Assessing bioaccumulation potential of personal care, household and industrial products in a marine echinoderm (Holothuria tubulosa).

A bioaccumulation study of 16 emerging contaminants including preservatives, UV-filters, biocides, alkylphenols, anionic surfactants and plasticizers, in Holothuria tubulosa Gmelin, 1791 specimens was developed. Water and sediments from their coastal habitat were also analyzed. Sediment-water distribution coefficients (log Kd) were in the range 0.78 to 2.95. A rapid uptake and bioaccumulation of pollutants was found. Compounds were detected in intestine and gonads of H. tubulosa after only eight days of exposure. Field-based bioconcentration (BCF) and biota-sediment accumulation factors (BSAF) were calculated. Log BCF > 1 were obtained for most of the compounds studied, indicating their tendency to accumulate in tissue of H. Tubulosa. BCF values decrease as follow: Triclocarban > anionic surfactants > benzophenone 3 > non-ionic surfactants > bisphenol A > parabens. These data provide a detailed accounting of the distribution patterns of some emerging contaminants in organisms at the lower trophic level, representing a potential source of contaminants for organisms in higher levels of the food chain.

A method to measure Representativity and Univocity of traffic signs and to test their effect on movement.

OBJECTIVE: The present protocol aims to understand how participants represent traffic signs (Psychology of Thinking) and how the attention of these signs-and the way of processing them-can influence on their path movement (Motor Processes). Knowing how humans process the meaning of signs (not just by learning but instinctively understood) will improve reaction times and decision making when driving. BACKGROUND: In laboratory tasks, a number of models have attempted to explain the general relationship between attention and movement. The cornerstone of the effects is found on the meaning of attentional cues. METHOD: By using a tracking task, the influence of traffic signs on movement is been tested. RESULTS: Results point out that the signs least representative of their meaning produce a greater deviation from the center of the simulated road than the most representative signs. CONCLUSIONS: The economic, social and psychological consequences of car accidents are well-established. Every single effort orientated to amend this social problem is welcome. Taking into account the results reported in this work, it is recommended that the traffic signs are designed as much representative of their meaning as possible. APPLICATION: The methodology used in this study can be applied to testing the Cognitive Ergonomics of signposting on roads; analyzing, classifying, and discarding the traffic signs that produce counterproductive effects on movement from the current Manuals of Traffic Signposting all around countries.•An original methodology has been generated for classifying traffic signs, which has not been never tested in the literature.•The well-consolidated tracking task is used for evaluating their effect on movement.•The main result is that traffic signs, that do not represent properly their meaning, provoke a significant and dangerous deviation from the drivers' path.

Bioaccumulation of perfluoroalkyl substances in marine echinoderms: Results of laboratory-scale experiments with Holothuria tubulosa Gmelin, 1791.

Bioaccumulation of six perfluoroalkyl substances (PFAS) was assessed using the marine echinoderm Holothuria tubulosa Gmelin, 1791. Batch experiments were conducted to establish the relationship between concentrations in water, sediment and biota over 197 days. The sample treatment for the determination of compounds involves steps of lyophilization, solvent extraction and clean-up of the extracts with dispersive sorbents. PFAS were then analysed by liquid chromatography-tandem mass spectrometry. During contaminant exposure, detectable levels of compounds were found in all samples collected. Mean concentrations of selected PFAS were higher in sediments than in water samples. This fact is explained by the strong adsorption of these compounds into sediments. Sediment-water distribution coefficients (log Kd) were in the range 0.11 (PFBuA) to 2.46 (PFOA). Beside this, PFAS accumulation was observed in Holothuria tubulosa organisms. The uptake of PFAS was very rapid, reaching the maximum between 22 and 38 days of assay. Bioaccumulation factors (mean log BAF: 1.16-4.39) and biota sediment accumulation factors (mean log BSAF: 1.37-2.89) indicated a high bioaccumulation potential for the target compounds. Both parameters increased with perfluoroalkyl chain length (R2 > 0.93; p < 0.05). In organ-specific distributions of PFAS, greater concentrations were found in intestine than in gonads. Also, male specimens showed higher concentration levels than female (student t-test: tcal = 2.788, ttab = 2.262; p < 0.05). These data provide a detailed accounting of PFAS fate and distribution in the marine environment highlighting accumulation at lower trophic levels, a potential source for contamination in higher organisms.

