Seasonal, spatial and inter-annual variations of trace metals in mussels from the Adriatic sea: a regional gradient for arsenic and implications for monitoring the impact of off-shore activities

Mussels are widely used as bioindicator organisms for monitoring chemical pollutants including trace metals. These elements are natural constituents in the marine environment and their basal concentrations in the organisms can be influenced by several environmental and biological factors. The aim of this work was to extend our knowledge on the natural variability of trace metals in mussels tissues, focusing on seasonal and inter-annual fluctuations in a coastal reference site of the Adriatic coast (Portonovo); a total of 39 samplings were performed during 5 years, providing an extended data-set for tissue levels of As, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, V and Zn. Concentrations of trace metals in mussels tissues revealed marked seasonal fluctuations with significant differences between various sampling years. Such fluctuations appeared mostly related to phytoplanctonic blooms and especially to reproductive cycle which exhibited a certain inter-annual shift of the gametogenesis period. Lower concentrations were measured in summer months for the majority of elements while a different seasonal cycle was observed for arsenic, not correlated with gonadic development, neither with other elements. Chemical speciation of arsenic was characterized to distinguish compounds of natural origin from those potentially reflecting an anthropogenic impact. Arsenobetaine and arsenocholine were always the predominant forms (up to 85% of total arsenic), while a significant increase of dimethylarsine and trimethylarsine oxide in spring (24% of total arsenic) might reflect the effect of phytoplanctonic bloom on both geochemistry and trophic transfer of this element. A significant inter-annual variability was observed for both the seasonal cycle and the range of values measured for all the elements, with particularly marked differences for arsenic, ranging from less than 10 to more than 40 microg/g in summer periods of different years. Data obtained on reference mussels were used to assess the impact of 41 off-shore platforms distributed along 5 nautical districts in the Northern and Central Adriatic Sea. Organisms sampled on these structures from 2001 to 2005 exhibited a certain enrichment of cadmium and zinc, probably associated to the use of anodic electrodes. Marked annual and geographical variations were measured for concentrations of arsenic in mussels of different platforms. However, the comparison with results of Portonovo, allowed to exclude the anthropogenic impact of exploitation activities and revealed a natural regional gradient of arsenic levels in mussels tissues associated to the changing influence of the Po river runoff on seawater salinity. In particular the higher concentrations measured in organisms sampled from platforms in the Central compared to Northern Adriatic confirmed a significant relationship between salinity and arsenic bioaccumulation, consistent with a role of arsenobetaine as an acquired osmolyte for mussels. The overall results confirmed the importance of natural variability when assessing the potential impact of anthropogenic activities.     

Species-dependent chromium accumulation, lipid peroxidation, and glutathione levels in germinating kiwifruit pollen under Cr(III) and Cr(VI) stress

The accumulation of chromium by germinating kiwifruit pollen appears to be significantly affected by Cr species, Cr concentration and calcium availability. Cr(III) accumulation always occurred in a linear manner while Cr(VI) uptake followed a logarithmic model. In the absence of exogenous calcium, Cr(III) accumulation was much higher than that of Cr(VI). It was observed that, as the Cr(III) concentration increased, there was a significant decrease in the endogenous calcium content of pollen, ultimately leading to complete calcium depletion after 90 min of incubation at 150 microM Cr(III). This loss of calcium could be responsible for the strong inhibition of tube emergence and growth following exposure of pollen to Cr(III). Indeed, when exogenous calcium was added to the kiwifruit pollen culture medium, significant growth recovery and reduced Cr(III) uptake occurred; the opposite was true in Cr(VI)-treatments. A significant rise in lipid peroxide production occurs in the presence of both Cr species; the effect was more pronounced following Cr(VI) exposure. Finally, glutathione pool dynamics appears to be differentially affected by chromium species and concentrations. In conclusion, results of the present study have provided important information regarding the different activity profiles of Cr(III) and Cr(VI) in relation to kiwifruit pollen performance, and have also demonstrated differences in some biochemical responses of pollen to metal stress.     

