Thermogravimetric kinetic analysis and pollutant evolution during the pyrolysis and combustion of mobile phone case

The increase in electronic waste, including cellular telephones, worldwide is a worrying reality. For this reason, urgent action on the management of these wastes is necessary within a framework that respects the environment and human health. Mobile phone components can be physically segregated through grinding at the dismantling sites, in order to reuse or reprocess (via chemical or physical recycling) the recovered plastics and valuable metals. A kinetic study of the thermal decomposition of a mobile phone case has been carried out under different conditions by thermogravimetry. Several experiments were performed in a nitrogen atmosphere (pyrolysis runs) and also in an oxidative atmosphere with two different oxygen concentrations (10% and 20% oxygen in nitrogen). Dynamic runs and dynamic+isothermal runs have been carried out to obtain much decomposition data under different operating conditions. Moreover some TG-MS runs were performed in order to better understand the thermal decomposition of a mobile phone case and identify some compounds emitted during the controlled heating of this material. A scheme of two independent reactions for pseudocomponents has been proposed for the pyrolysis process. For the combustion runs, the scheme proposed includes two pyrolytic reactions competing with other two reactions with formation of an intermediate residue, and finally the reaction of oxidation/burning of the intermediate residue. Furthermore, pyrolysis and combustion runs at 500 °C in a horizontal laboratory furnace were carried out. More than 50 compounds, including carbon oxides, light hydrocarbons, and polycyclic aromatic hydrocarbons (PAHs) have been identified and quantified. The main semivolatile compounds detected were phenol and styrene. Furthermore, polychlorodibenzo-p-dioxin and polychlorodibenzofurans (PCDD/Fs) and dioxin-like PCBs produced were analyzed. In the combustion run, PCDDs were obtained in higher amounts than PCDFs and HxCDD was the most emitted homologue.     

Responses of evergreen and deciduous Quercus species to enhanced ozone levels

Plants of one evergreen oak (Quercus ilex) and three deciduous oaks (Q. faginea, with small leaves; Q. pyrenaica and Q. robur, with large leaves) were exposed both to filtered air and to enhanced ozone levels in Open-Top Chambers. Q. faginea and Q. pyrenaica were studied for the first time. Based on visible injury, gas exchange, chlorophyll content and biomass responses, Q. pyrenaica was the most sensitive species, and Q. ilex was the most tolerant, followed by Q. faginea. Functional leaf traits of the species were related to differences in sensitivity, while accumulated ozone flux via stomata (POD_1.6) partly contributed to the observed differences. For risk assessment of Mediterranean vegetation, the diversity of responses detected in this study should be taken into account, applying appropriate critical levels.     

Air pollution assessment based on elemental concentration of leaves tissue and foliage dust along an urbanization gradient in Vienna

Foliage dust contains heavy metal that may have harmful effects on human health. The elemental contents of tree leaves and foliage dust are especially useful to assess air environmental pollution. We studied the elemental concentrations in foliage dust and leaves of Acer pseudoplatanus along an urbanization gradient in Vienna, Austria. Samples were collected from urban, suburban and rural areas. We analysed 19 elements in both kind of samples: aluminium, barium, calcium, copper, iron, potassium, magnesium, sodium, phosphor, sulphur, strontium and zinc. We found that the elemental concentrations of foliage dust were significantly higher in the urban area than in the rural area for aluminium, barium, iron, lead, phosphor and selenium. Elemental concentrations of leaves were significantly higher in urban than in rural area for manganese and strontium. Urbanization changed significantly the elemental concentrations of foliage dust and leaves and the applied method can be useful for monitoring the environmental load.     

Agricultural reuse of the digestate from low-cost tubular digesters in rural Andean communities

This research aimed at assessing the properties of guinea pig manure digestate from low-cost tubular digesters for crops fertilization in rural Andean communities. To this end, field trials were carried out to evaluate the effect of the digestate on two common Andean crops: potato (Solanum tuberosum) and forage (Lolium multiflorum and Trifolium pratense L.). The potato yield (20-25 tha(-1)) increased by 27.5% with digestate, by 15.1% with pre-compost and by 10.3% with the mixture, compared to the control. The forage yield (20-21 tha(-1)) increased by 1.4% with digestate - 50% dose, and by 8.8% with digestate - 100% dose and digestate - 150% dose, compared to the control. The results suggest that the digestate is an appropriate substitute of manure pre-compost for potato fertilization. The results with forage indicate that it can be applied in a range of doses, according to the amount produced by the digester. Currently, manure is either used for cooking or as fertilizer. With low-cost tubular digesters implementation, it could be used to feed the digester, using the digestate for crops fertilization and biogas for cooking; improving household living conditions and protecting the environment. Since soil properties in rural Andean communities differ from experimental layouts, the effect of fertilizers should be re-evaluated in-situ in future research studies.     

