Comparative effects of several cyclodextrins on the extraction of PAHs from a real contaminated soil

Polycyclic aromatic hydrocarbons (PAHs) are persistent organic pollutants (POPs) attracting extensive attention worldwide. Soils from many sites, such as areas of coal storage, coke oven plants, manufactured gas plants and areas of coal tar spillage present a high contamination level by PAHs. Due to their low solubility in water, the presence of PAHs in the soil matrix constitutes a long-term source of groundwater contamination, and their toxic, mutagenic and carcinogenic properties are responsible that the remediation of PAH-contaminated soil becomes a major environmental concern. In order to enhance the desorption rate of organic pollutants, various extracting agents have been used. Recently, cyclodextrins (CDs) have been proposed as an alternative agent to enhance the water solubility of hydrophobic compounds and thus their availability for biodegradation. The objectives of the present work were: to identify the level of PAHs of an aged-contaminated soil sample from a former chemical industry plant and to evaluate the ability of a natural cyclodextrin (ß-cyclodextrin, BCD) and three chemically modified cyclodextrins: 2-hydroxypropyl-ß-cyclodextrin (HPBCD), partially methylated-ß-cyclodextrin (PMBCD), and hydroxypropyl-¿-cyclodextrin (HPGCD) to extract the sixteen PAHs considered as priority pollutants by US-EPA. A real contaminated soil from the surrounding area of a deserted chemical industry situated in Asturias (North of Spain) was analyzed exhaustively in order to know its PAHs content. Then extraction experiments using Ca(NO3)2 solution or three types of different cyclodextrins solutions were carried out about the same soil. The results presented in this study show that according to Spanish legislation the analyzed soil had to be considered as contaminated soil. Its total PAHs content was about 1068.77±100.81 mg Kg-1, being phenanthrene, anthracene and naphthalene the most abundant compounds (25.3, 24.7 and 17.1 % of the total PAHs content of the soil, respectively). After the extractions experiments using CDs solutions, it was observed that the percentages of PAHs obtained were always higher than when an aqueous solution was used, although the three chemically modified cyclodextrins achieved higher extractions percentages than the natural cyclodextrin (BCD). From the sixteen selected PAHs, the highest extraction percentages was always obtained for the 3-rings PAHs, what is related with the more appropriated size and shape of this compounds with respect to the CDs cavity dimensions

Comparative effects of several cyclodextrins on the extraction of PAHs from an aged contaminated soil

7 páginas.-- 3 figuras.-- 2 tablas.-- 52 referencias.-- Supplementary dataThe objective of the present study was to characterise the polycyclic aromatic hydrocarbons (PAHs) content of an aged contaminated soil and to propose remediation techniques using cyclodextrins (CDs). Four CDs solutions were tested as soil decontamination tool and proved more efficient in extracting PAHs than when an aqueous solution was used; especially two chemically modified CDs resulted in higher extraction percentages than natural β-CD. The highest extraction percentages were obtained for 3-ring PAHs, because of the appropriate size and shape of these compounds relative to those of the hydrophobic cavities of the CDs studied. A detailed mechanistic interpretation of the chemical modification of CDs on the extraction of the different PAHs has been performed, and connected with the role that the different hydrophobicities of the PAHs play in the extraction behaviour observed for the 16 PAHs, limiting their accessibility and the remaining risk of those PAHs not extractable by CDs. © 2013 Elsevier Ltd. All rights reserved.The authors thank to Dr. J.R. Gallego from the Universidad de Oviedo for providing the contaminated soil sample. Support from projects CTM2006-04626 and CTM2009-07335, Spanish Ministry of Science and Innovation (co-funded by Fondo Europeo de Desarrollo Regional, FEDER), are greatly appreciated. M.A. Sánchez-Trujillo acknowledges a research contract from CSIC (JAEPre 0800763) cofinanced by Fondo Social Europeo (FSE).Peer Reviewe

Decontamination of polycyclic aromatic hydrocarbons and nonylphenol from sewage sludge using hydroxypropyl-β-cyclodextrin and evaluation of the toxicity of leachates

