Presence, biotransformation and effects of sulfophenylcarboxylic acids in the benthic fish Solea senegalensis

The presence of linear alkylbenzene sulfonates (LAS) and their degradation intermediates, sulfophenylcarboxylic acids (SPCs), with concentrations up to 100 ppb has been found in surface waters taken from the estuary of the river Guadalete (Cádiz, SW of Spain). Higher concentrations were found at the sampling site located adjacent to the discharge outlet of a wastewater treatment plant (WWTP). The concentrations decreased downstream to a few ppb as a result of dilution, sorption, and degradation processes, which were taking place along the estuary. Once the presence of both xenobiotics was confirmed in the environment, an in vivo assay was conducted to study their biotransformation and effects in the benthic fish Solea senegalensis. A flow-through system was employed, consisting of an exposure phase (120 h) with environmental levels of the surfactant (200, 500 and 800 microg/L of 2?C(10)LAS), followed by a depuration stage (72 h). The generation of SPCs has been quantified during these phases in both water and fish, with LAS biotransformation shown in all cases. The antioxidant enzymes catalase (CAT), glutathione peroxidase (GPX), glutathione reductase (GR), the phase II enzyme glutathione S-transferase (GST), and the phase III acid and alkaline phosphatases (AcP, ALP) were also estimated and utilized as biomarkers.     

The use of a metallothionein-like-proteins (MTLP) kinetic approach for metal bioavailability monitoring in dredged material

Ecotoxicological effects associated with contaminants present in dredged material from Spain were determined using a marine biotest based on the determination of metallothionein-like-protein concentrations (MTLPs) in the shore crab Carcinus maenas. Intermoult female C. maenas were exposed in the laboratory to sediments from three Spanish ports, Ría de Huelva (SW, Spain), La Coru?a (NW, Spain) and Bahía de Cádiz (SW, Spain) per replicate during 21 days. Hepatopancreas samples from crabs were taken for metallothioneins analysis on days 0, 7 and 21. Furthermore, chemical analysis was performed in the stations to determine the degree and nature of sediment contamination (Cr, Ni, Cu, Zn, Cd, Pb, Hg, As, PAHs and PCBs). A significant increase (p<0.05) in metallothionein concentration was observed over time in individuals exposed to sediment from the port Ría de Huelva characterized by high concentrations of metals. A toxicokinetic approach is proposed in this study related to the use of this biomarker in C. maenas to evaluate bioavailability associated with metals present in dredged material. As a first step, this toxicokinetic approach might reveal as a sensitive tool for evaluating bioavailability of contaminants present in dredged material.     

Metal/metalloid contamination and isotopic composition of lead in edible mushrooms and forest soils originating from a smelting area

High metal contents in edible mushrooms growing in severely contaminated industrial areas pose an important toxicological risk. In the presented study, trace element (Pb, Cd, Zn, Cu, Ag, As, Se) contents were determined in caps and stipes of three different edible mushroom species (Boletus edulis Bull. Fr., Xerocomus badius Fr. Gilb., Xerocomus chrysenteron Bull. Quél.). Additionally, information about the chemical fractionation of metals in separate soil horizons and Pb isotopic data from soils and fruiting bodies allowed a more detailed insight on the uptake mechanisms of metals by the studied mushroom species. Total metal and metalloid concentrations in the organic soil horizons reached 36234 mg Pb kg(-1); 11.9 mg Cd kg(-1); 519 mg Zn kg(-1); 488 mg Cu kg(-1); 25.1 mg Ag kg(-1); 120 mg As kg(-1) and 5.88 Se mg kg(-1). In order to evaluate the accumulation capacity of the studied species, bioconcentration factors (BCF) were calculated for separate trace elements. For selected metals (Pb, Cd, Zn, Cu), a modified BCF calculation (using EDTA-extractable concentrations of metals in soil) was proposed. High contents of Pb (up to 165 mg kg(-1)) and Cd (up to 55 mg kg(-1)) exceeded all the regulatory limits in all the studied species. This was also the case for Se (up to 57 mg kg(-1)) in B. edulis. Intensive consumption of this species grown in such polluted areas can therefore pose toxicological risks for human health. A novel finding was that X. badius can act as an Ag accumulating species when grown at polluted sites due to the high concentrations of Ag (up to 190 mg kg(-1)) in caps. Pb isotopic data showed that Pb originating from the recent air pollution control residues is present mainly in the exchangeable/acid-extractable fraction of the organic horizons and is taken up by fruiting bodies; especially in the case of B. edulis, where fast Pb accumulation occurs. Due to the high species-dependent variations of metal contents, the studied mushrooms are not suitable as bioindicators of environmental pollution.     