Thermal decomposition of electronic wastes: mobile phone case and other parts

Pyrolysis and combustion runs at 850°C in a horizontal laboratory furnace were carried out on different parts of a mobile phone (printed circuit board, mobile case and a mixture of both materials). The analyses of the carbon oxides, light hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), polychlorodibenzo-p-dioxin, polychlorodibenzofurans (PCDD/Fs), and dioxin-like PCBs are shown. Regarding semivolatile compounds, phenol, styrene, and its derivatives had the highest yields. In nearly all the runs the same PAHs were identified, naphthalene being the most common component obtained. Combustion of the printed circuit board produced the highest emission factor of PCDD/Fs, possibly due to the high copper content.     

Effects of pre and postnatal exposure to low levels of polybromodiphenyl ethers on neurodevelopment and thyroid hormone levels at 4 years of age

There are at present very few studies of the effects of polybromodiphenyl ethers (PBDEs), used as flame retardants in consumer products, on neurodevelopment or thyroid hormone levels in humans. The present study aims to examine the association between pre and postnatal PBDE concentrations and neurodevelopment and thyroid hormone levels in children at age 4years and isolate the effects of PBDEs from those of PCBs, DDT, DDE and HCB. A prospective birth cohort in Menorca (Spain) enrolled 482 pregnant mothers between 1997 and 1998. At 4years, children were assessed for motor and cognitive function (McCarthy Scales of Children's Abilities), attention-deficit, hyperactivity and impulsivity (ADHD-DSM-IV) and social competence (California Preschool Social Competence Scale). PBDE concentrations were measured in cord blood (N=88) and in serum of 4years olds (N=244). Among all congeners analyzed only PBDE 47 was quantified in a reasonable number of samples (LOQ=0.002ng/ml). Exposure to PBDE 47 was analyzed as a dichotomous variable: concentrations above the LOQ (exposed) and concentrations below (referents). Scores for cognitive and motor functions were always lower in children pre and postnatally exposed to PBDE47 than in referents, but none of these associations was statistically significant (β coefficient (95%CI) of the total cognition score: -2.7 (-7.0, 1.6) for postnatal exposure, and -1.4 (-9.2, 6.5) for prenatal exposure). Postnatal exposure to PBDE 47 was statistically significantly related to an increased risk of symptoms on the attention deficit subscale of ADHD symptoms (RR (95%CI)=1.8 (1.0, 3.2)) but not to hyperactivity symptoms. A statistically significant higher risk of poor social competence symptoms was observed as a consequence of postnatal PBDE 47 exposure (RR (95%CI)=2.6 (1.2, 5.9)). Adjustment for other organochlorine compounds did not influence the results. Levels of thyroid hormones were not associated to PBDE exposure. This study highlights the importance of assessing the effects of PBDE exposure not just prenatally but also during the early years of life. In the light of current evidence a precautionary approach towards PBDE exposure of both mothers and children seems warranted.     

210Pb-dating of a lake sediment core from Lough Carra (Co. Mayo, western Ireland): use of paleolimnological data for chronology validation below the 210Pb dating horizon

The chronologies and sediment accumulation rates for a lake sediment sequence from Lough Carra (Co. Mayo, western Ireland) were established by applying the constant initial concentration (CIC) and constant rate of supply (CRS) hypotheses to the measured ²¹⁰Pb_excess profile. The resulting chronologies were validated using the artificial fallout radionuclides ¹³⁷Cs and ²⁴¹Am, which provide independent chronostratigraphic markers for the second half of the 20th century. The validity of extrapolating the derived CIC and CRS dates below the ²¹⁰Pb dating horizon using average sedimentation rates was investigated using supplementary paleolimnological information and historical data. Our data confirm that such an extrapolation is well justified at sites characterised by relatively stable sedimentation conditions.     

