Paloma Sanz

Dechlorane-Related Compounds in Franciscana Dolphin (Pontoporia blainvillei) from Southeastern and Southern Coast of Brazil

Concentrations of Dechlorane (Dec) 603 (0.75 ng/g lipid weight (lw); mean) and Dec 602 (0.38 ng/g lw; mean) were quantified in more than 95% of the franciscana (Pontoporia blainvillei) dolphin samples, whereas the frequency of detection decreased to 75% for Dechlorane Plus (DP) (1.53 ng/g lw, mean). The presence of Chlordene Plus (CP) was also observed (0.13 ng/g lw, mean) in half of the samples. On the contrary, Dec 604, decachloropentacyclooctadecadiene (aCl(10)DP), and undecachloropentacyclooctadecadiene (aCl(11)DP) concentrations were below the limit of quantifications in all cases. To the best of our knowledge, this is the first article reporting the presence of Dec 603, Dec 602, and CP in mammals. For comparative purposes, levels of Mirex, polybrominated diphenyl ethers (PBDEs), and decabromodiphenylethane (DBDPE) are also reported. Considering geographic distribution evaluation together with the strong positive correlations found between DP and PBDEs (r(s) = 0.63; p < 0.01), highly anthropogenic areas were identified as potential sources of these chemicals in this dolphin species. However, local sources for Dec 602, 603, Mirex, CP, and DBDPE were not found indicating that in this case historical use and/or atmospheric transport and deposition may play an important role in their fate.

Sources and behaviour of polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in Spanish sewage sludge

Presence, sources and behaviour of polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were evaluated in Spanish sewage sludge. A total of 120 samples were seasonally collected from October 2005 to September 2006 at 31 urban wastewater treatment plants (WWTPs). Concentrations of PBDEs (ranging between 57.5 and 2606 ng/g dry weight) were two to three orders of magnitude higher than those obtained for PCDDs (0.17-5.03 ng/g d.w.) and PCDFs (0.05-3.07 ng/g d.w.). All the samples presented International Toxicity Equivalents (I-TEQ) levels (ranging between 2.06 and 44.4 ng/kg d.w.) below the limit values proposed by European Union for land application. Congener patterns evaluation revealed that the use of Deca-BDE commercial mixture seems to be the major source of PBDEs in the sludge. Nevertheless, origin of PCDD/Fs should be related to atmospheric deposition, faeces and presence of PCDD/Fs precursors such as pentachlorophenol in the sludge. No correlations (p>0.05) were found between pollutant concentrations (PBDEs and PCDD/Fs) and wastewater treatment plant (WWTP) characteristics (capacity nor sludge rate). Lower levels of PBDEs and PCDFs were found in WWTPs using biological nitrogen and phosphorous elimination, suggesting that these compounds are susceptible of microbial elimination. According to our knowledge, this is the first work comparing together both PBDEs and PCDD/Fs sludge patterns.

Distribution and biological impact of dioxin-like compounds in risk zones along the Ebro River basin (Spain)

The aim of this investigation was to evaluate the environmental impact associated to PCDDs/Fs and dioxin-like PCBs in the Ebro River basin. Sediments and fish from several species were sampled at three sites with different historical pollution records, including the Barbastro area with different industrial activities, and the Flix and Monzón sites, associated to heavy organochlorine compound pollution. Seventeen toxic PCDDs/Fs and 12 dioxin-like PCBs were analyzed by GC-MS. The results obtained indicated significant accumulation of dioxin-like PCBs, but not PCDDs/Fs, in sediments and fish at the Flix site compared to the other sites. Concomitantly, cytochrome p450 1A (CYP1A) expression, a known indicator for pollution by dioxins and dioxin-like PCBs, was significantly elevated in barbel (Barbus graellsii) from the Flix site, compared to the population from the Barbastro site. CYP1A expression correlated with the concentration of dioxin-like PCBs in the fish fat, whereas no significant correlation was found with PCDDs/Fs concentrations. Our data suggest a significant biological impact at the Flix site, closely related to the presence of dioxin-like PCBs, whereas the PCDDs/Fs contribution to this impact appears to be non-significant, at least in the studied sites.

