Mercury speciation in contaminated soils by thermal release analysis

Thermal release analysis of mercury species in contaminated soils was performed by temperature controlled continuous heating of the samples in a furnace coupled to an Atomic Absorption Spectrophotometer (AAS). It was shown that this method allows the identification of different redox states of Hg-species through their characteristic releasing temperature ranges. The method was applied to Hg-contaminated samples from an inactive chlor-alkali production plant in former East Germany (GER), and from a gold mining area in Poconé, Mato Grosso, Brazil (BRA), as well as synthetic soil samples obtained by spiking pre-heated soil matrices (GER and BRA) with the following mercury species: Hg⁰, Hg₂Cl₂, HgCl₂, HgO and HgS. The samples GER, in general, frequently showed the presence of Hg²⁺ probably bound to humic substances, in the case of samples with higher total carbon content. Only in highly contaminated samples (>3000 ppm of mercury) was Hg⁰ the predominant species. The samples BRA more frequently showed the presence of mercury species in the lower oxidation states, i.e. Hg¹⁺ in combination with Hg⁰. The method allows observing changes in Hg-speciation in the samples with time, mainly changes among the oxidation states Hg⁰, Hg¹⁺ and Hg²⁺. The treated GER matrix showed a stronger tendency to oxidise Hf-species than the BRA treated matrix, in which only added Hg⁰ is partially oxidised to Hg²⁺ and Hg¹⁺. In contrast, the BRA matrix showed a pronounced tendency to reduce spiked Hg²⁺ to Hg¹⁺. This may be the reason for the presence of Hg¹⁺ in the majority of original BRA samples. The method appears to be very useful to study speciation of mercury and its dynamics. It can be used as a tool for monitoring mercury oxidation states and/or reactions of mercury in soils.     

Influence of Soil Type on the Effects of Elevated Atmospheric CO2 and N Deposition on the Water Balance and Growth of a Young Spruce and Beech Forest

Sixteen open-top chambers, each equipped with two non-weighablegravity-drained lysimeter compartments, were used to investigate the impacts of elevated atmospheric carbon dioxide (CO₂) concentration and nitrogen (N) deposition on the water relations and growth of young model forest ecosystems on two different types of soils. The same vegetation of a mixed spruce and beech overstorey and various herbs in the understorey was planted in all treatments on both soils. The soils were repacked on top of a drainage layer. Four combinations of treatments were applied in four replicates each: ambient (370 cm³ m^-3) CO₂ + low (7 kg N ha^-1 a^-1) N deposition, ambient CO₂ + high(70 kg N ha^-1 a^-1) N deposition, elevated (590 cm³ m^-3) CO₂ + low N deposition, and elevated CO₂ + high N deposition. After canopy closure, treatment effects on evapotranspiration and growth during the third year of study were very different for the two soils.On the acidic sandy loam, elevated CO₂ enhanced growth(leaf biomass +21%, roots +27%) at reduced evapotranspiration (–9%). High N deposition increased aboveground growth even more strongly (+50%), but also increased evapotranspiration (+16%). Together, elevated CO₂ and high N had a more than additive fertilizer effect on growth, while their effects on evapotranspirationcompensated. On the calcareous loamy sand, elevated CO₂not only tended to enhance growth (leaf biomass +17%, roots +20%), but also increased evapotranspiration (+5%).On this soil, aboveground growth was stimulated by N only incombination with elevated CO₂, but less than on the acidic soil, while evapotranspiration (–6.5%) and root growth into the subsoil (–54%) were decreased by increased N deposition at both CO₂ concentrations, in contrast to the N treatments on the acidic sandy loam. The influence of the soil on the observed ecosystem responses canbe interpreted in terms of the concept of optimal resource allocation.     

