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During the last decades, many efforts have been devoted to the adaptation of sample preparation techniques and methods to the principles of Green Analytical Chemistry. Among them, this article review focusses on those aimed to green the solvents involved in sample treatment. Research in this field started in the late 1990s with the synthesis of room temperature ionic liquids, which were later replaced by the deep eutectic solvents (DESs). During the last years, a subclass of DESs, the so-called hydrophobic deep eutectic solvents (HDESs) have attracted attention. HDESs have contributed to circumventing some of the limitations of early-synthesised hydrophilic DESs regarding the cost of raw materials, the simplicity of synthesis, and the biocompatibility and, apparently, the biodegradability of the mixtures. In addition, these mixtures allowed the treatment of aqueous samples and the extraction of non-polar analytes. This article discusses fundamental aspects regarding the nomenclature used concerning HDESs, summarises the main physicochemical properties of these mixtures, and through discussion of key application studies, de- scribes current progress in the use of these green solvents for the extraction of trace organic contaminants from a variety of matrices. Remaining gaps and possible lines of future development in this emerging, active and attractive research area are also identified and critically discussed.

Endocrine disruptors (ECD, Endocrine Disrupting Chemicals) are chemicals that may interfere with the body’s endocrine system and produce adverse developmental, reproductive, neurological, and immune effects in both humans and wildlife[1]. Due to this, it has been necessary to develop rapid and sensitive method for the determination of ECD. This work presents the results of the analysis of four phthalates[2] (PAEs: dimethyl phthalate, diethyl phthalate, dibutyl phthalate and butyl benzyl phthalate), seven parabens[3] (PBs: methyl paraben, ethyl paraben, n-propyl paraben, iso-propyl paraben, n-butyl paraben, iso-butyl paraben and benzyl paraben) and bisphenol A[4] (BPA) in 42 commercially available milk samples, related to the packaging and storage. Because of contamination problems, a method based on the simultaneous extraction and purification of the sample, was chosen to reduce the manipulation[5]. Briefly, extraction in glass column was carried out by matrix solid phase dispersion (MSPD) put on a layer of Florisil® (purification). The column was eluted with ethyl acetate and concentrated for its final quantification by ultra-high performance liquid chromatography coupled to mass spectrometry (UHPLC-MS). With this method, all the analyte recoveries were higher than 70%. Different brands (11 commercial trademarks) and different types of containers (metallic bag, metal pail, HDPE, PET, Combibloc®, Tetra Brick®, Tetra Gemina® and Tetra Prisma®) have been investigated to study the effect of the container and the possible contamination during the production and processing of the product. The concentration levels and profiles found (expressed as median in pg/g fresh weight) were different for each type of analyte. PBs showed the highest concentration (1564 – 42879 pg/g f.w.), followed by PAEs (2810 – 9094 pg/g f.w.). Finally, BPA showed the lowest concentration (7 – 13 pg /g f.w.). Depending on the type of packaging, the highest PAE concentrations were found for metal pa

Phthalates (diesters of 1,2-benzenedicarboxylic acid), also known as phthalic acid esters (PAEs), are synthetic organic compounds that are used in a broad spectrum of industrial and commercial applications, like toys, food packaging, lubricants, vinyl flooring, adhesives, detergents, hair spray, shampoo, etc. [1] . They have endocrine disrupting potency and have become nearly ubiquitous. For the general population, the human exposure to phthalates is through ingestion, inhalation, dermal absorption, and/or contact with medical devices [2]. Once they are ingested, PAEs are rapidly metabolized to their respective monoesters in human body and some of these primary metabolites can be further metabolized to secondary metabolites and excreted by urine. All of these metabolites can be used as biomarkers of human exposure to phthalates [3]. The sample preparation and instrumental determination methods have been previously described elsewhere [4]. Briefly, the sample preparation consisted of an enzymatic deconjugation of the glucuronide phthalates followed by a purification step with OASIS© HLB SPE cartridge (Waters, MA, USA). The instrumental determination was carried out by using UPLC QqQ MS2 (Xevo-TQS, Waters) working in MRM mode, with a BEH-phenyl column (50 mm x 2.1 mm, 1.7 µm),. We present here, for the first time, the levels and temporal trends of 9 PAE metabolites (6 phthalate monoesters (monomethyl phthalate [MMP], monoethyl phthalate [MEP], mono-iso-buthyl phthalate [MiBP], mono-n-butyl phthalate [MBP], monobenzyl phthalate [MBzP] and monoethylhexyl phthalate [MEHP]) and 3 secondary metabolites of DEHP (5-OH-mono(2-ethylhexyl) phthalate [5-OH-MEHP], 5-oxo-mono(2-ethylhexyl) phthalate [5oxo-MEHP] and 5-carboxy-mono(2-ethylpentyl) phthalate [5cx-MEPP]) in human urine samples collected in 2012 and 2015 from 9 volunteers living in the Community of Madrid. Detectable amounts of the 9 MPAEs were obtained in all the studied samples, being the MPAE levels found in almost a

