Bioaccessibility of metals in soils: comparison between chemical extractions and in vitro tests

It is well-known that the total metal content in soils is not a good indicator of their harmful effects, leading to an overestimation of risks. Toxicological and environmental hazards depend on the chemical species and on its bioavailability to target organisms. Because a good estimation of bioavailability is difficult, a good compromise is to assess bioaccessibility, defined as the maximum amount of a pollutant which is potentially absorbable by a target organism. This study presents a comparison of different strategies to measure metal bioaccessibility in soils. Three procedures were applied to real soil samples with different levels of metal contamination: pseudo-total metal attack, selective sequential extractions and in vitro tests (deliberately developed to simulate human or mammals digestion). Considering the first step of the selective extraction procedure, which can provide the bioaccessible fraction for deposit-feeder organisms, data obtained for each metal were lower than those obtained from in vitro tests. Therefore, it is possible to highlight that this extraction tends to underestimate metal bioaccessibility in soils for humans, while in vitro tests certainly will overestimate bioaccessibility for organisms as invertebrates. If the sum of first and second step of sequential procedure is considered, results are quite similar to those obtained from in vitro tests, but this kind of procedure would require two days of work rather than a few hours required to perform an in vitro test. Results highlight the diversity among the differently defined bioaccessible fractions and the need to apply the most suitable procedure depending on the target organism.     

Geochemical fingerprints of “Prosecco” wine based on major and trace elements

The terroir can be defined as interactive ecosystem that includes climate, geology, soil and grapevine, and it is used to explain the hierarchy of high quality of wine. In order to understand the terroir functions, it is necessary to analyse the interactions among the geology, soil and wine. To define a geochemical fingerprint, the relationship between geochemistry of vineyard soil and chemical composition of wine from Veneto Italian Region was studied. The vineyards tested belonged to four distinct wineries located in the Veneto alluvial plain, included in the Controlled Designation of Origin (DOC) area of Prosecco. We investigated the relationship between major and trace elements in soil and their concentrations in Prosecco wine according to geographical origin. The detection of chemical composition in soil and wine were analysed by inductively coupled plasma mass spectrometry, and data were elaborated by nonparametric test and multivariate statistics Linear Discrimination Analysis. The geochemical and statistical analyses allowed to discriminate the vineyard soils according to geo-lithological characteristics of each area and to identify the geochemical “Prosecco” fingerprints, useful against fraudulent use of DOC wine labels.     

Concentrations of PAHs,and nitro- and methyl- derivatives associated with a size-segregated urban aerosol

Size-segregated atmospheric particles were collected in Rome, Italy, using a low-pressure impactor.Twelve sampling campaigns were conducted under different meteorological conditions over a whole year covering 155 not consecutive days. The samples were analyzed for polycyclic aromatic hydrocarbons (PAHs) and their nitro- and methyl- derivatives known for their toxicity. An assessment of the carcinogenic potency of the particles known to penetrate into lungs, liver, heart and nervous system was performed.The distribution of the classes of compounds was unimodal and centrated at 0.4 μm size fraction for PAHs and bimodal and centrated at 0.1 and 0.4 μm for methyl- and nitro- derivatives. The 18% of toxic organic compounds we analyzed was distributed into the ultrafine fraction (PM_0.1) and 76% in the fine fraction; but substituted PAH distribution in the ultrafine particles shifted toward higher values during warm periods. In July, the 50% of the total nitro-PAHs was found in PM_0.1 and an average of 42% of the total methyl-PAHs was found in the same fraction in summer and intermediate seasons.An evaluation of the potential toxicity of the measured compounds was tentatively assessed based on Potency Equivalency Factors (PEF).     

