PCDD/Fs atmospheric deposition fluxes and soil contamination close to a municipal solid waste incinerator

Bulk depositions and surface soil were collected in a suburban area, near the Adriatic Sea, in order to assess the contribution of a municipal solid waste incinerator to the area’s total contamination with polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDDs and PCDFs). Samples were collected at two sites, situated in the area most affected by plant emissions (according to the results of the Calpuff air dispersion model), and at an external site, considered as a reference. Results show that the studied area is subject to low contamination, as far as these compounds are concerned. Deposition fluxes range from 14.3 pg m⁻² d⁻¹ to 89.9 pg m⁻² d⁻¹ (0.75 pg-TEQ m⁻² d⁻¹ to 3.73 pg-TEQ m⁻² d⁻¹) and no significant flow differences are observed among the three monitored sites. Total soil concentration amounts to 93.8 ng kg⁻¹ d.w. and 1.35 ng-TEQ kg⁻¹ d.w, on average, and confirms a strong homogeneity in the studied area. Furthermore, from 2006 to 2009, no PCDD/Fs enrichment in the soil was noticed. Comparing the relative congener distributions in environmental samples with those found in stack emissions from the incineration plant, significant differences are observed in the PCDD:PCDF ratio and in the contribution of the most chlorinated congeners. From this study we can conclude that the incineration plant is not the main source of PCDD/Fs in the studied area, which is apparently characterized by a homogeneous and widespread contamination situation, typical of an urban area.     

Phyt'Eaux Cités: application and validation of a programme to reduce surface water contamination with urban pesticides

This paper presents first results of Phyt’Eaux Cités, a program put in place by the local water supply agency, the SEDIF (Syndicat des Eaux d’Ile-de-France), in collaboration with 73 local authorities, private societies and institutional offices (365 km²). The challenges included: measurement of the previous surface water contamination, control of urban pesticide applications, prevention of pesticide hazard on users and finally a overall reduction of surface water contamination. An inquiry on urban total pesticide amount was coupled with a surface water bi-weekly monitoring to establish the impact of more than 200 molecules upon the Orge River. For 2007, at least 4400 kg and 92 type of pesticides (essentially herbicides) were quantified for all urban users in the Phyt’Eaux Cités perimeter. At the outlet of the Orge River (bi-weekly sampling in 2007), 11 molecules were always detected above 0.1 μg L⁻¹. They displayed the mainly urban origin of pesticide surface water contamination. Amitrole, AMPA (Aminomethyl Phosphonic Acid), demethyldiuron, diuron, glyphosate and atrazine were quantified with a 100% of frequency in 2007 and 2008 at the Orge River outlet. During the year, peaks of contamination were also registered for MCCP, 2,4 MCPA, 2,4 D, triclopyr, dichlorprop, diflufènican, active substances used in large amount in the urban area. However, some other urban molecules, such as isoxaben or flazasulfuron, were detected with low frequency. During late spring and summer, contamination patterns and load were dominated by glyphosate, amitrole and diuron, essentially applied by cities and urban users. Both isoproturon and chlortoluron were quantified during autumn and winter months according to upstream agricultural practices. In conclusion, 3 years after the beginning of this programme, the cities reduced the use of 68% of the total pesticide amount. An improvement on surface water quality was found from 2008 and during 2009 for all pesticides. In particular, glyphosate showed a decrease of the load above 60% in 2008, partly related to the Phyt’Eaux Cités action.     

Residues behavior of some fungicides applied on two greenhouse tomato varieties different in shape and weight

The degradation of 12 fungicides (azoxystrobin, cymoxanil, cyproconazole, cyprodinil, fenarimol, fludioxonil, iprovalicarb, mepanipyrim, penconazole, pyrimethanil, tolclofos-methyl, triadimenol), commonly used in pest management strategies on Sardinian greenhouse tomato crops was studied. A different residue behaviour was observed between the studied cultivar. On the smaller, a “cherry” type tomato, field data showed an initial residue mostly higher than the “beefsteak” tomato. In any case, except for penconazole, all pesticide residues were below their maximum residue levels (MRLs) reaching the pre-harvest interval (PHI). On both cultivar, triadimenol and cymoxanil residues completely disappeared reaching their PHI, while iprovalicarb, fenarimol, and fludioxonil disappeared in a time of 17 to 24 days. On the contrary, azoxystrobin, cyproconazole, cyprodinil, penconazole, tolclofos-methyl, mepanipyrim, and pyrimethanil showed a long persistence on both tested cultivar and may have residual problems due to an accumulation effect if repeated field treatments will be performed. The first group of molecules according to their rapid degradation could be used in low pesticide-input management in order to obtain tomatoes with low or no detectable residues.     

