Mobility of heavy metals from polluted sediments of a semi-enclosed basin: in situ benthic chamber experiments in Taranto’s Mar Piccolo (Ionian Sea,Southern Italy)

In situ benthic flux experiments were conducted at two stations in the Mar Piccolo of Taranto (Italy), one of the most industrialised and contaminated coastal areas of the Mediterranean. Sediments of the two stations are notably different in their trace metal content, with a station closer to a Navy harbour showing higher mean concentrations of almost all investigated metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn). Conversely, both stations are characterised by significant Hg contamination, compared to the local baseline. Results of a sequential extraction scheme on surface sediments suggest a relatively scarce mobility of the examined metals (Zn > Ni > Cr > As > Cu > Pb). A Hg-specific extraction procedure showed that most of the element (93.1 %) occurs in a fraction comprising Hg bound to Fe/Mn oxi-hydroxides. Reduction of these oxides may affect Hg remobilisation and redistribution. Porewater profiles of dissolved trace metals were quite similar in the two sites, although significant differences could be observed for Al, Cu, Fe and Hg. The highest diffusive fluxes were observed for As, Fe and Mn. Mobility rates of several trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) were directly measured at the sediment–water interface. Results from benthic in situ incubation experiments showed increasing dissolved metal concentrations with time, resulting in higher fluxes for Cu, Fe, Hg, V and Zn in the most contaminated site. Conversely, fluxes of Mn, Ni and Pb were comparable between the two stations. The estimated flux of Hg (97 μg m^?2 day^?1) was the highest observed among similar experiments conducted in other highly contaminated Mediterranean coastal environments. Benthic fluxes could be partially explained by considering rates of organic matter remineralisation, dissolution of Fe/Mn oxy-hydroxides and metal speciation in sediments. Seasonal and spatial variation of biogeochemical parameters can influence metal remobilisation in the Mar Piccolo area. In particular, metals could be promptly remobilised as a consequence of oxygen depletion, posing a serious concern for the widespread fishing and mussel farming activities in the area.     

A context-intensive approach to imputation of missing values in data sets from networks of environmental monitors

Although networks of environmental monitors are constantly improving through advances in technology and management, instances of missing data still occur. Many methods of imputing values for missing data are available, but they are often difficult to use or produce unsatisfactory results. I-Bot (short for “Imputation Robot”) is a context-intensive approach to the imputation of missing data in data sets from networks of environmental monitors. I-Bot is easy to use and routinely produces imputed values that are highly reliable. I-Bot is described and demonstrated using more than 10 years of California data for daily maximum 8-hr ozone, 24-hr PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm), mid-day average surface temperature, and mid-day average wind speed. I-Bot performance is evaluated by imputing values for observed data as if they were missing, and then comparing the imputed values with the observed values. In many cases, I-Bot is able to impute values for long periods with missing data, such as a week, a month, a year, or even longer. Qualitative visual methods and standard quantitative metrics demonstrate the effectiveness of the I-Bot methodology.Implications: Many resources are expended every year to analyze and interpret data sets from networks of environmental monitors. A large fraction of those resources is used to cope with difficulties due to the presence of missing data. The I-Bot method of imputing values for such missing data may help convert incomplete data sets into virtually complete data sets that facilitate the analysis and reliable interpretation of vital environmental data.     

Influence of natural events on the concentration and composition of atmospheric particulate matter

A ten-month field study aimed to determine the contribution of natural events (i.e. sea-salt and mineral dust events) to urban PM concentration was carried out at six sampling sites in Central Italy (Lazio region). Four indicators have been used to identify natural events during the period of the study. The first one is constituted by the ratio between number of particles in the coarse to the accumulation mode. It is simple, cheap, and the information are given in quasi-real time, but the nature of the event (sea-salt or mineral dust) is not detectable. The second indicator relies on the chemical analysis of the collected PM by X-ray fluorescence (XRF) and allows a robust identification of sea-salt and crustal components. The third one is based on diagnostic ratios of elemental fractions: Mg_extractable/Ti_residue for sea-salt and Ti_residue/Sb_residue for mineral dust. It requires skilled staff but it is most accurate and sensible. The last indicator, constructed on the basis of natural radioactivity data, is not diagnostic for the nature of the event but it is able to estimate the increase in PM concentration with respect to the expected concentration in the absence of natural events.The relevance of natural events and the variations in PM concentration and composition during the study are discussed. The joined use of the four indicators allowed the identification of about 20 natural PM episodes. In general, sea-salt aerosol events did not cause exceedance of the daily EU limit value for PM₁₀. Saharan dust events, instead, were in most cases responsible for the exceedance of the limit value at all stations.     

