Fate of CL-20 in sandy soils: degradation products as potential markers of natural attenuation

Hexanitrohexaazaisowurtzitane (CL-20) is an emerging explosive that may replace the currently used explosives such as RDX and HMX, but little is known about its fate in soil. The present study was conducted to determine degradation products of CL-20 in two sandy soils under abiotic and biotic anaerobic conditions. Biotic degradation was prevalent in the slightly acidic VT soil, which contained a greater organic C content, while the slightly alkaline SAC soil favored hydrolysis. CL-20 degradation was accompanied by the formation of formate, glyoxal, nitrite, ammonium, and nitrous oxide. Biotic degradation of CL-20 occurred through the formation of its denitrohydrogenated derivative (m/z 393 Da) while hydrolysis occurred through the formation of a ring cleavage product (m/z 156 Da) that was tentatively identified as CH₂N-C(N-NO₂)-CHN-CHO or its isomer N(NO₂)CH-CHN-CO-CHNH. Due to their chemical specificity, these two intermediates may be considered as markers of in situ attenuation of CL-20 in soil.     

Ectopic expression of Arabidopsis ABC transporter MRP7 modifies cadmium root-to-shoot transport and accumulation

Arabidopsis MRPs/ABCCs have been shown to remove various organic and inorganic substrates from the cytosol to other subcellular compartments. Here we first demonstrate that heterologous expression of AtMRP7 in tobacco (Nicotiana tabacum var. Xanthi) modifies cadmium accumulation, distribution and tolerance. Arabidopsis MRP7 was localized both in the tonoplast and in the plasma membrane when expressed in tobacco. Its overexpression increased tobacco Cd-tolerance and resulted in enhanced cadmium concentration in leaf vacuoles, indicating more efficient detoxification by means of vacuolar storage. Heterologous AtMRP7 expression also led to more efficient retention of Cd in roots, suggesting a contribution to the control of cadmium root-to-shoot translocation. The results underscore the use of AtMRP7 in plant genetic engineering to modify the heavy-metal accumulation pattern for a broad range of applications.     

Study of the spatial variation of the biodegradation rate of the herbicide bentazone with soil depth using contrasting incubation methods

Vertical and horizontal spatial variability in the biodegradation of the herbicide bentazone was compared in sandy-loam soil from an agricultural field using sieved soil and intact soil cores. An initial experiment compared degradation at five depths between 0 and 80 cm using sieved soil. Degradation was shown to follow the first-order kinetics, and time to 50% degradation (DT(50)), declined progressively with soil depth from 56 d at 0-10 cm to 520 d at 70-80 cm. DT(50) was significantly correlated with organic matter, pH and dehydrogenase activity. In a subsequent experiment, degradation rate was compared after 127 d in sieved soil and intact cores from 0 to 10 and 50 to 60 cm depth from 10 locations across a 160x90 m portion of the field. Method of incubation significantly affected mean dissipation rate, although there were relatively small differences in the amount of pesticide remaining in intact cores and sieved soil, accounting for between 4.6% and 10.6% of that added. Spatial variability in degradation rate was higher in soil from 0 to 10 cm depth relative to that from 50 and 60 cm depth in both sieved soil and intact core assessments. Patterns of spatial variability measured using cores and sieved soil were similar at 50-60 cm, but not at 0-10 cm depth. This could reflect loss of environmental context following processing of sieved soil. In particular, moisture content, which was controlled in sieved soil, was found to be variable in cores, and was significantly correlated with degradation rate in intact topsoil cores from 0 to 10 cm depth.     

On the performance of Fe and Fe,F doped Ti-Pt/PbO2 electrodes in the electrooxidation of the Blue Reactive 19 dye in simulated textile wastewater

