Natural product biomarkers as indicators of sources and transport of sedimentary organic matter in a subtropical river

The sources and transformations of sedimentary organic matter along the Harney River, a representative subtropical river of the Florida Everglades, were assessed using a natural product biomarker approach. Sediment samples were collected from the headwaters to the Continental Shelf, with characteristic vegetation dominated by freshwater marsh species, mangrove (middle to lower estuary), and seagrass as the marine end-member. A peat sample was collected inland. All sample extracts were analyzed by GC–MS as underivatized and as silylated compounds. With these total extract analyses, major compound classes can be defined: n-alkanols, n-alkanoic acids, methyl alkanoates, methyl - and ω-hydroxyalkanoates, triterpenoids, phytosterols and saccharides, with traces of hydrocarbons. In general, the peat sample extract has a different overall composition compared to the sediment extracts. The major differences include distinct carbon number maxima for the lipid series (e.g., C_max = 28 for n-alkanols) probably from sawgrass and periphyton biomass, and predominance of phytosterols (sitosterol and stigmasterol) from higher plant detritus. In contrast, river sediment extracts contain biomarkers predominantly from mangrove-derived organic matter, such as the triterpenoids taraxerol and myricadiol. Significant amounts of saccharides and ω-hydroxyalkanoates are also found. Generally, compound concentrations decrease downstream due to dilution, and alteration of organic compounds from plant waxes and coastal vegetation is obvious in both peat and sediment samples. This is confirmed by the significant low abundance of n-alkanes and n-alkenoic acids due to biodegradation, oxidation of -tocopherol to homophytanic acid γ-lactone, and presence of traces of dihydrolacunosic acid, a photochemical alteration product of taraxerol.     

Determination of PM2.5 sources using time-resolved integrated source and receptor models

Multivariate statistical techniques are applied to particulate matter (PM) and meteorological data to identify the sources responsible for evening PM spikes at Sunland Park, NM (USA). The statistical techniques applied are principal components analysis (PCA), redundancy analysis (RDA), and absolute principal components scores analysis (APCSA), and the data evaluated are 3-h average (6–9 p.m.) PM_2.5 mass and chemical composition and 1-h average PM_2.5 and PM₁₀ mass and environmental data collected in the winter of 2002. Although the interpretation of the data was complicated by the presence of sources which are likely changing in time (e.g. brick kilns), the multivariate analyses indicate that the evening high PM_2.5 is associated with burning-activities occurring to the south of Sunland Park, and these emissions are characterized by elevated Sb, Cl⁻, and elemental carbon; 68% of the PM_2.5 mass can be attributed to this source. The PM₁₀ evening peaks, on the other hand, are mainly caused by resuspended dust generated by vehicular movements south of the site and transported by the local terrain-induced drainage flow.     

A new bacterial strain mediating As oxidation in the Fe-rich biofilm naturally growing in a groundwater Fe treatment pilot unit

A bacterial strain B2 that oxidizes arsenite into arsenate was isolated from the biofilm growing in a biological groundwater treatment process used for Fe removal. This strain is phylogenetically and morphologically different from the genus Leptothrix commonly encountered in biological iron oxidation processes. T-RFLP fingerprint of the biofilm revealed that this isolated strain B2 corresponds to the major population of the bacterial community in the biofilm. Therefore, it is probably one of the major contributors to arsenic removal in the treatment process.     

Mercury distribution in abiotic and biological compartments within several estuarine systems from Argentina: 1980-2005 period

Total mercury contents from both abiotic and biological compartments within several estuaries from Argentina have been studied since the 1980s. The assessment of mercury occurrence in surface sediments, suspended particulate matter and crab and fish species from Mar Chiquita coastal lagoon, Bahía Blanca estuary and Samborombón Bay (in La Plata river estuary) are included in the present study. All samples were analyzed through Cold Vapor-Atomic Absorption Spectroscopy, following internationally standardized methods. In all cases analytical quality was checked against international reference materials. During the 1980s, Hg contents in sediments and SPM, as well as in edible fish species from Bahía Blanca estuary were significantly higher (p<0.01) than those of the 1990s and 2000s, and the large industrial nucleus located in the northern margin of this estuary was elsewhere identified as the main source of this metal. A permanent monitoring program carried out in 1986 and that is being implemented up to the present has demonstrated that Hg concentration values have significantly decreased (p<0.01) compared to the values of the 1980s. Both, Mar Chiquita coastal lagoon and Samborombón Bay have intermediate mercury levels in their biological compartments. In both cases, the possible occurrence of remote sources of this metal was considered. Even though, Hg values as determined in sediments and suspended particulate matter from Samborombón Bay were the highest ones for the whole analyzed period. Both mercury bioaccumulation and biomagnification processes were evaluated in the studied estuaries, as well as the potential qualification of estuarine foodstuffs for human consumption.     

