Mineralization of the biocide chloroxylenol by electrochemical advanced oxidation processes

Electrochemical advanced oxidation processes (EAOPs) are environmentally friendly methods based on the destruction of organic pollutants in wastewaters with in situ electrogenerated hydroxyl radical. This species is formed in anodic oxidation (AO) from water oxidation at the anode and in indirect electro-oxidation methods like electro-Fenton (EF) and photoelectro-Fenton (PEF) also from reaction between catalytic Fe2+ and H2O2 continuously produced at the O2-diffusion cathode. The PEF method involves the irradiation of the treated solution with UVA light to enhance the photolysis of organics including Fe(III) complexes. In this work, the oxidation power of such EAOPs to decontaminate synthetic wastewaters of the biocide chloroxylenol (4-chloro-3,5-dimethylphenol) at pH 3.0 is comparatively examined with an undivided electrolytic cell containing a Pt or boron-doped diamond (BDD) anode and a stainless steel or O2-diffusion cathode. The initial chlorine is released as Cl(-) ion, which remains stable in the medium using Pt or is oxidized to Cl2 on BDD. The biocide solutions can be completely decontaminated using AO with a BDD anode, as well as PEF with a Pt or BDD anode. The PEF procedure with a BDD anode is the most powerful method leading to total mineralization in about 300 min, practically independent of current density. When current density rises, the degradation rate of processes increases, but they become less efficient due to the larger enhancement of waste reactions of oxidants. Chloroxylenol is much more rapidly removed in EF and PEF than in AO. 2,6-dimethylhydroquinone, 2,6-dimethyl-p-benzoquinone and 3,5-dimethyl-2-hydroxy-p-benzoquinone are identified as aromatic by-products, and maleic, malonic, pyruvic, acetic and oxalic acids are found as generated carboxylic acids. A general pathway for chloroxylenol mineralization by all EAOPs including the above by-products is proposed.     

Neanderthal medics? Evidence for food, cooking, and medicinal plants entrapped in dental calculus

Neanderthals disappeared sometime between 30,000 and 24,000?years ago. Until recently, Neanderthals were understood to have been predominantly meat-eaters; however, a growing body of evidence suggests their diet also included plants. We present the results of a study, in which sequential thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) were combined with morphological analysis of plant microfossils, to identify material entrapped in dental calculus from five Neanderthal individuals from the north Spanish site of El Sidrón. Our results provide the first molecular evidence for inhalation of wood-fire smoke and bitumen or oil shale and ingestion of a range of cooked plant foods. We also offer the first evidence for the use of medicinal plants by a Neanderthal individual. The varied use of plants that we have identified suggests that the Neanderthal occupants of El Sidrón had a sophisticated knowledge of their natural surroundings which included the ability to select and use certain plants.     

Effect of Cadmium on Microbial Activity and a Ryegrass Crop in Two Semiarid Soils

Soil pollution with Cd is an environmental problem common in the world, and it is necessary to establish what Cd concentrations in soil could be dangerous to its fertility from toxicity effects and the risk of transference of this element to plants and other organisms of the food chain. In this study, we assessed Cd toxicity on soil microorganisms and plants in two semiarid soils (uncultivated and cultivated). Soil ATP content, dehydrogenase activity, and plant growth were measured in the two soils spiked with concentrations ranging from 3 to 8000 mg Cd/kg soil and incubated for 3 h, 20 days, and 60 days. The Cd concentrations that produced 5%; 10%;, and 50%; inhibition of each of the two soil microbiological parameter studied (ecological dose, ED, values) were calculated using two different mathematical models. Also, the effect of Cd concentration on plant growth of ryegrass (Lolium perenne, L.) was studied in the two soils. The Cd ED values calculated for soil dehydrogenase activity and ATP content were higher in the agricultural soils than in the bare soil. For ATP inhibition, higher ED values were calculated than for dehydrogenase activity inhibition. The average yields of ryegrass were reduced from 5.03 to 3.56 g in abandoned soil and from 4.21 to 1.15 g in agricultural soil with increasing concentrations of Cd in the soil. Plant growth was totally inhibited in abandoned and agricultural soils at Cd concentrations above 2000 and 5000 mg/kg soil, respectively. There was a positive correlation between the concentration of Cd in the plants and the total or DTPA-extractable concentrations of Cd in the soil.     

