Metal ion uptake from aqueous solution by olive stones: a carbon-13 solid-state nuclear magnetic resonance and potentiometric study.

The use of biomasses that result from the agriculture and food industries in removing heavy metals from wastewaters is attracting increasing interest. We present a joined potentiometric and cross polarization magic angle spinning (CP-MAS) carbon-13 (13C) nuclear magnetic resonance (NMR) study on the interaction of olive stones with copper(II), nickel(II), and cadmium(II). The potentiometric measurements allow both to distinguish two kind of basic sites in the olive stones and to postulate the coordination models for the three studied metals. The NMR spectral analysis allows the attribution of the different signals to the components of the olive stone matrix. A comparison of CP-MAS 13C NMR spectra of the samples after metal treatment suggests a specific complexation between metal ions and hydroxyl groups on guaiacyl and syringyl moieties.     

Cellular localisation of secondary metabolites isolated from the Caribbean sponge <Emphasis Type="Italic">Plakortis simplex</Emphasis>

The Caribbean sponge, Plakortis simplex, is known to contain a large array of secondary metabolites, including the antimalarial polyketide plakortin, several unusual glycolipids, and some hopanoids, which closely resemble typical bacterial metabolites. The hypothesis that they could be products of bacterial metabolism was tested by localizing specific metabolites in cells using physical separation of sponge cells, bacterial symbionts and supernatant by differential centrifugation. The obtained fractions were analysed separately for the typical P. simplex metabolites by NMR and mass spectrometry, and most of them were shown to be present in the bacterial cells but not in the sponge cells. In addition, PCR screening showed that the biosynthetic pathway for glycosphingolipids was present in the bacterial cells. Isolation of a Sphingomonas strain PS193 from P. simplex and subsequent glycosphingolipid analysis resulted in the detection of a known glycosphingolipid, GSL-1, that did, however, not match the glycosphingolipid profile of P. simplex. Therefore, it is unlikely that Sphingomonas strain PS193 is an abundant member of the microbial community associated with P. simplex. Other glycosphingolipid producing bacteria in P. simplex remain to be identified. In conclusion, this study provides experimental evidence that the glycolipids and hopanoids and possibly also the polyketide plakortin are produced by microbial symbionts rather than the sponge from which the metabolites were originally isolated.     

Environmental and lifestyle factors affect benzene uptake biomonitoring of residents near a petrochemical plant

Background

We monitored urinary benzene excretion to examine factors affecting benzene uptake in a sample of the general population living near a petrochemical plant.

Methods

Our study population included 143 subjects: 33 petrochemical plant workers (W) with low level occupational benzene exposure; 30 residents in a small town 2 km from the plant (2kmR); 26 residents in a second small town located 2 to 4 km from the plant (4kmR); and 54 urban residents 25 km from the plant (25kmR). Exposure to benzene was evaluated by personal air sampling during one work-shift for the W group, and from 8.00 to 20:00 for general population subgroups, and by urinary benzene (BEN-U).

Results

Median airborne benzene exposure was 25, 9, 7 and 6 μg/m³ benzene among the W, 2kmR, 4kmR, and 25kmR subgroups, respectively; the highest level was found among the workers, while there was no significant difference among the other groups. Median BEN-U was 2 to 14-fold higher in smokers compared to non-smokers; among non-smokers BEN-U was the highest in W (median 236 ng/L), and lower in the 2kmR (48 ng/L) and 4kmR (63 ng/L) subgroups than in the 25kmR (120 ng/L) subgroup. A multiple linear regression analysis, explaining up to 73% of BEN-U variability, confirmed that active smoking and airborne benzene most strongly affected BEN-U. Among the non-smoking, non-occupationally exposed study subjects, a positive association was found between BEN-U and the distance of residence from the plant. This association was explained by increased exposure to urban traffic emissions in the study group residing at a greater distance from the plant. Environmental tobacco smoke had a marginally positive role.

Conclusion

Among factors affecting benzene uptake in non-occupationally exposed individuals, urban residence contributes to benzene exposure more than residing in close proximity to a petrochemical plant.     

