Applicability of microwave-assisted extraction combined with LC-MS/MS in the evaluation of booster biocide levels in harbour sediments

A new sample treatment method for the determination of four common booster biocides (Diuron, TCMTB, Irgarol 1051 and Dichlofluanid) in harbour sediment samples has been developed that uses liquid chromatography-tandem mass spectrometry (LC-MS/MS) after microwave-assisted extraction, followed by clean-up and a solid phase extraction preconcentration step (MAE-SPE). The effects of different variables on MAE-SPE were studied. The recoveries obtained were greater than 75%, and the relative standard deviation was less than 7%. The detection limits ranged between 0.1 and 0.3 ng g⁻¹. The developed methodology was successfully applied to the evaluation of the presence of booster biocides in sediment samples from different harbours and marinas of Gran Canaria Island (Canary Islands, Spain).     

Determination of lipid peroxidation and cytotoxicity in calcium, magnesium, titanium and hectorite (SHCa-1) suspensions

This paper reports data on the relative ability of CaO, CaCl₂, MgO, MgCl₂, TiO₂, and hectorite (SHCa-1) to induce oxidative stress (as determined by lipid peroxidation, LP) in biological matrices. The effectiveness of structural (oxide form) versus soluble Ca and Mg to induce LP is compared. An assessment on cytotoxicity as affected by soluble and structural Ca, Mg, TiO₂ and SHCa-1 is also addressed. LP was screened and monitored using the Thiobarbituric Acid Reactive Substances (TBARS). The extent of TBARS production was found to vary with the type and initial concentration of the soluble or structural cation, Ca or Mg respectively. Obtained results showed higher magnitude values for the latter set of experiments. In the presence of TiO₂ no significant TBARS production was detected pointing out a negligible effect of TiO₂ on LP. At solid concentrations ca. 100 ppm, CaO appears to be more effective than SHCa-1 to induce LP. By contrast at ca. 25 ppm, MgO appears to be more effective than the clay mineral. The SHCa-1 LP-inducing activity has been proven to closely relate to structural Ca. The prevalence of mechanisms that may induce LP but not cytotoxicity (as determined by cell growth inhibition) was also addressed. Results on cell growth inhibition as affected by soluble and structural Ca, Mg, TiO₂ and hectorite provide evidence to support that structural Ca or Mg brings about significantly higher variations than soluble Ca.     

Enhanced retention of linuron, alachlor and metalaxyl in sandy soil columns intercalated with wood barriers

A study has been made of the effect a reactive barrier made of pine (softwood) or oak (hardwood) wood intercalated in a sandy soil column has on the retention of linuron, alachlor and metalaxyl (pesticides with contrasting physicochemical characteristics). The leaching of pesticides has been carried out under a saturated flow regime and breakthrough curves (BTCs) have been obtained at flow rates of 1 mL min⁻¹ (all pesticides) and 3 mL min⁻¹ (linuron). The cumulative curves in the unmodified soil indicate a leaching of pesticides >80% of the total amount of compound added. After barrier intercalation, linuron leaching decreases significantly and a modification of the leaching kinetics of alachlor and metalaxyl has been observed. The theoretical R factors increased ∼2.6-3.3, 1.2-1.6-fold, and 1.4-1.7-fold and the concentration of the maximum peak decreased ∼6-12-fold, 2-4-fold and 1.2-2-fold for linuron, alachlor and metalaxyl, respectively. When considering the three pesticides, significant correlations have been found between the theoretical retardation factor (R) and the pore volume corresponding to the maximum peaks of the BTCs (r = 0.77; p < 0.05) or the total volume leached (r = −0.78; p < 0.05). The results reveal the efficacy of reactive wood barriers to decrease the leaching of pesticides from point sources of pollution depends on the type of wood, the hydrophobicity of the pesticide and the adopted water flow rate. Pine was more effective than oak in decreasing the leaching of hydrophobic pesticide linuron or in decreasing the maximum peak concentration of the less hydrophobic pesticides in soils. Efficacy of these wood barriers was limited for the least hydrophobic pesticide metalaxyl.     

Nonparametric functional data estimation applied to ozone data: prediction and extreme value analysis

The study of extreme values and prediction of ozone data is an important topic of research when dealing with environmental problems. Classical extreme value theory is usually used in air-pollution studies. It consists in fitting a parametric generalised extreme value (GEV) distribution to a data set of extreme values, and using the estimated distribution to compute return levels and other quantities of interest. Here, we propose to estimate these values using nonparametric functional data methods. Functional data analysis is a relatively new statistical methodology that generally deals with data consisting of curves or multi-dimensional variables. In this paper, we use this technique, jointly with nonparametric curve estimation, to provide alternatives to the usual parametric statistical tools. The nonparametric estimators are applied to real samples of maximum ozone values obtained from several monitoring stations belonging to the Automatic Urban and Rural Network (AURN) in the UK. The results show that nonparametric estimators work satisfactorily, outperforming the behaviour of classical parametric estimators. Functional data analysis is also used to predict stratospheric ozone concentrations. We show an application, using the data set of mean monthly ozone concentrations in Arosa, Switzerland, and the results are compared with those obtained by classical time series (ARIMA) analysis.     