Representativity and univocity of traffic signs and their effect on trajectory movement in a driving-simulation task: Regulatory signs.

INTRODUCTION: The effect of traffic signs in the motor behavior of drivers is not completely understood. Knowing how humans process the meaning of signs (not just by learning, but instinctively) will improve reaction time and decision making when traveling. The economic, social, and psychological consequences of car accidents are well studied. Every effort to find the solution of this social problem is encouraged. METHOD: This study identifies which traffic signs are more ergonomic for participants, from a cognitive point of view, and determines, at the same time, their effect in participants' movement trajectory in a driving-simulation task: the tracking task. RESULTS: The results point out that the signs least representative of their meaning produce a quantitative and qualitative different deviation from the center of the road than the most representative ones.

Mental Footnotes. Knowledge Constructivism From Logical Thinking and Personal Beliefs to Social Rationality and Spiritual Freedom.

Cognition is an efficient but limited system that deals with mundane tasks. Daily life demands the system to save energy in order to be able to solve other more relevant tasks. Reasoning out every single problem would immeasurably increase our mental load and fatigue. Our minds avoid this waste of resources by taking shortcuts when reasoning. Outputs from previous episodes of reasoning turn into pieces of implicit information. These outputs go on to constitute the meanings that we give to things or circumstances, which in turn become the general framework where other reasonings occur. These implicit meanings determine the manner in which we represent our social environment and, therefore, our emotions and behaviors. These "mental footnotes" set the way in which we contemplate and conceive the world and deal with reality. World order capitalizes on the mechanisms of the mind to control and guide humanity. The better we understand these processes, the better we can control and restructure them. Academic psychology often ignores the power of the discipline to set humankind free from those meanings that restrict spiritual and human development.

Development of a New Microextraction Fiber Combined to On-Line Sample Stacking Capillary Electrophoresis UV Detection for Acidic Drugs Determination in Real Water Samples.

A new analytical method coupling a (off-line) solid-phase microextraction with an on-line capillary electrophoresis (CE) sample enrichment technique was developed for the analysis of ketoprofen, naproxen and clofibric acid from water samples, which are known as contaminants of emerging concern in aquatic environments. New solid-phase microextraction fibers based on physical coupling of chromatographic supports onto epoxy glue coated needle were studied for the off-line preconcentration of these micropollutants. Identification and quantification of such acidic drugs were done by capillary zone electrophoresis (CZE) using ultraviolet diode array detection (DAD). Further enhancement of concentration sensitivity detection was achieved by on-line CE "acetonitrile stacking" preconcentration technique. Among the eight chromatographic supports investigated, Porapak Q sorbent showed higher extraction and preconcentration capacities. The screening of parameters that influence the microextraction process was carried out using a two-level fractional factorial. Optimization of the most relevant parameters was then done through a surface response three-factor Box-Behnken design. The limits of detection and limits of quantification for the three drugs ranged between 0.96 and 1.27 µg∙L-1 and 2.91 and 3.86 µg∙L-1, respectively. Recovery yields of approximately 95 to 104% were measured. The developed method is simple, precise, accurate, and allows quantification of residues of these micropollutants in Genil River water samples using inexpensive fibers.

Representativity and univocity of traffic signs and their effect on trajectory movement in a driving simulation task: Warning signs.

