Role of natural attenuation, phytoremediation and hybrid technologies in the remediation of a refinery soil with old/recent petroleum hydrocarbons contamination.

Within a search for a biological remediation technology to remove petroleum hydrocarbons (PHC) from a contaminated soil from a refinery, the potential of monitored natural attenuation (MNA) was compared with the use of transplants of Cortaderia selloana both in the absence and in the presence of soil amendments. After 31 months of experiments, MNA was effective in removing most of the recent PHC contamination (50% of the initial total contamination) at 5-20 cm depth. The presence of weathered contamination explains the existence of an established community of PHC degraders, as can be inferred by the most probable number technique. C. selloana, in its turn, showed capacity to mobilize the most recalcitrant fraction of PHC to its roots, nevertheless masking its remediation capacity. The use of a hybrid technology (C. selloana together with treatments with a surfactant and a bioaugmentation product) improved the removal of PHC at 15-20 cm depth, the presence of C. selloana facilitating the migration of additives into the deeper layers of soil, which can be considered a secondary but positive role of the plant. In the surface soil layer, which was exposed to both microorganisms and the atmosphere, a further 20% of weathered PHC contamination disappeared (70% total removal) as a result of photo- and chemical degradation. Periodic revolving of the soil, like tillage, to expose all the contaminated soil to the atmosphere will therefore be a reliable option for reducing the contamination of the refinery soil if conditions (space and equipment) permit this operation.

Validated method for determination of bromopride in human plasma by liquid chromatography--electrospray tandem mass spectrometry: application to the bioequivalence study.

A simple, sensitive and specific liquid chromatography-tandem mass spectrometry method for the quantification of bromopride I in human plasma is presented. Sample preparation consisted of the addition of procainamide II as the internal standard, liquid-liquid extraction in alkaline conditions using hexane-ethyl acetate (1 : 1, v/v) as the extracting solvent, followed by centrifugation, evaporation of the solvent and sample reconstitution in acetonitrile. Both I and II (internal standard, IS) were analyzed using a C18 column and the mobile-phase acetonitrile-water (formic acid 0.1%). The eluted compounds were monitored using electrospray tandem mass spectrometry. The analyses were carried out by multiple reaction monitoring (MRM) using the parent-to-daughter combinations of m/z 344.20 > 271.00 and m/z 236.30 > 163.10. The areas of peaks from analyte and IS were used for quantification of I. The achieved limit of quantification was 1.0 ng/ml and the assay exhibited a linear dynamic range of 1-100.0 ng/ml and gave a correlation coefficient (r) of 0.995 or better. Validation results on linearity, specificity, accuracy, precision and stability, as well as application to the analysis of samples taken up to 24 h after oral administration of 10 mg of I in healthy volunteers demonstrated the applicability to bioequivalence studies.

[Vitamin A deficiency in children of rural areas of the semi-arid region in Bahia]. / Hipovitaminose A em criancas de areas rurais do semi-árido baiano.

The distribution and magnitude of vitamin A deficiency and dietary consumption of 161 children at 6 to 72 months of age in rural zones in Cansancao-Bahia-Brazil were evaluated. The serum retinol levels were measured by the spectrophotometric method (Bassey-Lowry modified by Araujo and Flores). The serum retinol average was found to be distributed homogeneously throughout the different age groups. Inadequate serum retinol levels (<20,0 mu g/dl) were detected in 44.7% of the children, which characterized the deficiency as constituting a public health problem. The serum retinol levels showed no statistically significant association as between the sex and age of the children; however the children of less than 24 months showed a higher prevalence of inadequate serum retinol levels. The main available source of vitamin A for these children was represented by carotenoids, especially beta-carotene. Foods regarded as being rich in vitamin A were consumed by all age groups. The greatest diversification of consumption of foodstuffs with moderate and low vitamin A content was observed in the group of children of from 24 to 72 months of age, through this was no guarantee of adequate serum retinol levels in this group however.

Suitability of Scirpus maritimus for petroleum hydrocarbons remediation in a refinery environment.

PURPOSE: In the ambit of a project searching for appropriate biological approaches for recovering a refinery soil contaminated with petroleum hydrocarbons (PHC), we compared results obtained in the absence and in the presence of the salt marsh plant Scirpus maritimus or Juncus maritimus or an association of these two plants, which were tested in the refinery environment. Synergistic effects caused by addition of a non-ionic surfactant and/or a bioaugmentation product were also investigated. Major challenges of this study were: field conditions and weathered contamination. METHODS: Transplants of the plants were carried out in individual containers filled with a weathered contaminated soil, which was recontaminated with turbine oil with two purposes: for increasing PHC level and allowing a comparison of the potential of plants for remediation of ancient and recent contamination. RESULTS: Analysis of total PHC led to the conclusion that, after 24-month exposure, neither J. maritimus nor the association caused any improvement in remediation. In contrast, S. maritimus revealed potential for PHC remediation, favoring degradation of both recent and older contamination (which was refractory to natural attenuation). About 15% of remediation improvement was found in the soil layer with higher root density (5-10 cm). A more marked improvement in that layer (28%) was observed when non-ionic surfactant amendment and bioaugmentation were used jointly. CONCLUSIONS: The fact that S. maritimus has demonstrated capability for PHC remediation, leads to admit that it has potential to be also used for recovering sediments that have suffered accidental oil spills.

