Sampling and analytical methods for assessing the levels of organic pollutants in the atmosphere: PAH, phthalates and psychotropic substances: a short review

This short review presents the procedures used to monitor PAHs, phthalates and psychotropic substances in the air, and the results of some measurements made in Italy and abroad. Organic contaminants are characterized by a variety of physical and chemical properties, including aggregation phase, concentration level, and life time. This variety widens the spectrum of procedures developed to assess their occurrence in the environment and biota, but prevents the complete speciation of the "organic fraction" of air, waters and particulates, and attention is paid to a few substances. The progress in health sciences stimulates the concern on contaminants and the development of new instrumental apparatuses and methods; new chemicals are continuously identified or recognized as capable of injuring the environment and organisms. Persistent organic pollutants and persistent biologically active toxicants are subject to regulation and extensively measured by means of standard procedures. For instance, polycyclic aromatic hydrocarbons, polychlorobiphenyls and polychlorodibenzodioxins are recovered from air through phase partition, thermal desorption or solvent extraction, then separated and detected through GC-MS or HPLC-MS procedures. By contrast, dedicated methods must be still optimized to monitor candidates or possible candidates as emerging organic pollutants, e.g. phthalates, flame retardants and perfluoroalkanes. Also, psychotropic substances appear of potential concern. Legal and illicit substances are commonly detected in the urban air besides waste and surface waters. If nicotine, caffeine and cocaine will result to enough persistence in the air, their monitoring will become an important issue of global chemical watching in the next future.     

Poly(lactic acid)-Based Composites Containing Natural Fillers: Thermal,Mechanical and Barrier Properties

Natural filler/poly(lactic acid)-Based composites have been prepared by melt blending in order to investigate the resulting thermal, mechanical, and oxygen permeability properties. To this aim, several wastes or by-products (namely, cellulose fibers, wood sawdust, hazelnut shells, flax fibers, corn cob and starch) have been used, ranging from 10 to 30 wt%. The presence of these fillers is responsible of a slight reduction of the polymer degradation temperature in nitrogen as well as of a significant increase of the storage modulus as a function of the filler content. The experimental data obtained by dynamic mechanical analysis have been mathematically fitted, employing three micromechanical models (namely, Voigt, Reuss and Halpin–Tsai). Furthermore, the presence of cellulose or starch has turned out to significantly reduce the polymer oxygen permeability. Finally, in order to fully assess the feasibility of such materials, an economic analysis has been carried out and discussed.     

Effects of the herbicide molinate on the metabolic activities of a degradative Streptomyces griseus strain

Abstract

Cometabolic degradation of the herbicide molinate was tested using two microorganisms, Arthrobacter sp., strain M3 and Streptomyces griseus strain M2; the latter classified on the basis of the presence of the enzymatic cofactor SF‐420. The strains M3 and M2, inoculated in a basic salts medium with glucose as carbon source and added with 100 mg L^‐1 of molinate, degraded respectively 35 and 51% of the herbicide in 36 days.

Increasing concentrations of molinate, ranging from 50 to 200 mg L^‐1 in glucose medium, did not affect the final ATP yield of the strain M2, but decreased the final growth yield and the ATP synthesis rate. Moreover, the onset of coenzyme SF‐420 synthesis was progressively delayed.

In contrast, surprisingly, SF‐420 final yield and production rate were increased by progressive increasing concentrations of molinate in the mineral medium.     

Enzyme and fungal treatments and a combination thereof reduce olive mill wastewater phytotoxicity on Zea mays L. seeds

The phytotoxicity of olive-mill wastewater (OMW) has been suggested to be mainly due to its phenolic components. This study investigated the impact of three different low-cost dephenolization treatments on the wastewater phytotoxicity. To this aim, germinability of maize (Zea mays L.) seeds sown on a sandy-loamy soil which had been spread with different volumes (from 40 to 160m(3)ha(-1)) of either biologically-treated OMW or relative incubation control was determined. Biological treatments included either Panus tigrinus liquid cultures or incubation with commercial laccase (1UIml(-1)) or an innovative sequential combination of laccase and P. tigrinus cultures. All treatments markedly reduced phytotoxicity and promising results were obtained with commercial laccase. In fact, germinability and mean germination times in soil spread with laccase-treated OMW, did not significantly differ from those observed in soil irrigated with tap water (control) up to OMW volumes of 120m(3)ha(-1). Although the highest phenol reduction (ca. 81%) was obtained by the sequential use of laccase and P. tigrinus, the feasibility of the enzyme treatment is undoubtedly more convincing under the technological point of view.     

Probability density function of non-reactive solute concentration in heterogeneous porous formations

Available models of solute transport in heterogeneous formations lack in providing complete characterization of the predicted concentration. This is a serious drawback especially in risk analysis where confidence intervals and probability of exceeding threshold values are required. Our contribution to fill this gap of knowledge is a probability distribution model for the local concentration of conservative tracers migrating in heterogeneous aquifers. Our model accounts for dilution, mechanical mixing within the sampling volume and spreading due to formation heterogeneity. It is developed by modeling local concentration dynamics with an Ito Stochastic Differential Equation (SDE) that under the hypothesis of statistical stationarity leads to the Beta probability distribution function (pdf) for the solute concentration. This model shows large flexibility in capturing the smoothing effect of the sampling volume and the associated reduction of the probability of exceeding large concentrations. Furthermore, it is fully characterized by the first two moments of the solute concentration, and these are the same pieces of information required for standard geostatistical techniques employing Normal or Log-Normal distributions. Additionally, we show that in the absence of pore-scale dispersion and for point concentrations the pdf model converges to the binary distribution of [Dagan, G., 1982. Stochastic modeling of groundwater flow by unconditional and conditional probabilities, 2, The solute transport. Water Resour. Res. 18 (4), 835-848.], while it approaches the Normal distribution for sampling volumes much larger than the characteristic scale of the aquifer heterogeneity. Furthermore, we demonstrate that the same model with the spatial moments replacing the statistical moments can be applied to estimate the proportion of the plume volume where solute concentrations are above or below critical thresholds. Application of this model to point and vertically averaged bromide concentrations from the first Cape Cod tracer test and to a set of numerical simulations confirms the above findings and for the first time it shows the superiority of the Beta model to both Normal and Log-Normal models in interpreting field data. Furthermore, we show that assuming a-priori that local concentrations are normally or log-normally distributed may result in a severe underestimate of the probability of exceeding large concentrations.     