Spatial and seasonal variability of dissolved oxygen and nutrients in the Southern Adriatic coastal waters

The main objective of this paper is to present vertical and horizontal patterns of dissolved oxygen and nutrients found during four seasonal surveys (March, June, September and December 2000) in the Southern Adriatic Sea coastal waters. The multivariate technique Principal Component Analysis has been applied to our dataset considering the following parameters: seawater temperature, salinity, dissolved oxygen and nutrients (nitrate, nitrite, phosphate, silicate). The resulting plot shows in a self-explanatory way that a seasonal trend was not observable in the investigated period and that no significant differences occur between the stations sampled in the Taranto Gulf and those along the Adriatic coast. Water column stratification persists in all seasons, except in spring, in the shallowest stations. The surface layer is characterized by a low nutrient content. The influence of the Northern Adriatic Surface Water in the Southern Adriatic sub-basin seems to be very low and can be traced by nitrate and silicate only in spring and winter. Regarding deep waters, nitrate distribution shows an increasing gradient moving from the coast to the open sea, having the lowest concentration in the shelf area and the highest in the most offshore stations of the Otranto Strait. In the Otranto Strait area the vertical distributions of physical and chemical parameters show, at middle depths, the inflow of Levantine Intermediate Water, traced by both the maximum of salinity, nitrate and phosphate and the minimum of oxygen. The LIW signal is lost moving northward. The outflow of Adriatic Dense Water is less evident, being traced only in spring by an oxygen increase at the bottom layer in the shelf area. The N:P ratio is highly variable but in the range already observed in the Southern Adriatic, suggesting a P-limitation, which can both contribute to the low primary productivity of the area and support the N:P ratio anomaly of the Eastern Mediterranean.     

Spatial and seasonal variability of dissolved oxygen and nutrients in the Southern Adriatic coastal waters

The main objective of this paper is to present vertical and horizontal patterns of dissolved oxygen and nutrients found during four seasonal surveys (March, June, September and December 2000) in the Southern Adriatic Sea coastal waters. The multivariate technique Principal Component Analysis has been applied to our dataset considering the following parameters: seawater temperature, salinity, dissolved oxygen and nutrients (nitrate, nitrite, phosphate, silicate). The resulting plot shows in a self-explanatory way that a seasonal trend was not observable in the investigated period and that no significant differences occur between the stations sampled in the Taranto Gulf and those along the Adriatic coast. Water column stratification persists in all seasons, except in spring, in the shallowest stations. The surface layer is characterized by a low nutrient content. The influence of the Northern Adriatic Surface Water in the Southern Adriatic sub-basin seems to be very low and can be traced by nitrate and silicate only in spring and winter. Regarding deep waters, nitrate distribution shows an increasing gradient moving from the coast to the open sea, having the lowest concentration in the shelf area and the highest in the most offshore stations of the Otranto Strait. In the Otranto Strait area the vertical distributions of physical and chemical parameters show, at middle depths, the inflow of Levantine Intermediate Water, traced by both the maximum of salinity, nitrate and phosphate and the minimum of oxygen. The LIW signal is lost moving northward. The outflow of Adriatic Dense Water is less evident, being traced only in spring by an oxygen increase at the bottom layer in the shelf area. The N:P ratio is highly variable but in the range already observed in the Southern Adriatic, suggesting a P-limitation, which can both contribute to the low primary productivity of the area and support the N:P ratio anomaly of the Eastern Mediterranean.     

Environmental and human exposure assessment monitoring of communities near an abandoned mercury mine in the Philippines: a toxic legacy

