[en] The aim of this study was to evaluate the influence of dioxins in the emission levels to the atmosphere by using some waste materials, such as used tires or meat meal, as secondary fuel during the production of clinker. For this purpose, three different cement plants operating in Spain were chosen to perform the project in different sampling episodes. Moreover, different materials were separately evaluated in each plant. Thus, the first plant included the addition in the kiln of meat meal. In the second plant, rejected tires were checked and finally, in the third plant a mixture of both, tires and meat meal, were burned. In all cases, the emission values of dioxins, kept below the limits established by European Union Directives of 0,1 ng I-TEQ/Nm³ with values ranging between 0,001 and 0,042 ng I-TEQ/Nm³. Furthermore, no remarkable differences were found in comparison with reported data obtained in Spanish cement kiln plants when using conventional fuel

[en] Highlights: • A suspected screening process to assess polymers and additives of MPLs/NPLs is presented. • The method was used to study the area of Ebro River. • Most commonly found polymers were PS, PE, PI, PBD, PP and polysiloxanes. • PP and PE were found at concentrations reaching up to 7000 ng/L in some areas. • The additives more frequently detected were pentadecanoic acid, 2-EHA, and phthalates. This is the first work reporting the use of a double suspect-screening to assess most common polymers and additives in micro(nano)plastics (NPLs/MPLs) found in environmental waters. The method consisted of water filtration followed by ultrasonic-assisted extraction with toluene and analysis employing size exclusion chromatography using an advanced polymer chromatography column coupled to high-resolution mass spectrometry with an atmospheric pressure photoionisation source by negative ionisation conditions (LC(APC)-APPI(−)-HRMS). The identification of NPL/MPLs polymers has been based on increasing confirmation level, including the monomers characterisation by the Kendrick Mass Defect and confirmation and quantification when standards were available. In parallel, the identification of main additives in NPL/MPLs composition, as well organic contaminants adsorbed onto the plastic particles were carried out by analysis of the extracts by LC(C18)-APPI (+/−)-HRMS. To assess the impact of plastic pollution it is necessary to assess the composition in terms of polymers but also the additives. This screening approach has been employed to study composition of NPL/MPLs in the Ebro Delta. Two sampling campaigns including freshwater and seawater samples have been investigated to assess plastic composition in the top 5 cm. Polystyrene (PS), polyethylene (PE), polyisoprene (PI), polybutadiene (PBD), polypropylene (PP) and polysiloxanes were the most detected polymers and PP and PE, sizing between < 1000 and 2000 Da, were found at concentrations reaching up to 7000 ng/L in some areas. The pentadecanoic acid, 1,2,3-benzotriazoles, 2-ethylhexanoic acid (2-EHA), and phthalates such as dimethyl phthalate, mono(2-ethylhexyl) phthalate (MEHP) and the phthalimide were more frequently detected plastic additives. Finally, series of organic contaminants were as well detected in the particulate fraction. These organic contaminants cannot be associated to plastic compositions but can be associated to their adsorption to the particulate matter, in particular to NPL/MPLs, due to their non-polar character. Among these organic contaminants, the more frequently detected were pharmaceutical compounds, food additives and pesticides.

[en] 

Background

Species that are at high levels of the food web have often been used as bioindicators to evaluate the presence of persistent contaminants in ecosystems. Most of these species are long-lived, so pollutant burdens may be integrated in some complex way over time. This makes them particularly sensitive to deleterious effects of Persistent Organic Pollutants (POPs). Birds have been suggested as useful organisms for monitoring pollutant levels. Traditionally such studies have been carried out with raptors such as osprey (Pandion haliaetus), peregrine falcon (Falco peregrinus), bald eagle (Haliaetus leucocephalus), etc. In this paper we present the results of a monitoring study conducted on two raptor species, osprey (Pandion haliaetus) and red kite (Milvus milvus), inhabiting a Mediterranean island (Menorca, Spain). These two species have different feeding habits; ospreys prey on fish and red kites feed on terrestrial species. This study constitutes a good opportunity to investigate if differences in feeding habits (aquatic vs. terrestrial) influences the contaminants pattern in two species inhabiting the same area.