Suitability of different salt marsh plants for petroleum hydrocarbons remediation.

The suitability of the salt-marsh species Halimione portulacoides, Scirpus maritimus, Juncus maritimus and an association of the last two for remediation of petroleum hydrocarbons (PHC) in soil was investigated. An outdoor laboratory experiment (microcosm-scale) was carried out using contaminated soil collected in a refinery, as a complement of another study carried out in the refinery environment (mesocosm-scale). Soil samples with old contamination (mainly crude oil) and with a mixture of the old and recent (turbine oil) contamination were tested. Studies in both micro- and mesocosm-scale provided results coherent in substance. The presence of S. maritimus caused removal of old contamination which was refractory to natural attenuation (after 7months of exposure, efficiency was 13% when only old contamination was present and 40% when the soil also contained recent contamination). H. portulacoides (only included in the microcosm-scale study) revealed also potentiality for PHC remediation, although with less efficiency than S. maritimus. Degradation of recent contamination was also faster in the presence of plants (after 7months: 100% in the presence of S. maritimus vs. 63% in its absence). As these species are common in salt marsh areas in Atlantic coast of Europe, it is probable they will be also useful for recovering coast sediments. In contrast, J. maritimus and association did not reveal capability to remove PHC from soil, the presence of J. maritimus inhibiting the capability of S. maritimus.

Mesocosm trials of bioremediation of contaminated soil of a petroleum refinery: comparison of natural attenuation, biostimulation and bioaugmentation.

PURPOSE: Contamination with petroleum hydrocarbons (PHC) is a global problem with environmental implications. Physico-chemical treatments can be used for soil cleanup, but they are expensive, and can have implications for soil structure and environment. Otherwise, biological remediation treatments are cost-effective and restore soil structure. Several remediation experiments have been carried out in the lab and in the field; however, there is the challenge to achieve as good or better results in the field as in the laboratory. In the ambit of a project aiming at investigating suitable biological remediation approaches for recovering a refinery contaminated soil, we present here results obtained in bioremediation trials. The approaches biostimulation and bioaugmentation were tested, in parallel, and compared with natural attenuation. For this purpose, mesocosm experiments were carried out inside the refinery area, which constitutes a real asset of this work. METHODS: Soil contaminated with crude oil was excavated, re-contaminated with turbine oil, homogenised and used to fill several 0.5 m(3) high-density polyethylene containers. The efficiency of procedures as follows: (1) natural attenuation; (2) manual aeration; (3) biostimulation by adding (3.1) only nutrients; and (3.2) nutrients and a non-ionic surfactant; and (4) bioaugmentation in the presence of added (4.1) nutrients or (4.2) nutrients and a non-ionic surfactant were evaluated after a 9-month period of experiment. For bioaugmentation, a commercial bacterial product was used. In addition to physico-chemical characterization, initial and final soil contents in total petroleum hydrocarbons (TPH) (by Fourier transform infrared spectrophotometry) and the total number of bacteria (by total cell counts) were carried out. For TPH degradation evaluation the soil was divided in four fractions corresponding to different depths: 0-5; 5-10; 10-15; and 15-20 cm. Mean values of percentages of PHC degradation varied between 20 and 50% at surface and between 10 and 35% below 5-cm depth. Natural attenuation was as efficient as most of the tested treatments (about 30% TPH degradation) being exceeded only by bioaugmentation combined with nutrient and surfactant amendments (about 50% TPH degradation). Higher TPH degradation at surface suggests that a combination of sufficient dioxygen, propitious for aerobically degradation, with sunlight required for production of strong photochemical oxidants like ozone, contributed for enhancing degradation. Indeed, the atmosphere of the refineries is relatively rich in volatile organic compounds and nitrogen dioxide (a side-product of the combustion of residual volatile PHC released by the chimneys), which are precursors of O(3) and other photochemical oxidants produced in sunny days, which are very common in Portugal. The fact that natural attenuation was as efficient as most of the soil treatments tested was very probably a result of the presence, in the initial soil, of physiologically adapted native microorganisms, which could be efficient in degrading PHC. CONCLUSIONS: A cost-effective way to reduce half-life for the degradation of PHC of contaminated soil of the refinery will be a periodic revolving of the soil, like tillage, in order to expose to the oxidative atmosphere the different layers of contaminated soil. A combination of soil revolving with bioaugmentation together with nutrients and surfactant amendments may result in an additional improvement of PHC degradation rate. However, this last procedure will raise markedly the price of the remediation treatment.