11 páginas.-- 2 tablas.-- 3 figuras.-- 61 referenciasA decontamination technique based in cyclodextrin extraction has been developed to eliminate nonylphenol (NP) and 16 polycyclic aromatic hydrocarbons (PAHs; the US Environmental Protection Agency priority pollutants list) from sewage sludge. In a first step, PAHs and NP were characterised in six sludges to determine contamination levels according to limit values proposed by the European Union Sludge Directive draft. There were few variations in the total PAHs content with levels of 1.88 to 3.05 mg kg-1. Three-ring PAHs predominated, but fluoranthene and pyrene were also present. None of the sludge exceeded the PAHs limit proposed by the European Union's draft Directive. On the contrary, NP content in four of the six sludges was over the recommended limits of 50 mg kg-1 for NP ethoxylates. With the aim of obtaining NP values below the concentration limits proposed to use the sewage sludge as agricultural amendments, a preliminary study using hydroxypropyl-β-cyclodextrin (HPBCD) extractions as a decontamination technique was carried out. About 90 % of NP content was removed with only one extraction with HPBCD, whereas after three sequential extractions using an aqueous solution without HPBCD, the NP extraction percentage was less than 1 %. Simultaneously, PAHs extraction percentages obtained with HPBCD were also much higher than when aqueous solution was used, especially in the case of two- and three-ring PAHs. Finally, the potential environmental hazard of HPBCD leachates to aquatic organisms (Daphnia magna) was tested. These results indicate that the treatment of sewage sludge with cyclodextrin could allow their safe use as fertiliser in agriculture. © 2013 Springer-Verlag Berlin Heidelberg.Support from projects CTM2006-04626 and CTM2009-07335, Spanish Ministry of Science and Innovation (cofunded by Fondo Europeo de Desarrollo Regional, FEDER), are greatly appreciated. M.A. Sánchez-Trujillo acknowledges a research contract from Consejo Superior de Investigaciones Científicas (CSIC, JAEPre 0800763) cofinanced by Fondo Social Europeo (FSE).Peer Reviewe

Impacts of metals and nutrients released from melting multiyear Arctic sea ice

Nutrients (C, N, and P) and metals (iron, molybdenum, nickel, zinc, vanadium, copper, and cobalt) were determined in water and multiyear ice sampled along the Greenland current and Fram Strait in July 2007. Total metal and nutrient concentrations in ice varied fivefold to tenfold, for most elements, across the area sampled. Data show that some nutrients (i.e., NH4+) and metals (i.e., Fe, Zn, V, Cu, Ni, Mo, and Co) are enriched in Arctic ice relative to surface seawaters, suggesting that ice melting is a significant source of metals to the receiving seawaters, particularly Fe and Zn whose concentrations were significantly (t test, P < 0.05) more than 2 orders of magnitude higher in ice than in surface seawater.This research is part of the ATOS project, funded as part of the Spanish contribution to the International Polar Year (IPY) by the Spanish Ministry of Science and Innovation (POL2006-00550/CTM). This is a contribution to the GEOTRACES cluster of the IPY. We thank the ATOS participants, UTM and crew of R/V Hespérides for help with ice sampling and logistics. We thank R. Santiago, R. Martínez, and A. Massanet at IMEDEA and J. A. González (SCT, UIB) for help with chemical analyses. This manuscript was written in the field stations of Ses Salines Lighthouse.Peer reviewe

A review of constraints and solutions for collecting raptor samples and contextual data for a European Raptor Biomonitoring Facility

The COST Action ‘European Raptor Biomonitoring Facility’ (ERBFacility) aims to develop pan-European raptor biomonitoring in support of better chemicals management in Europe, using raptors as sentinel species. This presents a significant challenge involving a range of constraints that must be identified and addressed. The aims of this study were to: (1) carry out a comprehensive review of the constraints that may limit the gathering in the field of raptor samples and contextual data, and assess their relative importance across Europe; and (2) identify and discuss possible solutions to the key constraints that were identified. We applied a participatory approach to identify constraints and to discuss feasible solutions. Thirty-one constraints were identified, which were divided into four categories: legal, methodological, spatial coverage, and skills constraints. To assess the importance of the constraints and their possible solutions, we collected information through scientific workshops and by distributing a questionnaire to stakeholders in all the countries involved in ERBFacility. We obtained 74 answers to the questionnaire, from 24 of the 39 COST participating countries. The most important constraints identified were related to the collection of complex contextual data about sources of contamination, and the low number of existing raptor population national/regional monitoring schemes and ecological studies that could provide raptor samples. Legal constraints, such as permits to allow the collection of invasive samples, and skills constraints, such as the lack of expertise to practice necropsies, were also highlighted. Here, we present solutions for all the constraints identified, thus suggesting the feasibility of establishing a long-term European Raptor Sampling Programme as a key element of the planned European Raptor Biomonitoring Facility.This paper is based on work from COST Action European Raptor Biomonitoring Facility (COST Action CA16224) supported by COST (European Cooperation in Science and Technology), including a grant for a short-term scientific mission awarded to the lead author. COST is funded by the Horizon 2020 Framework Programme of the European Union. Silvia Espín was financially supported by Ministerio de Ciencia, Innovación y Universidades (Juan de la Cierva-Incorporación postdoctoral contract, IJCI-2017-34653).Peer reviewe