Properties of Glauconite/Polyaniline Composite Prepared in Aqueous Solution of Citric Acid

Hybrid composite made of glauconite and polyaniline was prepared in aqueous solution of citric acid. Scanning electron microscopy combined with energy dispersive X-ray analysis shows uniform aggregates made of glauconite microparticles and polyaniline matrix. The results of X-ray powder diffraction suggest that: (1) citric acid used for the polymerisation of aniline causes formation of emeraldine salt where macromolecular ordering in the amorphous polymer takes place; (2) no chemical interaction between glauconite and emeraldine takes place in the prepared composite. FT-IR spectra of the prepared polymer and composite show features indicating all the functional groups that are present in the diiminoquinone–diaminobenzene state of polyaniline. Thermal stability of the composite was higher than the prepared polymer suggesting the occurrence of an interphase interaction between glauconite and emeraldine. After pyrolysis in purified nitrogen the composite still remained glauconite, and ε-Fe3N together with amorphous and graphitic carbon were found as reaction products. The values of electrical conductivity and magnetization of the composite suggest that optimization of these values might be achieved based upon the relationship between glauconite and polyaniline.     

Spatially-balanced sampling versus unbalanced stratified sampling for assessing forest change: evidences in favour of spatial balance

Large-scale remote sensing-based inventories of forest cover are usually carried out by combining unsupervised classifications of satellite pixels into forest/non forest classes (map data) with subsequent time-consuming visual on-screen imagery classification of a probabilistic sample of pixels taken as the ground truth (reference data). In this paper the estimation of forest change from a sample of reference data is approached by: (i) exploiting map data to construct strata in which changes are occurred, and then adopting the stratified sampling joined with the HT estimator with most sampling effort devoted to strata where changes are occurred irrespective of their size, as suggested in most remote sensing literature regarding land change assessments; (ii) adopting a spatial scheme ensuring spatially balanced samples, as suggested in most recent statistical literature regarding spatial surveys, and exploiting the map data in the difference estimator. The results of a comparison performed on an artificial population of reference data generated from a real population of map data recorded in Sardinia (Italy) discourage the use of unbalanced stratified samples that achieve the worst precision. The best results are obtained by means of spatially balanced samples or stratification with nearly proportional allocation to strata.     

Contribution of harbour activities and ship traffic to PM2.5, particle number concentrations and PAHs in a port city of the Mediterranean Sea (Italy)

In this work, an assessment of the impact of ship traffic and related harbour activities (loading/unloading of ships and hotelling in harbour) on PM 2.5 and particle number concentrations (PNC) separating the contribution associated to ship traffic from that of harbour-related activities is reported. Further, an assessment of the impact and environmental risks associated to polycyclic aromatic hydrocarbon (PAH) concentrations was performed. Results refer to the city of Brindisi (88,500 inhabitants) in the south-eastern part of Italy and its harbour (with yearly 9.5 Mt of goods, over 520,000 passengers and over 175,000 vehicles). PM2.5 and PNC concentrations show a clear daily pattern correlated with daily ship traffic pattern in the harbour. High temporal resolution measurements and correlations with wind direction were used to estimate the average direct contribution to measured concentrations of this source. The average relative contribution of ship traffic was 7.4 % (±0.5 %) for PM2.5 and 26 % (±1 %) for PNC. When the contribution associated to harbour-related activities is added, the percentages become 9.3 % (±0.5 %) for PM2.5 and 39 % (±1 %) for PNC. In the site analysed, air coming from the harbour/industrial sector was richer in PAHs (5.34 ng/m³) than air sampled from all directions (3.89 ng/m³). The major compounds were phenanthrene, fluoranthene and pyrene, but the congener profiles were different in the two direction sectors: air from the harbour/industrial sector was richer in phenanthrene and fluorene, which are the most abundant PAHs in ship emissions. Results showed that lighter PAHs are associated to the gas phase, while high molecular weight congeners are mostly present in the particulate phase. The impact on the site studied of the harbour/industrial source to PAHs was 56 % (range, 29–87 %).     

Environmental evaluation of municipal waste prevention

Waste prevention has been addressed in the literature in terms of the social and behavioural aspects, but very little quantitative assessment exists of the environmental benefits. Our study evaluates the environmental consequences of waste prevention on waste management systems and on the wider society, using life-cycle thinking. The partial prevention of unsolicited mail, beverage packaging and food waste is tested for a "High-tech" waste management system relying on high energy and material recovery and for a "Low-tech" waste management system with less recycling and relying on landfilling. Prevention of 13% of the waste mass entering the waste management system generates a reduction of loads and savings in the waste management system for the different impacts categories; 45% net reduction for nutrient enrichment and 12% reduction for global warming potential. When expanding our system and including avoided production incurred by the prevention measures, large savings are observed (15-fold improvement for nutrient enrichment and 2-fold for global warming potential). Prevention of food waste has the highest environmental impact saving. Prevention generates relatively higher overall relative benefit for "Low-tech" systems depending on landfilling. The paper provides clear evidence of the environmental benefits of waste prevention and has specific relevance in climate change mitigation.