Chelate-induced phytoextraction of metal polluted soils with Brachiaria decumbens

Chelate-induced phytoextraction with high biomass plant species has been proposed for the clean-up of heavy metal polluted soils. In the current work, the effect of the application of two different chelating agents, i.e. EDTA and EDDS, on the metal phytoextraction capacity of Brachiaria decumbens was studied. Although EDTA was, in general, more effective in soil metal solubilization, EDDS, a chelate less harmful to the environment, was more efficient inducing metal accumulation in B. decumbens shoots than EDTA. Indeed, in a moderately heavy metal polluted soil, EDDS caused a 2.54, 2.74 and 4.30-fold increase in Cd, Zn, and Pb shoot metal concentration, respectively, as compared to control plants. In this same soil, EDTA caused a 1.77, 1.11 and 1.87-fold increase in Cd, Zn, and Pb shoot metal concentration, respectively, as compared to control plants. EDDS was also more effective than EDTA in stimulating the translocation of metals from roots to shoots. B. decumbens plants were able to grow in the metal polluted soils showing no visible symptoms of phytotoxicity, which suggests their metal tolerance. Finally, B. decumbens, a fast-growing, high biomass, aluminum tolerant plant species, that has a well-established agronomic system, fulfills most of the requirements for chemically-induced phytoextraction.     

Electrochemical combustion of herbicide mecoprop in aqueous medium using a flow reactor with a boron-doped diamond anode

The anodic oxidation of 1.8l of solutions with mecoprop (2-(4-chloro-2-methylphenoxy)-propionic acid or MCPP) up to 0.64 g l(-1) in Na2SO4 as background electrolyte within the pH range 2.0-12.0 has been studied using a flow plant containing a one-compartment filter-press electrolytic reactor with a boron-doped diamond (BDD) anode and a stainless steel cathode, both of 20-cm2 area. Electrolyses carried out in batch under steady conditions and operating at constant current density between 50 and 150 mA cm(-2) always yield complete mineralization due to the great concentration of hydroxyl radical generated at the BDD anode. The degradation rate is practically independent of pH and Na2SO4 concentration, but it becomes faster with increasing MCPP concentration, current density, temperature and liquid flow rate. The effect of these parameters on current efficiency and energy cost has also been investigated. Generated weak oxidants such as H2O2 and peroxodisulfate ion have little influence on the mineralization process. The kinetics for the herbicide decay follows a pseudo first-order reaction with a higher rate constant when current density increases. Aromatic products such as 4-chloro-o-cresol, 2-methylhydroquinone and 2-methyl-p-benzoquinone, and generated carboxylic acids such as maleic, fumaric, lactic, pyruvic, tartronic, acetic and oxalic, have been identified as intermediates by chromatographic techniques. The initial chlorine is completely released in the form of chloride ion, which is slowly oxidized to Cl2 at the BDD anode. A reaction pathway for MCPP mineralization involving all products detected is proposed.     

Landscape bioacoustics allow detection of the effects of habitat patchiness on population structure

Landscape structure may affect individual dispersal abilities, thus influencing the genotypic and phenotypic composition of populations. We analyzed the interplay among landscape, behavior, and evolutionary processes by correlating habitat patchiness to the variability in vocalizations of Dupont's Lark Chersophilus duponti, one of the most habitat-selective and rare European songbirds. We tape-recorded males throughout the species distribution in Spain, analyzed the spatial patterns of territorial call variation at different scales (individuals, populations, and broad geographic areas), and related acoustic variability to patterns of isolation by geographic distance and by landscape unsuitability (calculated by building a predictive model of habitat suitability). The differentiation of spectro-temporal call features resulted from both isolation by distance and isolation by landscape unsuitability mechanisms. Landscape connectivity was often a better determinant of call differentiation than simple straight-line distance between individuals, providing the first evidence that call transmission can be limited by the presence and distribution of patches of adequate habitat, which likely mediates bird dispersal. Landscape patchiness resulted in a reduction of acoustic diversity (repertoire size) within populations, and a parallel increase in differentiation among populations. Landscape bioacoustics can represent a promising tool for estimating population structure, although the study of animal communication cannot be viewed as an alternative, but a source of complementary information to genetics, given that it provides evidence of male-male transmission and social and cultural phenomena that are currently undetectable from molecular data.     

