Biological activity in metal-contaminated calcareous agricultural soils: the role of the organic matter composition and the particle size distribution

Organic matter (OM) plays a key role in microbial response to soil metal contamination, yet little is known about how the composition of the OM affects this response in Mediterranean calcareous agricultural soils. A set of Mediterranean soils, with different contents and compositions of OM and carbonate and fine mineral fractions, was spiked with a mixture of Cd, Cu, Pb, and Zn and incubated for 12 months for aging. Microbial (Biolog Ecoplates) and enzyme activities (dehydrogenase, DHA; β-galactosidase, BGAL; phosphatase, PHOS; and urease, URE) were assessed and related to metal availability and soil physicochemical parameters. All enzyme activities decreased significantly with metal contamination: 36–68 % (DHA), 24–85 % (BGAL), 22–72 % (PHOS), and 14–84 % (URE) inhibitions. Similarly, catabolic activity was negatively affected, especially phenol catabolism (～86 % compared to 25–55 % inhibition for the rest of the substrates). Catabolic and DHA activities were negatively correlated with ethylenediaminetetraacetic acid (EDTA)-extractable Cd and Pb, but positively with CaCl₂, NaNO₃, and DTPA-extractable Cu and Zn. Soluble OM (water- and hot-water-soluble organic C) was positively related to enzyme and catabolic activities. Recalcitrant OM and fine mineral fractions were positively related to BGAL and PHOS. Conversely, catabolic activity was negatively related to clay and positively to silt and labile OM. Results indicate that the microbial response to metal contamination is highly affected by texture and OM composition.     

Effect of water composition on the photocatalytic removal of pesticides with different TiO2 catalysts

The objective of this work is double—firstly to explore the photocatalytic efficiency of five different commercial TiO₂ catalysts in the photodegradation of a mixture of pesticides classified by the EU as priority pollutants and secondly to analyze the correlation between their physicochemical properties and the inhibition of the studied photocatalytic process when natural water was employed. Photocatalytic efficiencies when ultrapure water was used seem to point out that surface area was not a prerequisite for the photodegradation of the selected mixture of pesticides. On the other hand, significant differences in total organic carbon (TOC) conversions were obtained with the two studied water compositions. On one side, Evonik materials appear to be mostly inhibited when natural water was employed, whereas on the other, it should be remarked that anatase Sigma-Aldrich (SA) and, particularly, Hombikat UV100 (HBK) materials presented a very limited photo-efficiency inhibition or even a higher initial rate of TOC removal when a natural water matrix was used, probably due to their specific surface properties (PZC, S _BET). Therefore, heterogeneous photocatalysis has proved to be a promising technology for the degradation of the selected mixture of pesticides where the final photo-efficiency of the five commercial titania catalysts studied here responds to a complex balance between its surface and structural properties.     

Metallophyte status of violets of the section Melanium

Violets from metal-enriched soils have controversially been described as both heavy-metal accumulators and excluders in the literature. The present study solves the issue for violets of the section Melanium (zinc violets, Viola lutea ssp. calaminaria and V. lutea ssp. westfalica; hartsease or wild pansy, Viola tricolor; and mountain pansy, V. lutea). The aims were to determine the concentrations of heavy metals in the soil and in the roots and shoots of field-collected plants, to evaluate the potential impact of colonisation by arbuscular mycorrhizal fungi on heavy-metal concentrations in the plant tissues, and to quantitatively define the localisation of the elements in root cross-sections. When these violets grow in low-metal soils, higher concentrations of the heavy metals were found in the roots and shoots than in the soil, whereas the opposite was seen in samples from high-metal soils. Under all field conditions examined, the roots of all of these species were colonised by arbuscular mycorrhizal fungi. However, V. tricolor was marginally colonised when the concentrations of Zn and P were higher in the soil. Determination of the spatial distribution of the elements in root cross-sections of these violets indicates tissue-specific deposition of elements within the vascular tissue, the cortex, and the rhizodermis. These data indicate that violets of the section Melanium are heavy-metal excluders.     

Copper toxicity to Lemna minor modelled using humic acid as a surrogate for the plant root

Humic acids are chemically analogous to plant root cell walls in that their surface sites are principally comprised of carboxylic and phenolic acids which bind both metals and protons. Based on this analogy, we developed a biotic-ligand type of model to predict Cu toxicity to Lemna minor, using particulate humic acid (HA(part)) of the Windermere Humic Aqueous Model (WHAM), and 7d static-renewal exposures with five surface waters and one nutrient media which varied in DOC (1-10 mg L(-1)), pH (6.9-8.7), and water hardness (35-236 mg equivalent CaCO(3)L(-1)). Although the range of waters tested resulted in a 36-fold variation in 50% inhibitory concentration (IC50) values, the calculated concentration of Cu bound to HA(part) using this framework was highly correlated with pooled percent net root elongation (%NRE) (R(2)=0.95). Ten and fifty percent IC values based on [Cu-HA(part)] were additionally within a factor of ±1.5 and ±1.4, respectively, inclusive of 95% confidence limits. This model construct, which defines the free metal ion and the first hydrolysis product (but not metal carbonate complexes) as being bioavailable, provides an alternative means of defining the binding surface in bioavailability models, whereby a heterogeneous mixture of ligands collectively influence root-metal sorption and toxicity.     