Herbicide losses in runoff events from a field with a low slope: role of a vegetative filter strip

Herbicide runoff and the effects of a narrow vegetative filter strip (VFS) were studied on an arable field in the low-lying plains of the Veneto Region (north-east Italy). Cultivated plots were compared with and without a 6m wide VFS composed of trees, shrubs and grass. Natural and simulated runoff were monitored during 2000 and 2001. Herbicides applied on the field were: metolachlor (2184-2254 g ha(-1)), terbuthylazine (1000-1127 g ha(-1)) and isoproturon (1000 g ha(-1)). The VFS reduced both runoff depth (10.2-91.2%) and herbicide losses (85.7-97.9%) in the monitored rainfall events. Total herbicide loss with runoff was low (0.69-3.98 g ha(-1) without VFS, less than 0.27 g ha(-1) with VFS), but concentrations were sometimes very high, especially of terbuthylazine and isoproturon during the first events after treatment. In these events there was a high probability of exceeding the ecotoxicological endpoint for algae, but the VFS helped to reduce the potential risk. Two VFS effectiveness mechanisms were identified: (i) dilution, and (ii) a "sponge-like" effect, which temporarily trapped chemicals inside the VFS before releasing them.     

mtDNA control region and D-HPLC analysis: a method to evaluate the mating system in Syngnathidae (Teleostei)

Mitochondrial DNA (mtDNA) has been used extensively in animals for phylogenetic and population studies but it has been applied only occasionally to mating systems analysis, where nuclear markers are usually preferred. We used denaturing-high performance liquid chromatography (D-HPLC) to detect mitochondrial DNA polymorphisms to assess the genetic mating system in Syngnathus abaster. Our study of ten pregnant males, revealed polygyny in 30% of the males, who carried embryos originating from multiple females. In addition, 30% of the pregnant males carried embryos with the same mitochondrial haplotype. This is not sufficient to demonstrate polyandry but allows a rapid selection and a reduced sample size for further studies. In conclusion, the proposed technique is time- and cost-effective, allows the certain identification of polygyny and provides useful information to study polyandry.     

The dissipation of three fungicides in a biobed organic substrate and their impact on the structure and activity of the microbial community

Biopurification systems (BPS) have been introduced to minimise the risk for point source contamination of natural water resources by pesticides. Their depuration efficiency relies mostly on the high biodegradation of their packing substrate (biomixture). Despite that, little is known regarding the interactions between biomixture microflora and pesticides, especially fungicides which are expected to have a higher impact on the microbial community. This study reports the dissipation of the fungicides azoxystrobin (AZX), fludioxonil (FL) and penconazole (PC), commonly used in vineyards, in a biomixture composed of pruning residues and straw used in vineyard BPS. The impact of fungicides on the microbial community was also studied via microbial biomass carbon, basal respiration and phospholipid fatty acid analysis. AZX dissipated faster (t _1/2?=?30.1 days) than PC (t _1/2?=?99.0 days) and FL (t _1/2?=?115.5 days). Fungicides differently affected the microbial community. PC showed the highest adverse effect on both the size and the activity of the biomixture microflora. A significant change in the structure of the microbial community was noted for PC and FL, and it was attributed to a rapid inhibition of the fungal fraction while bacteria showed a delayed response which was attributed to indirect effects by the late proliferation of fungi. All effects observed were transitory and a full recovery of microbial indices was observed 60 days post-application. Overall, no clear link between pesticide persistence and microbial responses was observed stressing the complex nature of interactions between pesticides in microflora in BPS.     

The effect of initial concentration, co-application and repeated applications on pesticide degradation in a biobed mixture

A 180 d laboratory experiment was conducted to investigate the degradation rates of chlorpyrifos (10 and 50 mg kg(-1)) and metalaxyl (100 mg kg(-1)) separately and co-applied in a biomix constituted by topsoil, vine-branches and urban-waste-garden compost. The effect of repeated application of metalaxyl was also investigated. Microbial biomass-C (MBC) content and metabolic quotient (qCO(2)) were measured to evaluate changes in microbial biomass size and activity induced by the presence of the two pesticides. Degradation rate decreased with increasing concentration of chlorpyrifos in all treatments. Metalaxyl half-life was significantly reduced in co-application with chlorpyrifos indicating a synergic interaction between the two pesticides in favour of enhanced degradation rate for metalaxyl but not for chlorpyrifos. Furthermore, repeated application resulted in a sharp reduction of metalaxyl half-life from 37 d after first application to 4 d after third application. MBC content was negatively influenced by the addition of pesticides but it started to recover immediately, in both separate and co-applied treatments, reaching the control value when pesticide residues were about 50% of the initial concentration. The qCO(2) reached a steady-state after about 20 d in separately applied and 40 d in co-applied treatments, indicating a tendency to arrive at a new metabolic equilibrium. In conclusion, the biomix tested has been shown to degrade pesticides relatively fast and to have a microbial community that is varied enough to allow selection of those microorganisms able to degrade metalaxyl and chlorpyrifos.     