Soil vapor extraction in sandy soils: influence of airflow rate

Airflow rate is one of the most important parameters for the soil vapor extraction of contaminated sites, due to its direct influence on the mass transfer occurring during the remediation process. This work reports the study of airflow rate influence on soil vapor extractions, performed in sandy soils contaminated with benzene, toluene, ethylbenzene, xylene, trichloroethylene and perchloroethylene. The objectives were: (i) to analyze the influence of airflow rate on the process; (ii) to develop a methodology to predict the remediation time and the remediation efficiency; and (iii) to select the most efficient airflow rate. For dry sandy soils with negligible contents of clay and natural organic matter, containing the contaminants previously cited, it was concluded that: (i) if equilibrium between the pollutants and the different phases present in the soil matrix was reached and if slow diffusion effects did not occur, higher airflow rates exhibited the fastest remediations, (ii) it was possible to predict the remediation time and the efficiency of remediation with errors below 14%; and (iii) the most efficient remediation were reached with airflow rates below 1.2 cm(3)s(-1) standard temperature and pressure conditions.     

Application of manure and compost to contaminated soils and its effect on zinc accumulation by Solanum nigrum inoculated with arbuscular mycorrhizal fungi

Zn accumulation in Solanum nigrum grown in naturally contaminated soil in the presence of different types of organic amendments was assessed. Under the same conditions, the response of the plant to inoculation with two different isolates of arbuscular mycorrhizal fungi (AMF) (Glomus claroideum and Glomus intraradices) was also evaluated. S. nigrum grown in the non-amended soil always presented higher Zn accumulation in the tissues, with the addition of amendments inducing reductions of up to 80 and 40%, for manure and compost, respectively, and enhancing plant biomass yields. The establishment of S. nigrum in the Zn contaminated soil combined with the application of amendments led to a 70-80% reduction in the amount of Zn leached through the soil. The use of S. nigrum in combination with manure appeared as an effective method for reducing the effects of soil contamination, diminishing Zn transfer to other environmental compartments via percolation.     

Airborne ammonia and ammonium within the Northern Adriatic area, Croatia

Determination of airborne ammonia started in the early 1980s, as a part of air pollution monitoring of industrial plants. Due to high emissions, the city of Rijeka was one of the most polluted in Croatia in the mid-1980s. Considerable reductions in SO2 and NO(x) emissions led to lower airborne levels of these pollutants in the mid 1990s. In spite of the coke plant closure in 1994, there was only a weak decline in airborne ammonia over the period 1980--2005, with annual means in the range of 12-20 microg m(-3) at urban Site 1 and 6-28 microg m(-3) at suburban Site 2. Similar behaviour has been observed with ammonium in bulk rainwater samples since 1996. Higher and approximately equal deposition of nitrogen as ammonium (N-NH4+) were obtained for the urban Site 1 and the mountainous Site 4, but with different causative facts. Ammonium's contribution to total nitrogen (NO3(-)+NH4+) deposition is approximately two thirds, even for a remote Site 3.     

Chronic copper exposure and fatty acid composition of the amphipod Dikerogammarus villosus: results from a field study

Field study allows assessment of long-term effects on fatty acid (FA) composition of organisms under chronic exposure to metals. One expected effect of copper is peroxidation of lipids and essentially polyunsaturated fatty acids (PUFA). FA analysis was established for the amphipod Dikerogammarus villosus subjected to different degrees of copper exposure (4–40 μg Cu L⁻¹). A previous study in our team showed that this species regulates its body Cu concentration (106–135 mg Cu kg⁻¹ dry weight). Despite the high capacity of bioaccumulation, the absence of a correlation between copper concentration in D. villosus and water prevents its use as bioindicator of copper pollution. Both sexes from the most polluted site showed the lowest total FA content, but the highest PUFA percent, mainly of the long-chained variety (C20–C22). Mechanisms leading to the prevention of lipid peroxidation in this species were discussed (metallothioneins and intracellular granules) and proposed with support from literature data.     

