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).     

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.     

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.     

A new typology for Portuguese beaches: An exploratory study

Beaches are now the most popular tourist destination and increased demand in the past 40 years has led not only to beach congestion but also to a differentiation between urban (resorts, overcrowded and under huge pressure), to natural (less crowded beaches). This diversity needs to be further explored not only to characterize individual beaches in a precise way, but also to understand the distinctive characteristics responsible for options made by beach users. Some attempts have been made to create a universal beach typology but sparse research has been undertaken. The topic is of extreme importance for beach management, as most studies only take into consideration beach usage type and few consider the surrounding environment (landscape). This paper presents an exploratory work for Portuguese beaches which creates a new classification, according to usage and surrounding environment, based on several variables, measured and weighted. The results scale between zero and five and assess how a beach can be classified along an urban (0) to natural (5) spectrum. Variables studied include population density, number of hotels urban density, car park distance to the beach, etc. A pilot study applied to 100 beaches in the Lisbon Metropolitan Area, found that a densely populated region, can also contain beaches with natural characteristics.     

Dividivi tannins: an ecological product for water-based drilling fluids

Modified tannins are used as deflocculant additives in the formulation of water-based drilling fluids (WBDF) for drilling operations in any scenario. Due to their high heavy metals content, these additives are toxic and hazardous for any environmental scenario. Deflocculant efficiency of unmodified tannins (UDT) extracted from fruit pods of “dividivi” (Caesalpinia coriaria) as an additive for WBDF was assessed. Raw materials for UDT elaboration come from the rural and sustainable exploitation of natural occurring dividivi trees, growing in dry tropical forests in Anzoátegui state (Orinoco Oil Belt, eastern Venezuela). The tannins extract, in the form of dividivi fruit powder, contains 47.0 % of total tannins (hydrolyzable tannins plus condensed tannins), of which 67.4 % corresponds to hydrolyzable tannins. Dividivi tannins in WBDF showed nine (9) times deflocculant efficiency than heavy metals commercial modified tannins. Moreover, commercial modified tannins do not improve their deflocculant efficiency with increased tannin content. Ecotoxicological studies were carried out for WBDF formulations with UDT, using freshwater microalgae Scenedesmus dimorphus as chronic toxicity bioindicator. Toxicity bioassays performed with these microalgae did not show significant effects on its population growth. The EC₅₀ values resulted in over 100,000 mg L^?1, and these formulations were therefore considered non-toxic. Values of LC₅₀ obtained this time with Poecilia reticulata, as acute toxicity bioindicator are around 100,000 mg L^?1, with no significant effects on population mortality. Thus, WBDF formulated with UDT can be considered non-toxic formulations for populations of this freshwater fish. From the social perspective, the use of UDT in WBDF fosters organized communities economical activities based on the maintenance of a sustainable supply chain for processing fruits in a quantity enough to obtain three thousand seven hundred fifty kilograms (3750 Kg). The UDT so obtained was used as deflocculant in four (4) oil wells producing excellent performance and relevant savings compared with commercial modified tannin.     

Photochemical generation of reactive intermediates from urban-waste bio-organic substances under UV and solar irradiation

Singlet oxygen (¹O₂), hydroxyl radicals (^•OH), and excited triplet states of organic matter (³OM^*) play a key role in the degradation of pollutants in aquatic environments. The formation rates and quantum yields (Φ) of these reactive intermediates (RI) through photosensitized reactions of dissolved organic matter (DOM) have been reported in the literature for decades. Urban biowaste-derived substances (UW-BOS), a form of organic matter derived from vegetative and urban waste, have recently been shown to be efficient sensitizers in the photo-degradation of different contaminants. Nevertheless, no quantitative measurements of photo-oxidant generation by UW-BOS have been reported. In this study, the formation quantum yields of ¹O₂ and ^•OH, as well as quantum yield coefficients of TMP degradation (indicative of ³OM^* formation), were quantified for two UW-BOS samples, under 254-nm UV radiation or simulated sunlight and compared to a DOM standard from the Suwanee River (SRNOM). Values of Φ for UW-BOS samples ranged from Φ(+¹O₂) = 8.0 to 8.8 × 10⁻³, Φ(+^•OH) = 4.1 to 4.3 × 10⁻⁶, and f _TMP = 1.22 to 1.23 × 10² L Einstein⁻¹ under simulated sunlight and from Φ(+¹O₂) = 1.4 to 2.3 × 10⁻², Φ(+^•OH) = 1.3 to 3.5 × 10⁻³, and f _TMP = 3.3 to 3.9 × 10² L Einstein⁻¹ under UV. Although UW-BOS are not necessarily better than natural DOM regarding photosensitizing properties, they do sensitize the production of RI and could potentially be used in engineered treatment systems.