OBJECTIVE: The effect of traffic signs on the behavior of drivers is not completely understood. Knowing about how humans process the meaning of signs (not just by learning but instinctively) will improve reaction time and decision making when traveling. The economic, social, and psychological consequences of car accidents are well known. METHODS: This study sounds out which traffic signs are more ergonomic for participants, from a cognitive point of view, and determines, at the same time, their effect in participants' movement trajectories in a driving simulation task. RESULTS: Results point out that the signs least representative of their meaning produce a greater deviation from the center of the road than the most representative ones. CONCLUSIONS: This study encourages both an in-depth analysis of the effect on movement of roadside signs and the study of how this effect can be modified by the context in which these signs are presented (with the aim to move the research closer to and analyze the data in real contexts). The goal is to achieve clarity of meaning and lack of counterproductive effects on the trajectory of representative signs (those that provoke fewer mistakes in the decision task).

Environmental monitoring of alcohol sulfates and alcohol ethoxysulfates in marine sediments.

The study describes the environmental monitoring of anionic surfactants-alcohol sulfates (AS) and alcohol ethoxysulfates (AES)-in marine sediments. Concentration values were obtained after pressurised liquid extraction (PLE) and liquid chromatography-tandem mass spectrometry analysis (LC-MS/MS). Samples were collected from a range of wastewater discharge points along the coast of the provinces of Huelva, Málaga, Granada and Almería. Urban, agricultural and industrial wastewaters are discharged at the selected 38 sampling sites. Principal component analysis was carried out in order to evaluate the distribution and behaviour of these compounds in these coastal environments. Evaluation of the data revealed that the behaviour and sources of AS and AES in marine sediments are different, and that the distribution of AES depends on the length of the alkyl chain, while the number of ethoxylated units is not relevant. Additionally, the 38 sampling sites can be grouped into only two types of outfalls according to their AS distribution. The concentration of compounds in sediment samples ranged from 7.52 to 13.50 mg kg(-1) for AS, from 3.04 to 10.68 mg kg(-1) for AES-C12Ex and from 3.83 to 11.56 mg kg(-1) for AES-C14Ex.

Sorption and desorption of alcohol sulfate surfactants in an agricultural soil.

Alcohol sulfates are one of the most important types of commercial anionic surfactants and may pose serious environmental problems. The present study examines the sorption behavior of alcohol sulfates in an agricultural soil using a batch reactor and column experiments. Kinetics and equilibrium isotherms of the sorption and desorption processes of the following alcohol sulfate homologues have been determined: AS-C12, AS-C14, AS-C16 , and AS-C18. Sorption and desorption occurred rapidly, and equilibrium was achieved in approximately 1 h. The sorbed mass percentages were 35.1% AS-C12 , 67.2% AS-C14 , and 100% for both AS-C16 and AS-C18. A pseudo-first-order kinetic model provided an adequate fit of data. Sorption and desorption equilibrium data were fitted into 1) a linear model, with r(2) values in the ranges 0.712 to 0.988 and 0.736 to 0.983, respectively, and 2) a Freundlich model, with r(2) values in the ranges 0.956 to 0.991 and 0.891 to 0.981, respectively. Continuous-flow experiments in soil columns were carried out to obtain the breakthrough curves for each compound. The present study provides basic theoretical concepts and key parameters for developing mathematical models that simulate the migration of alcohol sulfate into agricultural soils.

Ultra-performance liquid chromatography MS/MS method for the determination of parabens in compost from sewage sludge: comparison of the efficiency of two extraction techniques.

The efficiency of two extraction techniques--ultrasound-assisted extraction and pressurized liquid extraction--are compared and evaluated in the determination of parabens in compost samples. The extraction parameters for each technique were accurately optimized. The selected compounds were detected and quantified using ultra-performance LC MS/MS, operating in negative ESI and in SRM mode. The analytes were separated in less than 5 min. Ethylparaben (ring-(13)C6 labeled) was used as an internal standard. Two selective, sensitive, and accurate analytical methods were developed and validated. The LODs of the methods ranged from 3 to 7 ng/g and the LOQs from 10 to 23 ng/g, while inter- and intraday variability was under 6% in all cases. The methods were validated separately by using matrix-matched calibration and recovery assays with spiked samples. Recovery rates ranged from 94.0 to 105.0%. Compost samples were taken from different composting plants. Although the statistical comparison demonstrated no statistically significant differences between the two extraction techniques, the method based on pressurized liquid extraction was more sensitive than the ultrasound extraction based method.

