Heavy Metals in Soil and Salad in the Proximity of Historical Ferroalloy Emission

Emissions of manganese (Mn), lead (Pb), iron (Fe), zinc (Zn), copper (Cu) from ferro-alloy operations has taken place in Valcamonica, a pre-Alp valley in the province of Brescia, Italy, for about a century until 2001. Metal concentrations were measured in the soil of local home gardens and in the cultivated vegetables. Soil analysis was carried out using a portable X-Ray Fluorescence (XRF) spectrometer in both surface soil and at 10 cm depth. A subset of soil samples (n = 23) additionally was analysed using the modified BCR sequential extraction method and ICP-OES for intercalibration with XRF (XRF Mn = 1.33 * total OES Mn – 71.8;R = 0.830, p Lactuca sativa and Chichorium spp.) were analyzed with a Total Reflection X-Ray Fluorescence (TXRF) technique. Vegetable and soil metal measurements were performed in 59 home gardens of Valcamonica, and compared with 23 gardens from the Garda Lake reference area. Results indicate significantly higher levels of soil Mn (median 986 ppm vs 416 ppm), Pb (median 46.1 ppm vs 30.2 ppm), Fe (median 19,800 ppm vs 13,100 ppm) in the Valcamonica compared to the reference area. Surface soil levels of all metals were significantly higher in surface soil compared to deeper soil, consistent with atmospheric deposition. Significantly higher levels of metals were shown also in lettuce from Valcamonica for Mn (median 53.6 ppm vs 30.2) and Fe (median 153 vs 118). Metals in Chichorium spp. did not differ between the two areas. Surface soil metal levels declined with increasing distance from the closest ferroalloy plant, consistent with plant emissions as the source of elevated soil metal levels. A correlation between Mn concentrations in soil and lettuce was also observed. These data show that historic ferroalloy plant activity, which ended nearly a decade before this study, has contributed to the persistence of increased Mn levels in locally grown vegetables. Further research is needed to assess whether this increase can lead to adverse effects in humans and plants especially for Mn, an essential element that can be toxic in humans when exceeding the homeostatic ranges.

Simulating the fate of indigenous antibiotic resistant bacteria in a mild slope wastewater polluted stream

The fate of indigenous surface-water and wastewater antibiotic resistant bacteria in a mild slope stream simulated through a hydraulic channel was investigated in outdoor experiments.The effect of（i） natural（dark） decay,（ii） sunlight,（iii） cloudy cover,（iv） adsorption to the sediment,（v） hydraulic conditions,（vi） discharge of urban wastewater treatment plant（UWTP）effluent and（vii） bacterial species（presumptive Escherichia coli and enterococci） was evaluated.Half-life time（T1/2） of E. coli under sunlight was in the range 6.48–27.7 min（initial bacterial concentration of 10^5 CFU/mL） depending on hydraulic and sunlight conditions. E. coli inactivation was quite similar in sunny and cloudy day experiments in the early 2 hr, despite of the light intensity gradient was in the range of 15–59 W/m^2; but subsequently the inactivation rate decreased in the cloudy day experiment（T1/2= 23.0 min） compared to sunny day（T1/2= 17.4 min）. The adsorption of bacterial cells to the sediment（biofilm） increased in the first hour and then was quite stable for the remaining experimental time. Finally, when the discharge of an UWTP effluent in the stream was simulated, the proportion of indigenous antibiotic resistant E. coli and enterococci was found to increase as the exposure time increased, thus showing a higher resistance to solar inactivation compared to the respective total populations.