New methodological improvements in the Microtox® solid phase assay

The classic Microtox® solid phase assay (MSPA) based on the inhibition of light production of the marine bacteria recently renamed Aliivibrio fischeri suffers from various bias and interferences, mainly due to physico-chemical characteristics of the tested solid phase. To precisely assess ecotoxicity of sediments, we have developed an alternative method, named Microtox® leachate phase assay (MLPA), in order to measure the action of dissolved pollutants in the aqueous phase. Two hypotheses were formulated to explain the observed difference between MSPA and MLPA results: a real ecotoxicity of the solid phase or the fixation of bacteria to fine particles and/or organic matter. To estimate the latter, flow cytometry analyses were performed with two fluorochromes (known for their ability to stain bacterial DNA), allowing correction of MSPA measurements and generation of new (corrected) IC50. Comparison of results of MLPA with the new IC50 MSPA allows differentiating real ecotoxic and fixation effect in classic MSPA especially for samples with high amount of fines and/or organic matter.     

Concentrations of organochlorine pesticides and 2,4,6-trichloroanisole in cork bark

Organochlorine pesticides are persistent lipophilic organic pollutants and tend to accumulate in growing plants. During growth, cork is in contact with the open air for long periods (9-12 years). Owing to the previous widespread use of organochlorine pesticides and their high persistence in the environment, there is a risk that residues of such pesticides may be present in cork.In this study, the concentrations of 14 organochlorine pesticides—all of which are indicators of environmental pollution—were analyzed in cork bark samples from three regions in Spain and one in Portugal. In addition, the concentrations of 2,4,6-trichlorophenol (TCP) and 2,4,6-trichloroanisole (TCA) were also analyzed.Our results show only very low concentrations of lindane, γ-HCH (<2.6 ng g⁻¹) and its byproducts α-HCH (<3.5 ng g⁻¹) and β-HCH (<0.6 ng g⁻¹).Among the DDT and its metabolites, only two were found: p,p′-DDT was found in a cork sample from Extremadura (0.1 ng g⁻¹) and p,p′-DDE was present at a maximum concentration of 2.9 ng g⁻¹ in a cork sample from Castile-La Mancha. However, all concentrations were well below the legal limit established by Regulation (EC) No. 396/2005 (10 ng g⁻¹ in foodstuffs). We can conclude, therefore, that the cork samples we studied complied with food safety standards.     

Levels of organochlorine pesticides and polychlorinated biphenyls in the critically endangered Iberian lynx and other sympatric carnivores in Spain

Accumulation of organochlorine compounds is well studied in aquatic food chains whereas little information is available from terrestrial food chains. This study presents data of organochlorine levels in tissue and plasma samples of 15 critically endangered Iberian lynx (Lynx pardinus) and other 55 wild carnivores belonging to five species from three natural areas of Spain (Doñana National Park, Sierra Morena and Lozoya River) and explores their relationship with species diet. The Iberian lynx, with a diet based on the consumption of rabbit, had lower PCB levels (geometric means, plasma: <0.01 ng mL⁻¹, liver: 0.4 ng g⁻¹ wet weight, fat: 87 ng g⁻¹ lipid weight) than other carnivores with more anthropic and opportunistic foraging behavior, such as the red fox (Vulpes vulpes; plasma: 1.11 ng mL⁻¹, liver: 459 ng g⁻¹, fat: 1984 ng g⁻¹), or with diets including reptiles at higher proportion, such as the Egyptian mongoose (Herpestes ichneumon; plasma: 7.15 ng mL⁻¹, liver: 216 ng g⁻¹, fat: 540 ng g⁻¹), or the common genet (Genetta genetta; liver: 466 ng g⁻¹, fat: 3854 ng g⁻¹). Chlorinated pesticides showed interspecific variations similar to PCBs. Organochlorine levels have declined since the 80s in carnivores from Doñana National Park, but PCB levels are still of concern in Eurasian otters (Lutra lutra; liver: 3873-5426 ng g⁻¹) from the industrialized region of Madrid.     