Methods

The study was conducted in a non-destructive way, using only failed eggs, to avoid the damage of the population stability. Eggs were collected during the period 1994–2000. The contaminants examined were dichlorodiphenyltrichloroethanes (DDTs, including DDT and its main metabolite, DDE), polychlorinated biphenyls (PCBs), including ortho PCBs (PCBs with at least one Chlorine atom in the ortho position): #28, 52, 95, 101, 123+149, 118, 114, 153, 132+105, 138, 167, 156, 157, 180, 170, 189, 194; and non ortho PCBs (PCBs with no Chlorine atom in the ortho position): #77, 126, 169 and all the polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) with Chlorine atoms at the 2,3,7 and 8 position (2,3,7,8-substituted PCDDs and PCDFs). The analysis of organochlorine compounds was performed using a sample treatment based on a Solid Phase Matrix Dispersion procedure. Ortho PCBs and DDTs were determined by HRGC-µECD; non ortho PCBs and PCDD/Fs were determined by HRGC-HRMS.

Results and Discussion

The sum of the ortho PCB congeners analysed ranged from 0.94 to 15.03 µg/g wet weight (ww) for ospreys and from 1.0 to 11.2 µg/g ww for red kites. In both species, PCB congeners #153, #138 and #180 accounted about 75% to total ortho PCB concentrations. Regarding non ortho PCBs, for ospreys, concentrations ranged from 0.16 to 1.39 ng/g wet weight (ww) and for red kites from 0.12 to 0.51 ng/g ww, being congener #126 the most abundant. Concerning DDTs, concentration for ospreys ranged from 0.07 to 1.03 µg/g ww; and for red kites ranged from 0.90 to 2.10 µg/g ww, representing DDE more than 95% of the total DDTs, which proves a past use of DDT in the study area. Differences in contaminant levels between species are probably associated to feeding habits. The fish-eating species presents the highest PCB levels, whereas the terrestrial species exhibits the highest DDT levels. PCDD/Fs in ospreys were in the range 2.6–14.2 pg/g ww, while in red kites the range was slightly wider (22.2–43.2 pg/g ww), being PCDDs the major contributors in black kites. Ospreys had PCDDs similar to PCDF concentrations. PCDD/F profiles were mostly influenced by OCDD in both species. Non ortho PCBs were the major contributors to calculated Toxic Equivalent Quantity (TEQs) in both species.

Conclusion

In both species studied, ortho-PCBs could represent a problem of concern since 57% of the eggs exhibited levels higher than 4 µg/g ww, reported as the level that could cause reduced hatchability, embryo mortality, and deformities in birds.

Recommendations and Outlook

Results found in this study suggest that a more detailed study to clear up possible deleterious effects of PCBs on the bird populations studied here should be done.