High accumulation of PCDD, PCDF, and PCB congeners in marine mammals from Brazil: A serious PCB problem

Blubber samples from three delphinid species (false killer whale, Guiana and rough-toothed dolphin), as well as liver samples from franciscana dolphins were analyzed for dioxins and related compounds (DRCs). Samples were collected from 35 cetaceans stranded or incidentally captured in a highly industrialized and urbanized area (Southeast and Southern Brazilian regions). Dioxin-like PCBs accounted for over 83% of the total TEQ for all cetaceans. Non-ortho coplanar PCBs, for franciscanas (82%), and mono-ortho PCBs (up to 80%), for delphinids, constituted the groups of highest contribution to total TEQ. Regarding franciscana dolphins, significant negative correlations were found between total length (TL) and three variables, ΣTEQ-DRCs, ΣTEQ-PCDF and ΣTEQ non-ortho PCB. An increasing efficiency of the detoxifying activity with the growth of the animal may be a plausible explanation for these findings. This hypothesis is reinforced by the significant negative correlation found between TL and PCB126/PCB169 concentration ratio. DRC concentrations (ng/g lipids) varied from 36 to 3006, for franciscana dolphins, as well as from 356 to 30,776, for delphinids. The sum of dioxin-like and indicator PCBs varied from 34,662 to 279,407 ng/g lipids, for Guiana dolphins from Rio de Janeiro state, which are among the highest PCB concentrations ever reported for cetaceans. The high concentrations found in our study raise concern not only on the conservation of Brazilian coastal cetaceans, but also on the possibility of human health problem due to consumption of fish from Brazilian estuaries.

The Spanish dioxin inventory Part I: incineration as municipal waste management system

The main objectives of the Spanish dioxin inventory and the incidence of municipal waste incinerators in the PCDD/Fs releases in the period from January 1997-November 1999 are presented. Preliminary data about the stack emission levels, fly ashes and slags as solid residues and the PCDD/Fs input in the USW are also presented to elaborate an initial balance for the incineration sector. A great decrease, from 20 to 1.2 g I-TEQ/y, from incineration gas emissions has been observed since 1996. The preliminary balance in the MWI sector suggests an overall PCDD/Fs destruction. The calculated emission factor, 1.06 microg I-TEQ/Mg, indicates a high quality of the air pollution control systems. The assumption of PCDD/Fs in the USW permits an initial evaluation of other waste management systems.

Uptake of perfluoroalkyl substances and halogenated flame retardants by crop plants grown in biosolids-amended soils

Abstract The bioaccumulation behavior of perfluoroalkyl substances (PFASs) and halogenated flame retardants (HFRs) was examined in three horticultural crops and earthworms. Two species, spinach (Spinacia oleracea) and tomato (Solanum lycopersicum L.), were grown in field soil amended with a single application of biosolids (at agronomic rate for nitrogen), to represent the scenario using commercial biosolids as fertilizer, and the third crop, corn (Zea mays) was grown in spiked soil (˜50 mg PFOS/kg soil, ˜5 mg Deca‐BDE/kg soil and a mixture of both, ˜50 mg PFOS and ˜5 mg Deca‐BDE/kg soil) to represent a worst‐case scenario. To examine the bioaccumulation in soil invertebrates, earthworms (Eisenia andrei) were exposed to the spiked soil where corn had been grown. PFASs and HFRs were detected in the three crops and earthworms. To evaluate the distribution of the compounds in the different plant tissues, transfer factors (TFs) were calculated, with TF values higher for PFASs than PBDEs in all crop plants: from 2 to 9‐fold in spinach, 2 to 34‐fold in tomato and 11 to 309‐fold in corn. Bioaccumulation factor (BAF) values in earthworms were also higher for PFASs (4.06±2.23) than PBDEs (0.02±0.02). Graphical abstract Symbol. No caption available. HighlightsPFASs and HFRs were detected in plants cultivated in biosolids‐amended soils.Bioaccumulation of PFASs and HFRs in three hortical crops and earthworms was found.Transfer factors (TFs) were higher for PFASs than PBDEs in all crop plants.Long‐chain PFASs remained in roots and short‐chain ones translocated to aerial tissues.Bioaccumulation factor (BAF) values in earthworms were higher for PFASs than PBDEs.

In vitro cellular responses in the RTG-2 cell line to complex mixtures of dioxins and dioxin-like PCDDs, PCDFs and PCBs.

High‐resolution gas chromatography/mass spectrometry (HRGC/MS) is the standard method for analysing dioxin, furan and polybrominated retardants in hazardous waste. Determination of dioxin‐like compounds using in vitro bioassays such as ethoxyresorufin‐O‐deethylase (EROD) is an important tool to evaluate their Ah receptor‐mediated toxic effects, because it detects all arylhydrocarbon receptor ligands in a variety of sample matrices. In the present work, we compared RTG‐2 cell line EROD bioassay with HRGC/MS for assessing waste samples (liquid and solid) contaminated with polychlorinated dibenzo‐p‐dioxins and dibenzofurans, polychlorinated biphenyls (dioxin‐like PCBs) and other xenobiotics. For liquid samples, HRGC/MS‐toxic equivalent (HRGC/MS‐TEQ) values ranged from 273.26 to 5.84 ng TEQ l−1 and correlated well (correlation coefficient 0.99) with values obtained by EROD‐TEQ, which ranged from 128 to 2.5 ng TEQ l−1. For solid samples, HRGC/MS‐TEQ values ranged from 3.44 to 0.49 ng TEQ g−1 and correlated less well than liquid samples (correlation coefficient 0.64) with values obtained by EROD‐TEQ ranging from 2.27 to 0.93 ng TEQ g−1. The overestimation of RTG‐2 EROD‐TEQ (1.2 ± 0.92 of values established by HRGC/MS) and the absence of false‐negative results may limit analytical costs by eliminating the need for follow‐up GC/MS analysis on the negative samples. We suggest that RTG‐2 EROD bioassay is an inexpensive means for preliminary dioxin and furan positive screenings of waste samples. Copyright