Phenol and nitrophenols in the air and dew waters of Santiago de Chile

Phenol, nitrophenols and dinitrophenols were measured in air and dews in downtown Santiago de Chile. In both systems, phenol, 2-nitrophenol (2-NP), and 4-nitrophenol (4-NP) were the compounds found in higher concentrations and with major frequency. Temporal profiles in air were compatible with a significant direct incorporation from mobile sources. The data can be explained in terms of a faster removal of 2-NP than 4-NP, with the former predominating in fresh air masses and 4-NP in more aged samples. All these compounds, as well as dinitrophenols, were found in dew waters. Simultaneous measurements in air and dew indicate that phenol present in dew exceeds that expected in equilibrated samples, while the opposite occurs with 4-NP. This last result is associated to mass transfer limitations for the highly water soluble nitroderivative.     

Responses of Hyalella azteca and phytoplankton to a simulated agricultural runoff event in a managed backwater wetland

We assessed the aqueous toxicity mitigation capacity of a hydrologically managed floodplain wetland following a synthetic runoff event amended with a mixture of sediments, nutrients (nitrogen and phosphorus), and pesticides (atrazine, S-metolachlor, and permethrin) using 48-h Hyalella azteca survival and phytoplankton pigment, chlorophyll a. The runoff event simulated a 1 h, 1.27 cm rainfall event from a 16 ha agricultural field. Water (1 L) was collected every 30 min within the first 4 h, every 4 h until 48 h, and on days 5, 7, 14, 21, and 28 post-amendment at distances of 0, 10, 40, 300 and 500 m from the amendment point for chlorophyll a, suspended sediment, nutrient, and pesticide analyses. H. azteca 48-h laboratory survival was assessed in water collected at each site at 0, 4, 24, 48 h, 5 d and 7 d. Greatest sediment, nutrient, and pesticide concentrations occurred within 3 h of amendment at 0 m, 10 m, 40 m, and 300 m downstream. Sediments and nutrients showed little variation at 500 m whereas pesticides peaked within 48 h but at <15% of upstream peak concentrations. After 28 d, all mixture components were near or below pre-amendment concentrations. H. azteca survival significantly decreased within 48 h of amendment up to 300 m in association with permethrin concentrations. Chlorophyll a decreased within the first 24 h of amendment up to 40 m primarily in conjunction with herbicide concentrations. Variations in chlorophyll a at 300 and 500 m were associated with nutrients. Managed floodplain wetlands can rapidly and effectively trap and process agricultural runoff during moderate rainfall events, mitigating impacts to aquatic invertebrates and algae in receiving aquatic systems.     

Photocatalytic oxidation of monuron in the suspension of WO3 under the irradiation of UV-visible light

A comprehensive study of the degradation of monuron, one of the phenylurea herbicides, was conducted by UV-Vis/WO₃ process. It was found that hydroxyl radicals played a major role in the decay of monuron while other radicals (e.g. superoxide) and hole might also contribute to the decomposition of monuron. The oxidation path likely plays a major role in the generation of hydroxyl radicals. The effects of initial pH level, initial concentration of monuron, and inorganic oxidants on the performance of UV-Vis/WO₃ process were also investigated and optimized. Comparison between monuron decay pathways by UV-Vis/WO₃ and UV/TiO₂ was conducted. The decay mechanisms, including N-terminus demethylation, dechlorination and direct hydroxylation on benzene ring, were observed to be involved in the oxidation of monuron in these two processes. Sixteen intermediates were identified during the photodegradation of monuron and degradation pathways were proposed accordingly.     

Photocatalytic degradation of five sulfonylurea herbicides in aqueous semiconductor suspensions under natural sunlight

In the present study, the photocatalytic degradation of five sulfonylurea herbicides (chlorsulfuron, flazasulfuron, nicosulfuron, sulfosulfuron and triasulfuron) has been investigated in aqueous suspensions of zinc oxide (ZnO), tungsten (VI) oxide (WO₃), tin (IV) oxide (SnO₂) and zinc sulfide (ZnS) at pilot plant scale under natural sunlight. Photocatalytic experiments, especially those involving ZnO photocatalysis, showed that the addition of semiconductors in tandem with the oxidant (Na₂S₂O₈) strongly enhances the degradation rate of the herbicides in comparisons carried out with photolytic tests. The degradation of the herbicides follows a first order kinetics according to the Langmuir-Hinshelwood model. In our conditions, the amount of time required for 50% of the initial pesticide concentration to dissipate (t_½) ranged from 8 to 27 min (t_30W = 0.3-1.2 min) for sulfosulfuron and chlorsulfuron, respectively in the ZnO/Na₂S₂O₈ system. None of the studied herbicides was found after 120 min of illumination (except chlorsulfuron, 0.2 μg L⁻¹).     