Development of a fast instrumental method for the analysis of pharmaceuticals in environmental and wastewaters based on ultra high performance liquid chromatography (UHPLC)-tandem mass spectrometry (MS/MS)

This work describes the development, optimization and validation of an analytical method for the simultaneous detection and identification of 74 pharmaceutically active compounds (PhACs), from various therapeutic groups, in both environmental (ground and surface water) and wastewaters (WW). The method is based on the simultaneous extraction of all target compounds by solid phase extraction (SPE), using a hydrophilic-lipophilic balanced polymer followed by ultra high performance liquid chromatography (UHPLC) tandem mass spectrometry (MS/MS). Two selected reaction monitoring (SRM) transitions have been monitored per compound in order to fulfil the EC guidelines, as well as to ensure an accurate identification of target compounds in the samples. Quantification is performed by internal standard approach, applying 24 specific isotopically labeled compounds. The main advantages of the developed method, besides the selectivity and reliability of the results, is its high throughput. All compounds are extracted in a single step and the instrumental analysis lasts 5 min (NI mode) + 8 min (PI mode), allowing fast throughput of samples. The limits of detection range from 0.01 to 50 ng L⁻¹, depending on the matrix, for most of the compounds. Finally, the method developed has been applied to the analysis of pharmaceuticals in the Ebro river basin (NE Spain).     

Diastereoisomer- and enantiomer-specific determination of hexabromocyclododecane in fish oil for food and feed

Fish oils are one of the main sources of ω-3 fatty acids. However, they can present elevated levels of some lipophilic pollutants, such as hexabromocyclododecanes (HBCDs). Since data about HBCDs in fish oil samples are very limited, in this study, 25 samples of fish oil for feed and food have been analyzed. Total HBCDs, as well as, α-, β- and γ-diastereoisomers have been determined. Total HBCDs ranged from 0.09 to 26.8 ng g⁻¹, with higher concentrations in fish oil for feed (average value of 9.69 ng g⁻¹) than those for food (1.14 ng g⁻¹). Concentrations of α-HBCD (average value of 4.12 ng g⁻¹ in feed samples and 0.48 ng g⁻¹ in food samples) and γ-HBCD (5.05 and 0.43 ng g⁻¹ respectively) were higher than that of β-HBCD (0.52 and 0.19 ng g⁻¹ respectively) in most of the samples. However, none of them was predominant in the samples. Concentrations of HBCDs were compared to concentrations of other pollutants and correlation between dioxin and dioxin-like PCBs levels and HBCDs levels were observed. Intake of HBCDs was calculated for fish oil with human consumption purposes and it ranged from 0.08 to 5.38 ng HBCDs d⁻¹, which could contribute significantly to HBCDs total intake. Enantiomeric fractions were also determined. No clear enrichment was observed for γ-HBCD, while (−)-α-HBCD enrichment was detected in some samples.     

Occurrence of multiclass UV filters in treated sewage sludge from wastewater treatment plants

Many substances related to human activities end up in wastewater and accumulate in sewage sludge. So far, there is only one extensive survey on the occurrence of UV filter residues in sewage sludge. However, more data are required to draw a reliable picture of the fate and effects of these compounds in the environment. This study attempts to fill this gap through the determination of selected UV filters and derivatives namely 4-methylbenzylidenecamphor, benzophenone-3, octocrylene, ethylhexylmethoxycinnamate, ethylhexyldimethyl PABA, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, and 4,4′-dihydroxybenzophenone in treated sewage sludge.The target compounds were extracted using pressurized liquid extraction and after this, determined by ultra high resolution liquid chromatography-tandem mass spectrometry. The determination was fast and sensitive, affording limits of detection lower than 19 ng g⁻¹ dry weight (dw) except for 2,4-dihydroxybenzophenone (60 ng g⁻¹ dw). Good recovery rates, especially given the high complexity of sludge matrix (between 70% and 102% except for 2,4-dihydroxybenzophenone (30%)) were achieved.The application of developed method allowed reporting for the first time the occurrence of two major degradation products of benzophenone-3 that have estrogenic activity in sewage sludge: 4,4′-dihydroxybenzophenone (in 5/15 WWTPs) and 4-hydroxybenzophenone (in 1/15 WWTPs). Results revealed the presence of UV filters in 15 wastewater treatment plants in Catalonia (Spain) at concentrations ranging from 0.04 to 9.17 μg g⁻¹ dw.