No abstract available

[en] Highlights: • Airborne PCDD/F levels and composition were highly influenced by seasonality. • The low airborne PCDD/F levels did not differentiate between IWMF and traffic inputs. • 2,3,7,8-tetra-/1,2,3,4,6,7,8-heptachloroBF discriminated IWMF from traffic inputs. • New C₇-C₈ PCDD/Fs ratios are reported for evaluating potential air-soil transfers. • The soil PCDD/F distributions were similar to those of sewage sludge. A sampling and analysis scheme was implemented to discriminate between inputs of polychlorodibenzo-p-dioxins and polychlorodibenzofurans (PCDD/Fs) at low concentrations in urban areas. Ambient air and soils were sampled and analyzed in five stations in the Metropolitan area of Barcelona (2018–2019); one located in a reference urban traffic site and four in the area of influence of an integrated waste management facility (IWMF) that included a solid waste incinerator. Seasonality was the main factor determining the PCDD/F composition, and involved lower values in the warmer months. This seasonal effect was related to enhanced photooxidation of PCDDs compared to PCDFs and faster depletion of the less chlorinated congeners due to volatility at higher ambient temperature; consistent with the compounds' octanol-air partition coefficients. The ratio 2,3,7,8-tetrachlorobenzofuran/1,2,3,4,6,7,8-heptachlorobenzofuran allowed, for the first time, identifying cases of preferential contributions of IWMF and traffic inputs, i.e. values of 0.06 and 0.32, respectively. Combination of this ratio with the airborne PCDD/F levels illustrated that the quantitative PCDD/F levels were not a useful criterion for elucidation between IWMF and traffic inputs. PCDD/Fs levels in soils ranged between 9.0 and 22 pg WHO-TEQ/g in the two sites closest to the IWMF, while the other sites, including the traffic site, showed values between 0.8 and 1.9 pg WHO-TEQ/g. The levels in the former group were higher than those observed in other urban areas and above 5 pg WHO-TEQ/g, which is a limit reference value in several European countries. The C₇ and C₈ observed congener distributions in all soils examined were different from those in the air samples and similar to those reported in sewage sludge from waste water treatment plants, not showing influences from IWMF or traffic PCDD/F inputs.

[en] Highlights: • PCBs, PBDEs and PCDD/Fs were measured in krill from the Southern Ocean around the Antarctic Peninsula. • BAFs for PCBs were correlated with K_OW, consistent with krill-water equilibrium. • The settling flux of POPs is larger than their transfer from phytoplankton to krill. Persistent organic pollutants (POPs) reach Antarctica through atmospheric transport, oceanic currents, and to minor extent, by migratory animals. The Southern Ocean is a net sink for many POPs, with a key contribution of the settling fluxes of POPs bound to organic matter (biological pump). However, little is known about POP transfer through the food web in the Southern Ocean and Antarctic waters, where krill is an important ecological node. In this study, we assessed the occurrence of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs) in Antarctic krill (Euphausia superba) from the Bellingshausen, South Scotia and Weddell Seas around the Antarctic Peninsula. The concentrations of PCDD/Fs, PBDEs and PCBs in krill showed a large variability and the average were higher (generally within a factor 3) than those previously reported for eastern Antarctica. This result highlights regional differences related to atmospheric transport and deposition, and also probable regional sources due to human activities. Bioaccumulation and biomagnification factors for PCBs in krill were estimated using previously reported phytoplankton and seawater concentrations for this region. These suggested a near water-krill equilibrium for PCBs, which was not observed for water-phytoplankton partitioning. The estimated removal settling fluxes of PCBs due to the biological pump were several orders of magnitude higher than the estimated fluxes of PCBs transferred from phytoplankton to krill.

[en] Highlights: • PCDD/F and dl-PCB air levels from the Spanish Monitoring Program are presented. • TEQ concentrations decreased progressively from 2009 to 2015. • TEQs, PCDD/Fs and non-ortho PCBs tended to converge at urban and background sites. • Mono-ortho PCBs showed a steady flat temporal behavior. • Site-specific characteristics highly influence study POP air concentrations. Time series (2008–2015) of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in ambient air from the Spanish Monitoring Program were analyzed. A total of 321 samples were collected seasonally each year in 5 urban and 7 background sites by means of passive air sampling. Air concentrations were higher at urban than background sites (urban vs. background concentration ranges): PCDD/Fs (26.9–1010 vs. 20.0–357 fg/m³), non-ortho PCBs (0.113–3.14 vs. 0.042–2.00 pg/m³) and mono-ortho PCBs (0.644–41.3 vs. 0.500–32.8 pg/m³). Results showed significant decreases from 2009 for non-ortho PCBs and PCDD/Fs as well as for WHO₂₀₀₆-TEQs. These declines were sharper, and sometimes only significant, in urban places resulting in converging levels at urban and background sites for these pollutants at the end of the study period. In contrast, mono-ortho PCBs did not show any significant variation but a steady flat temporal behavior in their concentrations, suggesting the existence of different sources between mono-ortho and non-ortho PCBs. Seasonality was observed for air burdens of all these POPs. PCDD/Fs were mostly measured at higher concentrations in colder than in hot seasons, and the opposite was true for dl-PCBs. Seasonal variations for PCDD/Fs appeared to be related to changes in their sources (e.g. domestic heating, open burning) rather than to temperature per se. In contrast, environmental temperature dependent factors (e.g. increased partitioning into the gas phase) drove seasonal variations in dl-PCBs instead of seasonal changes in their sources. Regarding spatial patterns, significant greater levels of PCDD/Fs and dl-PCBs were generally found in cities compared to background areas, pointing out the role of densely populated areas as sources for these pollutants in Spain. As proven by our results, long-term monitoring activities are essential to assess and understand temporal behaviors for these POPs, as well as to evaluate the achievement of Stockholm Convention objectives.