Determination of 28 pesticides applied on two tomato cultivars with a different surface/weight ratio of the berries,using a multiresidue GC-MS/MS method

The behavior of 28 pesticides on two tomato cultivars with a different surface/weight (S/W) ratio of the berries (S/W, Birikino vs. Tombola) was studied, in order to provide appropriate indications about their persistence on crops reaching the pre-harvest interval (PHI). Quantitative analysis was performed using a GC MS/MS method. Birikino cv. (BIR) was a “cherry type tomato” with a double S/W ratio compared with Tombola cv. (TOM). The results showed a different pesticide behavior. Azoxystrobin, Boscalid, Bupirimate, Difenoconazole, Etofenprox, Iprodione, Mepanipyrim, Myclobutanil, Tebuconazole, Zoxamide, Metalaxyl M, Pyrimethanil, Tetraconazole, Benalaxyl, Cyprodinil, Fenamidone, Famoxadone and Fludioxonil immediately after treatments showed residues on BIR higher than TOM, and this behavior is consistent with its greater exposed surface. BIR showed higher decay rates of these pesticides during the whole trial, nevertheless residue averages remained higher than TOM reaching the time of harvest. Residues at the PHI were all below their Maximum Residue Levels (MRLs), but data indicated that they could exceed their legal limits especially if the above-mentioned active ingredients were employed more than once per crop cycle on cherry type tomatoes. As regards to Chlorpyrifos, Chlorpyrifos methyl, Triadimenol, Pyridaben and Tebufenpyrad, no different residual behavior related to S/W ratio of the cultivars was observed. Even in this case, residues at the PHI were all below MRLs. As for Cyfluthrin, Deltamethrin, Lambda cyhalothrin, Etoxazole and Cyproconazole, residues were lower than the limit of quantitation (LOQ) of the analytical method just after the treatment, according to their low doses of employment.     

Studying soil organic matter using 13C CP-MAS NMR: the effect of soil chemical pre-treatments on spectra quality and representativity

¹³C CP-MAS NMR spectroscopy is a technique that has proved to be useful in studying soil organic matter (SOM). Nevertheless, NMR spectra exhibit a weak signal and have very low resolution due to: the low natural abundance of ¹³C (1.1 % of C) in SOM, the generally low SOM content of soils, and the presence of paramagnetic impurities. This paper studies the effects of soil chemical pre-treatments on ¹³CP-MAS NMR spectra quality and spectra representativity i.e. soil C mass balance.

After chemical pre-treatment to increase total organic carbon (TOC) content and C/Fe ratio, eight soils characterized by different levels of organic carbon content and C/Fe ratios were studied using ¹³CP-MAS NMR. Moreover, where chemical treatments were not applicable due to high carbon losses, the number of ¹³CP-MAS NMR scans was increased in order to obtain satisfactory spectra.

Results show that chemical pre-treatment of soils with C/Fe > 1 caused high C losses. Bulk soils were therefore studied by increasing the number of ¹³CP-MAS NMR scans. Acceptable spectra were obtained from 8K scans (1K = 1024 transient). On the other hand, even when a large number of scan (32K) are used, soil with C/Fe < 1 cannot be studied. As these soils are characterized by low C losses after HCl treatments (range of 2.9–25.4%), a pre-treatment of at least 1.39 mol l⁻¹ HCl removes excess Fe and at the same time increases C/Fe ratio resulting in 32K scans providing good spectra.     