This study is part of the BioMadrid Project, a bio-monitoring study designed to assess pollutants in the environment surrounding children born in the Madrid region. Our aim in this report is to evaluate the association between prenatal lead exposure and fetal development using three biological samples (maternal and paternal blood lead at around 34 weeks of gestation as well as cord blood lead levels), three biomarkers of effect in cord blood peripheral lymphocytes (micronucleus in binucleated cells, nucleoplasmic bridges, and nuclear buds), and different anthropometrical characteristics at birth. Maternal and cord blood lead were not associated with newborn measurements or genotoxicity biomarkers. In contrast, increases in father blood lead were coupled with lower weight (mean difference (MD), -110.8 g; 95% confidence intervals (95%CI), -235.6 to 6.00; p < 0.10) and shorter abdominal (MD, -0.81 cm; 95%CI, -1.64 to 0.00; p < 0.05) and cephalic (MD, -0.32 cm; 95%CI, -0.65 to 0.00; p < 0.05) circumferences at birth as well as with the presence of nucleoplasmic bridges (odds ratio, 1.03; 95%CI, 1.00 to 1.06; p < 0.05) and nuclear buds (odds ratio, 1.02; 95%CI, 0.99 to 1.04; p < 0.10). These associations were mainly confined to female babies, in whom paternal lead was also inversely associated with length. Our results support the hypothesis that paternal lead exposure may be affecting the development of newborns.

Monitoring cytogenetic damage is frequently used to assess population exposure to environmental mutagens. The cytokinesis-block micronucleus assay is one of the most widely used methods employed in these studies. In the present study we used this assay to assess the baseline frequency of micronuclei in a healthy population of father-pregnant woman-newborn trios drawn from two Madrid areas. We also investigated the association between micronucleus frequency and specific socioeconomic, environmental, and demographic factors collected by questionnaire. Mercury, arsenic, lead, and cadmium blood levels were measured by atomic absorption spectrometry. The association between micronucleated cell frequency and the variables collected by questionnaire, as well as, the risk associated with the presence of elevated levels of metals in blood, was estimated using Poisson models, taking the number of micronucleated cells in 1,000 binucleated cells (MNBCs) as the dependent variable. Separate analyses were conducted for the 110 newborns, 136 pregnant women, and 134 fathers in whom micronuclei could be assessed. The mean number of micronucleated cells per 1,000 binucleated cells was 3.9, 6.5, and 6.1 respectively. Our results show a statistically significant correlation in MNBC frequency between fathers and mothers, and between parents and newborns. Elevated blood mercury levels in fathers were associated with significantly higher MNBC frequency, compared with fathers who had normal mercury levels (RR:1.21; 95%CI:1.02-1.43). This last result suggests the need to implement greater control over populations which, by reason of their occupation or life style, are among those most exposed to this metal.

[ES] En España, la vigilancia medioambiental se basa principalmente en medidas de ciertos contaminantes en muestras de aire, agua, alimentos y suelos. En Madrid se ha realizado un estudio para valorar la posibilidad de poner en marcha un sistema de vigilancia de exposiciones a contaminantes ambientales en la población general utilizando biomarcadores. El proyecto ha tenido como eje el estudio del entorno de los recién nacidos. Por tanto, la población de estudio la constituyen 145 «tríos» formados por mujeres en su octavo mes de embarazo, sus parejas y los recién nacidos de dos áreas geográficas, que representan los dos principales entornos urbanos de la región, es decir, Madrid capital y su área metropolitana. Se recogieron múltiples sustratos biológicos de cada participante con el objeto de valorar las muestras más adecuadas para un sistema de vigilancia de exposiciones ambientales. Los contaminantes elegidos representan los principales agentes tóxicos a los que una población como la de Madrid está expuesta diariamente, e incluyen metales pesados, contaminantes orgánicos persistentes e hidrocarburos aromáticos policíclicos; se ha añadido también una medida inespecífica de daño citogenético, los micronúcleos en sangre periférica. Además, se han colocado muestreadores pasivos de aire en los alrededores del domicilio de los participantes. Este artículo describe en detalle el diseño del estudio y la tasa de respuesta, resumen los resultados del trabajo de campo y comenta algunas enseñanzas prácticas de éste., [EN] In Spain environmental surveillance has mainly relied on measures of selected pollutants in air, water, food and soil. A study was conducted in Madrid to assess the feasibility of implementing a surveillance system of exposure among the general population to specific environmental pollutants, using bio-markers. The project was basically focused on the environment surrounding newborns. Hence, the study population was made up of 145 triplets of pregnant women at around 8 months' gestation, their partners, and newborns from two areas, representing the two main types of urban environments in the region, i.e., the City of Madrid and its outlying metropolitan belt. Multiple biologic substrates were collected from each participant in order to assess the most suitable samples for an environmental surveillance system. The selected contaminants represent the main agents to which a population like that of Madrid is exposed every day, including certain heavy metals, persistent organic pollutants and polycyclic aromatic hydrocarbons, as well as micronuclei in peripheral blood, a commonly used unspecific index of cytogenetic damage. In addition, passive air samplers were placed around subjects' place of residence. This paper reports in detail on the design and response rates, summarizes field work results, and discusses some lessons learned.