Losses and dissipation of penconazole in vineyard soil as affected by mid-row management system

A field experiment was performed with the aim to assess the amount of penconazole losses during field application and the spatial variability of penconazole concentration in a vineyard soil, under two different management techniques (tilled and grass covered). The field dissipation of penconazole under the two techniques was also followed for 114 days, highlighting the effects of spatial variability of the initial concentration and of the grass covering in terms of the different soil metabolic activity. Data found show that a high percentage of penconazole, from 42.5 % to 67.43 %, can reach the soil during the treatments, despite the fact that penconazole is applied to the foliage. The high values of the coefficient of variation for data within rows show considerable variability in all applications, ranging from 30 to 65 in the first application, from 35 to 79 in the second and from 36 to 75 in the third. Since the applications of penconazole occurred under almost same climatic conditions in terms of wind speed and direction, the high variability of concentration of penconazole found within mid-rows was attributed to the uneven slope of the vineyard causing an irregular speed of the sprayer equipment. However, least significant differences of the mean values did not end in a significant difference of penconazole concentration among mid-rows for all applications, indicating that the variability between rows does not contribute to the overall variability. The calculated half-life values for penconazole in tilled soil were 62.4 days for tilled and 33.0 for grassed soil, highlighting the tendency of penconazole to faster dissipate in grassed than in tilled soil. Grassed soil was characterised by a higher metabolic activity in terms of microbial biomass carbon content, basal respiration and total hydrolytic activity, than tilled soil. A significant correlation between penconazole dissipation and total hydrolytic activity, was found. The faster dissipation of penconazole in grassed soil was attributed to the higher amount of the total hydrolytic activity which, in grassed soil, was 1.5 fold-higher than in tilled soil.     

Retention capacity of an organic bio-mixture against different mixtures of fungicides used in vineyards

A laboratory experiment was carried out to test the efficiency of a bio-mixture made up of pruning residues at two (PR2) and five (PR5) years of composting and wheat straw (STW) in the biological cleaning of water contaminated by different mixtures of fungicides usually employed in vineyards. The experiment was conducted and reproduced at a scale of 1:100 of operating field conditions. Commercial formulates of penconazole (PC), (RS)-1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole), dimetomorph (DM), (EZ)-4-[3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloyl]morpholine), azoxystrobin (AZ), (methyl (E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate), iprovalicarb (IP), (isopropyl 2-methyl-1-[(RS)-1-p-tolylethyl]carbamoyl-(S)-propylcarbamate), metalaxyl (MX), (methyl N-(methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate), fludioxonil (FL), (4-(2,2-difluoro-1,3-benzodioxol-4-yl)-1H-pyrrole-3-carbonitrile) and cyprodinil (CY), (4-cyclopropyl-6-methyl-N-phenylpyrimidin-2-amine) were mixed in water and discharged into the bio-mixture following the time schedule of the treatments carried out in the grapevine in real field conditions. At each treatment, contaminated water with fungicides was circulated repeatedly through the bio-mixture to enhance the sorption of fungicides. In fact, it retained them between 98–100% with the exception of MX of which it was able to retain only 90.5%. The adsorption/desorption experiment showed that repeated circulation of water, instead of enhancing MX retention, can easily remove about 30% of MX already adsorbed by the bio-mixture. This finding suggests that water contaminated by very mobile pesticides should be discharged at the end of field treatments without re-circulating the water in order to avoid the release of pesticides weakly adsorbed on the bio-mixture.     

Moist olive husks addition to a silty clay soil: influence on microbial and biochemical parameters

To investigate the effects of moist olive husks (MOH-residues) on soil respiration, microbial biomass, and enzymatic (o-diphenoloxidase, beta-glucosidase, dehydrogenase and alkaline phosphatase) activities, a silty clay soil was incubated with 0 (control), 8 x 10(3) (D), 16 x 10(3) (2D) and 80 x 10(3) (10D) kg ha-1 of MOH-residues on a dry weight basis. Soil respiration and microbial biomass data indicated that the addition of MOH-residues strongly increased microbial activity proportionally to the amounts added. Data of qCO2 suggested that the respiration to biomass ratio of the microbial population was strongly modified by MOH-residues additions during the first 90 days of incubation. The qCO2 data suggested a low efficiency in energy yields from C oxidation during the first 2 months of soil incubation. qFDA seemed to be relatively unaffected for treatments D and 2D as compared to the control, but was significantly lowered by the application of 10D, showing the lowest hydrolytic activity of microbial biomass in this treatment up to 360 days of incubation. o-Diphenoloxidase activity was delayed, and this delay was extended with the addition of larger quantities of MOH-residues. Alkaline phosphatase, beta-glucosidase and dehydrogenase activities were in line with the findings on microbial biomass changes and activities. The biological and biochemical data suggest that the addition of a large quantity of MOH-residues (80 x 10(3) kg ha-1) strongly modifies the soil characteristics affecting the r- and K-strategist populations, and that these changes last for at least the 360 days of incubation. The data also suggest that application rates exceeding 16 x 10(3) kg ha-1 are not recommended until the agro-chemical and -physical functions of the soil are further studied.