The electrochemical performance of pure Ti–Pt/β-PbO₂ electrodes, or doped with Fe and F (together or separately), in the oxidation of simulated wastewaters containing the Blue Reactive 19 dye (BR-19), using a filter-press reactor, was investigated and then compared with that of a boron-doped diamond electrode supported on a niobium substrate (Nb/BDD). The electrooxidation of the dye simulated wastewater (volume of 0.1 l, with a BR-19 initial concentration of 25 mg l⁻¹) was carried out under the following conditions: current density of 50 mA cm⁻², volume flow rate of 2.4 l h⁻¹, temperature of 25 °C and electrode area of 5 cm². The performances of the electrodes in the dye decolorization were quite similar, achieving 100% decolorization, and in some cases 90% decolorization was achieved by applying only ca. 0.3 A h l⁻¹ (8 min of electrolysis). The reduction of the simulated wastewater organic load, monitored by its total organic carbon content (TOC), was greater for the Ti–Pt/β-PbO₂–Fe,F electrode obtained from an electrodeposition bath containing 1 mM Fe³⁺ and 30 mM F⁻. In this case, after 2 h of electrolysis the obtained TOC reduction was 95%, while for the pure β-PbO₂ and the Nb/BDD electrodes the reductions were 84% and 82%, respectively.     

Long-term variability of metals from fungicides applied in amended young vineyard fields of La Rioja (Spain)

The long-term variability of total Cu content from fungicides applied in a certified wine region of Spain (La Rioja) and of other metals (Cd, Cr, Ni, Pb, and Zn) was evaluated in three young vineyard soils and subsoils unamended and amended with spent mushroom substrates (SMS) over a 3-year period (2006–2008). SMS is a promising agricultural residue as an amendment to increase the soil organic matter content but may modify the behaviour of metals from pesticide utilisation in vineyards. Fresh and composted SMS was applied each year at a rate of 25 t ha⁻¹ (dry-weight). Copper concentrations in the three unamended soils were 21.2–88.5, 25.5–77.1, and 29.4–78.4 mg kg⁻¹. They exceeded natural Cu concentrations of the region and reference sub-lethal hazardous concentration for soil organism. The concentrations of Cd, Ni, Pb, and Zn were largely below the sub-lethal limits. Thus, although Cu levels were lower than those of established vineyards, vine performance, and productivity might be affected. The variation in behaviour between different amendments for each soil was high, so a generic conclusion could not be drawn. The amendment practice seemed to have caused temporarily Cu mobilization respect to untreated soils. Total zinc concentrations fall within the range of the natural soil of La Rioja and were significantly affected (p < 0.05) especially by fresh state SMS addition, with increasing up to 75% respect to untreated specimen. The results indicated a build-up of fresh sites for metal retention at both surface and subsurface level, although no accumulation of metals was observed in the short-term period. However, the benefit for soils and the negative effects need to be monitored in the long run.     

Application of a toxicity test battery integrated index for a first screening of the ecotoxicological threat posed by ports and harbors in the southern Adriatic Sea (Italy)

Ports and harbors may represent a threat for coastal ecosystems due to pollutant inputs, especially those derived from maritime activities. In this study, we report a first assessment of the ecotoxicological threat posed by six ports and harbors of opposite coastal regions, Apulia and Albania, in the southern Adriatic Sea (Italy). A bioassay battery consisting of four different species representing different trophic levels, algae Dunaliella tertiolecta, bacteria Vibrio fischeri, crustacean Artemia salina, and echinoids Paracentrotus lividus, has been used to assess sediment elutriates, pore waters, and sediment suspensions. Two different approaches of toxicity data integration, worst case and integrated index, have been used to determine the most appropriate procedure for the investigated sites. All sites with the worst case approach showed high toxicity levels. The chronic test with algae was the most sensitive identifying the highest effects in the battery. This effect can be attributable to contaminants derived from antifouling paints. The sediments, evaluated with V. fischeri test, often showed toxicity not found in the aqueous matrices of the same sites and that can be mainly linked to organic compounds. The test battery used in this study allowed us to perform a preliminary screening of the ecotoxicological risk of the studied area. In fact, the species utilized for toxicity tests responded differently to the investigated samples, showing different sensitivity. The test battery integrated index did not allow highlighting the differences among the sites and showed a general high ecotoxicological risk. A larger number of tests with higher sensitivity together with a tailored attribution of weights to endpoints and matrices will improve the final site evaluation.     

Specificity of metal tolerance and use of excluder metallophytes for the phytostabilization of metal polluted soils: the case of Silene paradoxa L.