HCH air levels derived from Bailín dumpsite dismantling (Sabiñánigo, Spain)

Remediation and management of dumpsites is a worldwide problem that must be addressed to protect human health and the environment. Aragon Government long-term objective is the control of air quality related to landfills used to dump organochlorine waste. The present study evaluated the influence of dismantling works performed in Bailín landfill, an hexachlorocyclohexane (1,2,3,4,5,6-hexaclorohexane; HCH) dumpsite located in the city of Sabiñánigo, Spain. A total of 65,000 t of HCH solid waste and 342,000 t of polluted soil were transferred to a new cell with additional isolating measures going beyond the Spanish legal requirements. To evaluate influence of excavation of the old cell, transfer of waste and the state once the works in Bailín area had finished, levels of α-, β-, γ-, δ- and ɛ- HCH isomers were analyzed in 112 air samples obtained from summer 2014 to autumn 2016 by using passive air samplers. Results showed that: i) the existence of the old landfill and/or the works performed during its dismantling were a source of HCH air contamination, ii) old landfill represented an HCH source even after dismantling work was completed, iii) other sources, tentatively associated to Sardas dumpsite and HCH production site (INQUINOSA Factory) were identified in the surroundings, where management should be addressed. Data comparison reflected a heavier contamination caused by the production, storage, and waste disposal than the corresponding to application of lindane and/or technical HCH in Spain. Meteorological dependence (temperature, solar radiation and relative humidity), α-/γ-HCH ratios and isomer profiles of HCH air concentrations were evaluated for temporal trends and geographic distribution.

Study of Cr(VI) in Ashes from Fluidised Bed Combustion of Leather Waste: Applicability of different Speciation Methods

Leather waste originated from shoe industry is considered potential hazardous waste as a consequence of the chrome tanned leather process. On the other hand, the leather waste has an inherent value as fuel that makes feasible its use as a very interesting potential source of energy; nevertheless ash residues are produced during the combustion process. This waste disposed in landfills can cause leachate problems. For that reason, determination of hexavalent chromium is considered as an essential input parameter for the safe disposal of these residues. However the current methods provide ambiguity in the results. The objective of this work was to evaluate two different speciation methods: Method SLC 22 (IUC 18) called Method I, used for leather technicians and Method II, developed by the Analytical Chemistry Laboratory of CIEMAT, to analyse the Cr(VI) content in ashes from fluidised bed combustion of leather waste. Both methods provide appropriate results for these kinds of samples when a non-reducing environment is present.

Gas/particle partitioning and particle size distribution of PCDD/Fs and PCBs in urban ambient air

Urban ambient air samples, including gas-phase (PUF), total suspended particulates (TSP), PM10, PM2.5 and PM1 airborne particle fractions were collected to evaluate gas-particle partitioning and size particle distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). Clausius-Clapeyron equation, regressions of logKp vs logPL and logKOA, and human respiratory risk assessment were used to evaluate local or long-distance transport sources, gas-particle partitioning sorption mechanisms, and implications for health. Total ambient air levels (gas phase+particulate phase) of TPCBs and TPCDD/Fs, were 437 and 0.07pgm-3 (median), respectively. Levels of PCDD/F in the gas phase (0.004-0.14pgm-3, range) were significantly (p<0.05) lower than those found in the particulate phase (0.02-0.34pgm-3). The concentrations of PCDD/Fs were higher in winter. In contrast, PCBs were mainly associated to the gas phase, and displayed maximum levels in warm seasons, probably due to an increase in evaporation rates, supported by significant and strong positive dependence on temperature observed for several congeners. No significant differences in PCDD/Fs and PCBs concentrations were detected between the different particle size fractions considered (TSP, PM10, PM2.5 and PM1), reflecting that these chemicals are mainly bounded to PM1. The toxic content of samples was also evaluated. Total toxicity (PUF+TSP) attributable to dl-PCBs (13.4fg-TEQ05 m-3, median) was higher than those reported for PCDD/Fs (6.26fg-TEQ05 m-3). The inhalation risk assessment concluded that the inhalation of PCDD/Fs and dl-PCBs pose a low cancer risk in the studied area.