Estimation of measurement uncertainty associated to the determination of pesticide residues: a case study

In the analytical analysis the measurement uncertainty is a quantitative indicator of the confidence describing the range around a reported or experimental result within which the true value can be expected. Several approaches can be used to estimate the measurement uncertainty associated to the analysis of pesticide residues: a) the top-down, the estimation can be referred to default values; b) the bottom-up the estimation is related to the uncertainty sources. Concerning the bottom-up approach, the following contributions have been investigated: weight of sample, calibration solutions, final volume of sample and intermediate repeatability studies. The commodity/residue combination selected in this study was celery/tau-fluvalinate pesticide. Tau-fluvalinate is a broad-spectrum insecticide in the pyrethroid class of pesticides. The Maximum Residue Limit (MRL) of tau-fluvalinate in celery has been set at 0.01 mg/kg. The tau- Fluvalinate showed two chromatographic peaks. Since the individual standards are not available, the two peaks were integrated separately and the instrumental responses were added. The total residue was calculated on the basis of resulted peaks. The present work aims to compare the uncertainty estimated by experimental data using repeated analysis (n = 12) of a real sample and a spiked sample. The relative expanded uncertainty for two data set, incurred and spiked, was 22 % and 20 %, respectively. No differences were observed from repeated determinations of real samples and spiked samples.     

Life cycle energy and CO2 emissions analysis of food packaging: an insight into the methodology from an Italian perspective

Packaging is strictly connected to environmental issues as it is a product characterised by high material consumption rate; it is often transported over long distances and has a short life. Providing environmental analysis is, therefore, urgent to identify energy and resources efficient solutions. The paper, taking advantage of a real case study, presents a life cycle-based comparative analysis among three different food packaging systems. The paper compares the life cycle of tin steel, polypropylene and glass-based packaging of an Italian preserves producer. The analysis leads to the conclusion that, for the baseline scenario, polypropylene packaging represents the greenest solution, whereas glass packaging is the worst choice. The paper presents a scenario analysis varying both the method used for accounting for recycling as well as the recycling rates of the packaging materials. Changes in overall results with parameters analysis changing are calculated and highlighted throughout the paper. The impact of a reuse policy of the glass-based solution is also analysed; a model for disposable glass packaging is proposed and the obtained results are compared with the single use polypropylene and tin steel-based packaging. In order to analyse the impact of different End of Life scenarios on the present case study, collecting as well as recycling rates of some European countries have been used. The results revealed a significant fluctuation both in energy consumption and in CO₂ emission as the nation changes. Summing up, a methodology for packaging environmental impact analysis is applied to a real case study, some crucial aspects of the methodology have been analysed in depth in order to give a contribution in packaging environmental impact analysis.     

Fast determination of phenoxy acid herbicides in carrots and apples using liquid chromatography coupled triple quadrupole mass spectrometry

A fast, simple and inexpensive method has been developed for the analysis of phenoxy acid herbicides: 2,4-dichlorophenoxyacetic acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2-(4-chloro-o-tolyloxy)propionic acid (MCPP), 2-(4-aryloxyphenoxy)propionic acid (Fluazifop) and 2-(4-aryloxyphenoxy)propionic acid (Haloxyfop) in carrots and apples by liquid chromatography coupled to triple quadrupole mass spectrometry (LC/MS/MS). The compounds were analyzed by QuEChERS (quick, easy, cheap, effective, rugged, safe) methodology without cleanup.

The recoveries were performed at two spiked levels (0.05 and 0.5 mg/kg) for both matrices with six replicates for each level. The mean recoveries ranged from 70–92% for both apples and carrots. The precision of the method expressed as relative standard deviation (RSD%) was found to be in the range 3–15%. For all compounds, good linearity (r² > 0.99) was obtained over the range of concentration from 0.05 μ g/mL to 0.5 μ g/mL, corresponding to the pesticide concentrations of 0.05 mg/kg and 0.5 mg/kg, respectively. The determination limits (LOQs) ranged from 0.01 ng/mL to 1.3 ng/mL in solvent, whereas, the LOQs calculated in matrix ranged from 0.05 ng/g to 21.0 ng/g for apples and from 0.06 ng/g to 10.2 ng/g for carrots. The developed methodology combines the advantages of both QuEChERS and LC/MS/MS producing a very rapid, sensitive and cheap method useful for the routine analytical laboratories.     