Sorption and desorption of Zn on Ca-Kaolinite

Experiments on Zn²⁺ sorption-desorption by Ca-kaolinite using a wide range of Zn²⁺ concentrations and two acid pH values allowed us to reach the following conclusions: (1) For Zn²⁺ surface coverages below the kaolinite C.E.C., Zn²⁺ was sorbed mainly via ion exchange; (2) At Zn^2? sorption values above the C.E.C., Zn²⁺ was sorbed with higher affinity by a mechanism stronger than ion exchange, involving a strong association of Zn ions with silicate solid phases; and (3) Use of C.E.C. values and/or Langmuir's calculated maxima would greatly underestimate Zn²⁺ sorption capacity by kaolinite, even at acid pH values.     

Diabetes and hypertension increases in a society with abdominal obesity: results of the Mexican National Health Survey 2000

OBJECTIVES: To determine the prevalences of overweight, obesity, type 2 diabetes mellitus (DM) and hypertension (HT) in the Mexican population and compare them with those of a previous Mexican urban survey and an American survey. DESIGN: A structured, randomised, nationally representative Mexican sample was compared with a 1993 Mexican urban survey and the US Third National Health and Nutrition Examination Survey (NHANES III) of non-Hispanic Whites. SETTING: The Mexican National Health Survey 2000.Subjects: Subjects were 12,856 men and 28,332 women, aged 20-69 years, who had their body weight, height, waist circumference (WC), blood pressure and fasting capillary blood glucose measured. RESULTS: Mexican adult men and women had a high prevalence of overweight (41.3 and 36.3%, respectively) and obesity (19.4 and 29.0%, respectively), similar to those in the USA in 1988-1992 and exceeding those of the 1993 Mexican survey. The prevalence of HT was 33.3% in men and 25.6% in women, with inferred DM rates of 5.6 and 9.7%, respectively. Abdominal obesity affected 46.3% of men (WC>or=94 cm) and 81.4% of women (WC>or=80 cm). There was a high prevalence of abdominal obesity in normal-weight women, with co-morbidities relating better to WC than to body mass index (BMI) in both sexes. Rates of DM and HT exceeded US rates on a comparable BMI or WC basis in adults aged <50 years. CONCLUSION: The high prevalence of obesity and abdominal obesity in Mexicans is associated with markedly increased prevalences of DM and HT to levels comparable with, or even higher than, those in NHANES III of non-Hispanic Whites.     

Bioactive cinchona alkaloids from Remijia peruviana

Three known Cinchona alkaloids of the quinine type, quinine (1), cupreine (2), cinchonine (3), and the possible artifact cinchonine-HCl (3-HCl), along with two new ones, acetylcupreine (4) and N-ethylquinine (5), have been isolated from the bark of Remijia peruviana (Rubiaceae). Their stereochemical structures were established by high resolution NMR spectroscopy. Alkaloids 2-4 had antifeedant effects on Leptinotarsa decemlineata with varying potencies. Compound 4 was cytotoxic to both insect Sf9 and mammalian CHO cells after 48 h of incubation, while 3-HCl had stronger and selective cytotoxicity to Sf9. Quinine 1 had a moderate to low effect on Trypanosoma cruzi. Tumoral cells were also affected by these alkaloids, with 4 and 3-HCl being the most cytotoxic to all the cell lines tested. Overall, the 8R, 9S configurations, as in 3 and 3-HCl, as well as the C-6'acetylated alkaloid 4, with an 8S, 9R configuration, showed stronger biological effects.     

Stability study of a sulfadimidine-containing medicated premix and its mixture with farm feed

The objective of this paper was to study the stability of a medicated premix and a medicated farm feed containing sulfadimidine as the active ingredient. The medicated premix is supplied as powdered form and administered orally after mixing with animal feed. The sulfadimidine analytical method described in United States Pharmacopoeia 23 cannot be used to carry out the stability study because of its lack of specificity for different degradation products. Therefore, a high-performance liquid chromatography method was developed to assay sulfadimidine. This method was optimized and validated for the stability study. According to International Committee Harmonization (ICH) guidelines, the samples were stored under long-term testing and accelerated conditions for the stability study of the premix and the medicated farm feed. Sulfadimidine degradation was not detected in either form under any of the conditions studied.     