Selection and application of a rainbow trout toxicity testing procedure for screening Sacramento River Watershed, California samples

A number of procedures have been developed to assess toxic effects on the early life stages of salmonid fish. In this study 13 rainbow trout embryo development relatively short-term (7 to 90 day) procedures were reviewed. Three 7-day methods from the published literature and three modifications developed at AQUA-Science (A-S) were evaluated in the laboratory. Based on that evaluation, A-S methods were selected for screening surface water samples (A-S 1) collected in the Sacramento River watershed (California) and for conducting toxicity identification evaluations (TIE) to identify cause(s) of toxicity. Test control performance, test sensitivity, and reference toxicant response variability in the A-S 1 were superior to those in commonly used freshwater toxicity testing methods. The incidence of Sacramento River watershed samples resulting in a notable decrease in embryo development was very low. Of 260 samples screened only 16 (6%) resulted in statistically significant inhibition of embryo development. Of the 16 toxic samples, nine caused minimal (less than 20% abnormal development) and four marginal (less than 30%) toxicity. Samples collected from the agriculture-dominated Colusa Basin Drain and rangeland/forest-dominated Battle Creek on June 16, 2005 caused significant toxicity. TIE procedures indicated that cationic chemicals were the primary cause of toxicity. Metals analysis did not reveal concentrations sufficient to inhibit embryo development, so the most probable cause of toxicity in the two samples was cationic chemicals (perhaps surfactants?) or metals that were not included in the analytical screening.     

Lettuce plants as bioaccumulators of trace elements in a community of central Italy

A survey, based on the use of vascular plants to describe the distribution of selected elements (21 in total) was performed in 11 sites in the area of Castelfiorentino (Tuscany, Central Italy) differing for land use, from urban to industrial and rural areas. Lettuce plants grown under standardized conditions were positively used as biodeposimeters of airborne trace elements. Washing was found to be highly significant in reducing concentrations of many elements in the samples, suggesting a general surface contamination of leaves. The typical crustal element Al showed good correlations with Co, Fe, Li and V; on the contrary, Zn and Cd were intercorrelated and showed no connection with crustal indicators. Lead was still a relevant environmental presence, as the experiments were carried out before the ban of leaded gasoline. Source apportionment by factor analysis put in evidence a major contribution of crustal materials, followed by man-related activities; a minor role was ascertained for marine aerosol. A comparison was made between analytical data of lettuce plants grown in our experimental sites and a bulk of commercial lettuce purchased at a local supermarket. It should be stressed how Cu concentrations of commercial material were significantly higher than those found in our plants; this is likely caused by phytosanitary treatments.     

POPs in the Lagoon of Venice: budgets and pathways

Dioxins and furans (PCDD/Fs), polychlorobiphenyls (PCBs) and hexachlorobenzene (HCB) in the ecosystem of the Lagoon of Venice were studied, in order to provide a general picture of conditions in the lagoon in terms of contamination by persistent organic pollutants (POPs). We present here novel data on atmospheric deposition, water, sediment and clam samples collected in the lagoon during the period January 2001-December 2004. Atmospheric deposition was sampled monthly at six sites located both close and far from large industrial and urban sources. Water samples were collected monthly from fifteen stations, and twenty-five samples of sediments and clams (Tapes philippinarum) were collected in four areas where clams are farmed and harvested inside the lagoon. All samples were analysed for PCDD/Fs, PCBs and HCB by HRGC/HRMS in the same laboratory. All samples examined (atmospheric deposition and water) substantially confirmed the spatial pattern reported in previously published data on sediments and atmospheric deposition: the zone surrounding the Porto Marghera petrochemical plant always had the highest levels of POPs (i.e., PCDD/Fs: atmosphere approximately 6 pg of 2,3,7,8-TCDD equivalents (I-TE) m(-2)d(-1); water 0.37 pg I-TEl(-1); sediment: 300 ng kg(-1); clam 2.8 pg I-TE g(-1)), and the minima were found at points on the margins of the lagoon (PCDD/Fs: atmosphere approximately 1 pg I-TEm(-2)d(-1); water 0.05 pg I-TEl(-1); sediment: approximately 5 ng kg(-1); clam approximately 0.2 pg I-TE g(-1)). Intermediate values were often encountered in the historical city centre of Venice and in the central part of the lagoon. To confirm this, new data on correlation between levels of PCDD/F in sediments and clams are reported, both for absolute values and for the PCDD/F "fingerprint". There is always a clear fingerprinting signature (PCDF/PCDD>1) for samples collected near Porto Marghera, and the opposite (PCDF/PCDD<1) in the rest of the lagoon.     

Degradation of the herbicide dichlobenil and its metabolite BAM in soils and subsurface sediments

The worldwide used herbicide dichlobenil (2,6-dichlorobenzonitrile) has resulted in widespread presence of its metabolite 2,6-dichlorobenzamide (BAM) in surface water and groundwater. To evaluate the potential for natural attenuation of this BAM pollution in groundwater, we studied the degradation of BAM and dichlobenil in 16 samples of clayey till, unconsolidated sand and limestone, including sediments from both oxidized and reduced conditions. The degradation of dichlobenil occurred primarily in the upper few meters below surface, although dichlobenil was strongly sorbed to these sediments. However, the degradation of dichlobenil to BAM could not be correlated to either sorption, water chemistry, composition of soils or sediments. Degradation of dichlobenil to BAM was limited (<2% degraded) in the deeper unsaturated zones, and no degradation was observed in aquifer sediments. This illustrates, that dichlobenil transported to aquifers does not contribute to the BAM-contamination in aquifers. A small, but significant degradation of BAM was observed in the upper part of the unsaturated zones in sandy sediments, but no degradation was observed in the clayey till sediment or in the deeper unsaturated zones. The insignificant degradation of BAM in aquifer systems shows that BAM pollution detected in aquifers will appear for a long time; and consequently the potential for natural attenuation of BAM in aquifer systems is limited.