Abandoned mines are an important global concern and continue to pose real or potential threats to human safety and health including environmental damage/s. Very few countries had government mine regulation and reclamation policies until the latter part of the century where legal, financial and technical procedures were required for existing mining operations. Major reasons for mine closure may be mainly due to poor economies of the commodity making mining unprofitable, technical difficulties and national security. If the mine is abandoned, more often than not it is the government that shoulders the burden of clean-up, monitoring and remediation. The topic of abandoned mines is complex because of the associated financial and legal liability implications. Abandoned mercury mines have been identified as one of the major concerns because of their significant long-term environmental problems. Primary mercury production is still ongoing in Spain, Kyrgzystan, China, Algeria, Russia and Slovakia while world production declined substantially in the late 1980s. In the Philippines, the mercury mine located southeast of Manila was in operation from 1955 to 1976, before ceasing operation because of the decline in world market price for the commodity. During this time, annual production of mercury was estimated to be about 140,000 kg of mercury yearly. Approximately 2,000,000 t of mine-waste calcines (retorted ore) were produced during mining and roughly 1,000,000 t of these calcines were dumped into nearby Honda Bay to construct a jetty to facilitate mine operations where about 2000 people reside in the nearby three barangays. In October, 1994 the Department of Health received a request from the Provincial Health Office for technical assistance relative to the investigation of increasing complaints of unusual symptoms (e.g. miscarriages, tooth loss, muscle weakness, paralysis, anemia, tremors, etc.) among residents of three barangays. Initial health reports revealed significant elevation of blood mercury levels exceeding the then recommended exposure level of 20ppb in 12 out of the 43 (27.9%) residents examined. The majority of the volunteers were former mine workers. In this study the abnormal findings included gingivitis, mercury lines, gum bleeding and pterydium. The most common neurologic complaints were numbness, weakness, tremors and incoordination. Anemia and elevated liver function tests were also seen in a majority of those examined. The assessment also revealed a probable association between blood mercury level and eosinophilia. The same association was also seen between high mercury levels and the presence of tremors and working in the mercury mine. To date, there are very limited environmental and health studies on the impact of both total and methylmercury that have been undertaken in the Philippines. Thus, this area of study was selected primarily because of its importance as an emerging issue in the country, especially regarding the combined effects of total and methylmercury low-dose and continuous uptake from environmental sources. At present the effects of total mercury exposure combined with MeHg consumption remain an important issue, especially those of low-dose and continuous uptake. Results of the study showed that four (4) species of fish, namely ibis, tabas, lapu-lapu and torsillo, had exceeded the recommended total mercury and methylmercury levels in fish (NV>0.5 microg/gf.w., NV>0.3 microg/gf.w., respectively). Saging and kanuping also exceeded the permissible levels for methylmercury. Total and methylmercury in canned fish, and total mercury in rice, ambient air and drinking water were within the recommended levels, however, additional mercury load from these sources may contribute to the over-all body burden of mercury among residents in the area. Surface water quality at the mining area, Honda Bay and during some monitoring periods at Palawan Bay exceeded total mercury standards (NV>0.002 ng/mL). Soil samples in two sites, namely Tagburos and Honda Bay, exceeded the EPA Region 9 Primary Remediation Goal recommended values for total mercury for residential purposes (NV>23 mg/kg). The hand to mouth activity among infants and children is another significant route for mercury exposure. Statistically significant results were obtained for infants when comparing the results after one year of monitoring for methylmercury levels in hair for both exposed and control sub-groups. Likewise, comparing the initial and final hair methylmercury levels among pregnant women/mothers in the exposed group showed statistically significant (p<0.05) results. Comparing the exposed and control sub-groups' mercury hair levels per sub-group showed statistically significant results among the following: (a) initial and final total mercury hair levels among children, (b) initial and final methylmercury hair levels among children, (c) final total mercury hair levels among pregnant women, (d) initial and final total mercury hair levels among mothers, and (e) initial and final methyl hair levels among mothers.     

Organochlorine contaminants in albatrosses and petrels during migration in South Atlantic Ocean

Albatrosses and petrels (Procellariiformes) are migratory oceanic birds of considerable conservational interest. Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed in the subcutaneous fat, liver and muscle of 100 birds belonging to eight species of Procellariiformes collected during their migration period in southern Brazil, one of the most important feeding areas for these species. Although the profiles of PCBs and OCPs were similar among the individuals, with predominance of penta, hexa and heptachlorobiphenyls and p′p-DDE, organochlorine concentrations exhibited a high degree of intra-species variability. The influence of body condition during the migration period in the distribution of organochlorine contaminants was also evaluated, showing that it is a significant factor in the variation and redistribution of these compounds in the tissues of these birds. The intense use of lipid reserves associated to the contamination from organochlorine compounds could be a troubling factor for seabirds with extended breeding periods and that spend most of their lives at sea migrating long distances, such as most of Procellariiformes. Studies on contamination are necessary to improve the knowledge of the threats to these birds and their populations as well as to contribute with information about persistent organic pollutants in the South Atlantic marine environment.