Obtaining polycyclic aromatic hydrocarbon concentration ratios and molecular markers for residential wood combustion: Temuco, a case study

It is known that residential wood combustion (RWC) is an important source of fine particle emissions. The purpose of this work was to characterize the chemical composition of the particulate matter present in the Temuco urban atmosphere during winter, specifically the polycyclic aromatic hydrocarbon (PAH) profile, because PAHs are considered to be among the key compounds in particulate matter toxicity. During the 2008 winter monitoring campaign, samples of particulate matter with aerodynamic diameters of < or = 10 (PM10) and < or = 2.5 (PM2.5) microm were taken on days with contamination episodes. Sixteen U.S. Environmental Protection Agency (EPA) PAH compounds were extracted with toluene and determined by gas chromatography-mass spectrometry (GC-MS). The results show that phenantrene was the predominant compound associated with particulate matter at a concentration range between 300 and 600 ng m(-3), 18 times higher than the second most abundant PAH compound. High-molecular-mass compounds such as dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3,c,d]pyrene were also found, but they were minorities in the set. It was recognized from the PAH concentration ratios of the Temuco atmospheric aerosol that the main contamination source was in fact residential wood combustion; although not all the concentration ratios evaluated match the reported reference values, probably due to the kind of biomass used, the characteristics of Chilean heating appliances and climate.     

‘End to end’ planktonic trophic web and its implications for the mussel farms in the Mar Piccolo of Taranto (Ionian Sea,Italy)

The Mar Piccolo is a semi-enclosed basin subject to different natural and anthropogenic stressors. In order to better understand plankton dynamics and preferential carbon pathways within the planktonic trophic web, an integrated approach was adopted for the first time by examining all trophic levels (virioplankton, the heterotrophic and phototrophic fractions of pico-, nano- and microplankton, as well as mesozooplankton). Plankton abundance and biomass were investigated during four surveys in the period 2013–2014. Beside unveiling the dynamics of different plankton groups in the Mar Piccolo, the study revealed that high portion of the plankton carbon (C) pool was constituted by small-sized (<2 μm) planktonic fractions. The prevalence of small-sized species within micro- and mesozooplankton communities was observed as well. The succession of planktonic communities was clearly driven by the seasonality, i.e. by the nutrient availability and physical features of the water column. Our hypothesis is that beside the ‘bottom-up’ control and the grazing pressure, inferred from the C pools of different plankton groups, the presence of mussel farms in the Mar Piccolo exerts a profound impact on plankton communities, not only due to the important sequestration of the plankton biomass but also by strongly influencing its structure.     

The size distribution of organic carbon in headwater streams in the Amazon basin

Despite the strong representativeness of streams in the Amazon basin, their role in the accumulation of coarse particulate organic carbon (CPOC), fine particulate organic carbon (FPOC), and dissolved organic carbon (DOC) in transport, an important energy source in these environments, is poorly known. It is known that the arboreal vegetation in the Amazon basin is influenced by soil fertility and rainfall gradients, but would these gradients promote local differences in organic matter in headwater streams? To answer this question, 14 low-order streams were selected within these gradients along the Amazon basin, with extensions that varied between 4 and 8 km. The efficiency of the transformation of particulate into dissolved carbon fractions was assessed for each stream. The mean monthly benthic organic matter storage ranged between 1.58 and 9.40 t ha^?1 month^?1. In all locations, CPOC was the most abundant fraction in biomass, followed by FPOC and DOC. Rainfall and soil fertility influenced the distribution of the C fraction (p?=?0.01), showing differentiated particulate organic carbon (POC) storage and DOC transportation along the basin. Furthermore, the results revealed that carbon quantification at the basin level could be underestimated, ultimately influencing the global carbon calculations for the region. This is especially due to the fact that the majority of studies consider only fine particulate organic matter and dissolved organic matter, which represent less than 50 % of the stored and transported carbon in streambeds.     

Leaching and persistence of ametryn and atrazine in red–yellow latosol

This study evaluated the mobility and persistence of atrazine and ametryn in red–yellow latosols using polyvinyl chloride columns with a diameter of 100 mm and a height of 15 cm. The assays simulated 60-mm rainfall events at 10-day intervals for 70 days. The persistence and leaching were evaluated for these two herbicides. The analytes obtained from the samples were quantified by gas chromatography using flame ionization detection. Compared with ametryn, atrazine showed a greater potential to reach depths below 15 cm over 30 days of simulated rain. Ametryn, however, showed greater persistence in soil at 70 days after application. The persistence of atrazine and ametryn in soil under sunlight was 10 and 144 days respectively. Atrazine was more susceptible to sunlight than ametryn because sunlight favored atrazine degradation in hydroxyatrazine. The results indicate that in red–yellow latosol, atrazine has a high leaching potential in short term, but that ametryn is more persistent and has a high leaching potential in long term.