Median concentration of total PBDEs in maternal serum, paternal serum, umbilical cord serum, and breast milk samples were 12, 12, 17, and 6.1 ng/g lipid weight (lw) in Vallecas and 9.7, 12, 15, and 5.5 ng/g lw in Getafe. The median value found in placentas was 1.9 ng/g lw (in Vallecas). BDE 47 was the predominant congener in serum samples (maternal, paternal, and umbilical cord), while BDE 209 was predominant in placenta and breast milk samples. BDEs 196 and 197 were detected in most of the placenta and breast milk samples. The results show that PBDEs, like other POPs, can cross the placenta barrier, although the speed of the process seems to differ for each PBDE congeners. The total PBDE concentrations found in this study are consistent with research reported elsewhere. They are in the same range as those recently reported by other European and Asian studies and lower than those conducted in the U.S.A. No significant differences were found (p > 0.05) between regions, sexes, and ages, while statistically significant differences (p < 0.05) were found between maternal serum, umbilical cord serum, and breast milk samples. The presence of PBDEs in cord blood and placenta samples indicates that there is prenatal exposure of PBDEs, which could continue after birth via breast milk.

The polychlorinated dibenzo-p-dioxin (PCDD), dibenzofuran (PCDF), and polychlorinated biphenyl (PCB) contents of 123 Spanish commercial salmon, tuna fish, sardine, oyster, mussel, and clam samples from 1995 to 2003 were investigated. A significant decrease of dioxin and non-ortho PCB concentrations in the studied species was found over the years. The decrease was greater in the case of dioxins than in that of non-ortho PCBs, especially during the early years of the study. PCB and PCDD/F concentrations in the years 2001−2003 were comparable to those reported in the literature for similar species collected after 1999. Mean PCB concentrations ranged from 3.46 ng/g of fresh weight (fw) in clams to 100 ng/g of fw in tuna fish. PCDD/F mean current levels ranged from 0.62 pg/g of fw in clams to 2.89 pg/g of fw in oysters. Toxic equivalent quantities (WHO-TEQ) ranged from 0.05 pg of WHO-TEQPCDD/Fs/g of fw in clams to 0.5 pg of WHO-TEQPCDD/Fs/g of fw in salmon (in the upper bound determination levels). When coplanar PCBs were included, the WHO-TEQPCDD/Fs+cop PCBs values increased by a range of 1.7 times in oysters to 14.1 times in tuna fish. The decrease in dioxin concentrations suggests that efforts to control dioxin emissions and to reduce human exposure through foodstuffs are succeeding. The high contribution of PCBs to total WHO-TEQs in the fish and shellfish species investigated suggests that it is important to determine PCBs in foodstuffs, and especially in fish products, and they should be included in further research and future legislation.

Congener-specific analyses of seventeen 2,3,7,8-substituted PCDD/Fs, three non-ortho and 8 mono-ortho dioxin-like polychlorinated biphenyls (PCBs) were performed on 258 Spanish foodstuff samples, mainly of animal origin, for 2000--03. Daily dietary intakes of PCDD/Fs and PCBs, expressed as toxic equivalents (WHO-TEQs), were estimated by combining food consumption data from the Spanish National Institute Statistics survey and concentration levels measured in individual samples, using upper bound determination values (not detectable = limit of detection). The calculated dietary intake of PCDD/Fs for a person weighing 70 kg was 1.35+/-0.11pg WHO-TEQs kg(-1) bw day(-1), and 3.22+/-0.75 pg WHO-TEQs kg(-1) bw day(-1) if dioxin-like PCBs (non- and mono-ortho PCBs) were included, showing the importance of their inclusion in monitoring studies. Both values were within the range of tolerable daily intake (TDI) proposed by the WHO (1-4pg WHO-TEQs kg(-1) bw day(-1)). The current levels are lower than earlier intakes estimates conducted in Spain. Meat and meat products accounted for more than 35% of the intake, followed by milk and milk products (29%), vegetables oils (19%), fish and seafood (11%) and eggs (4%). Dioxin-like PCBs are an important component in the total WHO-TEQs in foodstuffs. This is particularly true for the fish food group, where the total WHO-TEQs is dominated by dioxin-like PCBs (up to 80% of WHO-TEQs in some cases).