[en] The development of new sampling devices or strategies to assess the concentration of persistent organic pollutants (POPs) in the environment has increased in the last two decades. In this study, a selective sampling device was used to evaluate the impact of potential local sources of polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) and dioxin-like polychlorinated biphenyl (dl-PCBs) emissions on the ambient air levels of such compounds in a town near an important industrial estate. Average concentrations of target compounds of up to 2.5 times for PCDD/Fs and 2 times for dl-PCBs were found to come from the industrial state confirming this area as the main responsible for the majority of such compounds reaching the town. This finding was supported by a PCDD/F and dl-PCB sample profile analysis and a principal component analysis (PCA), which established a direct link between the dioxin-like compounds found in the samples collected in the town and their source. - Selective ambient air samplers provide a valuable information on POP emission sources

[en] Highlights: • Fullerene aggregates have been detected in the Sava River in two sampling campaigns. • Concentrations of C₆₀ fullerene in surface water ranged from 8 pg/l to 59 ng/l. • During high flow conditions, concentrations were significantly lower. • The fullerene derivatives [60]PCBM and [60]NMFP were detected in some samples. The presence of nanomaterials in the environment has caught the attention of the scientific because of the uncertainties in their fate, mobility and potential toxic effects. However, few studies have determined experimentally their concentration levels in aquatic systems up to date, which complicates the development of an adequate risk assessment. In the present study, the occurrence of ten fullerenes has been assessed in the Sava River (Southeastern Europe): 27 freshwater samples and 12 sediment samples from 12 sampling points have been analysed during two sampling campaigns. C₆₀ was the most ubiquitous fullerene, with concentrations of 8 pg/l–59 ng/l and 108–895 pg/g_dw in water and sediments, respectively. Statistically significant differences existed between the levels in 2014 and 2015, which has been attributed to the extreme hydrologic conditions (severe floods and drought, respectively). C₇₀ fullerene has been detected in most of the samples and the fullerene derivatives [6,6]-phenyl C₆₁ butyric acid methyl ester and N‑methyl fulleropyrrolidine have been detected eventually, which highlights that nanotechnology research and development activities are responsible for emitting these emerging contaminants to the environment. The role of diverse potential anthropogenic sources (including oil refinery, general industrial activity, river navigation, urban emissions and nanotechnology) is discussed.

[en] Organochlorine compounds (OCs) including polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs) and 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p-p'-DDE), heavy metals (Pb, Cd, Zn, Cu), and arsenic were measured in house sparrows (Passer domesticus) and common ground doves (Columbina passerina) from Baja California Sur, Mexico. Concentrations of PCDD/Fs were low, with 21 pg/g for house sparrows, and 7.7 pg/g for common ground doves. Non-ortho-PCB concentrations in house sparrow and common ground doves were 58 and 254 pg/g, respectively, and are within the highest concentrations reported in species that are in the low levels of food webs. The major differences in organochlorine levels between species were found for ortho-PCBs and DDTs. ortho-PCB levels were higher in the seedeater species, whereas DDT levels were higher in the omnivorous species. Heavy metal levels were far below those associated with negative effects. - Capsule: The first data on contaminants in birds from Baja California is given