Long-term effect of temperature on bioaccumulation of dietary metals and metallothionein induction in Sparus aurata

Previous studies have demonstrated that the commercial feed of aquacultured fish contains trace amounts of toxic and essential metals which can accumulate in tissues and finally be ingested by consumers. Recently rising temperatures, associated to the global warming phenomenon, have been reported as a factor to be taken into consideration in ecotoxicology, since temperature-dependent alterations in bioavailability, toxicokinetics and biotransformation rates can be expected. Sparus aurata were kept at 22 °C, 27 °C and 30 °C for 3 months in order to determine the temperature effect on metallothionein induction and metal bioaccumulation from a non-experimentally contaminated commercial feed. A significant temperature-dependent accumulation of cadmium (Cd), copper (Cu), mercury (Hg), zinc (Zn), lead (Pb) and iron (Fe) was found in liver, together with that of manganese (Mn), Fe and Zn in muscle. Hg presented the highest bioaccumulation factor, and essential metal homeostasis was disturbed in both tissues at warm temperatures. An enhancement of hepatic metallothionein induction was found in fish exposed to the highest temperature.     

Eichhornia crassipes capability to remove naphthalene from wastewater in the absence of bacteria

The aim of the current study was to investigate the potential of an aquatic plant, the water hyacinth (Eichhornia crassipes) devoid rhizospheric bacteria, to reduce naphthalene (a polyaromatic hydrocarbon) present in wastewater and wetlands.The capability of sterile water hyacinth plants to remove naphthalene from water and wastewater was studied in batch systems. Water hyacinths enhance the removal of pollutants through their consumption as nutrients and also through microbial activity of their rhizospheric bacteria.Experimental kinetics of naphthalene removal by water hyacinth coupled with natural rhizospheric bacteria was 100% after 9 d. Plants, decoupled of rhizospheric bacteria, reduced naphthalene concentration up to 45% during 7 d. Additionally, naphthalene uptake by water hyacinth revealed a biphasic behavior: a rapid first phase completed after 2.5 h, and a second, considerably slower rate, phase (2.5-225 h). In conclusion, water hyacinth devoid rhizospheric bacteria reduced significantly naphthalene concentration in water, revealing a considerable plant contribution in the biodegradation process of this pollutant.     

Lindane removal by pure and mixed cultures of immobilized actinobacteria

Stereoselective dissipation of epoxiconazole had been studied in grape and soil during plant growing under field conditions in this paper. A sensitive and rapid chiral method was developed and validated for the determination of epoxiconazole stereoisomers in grape and soil based on liquid chromatography coupled with triple quadrupole mass spectrometry (LC-MS/MS). Phenomenex Lux Cellulose-1 column was used for enantioseparation with a mixture of acetonitrile/water (90/10, v/v) as mobile phase at flow rate of 0.3 mL min⁻¹. Fortified recoveries in grape and soil samples ranged from 76.0% to 91.9% and relative standard deviations were less than 11.4% with fortified levels of 0.025-1.0 mg kg⁻¹. The limits of detection and quantification were 0.005 mg kg⁻¹ and 0.025 mg kg⁻¹, respectively, with linear calibration curves extending up to 5.0 mg kg⁻¹. The field experimental results showed that dissipations of epoxiconazole stereoisomers in grape followed first-order kinetics (R² > 0.92) and stereoselectivity occurred in 2 h after spraying. The (−)-stereoisomer with half-life of 9.3 d degraded faster than (+)-stereoisomer with that of 13.2 d, and resulted in relative enrichment of (+)-stereoisomer. However, the stereoisomeric dissipations in soil were triphasic (“increase-decrease-steady”) with lower dissipation rates, and also occurred with preferential degradation of (−)-stereoisomer under field condition. The results for stereoselective dissipations can be applied for food and environmental assessments of chiral pesticides.