Validation of a GC-MS/MS method for simultaneous determination of 86 persistent organic pollutants in marine sediments by pressurized liquid extraction followed by stir bar sorptive extraction.

A multiresidue method for the analysis of 86 persistent pollutants in marine sediments at ultra-trace level has been developed and validated using pressurized liquid extraction (PLE) and stir-bar sorptive extraction (SBSE) coupled with thermal desorption and gas chromatography-triple quadrupole mass spectrometry (TD-GC-MS/MS QqQ). The compounds analyzed belong to various families such as polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenylethers, organophosphorus and organochlorine pesticides and other pesticides such as urons, and triazines. The analytes have very different polarities and log K(ow) values, which is an important parameter in the optimization of a SBSE method. Due to PLE high efficiency and throughput rates, along with the proven ability for multiresidue analysis and excellent sensitivity of SBSE, we present an efficient method. The limits of quantification obtained ranged from 0.014 to 1.0 ng g(-1), with detection limits below pg g(-1) levels. In order to validate the proposed methodology, quality parameters such as recovery, linearity and reproducibility were studied. Recoveries ranged from 63% to 119%, reproducibility (in terms of Relative Standard Deviation for ten determinations) was lower than 35% in all cases, and determination coefficients higher than 0.990 for all analytes. The main factors that affect PLE, SBSE and GC-MS/MS procedures were optimized. The method was applied to the analysis of nine marine sediments obtained from the nine main submarine wastewater discharge points (emissaries) presents along the coast of Tenerife Island (Canary Islands, Spain).

Mobility and fate of carbetamide in an agricultural soil.

The objective of this work is to gain a better understanding of the fate of carbetamide, as a representative herbicide, after its soil application. To reach this goal, batch and column laboratory experiments were performed and a transport model was proposed consistent with these results. Then field-scale experiments were carried out for two years and the results compared with those that would be obtained from the transport model, once the degradation terms were introduced. All this is done for four different scenarios: first, considering that the soil is under its natural condition; second, the soil is amended with organic carbon by the addition of stabilized sewage sludge; third, considering that the percolating aqueous phase contains a significant quantity of surfactant [Linear Alkyl Benzene Sulfonate, (LAS)]; and fourth, the scenario in which the sewage sludge and the surfactant are present simultaneously. The Freundlich model yields a good fit to the data of the sorption isotherms obtained from batch equilibrium experiments, but the isotherms are close to linear. The batch sorption/desorption kinetic data together with the column and field results indicate that the retention kinetics are quite fast and local equilibrium can be assumed for the description of the sorption phenomenon. Results also prove that carbetamide is moderately retained in the original soil with a mean value of the partition coefficient of carbetamide about 0.46 (L kg(-1)). When the soil is amended with sewage sludge, this coefficient is somewhat lower, about 0.40 (L kg(-1)). A further decrease is observed 0.32 L kg(-1)) when the surfactant (LAS) at critical micelle concentration (CMC) is used. The two-region model yields a good reproduction of the results of carbetamide mobility in the soil, both at the laboratory scale and at the field scale.

Determination of sulfophenyl carboxylic acids in agricultural groundwater samples by CE with ultraviolet absorption detection.

An analytical method for the determination of six sulfophenyl carboxylic acids, namely (p-sulfophenyl)acetic, 2-(p-sulfophenyl)propionic, 2-(p-sulfophenyl)butyric, 3-(p-sulfophenyl)butyric, 4-(p-sulfophenyl)butyric, and 5-(p-sulfophenyl)valerianic acid, in agricultural irrigation water samples was developed. It involves an SPE procedure, an on-line preconcentration normal stacking mode and subsequent separation and determination using CE with UV detection (CE-UV). p-Sulfobenzoic acid was used as internal standard. The compounds were separated with an uncoated capillary and a 25 mM ammonium acetate/acetic acid buffer solution (pH 5.5) with 2-propanol (30% v/v) and 0.75 mM CTAB. Analyses were run at -25 kV, 25 degrees C, and 100 s of hydrodynamic injection with UV detection at 225 nm. Quantification limits found ranged between 4 and 6 ng/mL. The proposed method was validated using a recovery assay. It was satisfactorily used for the determination of these compounds in groundwater samples to track down the biodegradation of linear alkylbenzene sulfonates in an agricultural soil from the fertile plain of Granada (Spain).

