Open-pit coal-mining effects on rice paddy soil composition and metal bioavailability to Oryza sativa L. plants in Cam Pha, northeastern Vietnam

This study quantified Cd, Pb, and Cu content, and the soil–plant transfer factors of these elements in rice paddies within Cam Pha, Quang Ninh province, northeastern Vietnam. The rice paddies are located at a distance of 2 km from the large Coc Sau open-pit coal mine. Electron microprobe analysis combined with backscattered electron imaging and energy-dispersive spectroscopy revealed a relatively high proportion of carbon particles rimmed by an iron sulfide mineral (probably pyrite) in the quartz–clay matrix of rice paddy soils at 20–30 cm depth. Bulk chemical analysis of these soils revealed the presence of Cd, Cu, and Pb at concentrations of 0.146?±?0.004, 23.3?±?0.1, and 23.5?±?0.1 mg/kg which exceeded calculated background concentrations of 0.006?±?0.004, 1.9?±?0.5, and 2.4?±?1.5 mg/kg respectively at one of the sites. Metals and metalloids in Cam Pha rice paddy soils, including As, Cd, Cr, Cu, Hg, Mn, Ni, Pb, and Zn, were found in concentrations ranging from 0.2?±?0.1 to 140?±?3 mg/kg, which were in close agreement with toxic metal contents in mine tailings and Coc Sau coal samples, suggesting mining operations as a major cause of paddy soil contamination. Native and model Oryza sativa L. rice plants were grown in the laboratory in a growth medium to which up to 1.5 mg/kg of paddy soil from Cam Pha was added to investigate the effects on plant growth. A decrease in growth by up to 60 % with respect to a control sample was found for model plants, whereas a decrease of only 10 % was observed for native (Nep cai hoa vang variety) rice plants. This result suggests an adaptation of native Cam Pha rice plants to toxic metals in the agricultural lands. The Cd, Cu, and Pb contents of the native rice plants from Cam Pha paddies exceeded permitted levels in foods. Cadmium and Pb were highest in the rice plant roots with concentrations of 0.84?±?0.02 and 7.7?±?0.3 mg/kg, suggesting an intake of these metals into the rice plant as shown, for example, by Cd and Pb concentrations of 0.09?±?0.01 and 0.10?±?0.04 mg/kg respectively in the rice grain endosperm. The adaptation of native rice plants, combined with bioaccumulation ratios of 1?±?0.6 to 1.4?±?0.7 calculated for Cd transfer to the rice grain endosperm, and maximum Cd transfer factors of 4.3?±?2.1 to the plant roots, strongly suggest a continuous input of some toxic metals from coal-mining operations to agricultural lands in the region of Cam Pha. In addition, our results imply a sustained absorption of metals by native rice plant varieties, which may lead to metal accumulation (e.g., Cd) in human organs and in turn to severe disease.     

First evidence of polybrominated diphenyl ether (flame retardants) effects in feral barbel from the Ebro River basin (NE, Spain)

Polybrominated diphenyl ethers (PBDEs) are chemicals of environmental concern due to their lipophilic, persistent and bioaccumulable characteristics as well as for their potential endocrine disrupting role. Former studies carried out in a tributary of the Cinca river (Ebro basin, NE Spain) revealed high levels of PBDEs in fish due to the discharges of effluents rich in PBDEs coming from a nearby industrial park in Barbastro. In this study, several biomarkers of pollutants exposure were measured in barbel, Barbus graellsii, before (upstream) and after (downstream) the main industrial site (Barbastro) in the Vero river. The results evidenced an enhanced hepatic phase I and II metabolism (measured as reductases, glutathione S transferase and uridinediphospho-glucuronosyltransferase), and of the antioxidant enzyme glutathione peroxidase. Conversely, fishes collected from downstream reaches had their phase I CYP1A dependent ethoxyresorufin O-deethylase, antioxidant diaphorase and brain cholinesterase activities depleted. In addition, the histological study of the liver and kidney of these fish evidenced an increase of the number and size of macrophage aggregates in most individuals collected downstream. Bivariate correlated analyses showed that the above mentioned biomarkers were correlated to measured PBDE congeners, thus indicating that the observed biological effects were unlikely to be related to other environmental factors than PBDEs. Overall, the measured biochemical and histological markers provide new evidence that in field exposed fish, PBDEs levels were associated with high activities of phase I and II metabolic enzymes, oxidative stress in liver, neurotoxicity in brain and histopathological effects in both liver and kidney.     