This work was planned for providing useful information about the use of excluder metallophytes for phytostabilization of soils contaminated also with elements scarcely represented in the metalliferous environment of origin. To this aim, we investigated tolerance and accumulation of several different elements in a metallicolous and a nonmetallicolous population of Silene paradoxa through a hydroponic experiment. S. paradoxa metallicolous population showed increased tolerance not only to all the metals highly represented in the environment of origin but also to some of those scarcely present. Therefore, our results deposed in favor of the occurrence of the co-tolerance phenomenon in S. paradoxa for some elements. Metal accumulation was higher in the roots than in the shoots and lower in the metallicolous population than in the nonmetallicolous one, thus showing tolerance mechanisms to be based largely on metal exclusion. Anyway, the relative contribution of avoidance and of internal tolerance to metal tolerance was shown to be element-dependent. Present data revealed that metallicolous plants can effectively posses metal co-tolerances, which deserve to be investigated; as such, plants can actually represent a precious and exploitable tool also for the phytostabilization of soils contaminated with elements underrepresented in the environment of their origin.     

Studies on degradation of glyphosate by several oxidative chemical processes: Ozonation,photolysis and heterogeneous photocatalysis

Several different Advanced Oxidation Processes (AOPs) including ozonation at pH 6.5 and 10, photolysis and heterogeneous photocatalysis using TiO₂ as semiconductor and dissolved oxygen as electron acceptor were applied to study the degradation of glyphosate (N-phosphonomethyl glycine) in water. The degree of glyphosate degradation, the reactions kinetic and the formation of the major metabolite, aminomethyl phosphonic acid (AMPA), were evaluated. Ozonation at pH 10 resulted in the maximum mineralization of glyphosate. It was observed that under the experimental conditions used in this study the degradation of glyphosate followed the first-order kinetics. The half-life obtained for glyphosate degradation in the O₃/pH 10 process was 1.8 minutes.     

The application of HPLC ESI MS in the investigation of the flavonoids and flavonoid glycosides of a Caribbean Lamiaceae plant with potential for bioaccumulation

As part of an exchange technology program between the government of Barbados and Environment Canada, methanolic and aqueous extracts from the flavonoid-rich Lamiaceae family were characterized using negative-ion electrospray mass spectrometry. The species investigated is part of the Caribbean Pharmacopoeia, and is used for a variety of health issues, including colds, flu, diabetes, and hypertension. The extracts were investigated for structural elucidation of phenolics, identification of chemical taxonomic profile, and evidence of bio-accumulator potential. The methanolic and aqueous leaf extracts of Plectranthus amboinicus yielded rosmarinic acid, ladanein, cirsimaritin, and other methoxylated flavonoids. This genus also shows a tendency to form conjugates with monosaccharides, including glucose, galactose, and rhamnose. The aqueous extract yielded four isomeric rhamnosides. The formation of conjugates by Plectranthus amboinicus is thus evidence of high bioaccumulator significance.     

Optical Measurements of Aerosol Size Distributions in Great Smoky Mountains National Park: Dry Aerosol Characterization

ABSTRACT

Aerosol size distributions were measured during the summertime 1995 Southeastern Aerosol and Visibility Study (SEAVS) in Great Smoky Mountains National Park using an Active Scattering Aerosol Spectrometer (ASASP-X) optical particle counter. We present an overview of the experimental method, our data inversion technique, timelines of the size distribution parameters, and calculations of dry accumulation mode aerosol density and refractive index. Aerosol size distributions were recorded during daylight hours for aerosol in the size range 0.1 < Dp < 2.5 u,m. The particle refractive index used for the data inversion was calculated with the partial molar refractive index approach using 12-hr measured aerosol chemical composition. Aerosol accumulation mode volume concentrations ranging from 1 to 26 u,m³ cm^-3 were observed, with an average of 7 ± 5 u,m³ cm^-3. The study average dry accumulation mode geometric volume median diameter was 0.27 ± 0.03 u,m, and the mean geometric standard deviation was 1.45 ± 0.06. Using an internally mixed aerosol model, and assuming chemical homogeneity across the measured particle distribution, an average accumulation mode dry sulfate ion mass scattering efficiency of 3.8 ± 0.6 m² g^-1 was calculated.