO dissolution and dispersal in seawater and fresh water were also investigated.The effects of nano-ZnO on embryonic development,deformity,hatching,mortality,and histopathology were analyzed.In addition,the effects of the Zn~(2+) concentration on M.chulae hatching and mortality were compared.The results showed that nano-ZnO had higher solubility in seawater than in fresh water.Nano-ZnO significantly inhibited hatching.By the fifth day of exposure,the LC_(50) of nano-ZnO was 45.40 mg/L,and the mortality rate spiked.Hatching inhibition and lethality were dose-dependent over a range of1–25 mg/L nano-ZnO.Zn~(2+) inhibited hatching and increased lethality,but its effects were weaker than those of nano-ZnO at the same concentrations.Nano-ZnO also induced spinal bending,oedema,hypoplasia,and other deformities in M.chulae embryos and larvae.Histopathology revealed vacuolar degeneration,hepatocyte and enterocyte enlargement,and morphological abnormalities of the vertebrae.Therefore,nano-ZnO caused malformations in M.chulae by affecting embryonic growth and development.We conclude that nano-ZnO toxicity in seawater was significantly positively correlated with the associated Zn~(2+) concentration and sedimentary behaviour.The toxicity of nano-ZnO was cumulative and showed a critical point,beyond which embryonic and developmental toxicity in marine fish was observed.     

Solid state speciation and potential bioavailability of depleted uranium particles from Kosovo and Kuwait

A combination of synchrotron radiation based X-ray microscopic techniques (μ-XRF, μ-XANES, μ-XRD) applied on single depleted uranium (DU) particles and semi-bulk leaching experiments has been employed to link the potential bioavailability of DU particles to site-specific particle characteristics. The oxidation states and crystallographic forms of U in DU particles have been determined for individual particles isolated from selected samples collected at different sites in Kosovo and Kuwait that were contaminated by DU ammunition during the 1999 Balkan conflict and the 1991 Gulf war. Furthermore, small soil or sand samples heavily contaminated with DU particles were subjected to simulated gastrointestinal fluid (0.16 M HCl) extractions. Characteristics of DU particles in Kosovo soils collected in 2000 and in Kuwait soils collected in 2002 varied significantly depending on the release scenario and to some extent on weathering conditions. Oxidized U (+6) was determined in large, fragile and bright yellow DU particles released during fire at a DU ammunition storage facility and crystalline phases such as schoepite (UO₃·2.25H₂O), dehydrated schoepite (UO₃·0.75H₂O) and metaschoepite (UO₃·2.0H₂O) were identified. As expected, these DU particles were rapidly dissolved in 0.16 M HCl (84 ± 3% extracted after 2 h) indicating a high degree of potential mobility and bioavailability. In contrast, the 2 h extraction of samples contaminated with DU particles originating either from corrosion of unspent DU penetrators or from impacted DU ammunition appeared to be much slower (20–30%) as uranium was less oxidized (+4 to +6). Crystalline phases such as UO₂, UC and metallic U or U–Ti alloy were determined in impacted DU particles from Kosovo and Kuwait, while the UO_2,34 phase, only determined in particles from Kosovo, could reflect a more corrosive environment. Although the results are based on a limited number of DU particles, they indicate that the structure and extractability of DU particles released from similar sources (metallic U penetrators) will depend on the release scenarios (fire, impact) and to some extent environmental conditions. However, most of the DU particles (73–96%) in all investigated samples were dissolved in 0.16 M HCl after one week indicating that a majority of the DU material is bioaccessible.