Non-transferable signals on ant queen eggs

How biological systems resolve internal conflicts is a major evolutionary question. Social insect workers cooperate but also pursue individual interests, such as laying male eggs. The rewards of this individual selfishness can be reduced by policing, such as by killing worker-laid eggs. However, selfish individuals may evade policing. What factors prevent individuals from being able to evade policing? In the ant Pachycondyla inversa, workers kill (police) worker-laid eggs. Because the colony keeps eggs in piles and worker-laid and queen-laid eggs are chemically distinct, worker-laid eggs might become more acceptable once placed in the egg pile by odour transfer from touching queen-laid eggs. Here, we show that such “cue scrambling” does not occur. Worker-laid eggs that were sandwiched between three queen-laid eggs for 45 min were not more acceptable in a policing bioassay than control worker-laid eggs. Chemical analyses also showed that the surface hydrocarbon profile of these eggs was unchanged. Policing, therefore, is stable against this potential cheating mechanism probably because queen-laid eggs are made chemically distinct using chemicals, that are not easily transferred by physical contact.     

Macroalgae and DGT as indicators of available trace metals in marine coastal waters near a lead–zinc smelter

The levels of Cd, Cu, Pb, and Zn were determined in the commonest species of green, red, and brown algae collected from five coastal sites in south-western Sardinia (Italy), an area with a long history of mining and smelting. The usefulness of employing Enteromorpha sp. and Padina pavonica (L.) Thivy to monitor metal pollution was evaluated, while diffusive gradients in thin films (DGT) devices were used to measure dissolved metals in seawater. Levels of Cd and Pb were high enough to be of environmental concern in the whole study area. A significant relationship was found between the content of Pb in P. pavonica and DGT-labile Pb in seawater, suggesting that gross elemental concentrations of nonessential metals such as Pb in algal tissues are apparently controlled by the abundance of dissolved metal species in the ambient seawater. The results pointed out the usefulness of using both DGT and algal methods for a better understanding of trace metal availability in coastal waters.     

Thermoplastic Blends Based on Poly(Butylene Succinate-co-Adipate) and Different Collagen Hydrolysates from Tanning Industry—II: Aerobic Biodegradation in Composting Medium

Journal of Polymers and the Environment - Two different raw hydrolyzed collagens (HCs), by-products of the Tannery industry, were investigated in blends with a bioplastic, as poly(butylene...     

Levels of "toxic" and "essential" metals in samples of bovine milk from various dairy farms in Calabria, Italy

The aim of this research was to evaluate the possible contamination by heavy metals of milk from cows bred on various farms in Calabria. The concentrations of heavy metals were determined in 40 samples of bovine milk from the various dairy farms. Each sample, homogenized and powdered, was mineralized in a microwave oven. Quantitative analyses of Cd, Cr, Cu, Pb and Se were performed using an atomic absorption spectrophotometer with graphite furnace; As was analyzed by hot vapor generation technique and Zn with the flame method. As regards toxic heavy metals, highest values are those of As (g.m. 37.90 microg/kg w.w.) and Pb (g.m. 1.32 microg/kg w.w.), while lowest concentrations are those of Cd (g.m. 0.02 microg/kg w.w). With regard to essential metals, Zn (g.m. 2016 microg/kg w.w) and Se (g.m. 13.24 microg/kg w.w.) showed the highest concentrations, followed by Cr (g.m. 2.03 microg/kg w.w.) and Cu (g.m. 1.98 microg/kg w.w.). Further investigations of the levels of heavy metals (As) in a greater number of milk samples from various zones of Calabria are necessary, both to examine this problem from the clinical epidemiological point of view and to identify the possible causes of milk contamination.