     

Oxidative stress status,antioxidant metabolism and polypeptide patterns in Juncus maritimus shoots exhibiting differential mercury burdens in Ria de Aveiro coastal lagoon (Portugal)

This study assessed the oxidative stress status, antioxidant metabolism and polypeptide patterns in salt marsh macrophyte Juncus maritimus shoots exhibiting differential mercury burdens in Ria de Aveiro coastal lagoon at reference and the sites with highest, moderate and the lowest mercury contamination. In order to achieve these goals, shoot-mercury burden and the responses of representative oxidative stress indices, and the components of both non-glutathione- and glutathione-based H₂O₂-metabolizing systems were analyzed and cross-talked with shoot-polypeptide patterns. Compared to the reference site, significant elevations in J. maritimus shoot mercury and the oxidative stress indices such as H₂O₂, lipid peroxidation, electrolyte leakage and reactive carbonyls were maximum at the site with highest followed by moderate and the lowest mercury contamination. Significantly elevated activity of non-glutathione-based H₂O₂-metabolizing enzymes such as ascorbate peroxidase and catalase accompanied the studied damage-endpoint responses, whereas the activity of glutathione-based H₂O₂-scavenging enzymes glutathione peroxidase and glutathione sulfo-transferase was inhibited. Concomitantly, significantly enhanced glutathione reductase activity and the contents of both reduced and oxidized glutathione were perceptible in high mercury-exhibiting shoots. It is inferred that high mercury-accrued elevations in oxidative stress indices were obvious, where non-glutathione-based H₂O₂-decomposing enzyme system was dominant over the glutathione-based H₂O₂-scavenging enzyme system. In particular, the glutathione-based H₂O₂-scavenging system failed to coordinate with elevated glutathione reductase which in turn resulted into increased pool of oxidized glutathione and the ratio of oxidized glutathione-to-reduced glutathione. The substantiation of the studied oxidative stress indices and antioxidant metabolism with approximately 53-kDa polypeptide warrants further studies.     

Diversity and characterization of culturable bacterial endophytes from Zea mays and their potential as plant growth-promoting agents in metal-degraded soils

In this study, we evaluated the phylogenetic diversity of culturable bacterial endophytes of Zea mays plants growing in an agricultural soil contaminated with Zn and Cd. Endophytic bacterial counts were determined in roots and shoots, and isolates were grouped by random amplified polymorphic DNA and identified by 16S ribosomal RNA (rRNA) gene sequencing. Endophytes were further characterized for the production of plant growth-promoting (PGP) substances, such as NH₃, siderophores, indol-3-acetic acid (IAA), hydrogen cyanide and extracellular enzymes, and for the capacity to solubilize phosphate. The endophytes producing higher amounts of IAA were screened for their tolerance to Zn and Cd and used as bioinoculants for maize seedlings grown in the Zn/Cd-contaminated soil. The counts of endophytes varied between plant tissues, being higher in roots (6.48 log₁₀ g^?1 fresh weight) when compared to shoots (5.77 log₁₀ g^?1 fresh weight). Phylogenetic analysis showed that endophytes belong to three major groups: α-Proteobacteria (31 %), γ-Proteobacteria (26 %) and Actinobacteria (26 %). Pseudomonas, Agrobacterium, Variovorax and Curtobacterium were among the most represented genera. Endophytes were well-adapted to high Zn/Cd concentrations (up to 300 mg Cd l^?1 and 1,000 mg Zn l^?1) and showed ability to produce several PGP traits. Strains Ochrobactrum haematophilum ZR 3-5, Acidovorax oryzae ZS 1-7, Frigoribacterium faeni ZS 3-5 and Pantoea allii ZS 3-6 increased root elongation and biomass of maize seedlings grown in soil contaminated with Cd and Zn. The endophytes isolated in this study have potential to be used in bioremediation/phytoremediation strategies.