Simultaneous identification of natural dyes in the collection of drawings and maps from The Royal Chancellery Archives in Granada (Spain) by CE.

A simple and rapid capillary electrophoretic method with UV detection (CE-UV) has been developed for the identification of five natural dyes namely, carmine, indigo, saffron, gamboge and Rubia tinctoria root. The separation was performed in a fused-silica capillary of 64.5 cm length and 50 microm id. The running buffer was 40 mM sodium tetraborate buffer solution (pH 9.25). The applied potential was 30 kV, the temperature was 25 degrees C and detections were performed at 196, 232, 252, 300 and 356 nm. The injections were under pressure of 50 mbar during 13 s. The method was applied to the identification of carminic acid, gambogic acid, crocetin, indigotin, alizarin and purpurin in the collection of drawings and maps at the Royal Chancellery Archives in Granada (Spain). The method was validated by using HPLC as a reference method.

Sampling and identification of natural dyes in historical maps and drawings by liquid chromatography with diode-array detection.

A simple and rapid liquid chromatographic with diode-array UV-vis spectrophotometric detection (HPLC-DAD) method for identification of natural dyes has been developed. Chromatographic retention of carminic acid, indigotin, crocetin, gambogic acid, alizarin and purpurin has been studied. The mobile phase consisted of 40 mM SDS-10 mM phosphate buffer solution (pH 2.3)-0.1% TFA (eluent A) and acetonitrile (eluent B) using a programmed gradient (5% B to 95% B). Analyses were carried out on a Phenomenex, Luna 5u NH2 100(a) column (250 mm x 4.60 mm i.d., 5 microm particle) and the operating conditions were: 0.6 ml min(-1) flow rate, 20 microl volume injection and 35 degrees C column temperature. Extracts of samples of natural dyes taken from historical maps belonging to The Royal Chancellery Archives in Granada were successfully analyzed using the proposed method including a new technique for sampling.

Sensitive gas chromatographic-mass spectrometric method for the determination of phthalate esters, alkylphenols, bisphenol A and their chlorinated derivatives in wastewater samples.

Phthalate esters, alkylphenols, bisphenol A and their chlorinated derivatives are the suspected endocrine disrupters or mutagens. These compounds, commonly called endocrine disrupter chemicals (EDCs), are widely used as plastic additives, lacquers, resins, or surfactants and can be usually found in environmental samples, namely wastewaters. An accurate and reproducible gas chromatographic-mass spectrometric (GC-MS) method is proposed to measure these compounds in wastewater samples of Granada city (Spain). A solid-phase extraction with LiChrolut RP-18 cartridges was carried out and the elution was performed with a diethyl ether/methanol mixture. After isolation, solvent was removed and a silylation step was carried out using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA). Phthalate esters and silylated compounds were identified and quantified by GC-MS using a ZB-5 MS column. Bisphenol F was used as a surrogate. Quantification limits found were between 20 ng L(-1) for 4-nonylphenol and 400 ng L(-1) for benzylbutyl phthalate while inter and intra-day variability was under 5% in all cases. Recoveries for spiked samples were over 95% and under 105%. The method was validated using standard addition calibration and recovery assays.

Determination of pyrimethanil and kresoxim-methyl in soils by headspace solid-phase microextraction and gas chromatography-mass spectrometry.