New methodology for the determination of phthalate esters, bisphenol A, bisphenol A diglycidyl ether, and nonylphenol in commercial whole milk samples

6 pages, 1 figure, 2 tables.-- PMID: 15186085 [PubMed].-- Printed version published Jun 16, 2004.This paper reports a new methodology aimed at determining dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, butylbenzyl phthalate, bis(2-ethylhexyl) phthalate, nonylphenol, bisphenol A, and bisphenol A diglycidyl ether in commercial whole milk. These compounds are used as plastic additives, lacquers, resins, or surfactants and can be found in milk due to contact with plastic materials during food processing and storage. They are all suspected endocrine disrupters or mutagens. A multiresidue method based in solid-phase extraction with C-18 cartridges followed by a cleanup step using disposable cartridges was developed. Detection and quantification were performed by gas chromatography coupled to mass spectrometric (GC-MS) detection using an appropriate surrogate (4-n-nonylphenol) and internal standard [deuterated bis(2-ethylhexyl) phthalate]. Limits of detection were from 0.06 to 0.36 μg/kg and intraday variation from 3 and 27%, with recoveries between 73 and 119%. Five brands of commercial whole milk processed and packed in different ways were analyzed. All samples contained target compounds at concentrations between 0.28 and 85.3 μg/kg, and the total concentration ranged between 79.3 and 187.4 μg/kg, the levels being higher in sterilized milks. Nonylphenol, diethyl phthalate, dibutyl phthalate, and bis(2-ethylhexyl) phthalate were the major contributors.This work has been supported by the Col•legi Oficial de Farmacèutics de Catalunya.Peer reviewe

Presence and release of phthalic esters and other endocrine disrupting compounds in drinking water

7 pages, 3 figures, 4 tables.-- Available online Sep 21, 2006.An analytical method was developed to analyze 5 phthalate esters (dimethylphthalate, diethylphthalate, di-n-butylphthalate, butylbenzylphthalate, di(2-ethylhexyl)phthalate), nonylphenol, bisphenol A and BADGE (Bisphenol A diglycyleter) in distribution and bottled water. They are all industrial chemicals used in the manufacture of epoxy resins or paints, polycarbonate and polyethylene plastics (global production of phthalates over 4 Mton/year) or surfactants and have been classified as persistent, with high migration potential from plastic containers and with endocrine disrupting properties. The present paper reports a specific extraction protocol using solid phase extraction with Oasis 60 mg or C18 cartridges, followed by gas chromalography coupled to mass spectrometric detection using an appropriate surrogate and internal standard for process control. Quality parameters are reported, making special emphasis to limits of detection, reproducibility and blank analysis, which permitted to detect ng L−1 concentrations. In an application step, the method was used to determine target compounds in 7 distribution water and 9 mineral water bottled in polyethylene, polyethyleneter phthalate and glass containers which were analysed upon purchase and after 10 week storage at temperatures up to 30 °C. Distribution water coming from different aquifers which at some point are in contact with plastic or painted concrete reservoirs and pipes, contained dimethylphthalate, diethylphtalate, nonylphenol, buthylbenzylphthtalate and DEHP at concentrations ranging from 0.005 to 0.331 μgL−1, depending on the sampled crea whereas bottled water showed levels up to 1.7 μg L−1 of some of the studied compounds, attributed to 10 week storage conditions.This work has been supported by the Col.legi Oficial de Farmacèutics de Catalunya.Peer reviewe

