Metallothioneins failed to reflect mercury external levels of exposure and bioaccumulation in marine fish--considerations on tissue and species specific responses

The suitability of metallothioneins (MT) in fish as biomarker of exposure to mercury has been questioned. Therefore, this study aimed at investigating the relationship between external levels of exposure, mercury accumulation and MT content, assessing species and tissue specificities. Two ecologically different fish species - Dicentrarchus labrax and Liza aurata - were surveyed in an estuary historically affected by mercury discharges. Total mercury (T-Hg) and MT content were determined in gills, blood, liver, kidney, muscle and brain. All tissues reflected differences in T-Hg accumulation in both species, although D. labrax accumulated higher levels. Regarding MT, D. labrax revealed a depletion in brain MT content and an incapacity to induce MT synthesis in all the other tissues, whereas L. aurata showed the ability to increase MT in liver and muscle. Tissue-specificities were exhibited in the MT inducing potential and in the susceptibility to MT decrease. L. aurata results presented muscle as the most responsive tissue. None of the investigated tissues displayed significant correlations between T-Hg and MT levels. Overall, the applicability of MT content in fish tissues as biomarker of exposure to mercury was uncertain, reporting limitations in reflecting the metal exposure levels and the subsequent accumulation extent.     

Differential partitioning and speciation of Hg in wet FGD facilities of two Spanish PCC power plants

This paper evaluates the speciation and partitioning of mercury in two Spanish pulverised coal combustion power plants (PP1 and PP2), equipped with wet limestone-based flue gas desulphurisation facilities (FGD) operating with forced oxidation and re-circulation of FGD water streams. These plants are fed with coal (PP1) and coal/pet-coke blends (PP2) with different mercury contents. The behaviour, partitioning and speciation of Hg were found to be similar during the combustion processes but different in the FGD systems of the two power plants. A high proportion (86-88%) of Hg escaped the electrostatic precipitator in gaseous form, Hg²⁺ being the predominant mercury species (68-86%) to enter the FGD. At this point, a relatively high total Hg retention (72% and 65%) was achieved in the PP1 and PP2 (2007) FGD facilities respectively. However, during the second sampling campaign for PP2 (2008), the mercury removal achieved by the FGD was much lower (26%). Lab-scale tests point to liquid/gas ratio as the main parameter affecting oxidised mercury capture in the scrubber. The partitioning of the gaseous mercury reaching the FGD system in the wastes and by-products differed. In the low mercury input power plant (PP1) most of the mercury (67%) was associated with the FGD gypsum. Moreover in PP2 a significant proportion of the gaseous mercury reaching the FGD system remained in the aqueous phase (45%) in the 2007 sampling campaign while most of it escaped in 2008 (74%). This may be attributed to the scrubber operating conditions and the different composition and chemistry of the scrubber solution probably due to the use of an additive.     

Mercury cycling and sequestration in salt marshes sediments: an ecosystem service provided by Juncus maritimus and Scirpus maritimus

In this study two time scales were looked at: a yearlong study was completed, and a 180-day decay experiment was done. Juncus maritimus and Scirpus maritimus have different life cycles, and this seems to have implications in the Hg-contaminated salt marsh sediment chemical environment, namely Eh and pH. In addition, the belowground biomass decomposition rates were faster for J. maritimus, as well as the biomass turnover rates. Results show that all these species-specific factors have implications in the mercury dynamics and sequestration. Meaning that J. maritimus belowground biomass has a sequestration capacity for mercury per square metre approximately 4-5 times higher than S. maritimus, i.e., in S. maritimus colonized areas Hg is more extensively exchange between belowground biomass and the rhizosediment. In conclusion, J. maritimus seems to provide a comparatively higher ecosystem service through phytostabilization (Hg complexation in the rhizosediment) and through phytoaccumulation (Hg sequestration in the belowground biomass).     