Radiocarbon dating of archaeological samples (sambaqui) using CO(2) absorption and liquid scintillation spectrometry of low background radiation

Sambaqui means, in the Tupi language, a hill of shells. The sambaquis are archaeological sites with remains of pre-historical Brazilian occupation. Since the sambaqui sites in the Rio de Janeiro state region are older than 10,000 years, the applicability of CO(2) absorption on Carbo-sorb and (14)C determination by counting on a low background liquid scintillation counter was tested. In the present work, sambaqui shells were treated with H(3)PO(4) in a closed vessel in order to generate CO(2). The produced CO(2) was absorbed on Carbo-sorb. On saturation about 0.6g of carbon, as CO(2), was mixed with commercial liquid scintillation cocktail (Permafluor), and the (14)C activity determined by counting on a low background counter, Packard Tricarb 3170 TR/SL, for a period of 1000 mins to enable detection of a radiocarbon age of 22,400 BP. But only samples with ages up to 3500 BP were submitted to the method because the samples had been collected in the municipality of Guapimirim, in archaeological sambaqui-type sites belonging to this age range. The same samples were sent to the (14)C Laboratory of the Centro de Energia Nuclear na Agricultura (CENA/USP) where similar results were obtained.     

Light Availability Prevails Over Soil Fertility and Structure in the Performance of Asian Knotweeds on Riverbanks: New Management Perspectives

Asian knotweeds (Fallopia spp.) are considered one of the world’s most invasive species. Restoring habitats dominated by these exotic species requires a better understanding of the importance of abiotic factors controlling the invasive knotweeds performance. We used observational data obtained on the embankment of the Isère River (France) to study the performance of Fallopia spp. under different soil, light, and disturbance conditions. On the Isère riverbanks, light intensity assessed by light quantity transmitted through canopy was the most important factor explaining the variability observed on knotweed performance expressed as above-ground biomass per square meter. Asian knotweeds were more productive under intensive light conditions. Alternatively other factors such as mowing (twice a year), soil fertility, soil texture, position on the bank or exposure to the sun had no significant effect on knotweed biomass production. We conclude that decreasing light resources, for example, by increasing competitive pressure on sites dominated by Asian knotweeds could be included in management plans to control the populations of this invasive taxon.     

Gaseous nitrogen emissions and forage nitrogen uptake on soils fertilized with raw and treated swine manure

Treatments to reduce solids content in liquid manure have been developed, but little information is available on gaseous N emissions and plant N uptake after application of treated liquid swine manure (LSM). We measured crop yield, N uptake, and NH3 and N2O losses after the application of mineral fertilizer (NH4 NO3), raw LSM, and LSM that was decanted, filtered, anaerobically digested, or chemically flocculated. The experiment was conducted from 2001 to 2003 on a loam and a sandy loam cropped to timothy (Phleum pratense L.) with annual applications equivalent to 80 kg N ha(-1) in spring and 60 kg N ha(-1) after the first harvest. Raw LSM resulted in NH3 emissions three to six times larger (P < 0.05) than mineral fertilizer. The LSM treatments reduced NH3 emissions by an average of 25% compared with raw LSM (P < 0.05). The N2O emissions tended to be higher with raw LSM than with mineral fertilizer. The LSM treatments had little effect on N2O emissions, except for anaerobic digestion, which reduced emissions by >50% compared with raw LSM (P < 0.05). Forage yield with raw LSM was >90% of that with mineral fertilizer. The LSM treatments tended to increase forage yield and N uptake relative to raw LSM. We conclude that treated or untreated LSM offers an alternative to mineral fertilizers for forage grass production but care must be taken to minimize NH3 volatilization. Removing solids from LSM by mechanical, chemical, and biological means reduced NH3 losses from LSM applied to perennial grass.