Effects of a brine discharge over soft bottom Polychaeta assemblage

Desalination is a growing activity that has introduced a new impact, brine discharge, which may affect benthic communities. Although the role of polychaetes as indicators to assess organic pollution is well known, their tolerance to salinity changes has not been examined to such a great extent. The aim of this study was to examine the effect of brine discharge over soft bottom polychaete assemblage along the Alicante coast (Southeast Spain) over a two year period. Changes in the polychaete assemblage was analysed using univariate and multivariate techniques. We compared a transect in front of the discharge with two controls. At each transect we sampled at three depths (4, 10 and 15 m) during winter and summer. We have observed different sensitivity of polychaete families to brine discharges, Ampharetidae being the most sensitive, followed by Nephtyidae and Spionidae. Syllidae and Capitellidae showed some resistance initially, while Paraonidae proved to be a tolerant family.     

EGG PRODUCTION AND HATCHING SUCCESS IN NORTH ADRIATIC SEA POPULATIONS OF THE COPEPOD Acartia clausi

Egg production, fecal pellet production and hatching success are reported for Acartia clausi females sampled during three cruises in February 1997, 1998 and June 1997 at 20-24 stations along 4 transects in the North Adriatic Sea. Dramatically low hatching rates were recorded during both diatom bloom events in February as opposed to much higher rates during post-bloom conditions in June, even though A. clausi productivity during the bloom was apparently high. These results are discussed in the light of recent findings on the negative impact of diatoms on copepod reproductive potential.     

Changes in the Biochemical Composition of Tetraselmis Suecia and Isochrysis Galbana During Growth and Decay

The variations of the biochemical composition of Tetraselmis suecica and Isochrysis galbana during growth and decay were determined. the content of chlorophyll a (Chl-a) of the cultures, as expected, slowly degraded into phaeopigments during decay, confirming that chlorophyll measurements do not always provide an accurate estimate of phytoplanktonic biomass and, consequently, may fail if used to measure the food availability of particulate matter for consumers. Measurements of total amounts of proteins, carbohydrates and lipids, related to the nutritional value of particles in terms of caloric content, are shown to provide information on the readily available food for consumers, particularly during the blooms. the protein/carbohydrate, C/N and POC/Chl-a ratios were used to evaluate the differences between these two species during the growth and the decomposition processes. A comparison between experimental and field conditions was undertaken to implement our understanding of the growth and degradation processes of particulate organic matter of phytoplanktonic origin in the sea and its role on natural systems, during and after phytoplankton blooms.     

Reconstruction of historical trends of PCDD/Fs and PCBs in the Venice Lagoon, Italy

Historical trends of PCDD/Fs and PCBs from the year 1900 have been reconstructed for the Venice Lagoon area by using a fugacity-based dynamic multimedia model. A novel approach to estimate the inputs to the system was applied. Emissions to the lagoon were estimated by studying dated sediment cores taken from salt marshes located in the lagoon area. These cores have recently proven to be a suitable tool to reconstruct the temporal trends of atmospheric deposition of POPs. According to the model, concentrations of PCBs and PCDD/Fs in air and water reflect the trends of their production and usage, peaking during the 1960s. The peaks in the sediment were delayed by 5-40 years depending on the congener. Predicted concentrations are in good agreement with experimental results. The most important input parameters, identified by a sensitivity analysis, are the degradation constants, K(ow), the Henry's law constant, vapour pressure, active sediment depth, sediment resuspension, and deposition rates, and water residence time in the lagoon.