Phenol degradation using combined effects of hydrodynamic cavitation and oxidant: Doehlert matrix

Hydrodynamic cavitation (HC)-based treatments have been proposed for the degradation of phenol as a toxic pollutant. The present work aimed to optimize the degradation of phenol using HC by means of Doehlert experimental design, which has not been previously addressed. Initially, operational parameters of hydraulic characteristics of the pump, inlet pressure, solution pH, and initial concentration were optimized; later, the effects of pH solution and H₂O₂ loading or initial pollutant concentration on phenol degradation were explored using the Doehlert experimental design. It was observed that phenol degradation is strongly dependent on the pH of the solution. Also, the acidic condition favors the formation of hydroxyl radicals and thus, the degradation of phenol. Based on the Doehlert matrix, the 94.1% phenol degradation and 68.60% total organic carbon (TOC) were obtained in 180 min at 304.5 mg/L of hydrogen peroxide at an initial concentration of 20 mg/L, 2.0 pH, and 90 psi inlet pressure, providing a cavitational yield of 6.33 × 10⁻⁶ mg/J and minimum treatment cost of US$/L 0.13. Overall, it has been observed that HC can be a promising route for the removal of pollutants (phenol) effectively using hydrogen peroxide as an additive.     

Polychlorinated biphenyls and polybrominated diphenyl ethers in the North American atmosphere

To assess the spatial concentration variability of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in the atmosphere on a large continental scale, their annually integrated air concentrations were determined in 2000/2001 using XAD-based passive air samplers (PAS). The network included 40 stations in Canada, the United States, Mexico, Belize and Costa Rica, and covered 72 degrees of latitude and longitude. Total concentrations of PCB and PBDE congeners ranged from below the detection limit to 130 ng PAS-1 and 24 ng PAS-1, respectively. PCBs displayed a large variation between urban, rural and remote sites, whereas PBDEs did not follow such a pattern. Open burning of "Penta"-containing waste may have contributed to the PBDEs detected in the air samples from rural and remote areas. Air from the Canadian Arctic had a relatively higher percentage of lighter PCB congeners than air sampled in the tropical region, which is interpreted as evidence for global fractionation.     

Phthalides as promising insecticides against Tuta absoluta (Lepidoptera: Gelechiidae)

In this study, the insecticide potential of eight phthalides derived from furan-2(5H)-one was evaluated against Tuta absoluta (Meyrick) (Lepidoptera: Gelechiidae) larvae. The potency of the most active phthalides and the susceptibility of six different T. absoluta populations to these compounds were determined. The toxicity of these molecules to two non-target species (Solenopsis saevissima Smith and Tetragonisca angustula Latreille) was also evaluated. Two phthalides (3 and 4) presented insecticide potential against T. absoluta. Phthalide 4 was as toxic as piperine (positive control) and both phthalides exhibited rapid action (LT₅₀ < 2 hours). The variation in the susceptibility of T. absoluta populations to the phthalides 3 and 4 was low. Neither phthalide presented physiological selectivity for non-target species.

Therefore, the phthalides 3 and 4 are promising molecules, or at least, a starting point for a chemical optimization program leading to formulations for the management of the tomato leafminer. The application of such products should be conducted according to the principles of ecological selectivity.     

Effects of glyphosate on the non-target leaf beetle Cerotoma arcuata (Coleoptera: Chrysomelidae) in field and laboratory conditions

This study aimed to assess the glyphosate application effects on the Cerotoma arcuata Oliver (Coleoptera: Chrysomelidae) population in glyphosate-resistant soybean crops. Field studies were conducted with glyphosate and the insecticide endosulfan to observe the effects of these pesticides on C. arcuata, on its damages in the crop and on the populations of natural enemies in glyphosate-resistant soybean crops. Moreover, the lethal and behavioral sublethal response of C. arcuata to glyphosate and endosulfan was conducted in the laboratory. The results of the field and laboratory experiments showed that glyphosate caused moderate toxicity and high irritability in C. arcuata and that endosulfan caused high toxicity and irritability. Therefore, the direct effect of glyphosate on C. arcuata was negative and does not explain the population increases of this pest in glyphosate-resistant soybean. However, the glyphosate also decreased the density of predators. Thus, the negative effect of glyphosate on the predators may be related to population increases of C. arcuata in glyphosate-resistant soybean crops, however, more studies are needed to better evidence this relationship. This study suggests that glyphosate can impact other non-target organisms, such as herbivorous insects and natural enemies and that the use of this herbicide will need to be carefully stewarded to prevent potential disturbances in beneficial insect communities in agricultural systems.     