Cocaine and other illicit drugs in airborne particulates in urban environments: a reflection of social conduct and population size

Levels of cocaine and other psychoactive substances in atmospheric particulate matter (PM) were determined in urban environments representing distinct social behaviours with regard to drug abuse: night-life, university and residential areas. Three cities (with population >1 million and <0.3 million inhabitants) were selected. Mean daily levels of drugs in PM were 11-336 pg/m³ for cocaine, 23-34 pg/m³ for cannabinoids, and 5-90 pg/m³ for heroin. The highest levels were recorded on weekends, with factors with respect to weekdays of 1-3 for cocaine, 1-2 for cannabinoids and 1.1-1.7 for heroin. Higher levels were detected in the night-life areas, pointing towards consumption and trafficking as major emission sources, and possibly ruling out drug manufacture. The similarities in temporal trends at all sites suggested a city-scale transport of psychoactive substances. Correlations were detected between cocaine and amphetamine consumption (r² = 0.98), and between heroin and cannabinoids (r²>0.82).     

Arsenic distribution in soils and plants of an arsenic impacted former mining area

A mining area affected by the abandoned exploitation of an arsenical tungsten deposit was studied in order to assess its arsenic pollution level and the feasibility of native plants for being used in phytoremediation approaches. Soil and plant samples were collected at different distances from the polluting sources and analysed for their As content and distribution. Critical soil total concentrations of As were found, with values in the range 70-5330 mg kg⁻¹ in the uppermost layer. The plant community develops As tolerance by exclusion strategies. Of the plant species growing in the most polluted site, the shrubs Salix atrocinerea Brot. and Genista scorpius (L.) DC. exhibit the lowest bioaccumulation factor (BF) values for their aerial parts, suggesting their suitability to be used with revegetation purposes. The species Scirpus holoschoenus L. highlights for its important potential to stabilise As at root level, accumulating As contents up to 3164 mg kg⁻¹.     

Biomarker responsiveness in different tissues of caged Ruditapes philippinarum and its use within an integrated sediment quality assessment

Biomarkers comprising activities of biotransformation enzymes (ethoxyresorufin-O-deethylase -EROD-, dibenzylfluorescein dealkylase -DBF-, glutathione S-transferase -GST), antioxidant enzymes (glutathione reductase -GR- and glutathione peroxidase -GPX), lipid peroxidation -LPO- and DNA strand breaks were analyzed in the clam Ruditapes philippinarum caged at Cádiz Bay, Santander Bay and Las Palmas de Gran Canaria (LPGC) Port (Spain). Sediments were characterized. Digestive gland was the most sensitive tissue to sediment contamination. In Cádiz Bay, changes in LPO regarding day 0 were related with metals. In LPGC Port, DBF, EROD, and GST activity responses suggested the presence of undetermined contaminants which might have led to DNA damage. In Santander Bay, PAHs were related with EROD activity, organic and metal contamination was found to be associated with GR and GST activities and DNA damage presented significant (p < 0.05) induction. R. philippinarum was sensitive to sediment contamination at biochemical level. Biomarkers allowed chemical exposure and sediment quality assessment.     

Assessment of organochlorine pesticide residues in Atlantic Rain Forest fragments, Rio de Janeiro, Brazil

A superficial water quality survey in a watershed of the Paraíba do Sul River, the main water supply for the most populated cities of southeastern Brazil, was held in order to assess the impact of the expansion of agricultural activity in the near border of the Atlantic Rain Forest. The aim of this study was to investigate the presence of priority organochlorine pollutants in soils and superficial waters of Atlantic rainforest fragments in Teresópolis, Rio de Janeiro State. Soil sample preparations were compared by using ultrasound, microwave assisted extraction and Soxhlet extraction. Recoveries of matrix spiked samples ranged from 70 to 130%. Analysis of a certified soil material showed recoveries ranging from 71 to 234%. Although low concentrations of organochlorine residues were found in water and soil samples, this area is of environmental importance and concern, thus demanding a monitoring program of its compartments.     

Antiradical activity of natural honeys and antifungal effect against Penicillium genera

The purpose of the study was to examine the antiradical activity of 11 natural honeys and to evaluate the antifungal properties of honey. Honey samples (10) were collected from different locations of Slovak Republic. Honeys were native to different plant species of Robinia pseudoacaccia, Brassica napus subs. napus, Castanea sativa Mill. Thymus serpyllum vulgaris and the other samples had multifloral origin. The low antiradical activitity in honey samples was determined. The best results were found in thyme honey from Rhodos (11.84 %) and Castanea honey from Nitra (10.61 %). The lowest antiradical activity was found in Acacia honey and determined to be 7.62 %. Statistically significant differences (P< 0.001) were found among thyme/Rhodos and Castanea/Nitra. The antifungal activities of honey samples were tested by 10 %, 25 % and 50 % (by mass per volume) concentration against fungi Penicillium crustosum, P. expansum, P. griseofulvum, P. raistrickii and P. verrucosum and by the agar well diffusion method. The solutions containing 10 % (by mass per volume) of honey did not have any effect on the growth of fungi. The strongest antifungal effect was shown by 50 % honey concentration against P. raistrickii.     

Accumulation,biotransformation, and biochemical responses after exposure to arsenite and arsenate in the estuarine polychaete <Emphasis Type="BoldItalic">Laeonereis acuta</Emphasis> (Nereididae)

Introduction  

This study aimed to analyze antioxidant responses and oxidative damage induced by two inorganic forms of arsenic (As; As^III and As^V) in an estuarine polychaete species, Laeonereis acuta (Nereididae). The capacity of arsenic biotransformation was also evaluated through the methylation process considering the activity of a key enzyme involved in the metabolization process.