Sub-tropical urban environment affecting content and composition of non-structural carbohydrates of Lolium multiflorum ssp. italicum cv. Lema

This study analyzed the relationship between environmental factors, especially air pollution and climatic conditions, and non-structural carbohydrates (NSC) in plants of Lolium multiflorum exposed during 10 consecutive periods of 28 days at a polluted site (Congonhas) and at a reference site in São Paulo city (Brazil). After exposure, NSC composition and leaf concentrations of Al, Fe, Cu, Zn, Pb and Cd were measured. The seasonal pattern of NSC accumulation was quite similar in both sites, but plants at Congonhas showed higher concentrations of these compounds, especially fructans of low and medium degree of polymerization. Regression analysis showed that NSC in plants growing at the polluted site were explained by variations on temperature and leaf concentration of Fe (positive effect), as well as relative humidity and particulate material (negative effect). NSC in the standardized grass culture, in addition to heavy metal accumulation, may indicate stressing conditions in a sub-tropical polluted environment.     

Multibiomarker approach in fish to assess the impact of pollution in a large Brazilian river, Paraiba do Sul

This article examines the advantages of the use of biomarkers as environmental indicators by applying it to Paraiba do Sul watershed, one of the most important Brazilian water bodies, which is in a critical environmental situation. We use a multibiomarker approach in fish as an integrated strategy to assess the impact of pollution. It comprehends a general biomarker of fish health, the condition factor (CF), and specific biomarkers of contaminant exposure such as metallothionein (MT), acetylcholinesterase (AChE) activity and biliary polycyclic aromatic hydrocarbons (PAH) metabolites. Our results revealed different effects in the fish from diverse locations with varying degrees of pollution. Furthermore, fish located just upstream of the water-treatment plant of the metropolitan area of Rio de Janeiro has shown to be affected by metals. This study indicates the usefulness of integrating a set of biomarkers to define the effects of anthropogenic inputs in aquatic bodies under complex polluted situations.     

Kinetic studies of endosulfan photochemical degradations by ultraviolet light irradiation in aqueous medium

Kinetic studies of endosulfan photochemical degradation in controlled aqueous systems were carried out by ultraviolet light irradiation at lambda = 254 nm. The photolysis of (alpha + beta: 2 + 1) endosulfan, alpha-endosulfan and beta-endosulfan were first-order kinetics. The observed rate constants obtained from linear least-squares analysis of the data were 1 x 10(-4) s(-1); 1 x 10(-4) s(-1); and 2 x 10(-5) s(-1), respectively, and the calculated quantum yields (phi) were 1, 1 and 1.6, respectively. Preliminary differential pulse polarographic (DPP) analysis allowed to observe the possible endosulfan photochemical degradation pathway. This degradation route involves the formation of the endosulfan diol, its transformation to endosulfan ether and finally the ether's complete degradation by observing the potential shifts.     

Cyanide generation during preservation of chlorinated wastewater effluent samples for total cyanide analysis.

Dechlorinating agents and pH adjustment are often used to preserve wastewater samples for cyanide analysis. The effects of four approved preservation protocols on the results of the total cyanide analysis of effluents from four water reclamation plants were examined. The results differed widely, and a clear pattern emerged. Immediate analysis without pH adjustment generally gave total cyanide concentrations below the reporting limit of 5 microg/L, irrespective of the dechlorinating agents used. When the pH was adjusted to > or =12, a slight increase in the measured total cyanide concentration was observed when thiosulfate was used to dechlorinate the samples, and a significant increase (>10 microg/L) was observed when arsenite was used as the dechlorinating agent. These results provide evidence that approved preservation protocols may give rise to cyanide formation in chlorinated wastewater effluent matrices.