A method using headspace solid-phase microextraction (HS-SPME) then gas chromatography-mass spectrometry with selected ion monitoring (GC-MS, SIM) has been developed for determination of trace amounts of the fungicides pyrimethanil and kresoxim-methyl in soil and humic materials. Both fungicides were extracted on to a fused-silica fibre coated with 85 microm polyacrylate (PA). Response-surface methodology was used to optimise the experimental conditions. For soil samples the linear dynamic range of application was 0.004-1.000 microg g(-1) for pyrimethanil and 0.013-1.000 microg g(-1) for kresoxim-methyl. The detection limits were 0.001 microg g(-1) and 0.004 microg g(-1) for pyrimethanil and kresoxim-methyl, respectively. HP-SPME-GC-MS analysis was highly reproducible-relative standard deviations (RSD) were between 6.7 and 12.2%. The method was validated by analysis of spiked matrix samples and used to investigate the presence of pyrimethanil and kresoxim-methyl above the detection limits in soil and humic materials.

Determination of the antibacterial trovafloxacin by differential-pulse adsorptive stripping voltammetry.

A differential-pulse adsorptive stripping voltammetric method for the determination of trace amounts of the antibacterial trovafloxacin (TRFLX) is proposed. The optimal experimental parameters for the drug assay were: accumulation potential=-0.30 V (vs. Ag/AgCl), accumulation time=120 s, pulse amplitude=50 mV and scan rate=5 mV s(-1) in Britton-Robinson buffer (pH 4.5). The linear concentration range of application was 2.0-20.0 ng ml(-1) of TRFLX, with a relative standard deviation of 3.6% (for a level of 5.0 ng ml(-1)) and a detection limit of 0.6 ng ml(-1). The method was applied to determination of TRFLX in human urine and serum samples. It was validated using HPLC as a reference method. Recovery levels of the method reached 100% in all cases

Gas chromatographic-mass spectrometric method for the determination of bisphenol A and its chlorinated derivatives in urban wastewater.

The simultaneous determination of trace amounts of endocrine disruptors such as bisphenol A (BPA) and its monochloro, dichloro, trichloro and tetrachloro derivatives in wastewater has been developed using gas chromatography-mass spectrometry (GC-MS). Compounds were previously extracted from the aqueous samples using a liquid-liquid extraction procedure with a mixture of dichloromethane:carbon tetrachloride (25/75). After extraction, solvent was removed and a silylation step was carried out with N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA). The silylated compounds were identified and quantified by GC-MS using an HP1-MS column. The retention times were 6.64 min for BPA silylated, 7.26 min for Cl-BPA silylated, 7.99 min for Cl(2)-BPA silylated, 8.85 min for Cl(3)-BPA silylated and 9.95 min for Cl(4)-BPA silylated. A clean-up is not necessary using SIM mode. Deuterated anthracene (2H(10)-anthracene) was used as an internal standard. The detection limits obtained were 0.3, 0.6, 2.0, 4.5 and 13.0 ng L(-1) for silylated BPA, Cl-BPA, Cl(2)-BPA, Cl(3)-BPA and Cl(4)-BPA, respectively. The proposed method was applied satisfactory to the determination of these chemicals, in different types of wastewater previously spiked with different amounts of these chemicals at concentration levels ranging from 0.01 to 2.50 microg L(-1) for BPA, 0.05-2.50 micro L(-1) for Cl-BPA and 0.05-5.00 microg L(-1) for Cl(2)-BPA, Cl(3)-BPA and Cl(4)-BPA, respectively. The method was validated following standard addition methodology.

Determination of the antibacterial ofloxacin in human urine and serum samples by solid-phase spectrofluorimetry.

A method for the determination of trace amounts of ofloxacin has been developed, based on solid-phase spectrofluorimetry. The relative fluorescence intensity of ofloxacin fixed on Sephadex SP C-25 gel was measured directly after packing the gel beads in a 1-mm silica cell, using a solid-phase attachment. The wavelengths of excitation and emission were 294 and 494 nm, respectively. The linear concentration range of application was 0.5-16.0 ng ml(-1) of ofloxacin, with a relative standard deviation of 1.1% (for a level of 8.0 ng ml(-1)) and a detection limit of 0.14 ng ml(-1). The method was applied to the determination of ofloxacin in human urine and serum samples. It was validated applying the standard addition methodology and using HPLC as a reference method. Recovery levels of the method reached 100% in all cases.