Utilization of UV‐A and UV‐C radiation in advanced oxidation processes with the intention of removing color and organic matter from the gross leachate of a stabilized sanitary landfill

The present work investigated color and biochemical oxygen demand (COD) removal from treated landfill leachate via advanced oxidative processes (AOPs) artificially emitted. The AOP H₂O₂/UV, TiO₂/UV, and photolysis were tested in two bench‐scale photoreactors: The first one with UV‐C lamp and the other with UV‐A lamp associated or not with coagulation / flocculation pretreatment. Crude leachate samples with pH ranging from 8 to 3 were used, and time varied in 30, 45, and 60 minutes. Experiments were performed in two stages: step 1 with a 20 mL volume from each sample and step 2 with repetition of the best results from the previous step, adopting the 150 mL volume. In step 1, the AOP applied in the crude leachate sample showed the best results, standing out H₂O₂/UV‐C with 30 minutes and TiO₂/UV‐A with 60 minutes. In step 2, H₂O₂/UV‐C had a 60% color removal and 25% COD reduction, while TiO₂/UV‐A had a 10% color removal and 20% COD reduction. Therefore, the H₂O₂/UV‐C process was the most efficient, because the complex characteristics of the effluent interfered in the TiO₂/UV‐A efficiency, but it is necessary to eliminate the process interferences. The use of artificial radiation is a viable alternative; however, it can be costly, being relevant in the associations between processes with artificial UV and solar UV, as the natural radiation becomes more attractive and allows the process operating costs reduction.     

Organochlorine pesticides and polychlorinated biphenyl congeners in lanner Falco biarmicus feldeggli Schlegel chicks and lanner prey in Sicily, Italy

This paper reports on research conducted to elucidate the risk posed to the Sicilian population of the endangered lanner falcon Falco biarmicus feldeggii Schlegel by organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs), as part of a wider study on contaminant risk to the lanner. Seventeen lanner nest sites were studied in northern and central Sicily. Sampling (in 2005) and analysis were carried out for selected OC pesticides and PCB congeners in lanner chick blood (15 chicks from 6 nest sites) and in two of the main lanner prey species, magpie Pica pica (36 individuals from 6 lanner nest sites) and rock dove Columba livia (10 individuals from 2 lanner nest sites). No OC and PCB residues were found in lanner chick blood above the detection limits, except for one solitary congener PCB153 (21.8 ng g(-1) wet weight), suggesting that these contaminants do not pose a significant risk to lanner chicks in the study area. Magpie and dove appeared mostly free of contamination with OC pesticides, though contamination levels were significantly higher in magpie than in dove. The presence of exceptional DDE and HEOD values in approximately 8% of the P. pica sample, and one P. pica sample showing recent DDT contamination, may indicate a local OC pesticide hazard to some lanner. Future research to further elucidate the contaminant risk to lanner in Sicily is suggested.     

Long-term effects of mercury in a salt marsh: hysteresis in the distribution of vegetation following recovery from contamination

During four decades, the Ria de Aveiro was subjected to the loading of mercury from a chlor-alkali industry, resulting in the deposition of several tons of mercury in the sediments. The present study evaluates the impact of this disturbance and the recovery processes, temporally and spatially, by means of examining the richness of the species of salt marsh plants and mercury concentrations in sediments over the last fifty years. The temporal assessment showed that the mercury loading induced a shift in the species composition of the salt marsh from a non-disturbed salt marsh with higher species richness to an alternative state dominated by Phragmites australis. The horizontal assessment, through a mercury gradient, presents the same trend, indicating that P. australis is the species most tolerant to higher mercury concentrations, comparative to Halimione portulacoides, Arthrocnemum fruticosum, Triglochin maritima, Juncus maritimus and Scirpus maritimus. After the reduction of mercury discharges in 1994, the salt marsh shows a slowly return path recovery response. The hysteresis in the response results in the temporal gap between the reduction in mercury concentrations in the sediment and the salt marsh species richness response, comparatively to the existing diversity in the local reference marsh.