SPME-GC-pyrolysis-AFS determination of methylmercury in marine fish products by alkaline sample preparation and aqueous phase phenylation derivatization

Characterization of a cost-efficient analytical method based on alkaline sample digestion with KOH and NaOH, followed by aqueous phase phenylation derivatization with NaBPh4 and solid phase microextraction (SPME) for the determination of methylmercury in typical fish-containing food samples commercially available in Hungary, is reported. The sample preparation procedure along with the applied SPME-GC-pyrolysis-AFS system was validated by measuring certified reference materials (CRM) BCR-464, TORT-2, and a candidate CRM BCR 710. To carry out an estimation of average Hungarian methylmercury exposures via marine fish and/or fish-containing food consumption, 16 commercially available products and 3 pooled representative seafood samples of-according to a previous European survey--the three most consumed fish species in Hungary, herring, sardines, and hake, were analyzed. Methylmercury concentrations of the analyzed samples were in the range 0.016-0.137 microg of MeHg g(-1) dry weight as Hg.     

Rapid liquid chromatography tandem mass spectrometry assay to quantify plasma (-)-epicatechin metabolites after ingestion of a standard portion of cocoa beverage in humans

A rapid liquid chromatography electrospray ionization tandem mass spectrometry with negative ion detection method was developed and validated to determine cocoa flavonoid metabolites in human plasma and urine after the intake of a standard portion of a cocoa beverage. A chromatographic run time of only 9 min provided clear separation of all metabolites and internal standards. Samples were analyzed in a product-ion scan of m/z 289, 369, and 465 to identify the metabolites and in multiple reaction monitoring acquisition mode to quantify (-)-epicatechin ((-)-Ec) (289/ 245), (-)-epicatechin-glucuronide ((-)-EcG) (465/289), and (-)-epicatechin-sulfate ((-)-EcS) (369/289). One (-)-Ec-G and three (-)-Ec-S were identified and confirmed in urine as the major metabolites, and one (-)-Ec-G was the only metabolite present in plasma volunteers (n = 5) at a mean concentration of 625.7 +/- 198.3 nmol/L at 2 h after consumption of a cocoa beverage containing 54.4 mg of (-)-Ec.     

Lead dietary intake in a Spanish population (Canary Islands)

For most people diet is the main route of exposure to trace metals, so information about dietary intake is also important to assess risks to human health for these elements. The purpose of this study was to determine the levels of Pb in the foods and drinks of highest consumption in the authors' our community to estimate daily intakes of Pb for each of the seven Canary Islands. Four hundred and twenty samples were analyzed using GFAAS. The total Pb intake of the Canarian population is 72.8 microg/day, 29.12% (for a person of 70 kg body weight) of the provisional tolerable weekly intake limit of 25 microg/kg fixed by the FAO/WHO. The island that presents the highest lead intake is La Gomera, followed by Lanzarote, Tenerife, and Gran Canaria islands. These four islands present a lead dietary intake over the mean Pb intake for the whole archipelago. The islands with lower Pb intakes are La Palma and Fuerteventura, with intakes under 70 microg/day. These results have also been compared with the values found for other national and international communities.     

Genetic manipulation of proline accumulation influences the concentrations of other amino acids in soybean subjected to simultaneous drought and heat stress

The effect of simultaneous drought and heat stress on free amino acid levels was compared in wild type and transgenic soybean (Glycine max (L.) Merr cv Ibis) plants transformed with the cDNA coding for the last enzyme of Pro biosynthesis, l-Delta(1)-pyrroline-5-carboxylate reductase (EC 1.5.1.2), in sense and antisense directions. The most rapid increase in Pro content was found in the sense transformants that exhibited the least water loss, while the slowest elevation of Pro levels was detected in the antisense transformants that exhibited the greatest water loss during stress. Correspondingly, the level of the Pro precursors Glu and Arg was higher in sense transformants and lower in antisense ones compared to the wild type plants during the initial part of the stress. Interestingly, genetic manipulation of Pro levels also affected the stress-induced changes in the concentration of several other amino acids, which indicates the coordinated regulation of their metabolic pathways.