Relationship between blood concentrations of heavy metals and cytogenetic and endocrine parameters among subjects involved in cleaning coastal areas affected by the 'Prestige' tanker oil spill

The sinking of the 'Prestige' oil tanker in front of the Galician coast (NW of Spain) in November 2002 offered a unique opportunity to analyze intermediate cytogenetic and endocrine effects among people exposed to the complex mixture of substances that oil constitutes, including several toxic heavy metals. In this work we evaluated the relationship between exposure to heavy metals (blood concentrations of aluminium, cadmium, nickel, lead and zinc) and genotoxic parameters (sister chromatid exchanges, micronucleus test and comet assay) or endocrine parameters (plasmatic concentrations of prolactin and cortisol) in subjects exposed to 'Prestige' oil during cleaning tasks developed after the spillage. Concentrations of lead were significantly related to the comet assay even after adjusting by age, sex and smoking. Cortisol concentrations were significantly influenced by aluminium, nickel (both, inversely) and cadmium (positively). Women had clearly higher concentrations of prolactin and cortisol, even when adjusting by age, smoking, cadmium, aluminium or nickel. Plasmatic cortisol was jointly influenced by gender, smoking and aluminium or nickel (all p<0.05). In women there was a strong relationship between concentrations of cadmium and prolactin (beta=0.37, p=0.031). When the effects of cadmium, aluminium and nickel on cortisol were simultaneously assessed, only the latter two metals remained statistically significant. Among parameters analysed, cortisol appeared to be the most sensitive to the effects of metal exposure. Plasma levels of cortisol deserve further evaluation as a potentially relevant biomarker to assess the effects of exposure to heavy metals.     

Review of the complexation of tetravalent actinides by ISA and gluconate under alkaline to hyperalkaline conditions

Isosaccharinic (ISA) and gluconic acids (GLU) are polyhydroxy carboxylic compounds showing a high affinity to metal complexation. Both organic ligands are expected in the cementitious environments usually considered for the disposal of low- and intermediate-level radioactive wastes. The hyperalkaline conditions imposed by cementitious materials contribute to the formation of ISA through cellulose degradation, whereas GLU is commonly used as a concrete additive. Despite the high stability attributed to ISA/GLU complexes of tetravalent actinides, the number and reliability of available experimental studies is still limited. This work aims at providing a general and comprehensive overview of the state of the art regarding Th, U(IV), Np(IV), and Pu(IV) complexes with ISA and GLU.In the presence of ISA/GLU concentrations in the range 10^− 5–10^− 2 M and absence of calcium, An(IV)(OH)_x(L)_y complexes (An(IV) = Th, U(IV), Np(IV), Pu(IV); L = ISA, GLU) are expected to dominate the aqueous speciation of tetravalent actinides in the alkaline pH range. There is a moderate agreement among their stability, although the stoichiometry of certain An(IV)-GLU complexes is still ill-defined. Under hyperalkaline conditions and presence of calcium, the species CaTh(OH)₄(L)₂(aq) has been described for both ISA and GLU, and similar complexes may be expected to form with other tetravalent actinides.In the present work, the available thermodynamic data for An(IV)–ISA/GLU complexes have been reviewed and re-calculated to ensure the internal consistency of the stability constants assessed. Further modelling exercises, estimations based on Linear Free-Energy Relationships (LFER) among tetravalent actinides, as well as direct analogies between ISA and GLU complexes have also been performed. This approach has led to the definition of a speciation scheme for the complexes of Th, U(IV), Np(IV) and Pu(IV) with ISA and GLU forming in alkaline to hyperalkaline pH conditions, both in the absence and presence of calcium.     

2,3,7,8-Substituted PCDDs and PCDFs in sea lion (Otaria flavescens) skin biopsies from two South-western Atlantic populations

Congener specific 2,3,7,8-chlorinated PCDDs and PCDFs were determined in skin biopsies taken from sea lions (Otaria flavescens) living in two areas of the South-western Atlantic on the coast of Argentina (Mar del Plata and Punta Bermeja). This is the first report on PCDDs and PCDFs in sea lion skin biopsies from the southern hemisphere. Differences were found in the congener pattern according to the sampling area. Animals living in the polluted area (Mar del Plata harbour) had detectable levels of all seventeen 2,3,7,8-substituted congeners. Sea lions living in a control environment (Punta Bermeja, Patagonia) only exhibited 5 detectable congeners out of all seventeen 2,3,7,8-substituted congeners. However, total levels were low in both colonies studied. These data are consistent with previous work which has indicated that dioxins occur at relatively low levels in marine mammals, possibly due to rapid catabolism or elimination.     

Mechanical Properties, Water Vapor Permeability and Water Affinity of Feather Keratin Films Plasticized with Sorbitol

In poultry industry chicken feathers are normally hydrolyzed and used to prepare animal feed. In this work the use of this material to prepare films was investigated. Keratins were extracted from chicken feathers with 2-mercaptoethanol in concentrated urea solution using sodium dodecyl sulfate (SDS). The effect of varying the amount of sorbitol on properties of chicken feather keratin (CFK) was investigated. As the concentration of plasticizer increased, the moisture content (MC) of these films increase, the monolayer MC increased from 0.060 (without plasticizer) to 0.482 g water/g dry matter (0.30 g sorbitol/g keratin). The water vapor permeability (WVP) varied between 0.096 g/m s Pa and 8.098 g/m s Pa for films without sorbitol and with 0.30 g sorbitol/g keratin, respectively. Film strength decreased from 5.13 MPa to 0.45 MPa and the elongation at break achieved the maximum value of 52.75% for samples with 0.02 g sorbitol/g keratin. The dry matter density didn’t change significantly, varying between 0.86–0.89 g/cm³ for all samples. Films with potential applications in food packaging can be obtained from CFKs. However, further researches are necessary to decrease film solubility and increase mechanical resistance.