Nasal lavages as a tool for monitoring exposure to organic pollutants

Exposure to air and dust pollutants can cause several adverse effects on human health. This study proposes the use of nasal lavages as a non-invasive sampling technique to determine in a direct way pollutant intake through inhalation. We evaluate the occurrence of compounds widely used in domestic products and construction materials (organophosphorus flame retardants (OPFR), phthalates, alkylphenols and bisphenol A), applied for pest control in cities (pesticides) and emitted through car exhausts (polycyclic aromatic hydrocarbons, PAHs) or smoking (nicotine). Contaminants were liquid-liquid extracted from nasal lavages and analysed using gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). All 29 individuals inhabiting in Barcelona city had phthalates and bisphenol A at concentrations up to 31,300 ng mL−1 for diethylhexyl phthalate (DEHP) and 118 ng mL−1 for BPA. Individual PAHs, OPFR and alkylphenols had median values below their MQLs except for 2-ethylhexyldiphenyl phosphate (EHDPhP) with a median of 1.47 ng mL−1. Nicotine was detected at the highest concentrations in all active smokers (median 2.16 ng mL−1). Contrarily, pesticides were sporadically detected. Nasal lavages revealed to be an appropriate indicator likely to reflect exposure to dust and air contaminants.Authors want to thank all friends and relatives who offered as volunteers and gave their permission and time to sample their noses. In particular, Sergio Gaona, who helped us by collecting an important part of the sample set. Thanks too to Bruna Tresànchez for the physiological description of nasal cavities and to Marina Bantulà for discussions on this study. The pharmacy Trinquet is acknowledged for supplying the nebulizers with price reduction. M.V acknowledges financial support from the Spanish Ministry of Economy, Industry and Competitiveness (Programa Operativo Empleo Juvenil 2014–2020 and Iniciativa de Empleo Juvenil y Fondo Social Europeo).Peer reviewe

Organic pollutants in indoor dust from Ecuadorian Amazonia areas affected by oil extractivism

Fifty-five household dust samples collected within six settlements surrounding oil production complexes along the Ecuadorian Amazonia were analysed to evaluate the occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs), phthalates, alkylphenols (APs), bisphenol A (BPA), nicotine, organophosphorus flame retardants (OPFRs), polychlorinated biphenyls (PCBs), legacy organochlorine pesticides (OCs) and organophosphorus pesticides. Studied areas are mainly affected by gas flares emissions and oil spilling coming from extractivist operations and pesticides used in agriculture. Median ΣPAHs values ranged from 739 to 1182 ng g and up to 52% of the PAH dust concentrations were associated to petrogenic activities from crude oil extraction, according to diagnostic ratios. ΣPAHs and toxic equivalents based on benzo[a]pyrene concentration (ΣTEQ, ng g) suggested similar toxicities among the different areas. Individual lifetime cancer risk (ILCR) was calculated for ingestion and dermal contact exposure routes and a non-acceptable total carcinogenic risk of up to 10 (one case per ten thousand people) was found for newborns from 0 to 3 years-old in Pimampiro area. Plasticisers and OPFRs were present in dust at maximum median concentrations of 332,507 ng g (DEHP), 5,249 ng g (DBP), 1,885 ng g (BPA), 871 ng g (TBOEP) and 122 ng g (TEHP). Some dust samples from Ecuadorian houses had high maximum levels of legacy and modern pesticides such as chlorpyrifos (up to 44,176 ng g), 4,4′-DDT (12,958 ng g), malathion (34,748 ng g) and α+β-endosulfan (10,660 ng g) attributed to inappropriate use and storage of the pesticides. Finally, nicotine was seldom detected (36 ng g). The sources and risks of these compounds are discussed based on the activities carried out in the study areas and attending to an additional non-cancer risk assessment which showed high hazard quotients (HQ) and hazard indexes (HI) for DEHP, DBP, 4,4′-DDT, malathion, chlorpyrifos, naphthalene and benzo[a]pyrene in newborns and children up to 16 years-old.This work was funded by the financial support from the Programa Operativo Empleo Juvenil 2014–2020 and Iniciativa de Empleo Juvenil y Fondo Social Europeo from Ministerio de Economía y Competitividad, Spain

Investigation of Arctic and Antarctic spatial and depth patterns of sea water in CTD profiles using chemometric data analysis

In this paper we examine 2- and 3-way chemometric methods for analysis of Arctic and Antarctic water samples. Standard CTD (conductivity-temperature-depth) sensor devices were used during two oceanographic expeditions (July 2007 in the Arctic; February 2009 in the Antarctic) covering a total of 174 locations. The output from these devices can be arranged in a 3-way data structure (according to sea water depth, measured variables, and geographical location). We used and compared 2- and 3-way statistical tools including PCA, PARAFAC, PLS, and N-PLS for exploratory analysis, spatial patterns discovery and calibration. Particular importance was given to the correlation and possible prediction of fluorescence from other physical variables. MATLAB's mapping toolbox was used for geo-referencing and visualization of the results. We conclude that: 1) PCA and PARAFAC models were able to describe data in a satisfactory way, but PARAFAC results were easier to interpret; 2) applying a 2-way model to 3-way data raises the risk of flattening the covariance structure of the data and losing information; 3) the distinction between Arctic and Antarctic seas was revealed mostly by PC1, relating to the physico-chemical properties of the water samples; and 4) we confirm the ability to predict fluorescence values from physical measurements when the 3-way data structure is used in N-way PLS regression. © 2014 Elsevier B.V. and NIPR