Chemical characterisation of spent rechargeable batteries

A chemical characterisation of used batteries can give useful information to implement suitable recycling techniques and to estimate the flux of the different materials recovered. This work is aimed to provide quantitative data about the composition of mixed batteries (in particular, Ni–Cd, Ni-MH and Li-ion batteries) collected in a Northern Italian town in order to evaluate the feasibility of recovery processes applied to the selected material. The higher concentration of metals in the <3 mm fraction suggested that significant quantities of valuable elements could be recovered: in particular, for a kg of the <3 mm fraction deriving from disassembled batteries, about 390 g Ni and 330 g Cd can be recovered from Ni–Cd, 630 g Ni, 80 g Co from Ni-MH and 250 g Co, 110 g Ni, 120 g Cu from Li-ion ones. Leaching tests applied to the same fractions, to assess possible contaminant releases, resulted in low metal content in aqueous solutions (except for Al and Fe, the concentrations of all metals remained below 1 mg/kg). Even so, great care is required in all handling activities due to the high pH values of leachate solutions.     

Using textile industrial sludge,sewage wastewater,and sewage sludge as inoculum to degrade recalcitrant textile dyes in a co-composting process: an assessment of biodegradation efficiency and compost phytotoxicity

Environmental Science and Pollution Research - Recalcitrant dyes found in textile wastewater represent a threat for sustainable textile production due to their resistance to conventional...     

Genotoxicity of leachates from highly polluted lowland river sediments destined for disposal in landfill

The Matanza-Riachuelo is one of the most polluted rivers of Latin America. The complex chemical mixture of pollutants discharged into the river is accumulated in the river sediments. In this paper, Matanza-Riachuelo river sediment composition and genotoxicity were tested in order to develop a cost-effective, environmentally sound option for disposal and management of contaminated dredged materials. Sampling was performed in a rural area, in a solid waste dumpsite and also in an urban and industrial area. The concentrations of total heavy metals increased from the upper basin to the lower basin. The Ames Salmonella typhimurium test and the Saccharomyces cerevisiae D7 test were performed using toxicity characteristic leachate procedure (TCLP) leachates. The concentrations of copper, lead, and chromium in the leachates exceeded the guide levels for the protection of aquatic life. Low concentrations of organic chlorinated compounds were detected in the leachates. Genotoxic profiles were obtained by testing TCLP leachates from polluted sediment samples with Salmonella typhimurium, Saccharomyces cerevisiae D7, and water sediment suspension with Allium cepa test. No mutagenicity effects on Ames test were observed. Gene conversion and mitotic reversion in Saccharomyces cerevisiae D7 and chromosome aberration in Allium cepa were induced by the sediment samples. Results obtained suggest that dredged sediments could be classified as genotoxic hazardous waste.     

The environmental fate of heavy metals arising from a MSW incineration plant

Pollutant fluxes from municipal solid waste (MSW) incinerators are of a certain concern, especially gaseous emissions from the stack, which constitute the major effluent from the plant. In this work, heavy metals in soil and vegetation sampled in different sites around the plant are compared with those found in the gaseous emissions from an incinerator: the suspected source and environmental matrices are observed together, in order to detect a possible relationship of cause and effect, using statistical methods. The incinerator examined, regarding dimension and technology, can be considered a typical Italian one. Heavy metal concentrations in soil and vegetation show a clear dependence on sampling year; similar behaviour can be found in emission fluxes referring to the same years. A dependence on the distance from the incinerator is also apparent. This study supplies a methodological approach that can be easily extended and applied to other suspected contamination sources.     

The contribution of alkali soluble (humic acid-like) and unhydrolyzed-alkali soluble (core-humic acid-like) fractions extracted from maize plant to the formation of soil humic acid

Alkali soluble (humic acid-like material) (HA-like) (yield of 132 gkgdm(-1)) and the unhydrolized-alkali soluble (core-humic acid-like material) (core-HA-like) (yield of 33.4 gkgdm(-1)) fractions were extracted from maize plants and characterized by C and N determinations, DRIFT, and 1H and 13C-NMR spectroscopy. Fresh plants were subsequently incubated for 6 months in an artificial mineral soil, and the HA-like and core-HA-like trends were monitored quantitatively (C fraction content) and qualitatively (spectroscopic approach) in order to study their contribution to the formation of soil humic acid. During incubation the HAC-like partially degraded (loss of 320 gkgHAC(-1)) and partially formed new fulvic-like acids (160 gkgHAC(-1)). On the contrary, the stable fraction of HAC, the core-HAC-like, was maintained (loss of 153 kgcore-HAC(-1)), representing, after incubation, 846 gkg(-1) of the initial core-HAC-like content. The core-HA-like fraction is composed of lignin residues, polysaccharides, lipids and proteins, probably structured into a well-defined network, i.e. the plant cell wall.