Unexpected high PCB and total DDT levels in the breeding population of red kite (Milvus milvus) from Doñana National Park, south-western Spain

This study provides information on the current status of contamination by organochlorines (DDTs, PCBs, PCDDs and PCDFs) in the declining red kite (Milvus milvus L.) population breeding in the Do?ana National Park (DNP), south-western Spain. Analyses were performed in addled eggs collected between 1999 and 2001. DDE concentrations ranged from 0.1 to 33.5 microg/g ww, representing more than 86% of the total DDTs. Of the samples studied, 50% showed DDE levels above those associated with reproductive impairment in other raptor species. Concentrations of ortho PCBs (average 36.8 microg/g ww+/-37.7) in 50% of the eggs were much higher than levels reported to cause reduced hatching success, embryo mortality, and deformities in birds (>20 microg/g ww). It is remarkable that average ortho PCB and DDE concentrations showed an increase of one order of magnitude compared to previous data for the species during the 80s. Total PCDD/Fs showed levels in the low pg/g range (7.2-42 pg/g ww), having PCDDs and PCDFs similar contributions in most samples. Total mean TEQs were 238 pg/g (ww), being the range 7.02-667 pg/g (ww). Spatial variation within DNP was observed for PCBs, DDTs, as well as for TEQs. Since some eggs exceeded the NOEL (67%) and LOEL (33%) reported for other raptor species, we would expect the red kite to experience detrimental effects to dioxin-like toxicity. Our results suggest that organochlorine contaminants should be regarded as an element of concern in the population under study, in addition to other conservation problems already reported. Further investigations should be undertaken to identify potential sources of these chemicals in DNP, and to find out if organochlorine contamination is present in other predator species in the area, as well as their potential health effects on individuals and/or populations.     

Assessment of Self-Organizing Map artificial neural networks for the classification of sediment quality

The application of mathematical tools in initial steps of sediment quality assessment frameworks can be useful to provide an integrated interpretation of multiple measured variables. This study reveals that the Self-Organizing Map (SOM) artificial neural network can be an effective tool for the integration of multiple physical, chemical and ecotoxicological variables in order to classify different sites under study according to their similar sediment quality. Sediment samples from 40 sites of 3 estuaries of Cantabria (Spain) were classified with respect to 13 physical, chemical and toxicological variables using the SOM. Results obtained with the SOM, when compared to those of traditional multivariate statistical techniques commonly used in the field of sediment quality (principal component analysis (PCA) and hierarchical cluster analysis (HCA)), provided a more useful classification for further assessment steps. Especially, the powerful visualization tools of the SOM, which offer more information and in an easier way than HCA and PCA, facilitate the task of establishing an order of priority between the distinguished groups of sites depending on their need for further investigations or remediation actions in subsequent management steps.     

Stochastic Transfer Function Model and Neural Networks to Estimate Soil Moisture1

Abstract: A practical methodology is proposed to estimate the three‐dimensional variability of soil moisture based on a stochastic transfer function model, which is an approximation of the Richard’s equation. Satellite, radar and in situ observations are the major sources of information to develop a model that represents the dynamic water content in the soil. The soil‐moisture observations were collected from 17 stations located in Puerto Rico (PR), and a sequential quadratic programming algorithm was used to estimate the parameters of the transfer function (TF) at each station. Soil texture information, terrain elevation, vegetation index, surface temperature, and accumulated rainfall for every grid cell were input into a self‐organized artificial neural network to identify similarities on terrain spatial variability and to determine the TF that best resembles the properties of a particular grid point. Soil moisture observed at 20 cm depth, soil texture, and cumulative rainfall were also used to train a feedforward artificial neural network to estimate soil moisture at 5, 10, 50, and 100 cm depth. A validation procedure was implemented to measure the horizontal and vertical estimation accuracy of soil moisture. Validation results from spatial and temporal variation of volumetric water content (vwc) showed that the proposed algorithm estimated soil moisture with a root mean squared error (RMSE) of 2.31% vwc, and the vertical profile shows a RMSE of 2.50% vwc. The algorithm estimates soil moisture in an hourly basis at 1 km spatial resolution, and up to 1 m depth, and was successfully applied under PR climate conditions.     

Kinetics and thermodynamic studies of Methyl Orange removal by polyvinylidene fluoride-PEDOT mats

We report the preparation of poly(3,4-ethylene dioxythiophene) (PEDOT)-modified polyvinylidene fluoride electrospun fibers and their use as a novel adsorbent material for the removal of the anionic dye Methyl Orange (MO) from aqueous media. This novel adsorbent material can be used to selectively remove MO on a wide pH range (3.0–10.0), with a maximum capacity of 143.8 mg/g at pH 3.0. When used in a recirculating filtration system, the maximum absorption capacity was reached in a shorter time (20 min) than that observed for batch mode experiments (360 min). Based on the analyses of the kinetics and adsorption isotherm data, one can conclude that the predominant mechanism of interaction between the membrane and the dissolved dye molecules is electrostatic. Besides, considering the estimated values for the Gibbs energy, and entropy and enthalpy changes, it was established that the adsorption process is spontaneous and occurs in an endothermic manner. The good mechanical and environmental stability of these membranes allowed their use in at least 20 consecutive adsorption/desorption cycles, without significant loss of their characteristics. We suggest that the physical-chemical characteristics of PEDOT make these hybrid mats a promising adsorbent material for use in water remediation protocols and effluent treatment systems.