In this study samples of common trout, European eel and barbel have been analysed for the levels of heavy metals such as lead (Pb), cadmium (Cd), zinc (Zn), copper (Cu), and the metalloid arsenic (As). Polychlorinated biphenyls (PCBs), including three non-ortho substituted PCBs, 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and DDT and its two main metabolites were also analysed in some selected samples, in order to evaluate the extent of contamination of the River Turia basin. All samples presented detectable levels of the elements analysed, presenting zinc the highest concentrations. European eel was the species found to highly accumulate these contaminants. Regarding organochlorinated compounds, seven samples exhibited detectable levels of the most toxic PCDD/Fs congener, the 2,3,7,8-TCDD. Non-ortho PCBs were not detected or not quantified in almost all samples and the sum of the individual PCB congeners determined were low compared to other aquatic ecosystems with similar fish species.

Pollution can produce severe impacts on eggs leading to embryo death or abnormal embryonic development. We have analysed the presence of chemical toxicants inside chameleon eggs from southern Spain. In this area, the chameleon (Chamaeleo chamaeleon) is considered as an endangered species that usually inhabits in highly populated areas. Previous studies have shown high em- bryo mortality rates under natural incubation conditions. Lead and PCBs could be contributing to this low hatching success. Lead concentration in eggs was especially high with an average of 14.2 ppm on wet weight. This mean lead concentration has been toxic for other species. Resi- dues of Cu, and Zn were also found in the clutches. Zn concentration averaged 11.05 ppm. Cd was not detected in any egg. Total PCBs were present at high concentra- tions in eggs, with an average of 17 ppb on wet weight. Low concentrations of nine of ten analysed organochlo- rine pesticides appeared in all the clutches studied. Only DBF and DDE were found at concentrations above 1 ppb

Heavy metals from industrial and urban discharges are deposited in different components of the aquatic ecosystem, such as water, sediments, soils and biota. All heavy metals are potentially harmful to most organisms at some level of exposure and absorption. Under certain environmental conditions, heavy metals may accumulate to a toxic concentration, and cause ecological damage. This study has been carried out along Ebro River (Spain); this river is 928 km long and drains an area of 85,000 km2 approximately. The Ebro basin is the most economically important area of the North of the Iberian Peninsula. The primary sources of heavy metals in the river are the industrial activities along the basin, municipal effluents and pollution from tributaries, as is also the case of the Siurana and Segre Rivers. The aim of this study is to determine the levels of five metals (Hg, Pb, Cd, Cu and Zn) in water, sediments and earthworms sampled in seventeen stations along Ebro River, to evaluate regional patterns of residues and to identify the possible sources.

A long-term monitoring plan was established to study if bird populations around Donana National Park were affected by the toxic spill from the Aznalcollar mine. The concentrations of Zn, Pb, As, Cu, Sb, Co, Tl and Cd in the blood of 11 bird species feeding in the area were determined. The parameters which most affect the accumulation of trace elements in the birds studied are, firstly, species and, secondly, trophic position, sex, days of exposure and weight. In some individuals, Zn and Cu occurred at higher levels than the reference values for contaminated areas. Concentrations of Pb and Cd in a considerable number of individuals were higher than those found in birds from uncontaminated areas. The present data, together with the lack of data on blood metal concentration prior to the spill, do not offer any conclusive evidence of the influence of the spill on avian blood metal concentrations.

The impact of the spill from the mine in Aznalcollar (Seville, Spain) on waterfowl in the Donana National Park is assessed. The concentrations of Cu, Pb, Cd, Zn and As in the liver and eggs of 16 species of waterfowl found dead in the Park between April and November 1998 were determined. The highest levels were found for Zn, followed by Cu, Pb, Cd and As. The main parameters related to the accumulation of these elements in the waterfowl studied were species and trophic level. The other variables studied distance from the spill, days of exposure, sex, size, and age are important, although this depends on the element studied. Zn and Cu from the spill have entered the food chain of the aquatic birds studied, but Cd, Pb and As have not. There is currently no evidence to suggest that the trace element concentrations measured have reached toxic levels.

Polychlorinated terphenyls (PCTs) are compounds related to Polychlorinated biphenyls (PCBs), because of their physical and chemical properties. They have been used for similar applications, although to a lower degree. As a consequence, PCTs have been sprayed in the environment. In this paper, we have analyzed some samples of marine origin that are part of the spanish diet, purchased in municipal markets of Madrid. Levels found range between 146.6 ng/g to 32,966.8 ng/g (fat weight). The analytical technique employed is HRGC using ECD for quantification and HRMS (SIM) for correct identification due to the large number of peaks.

Residues of organochlorines, polychlorinated biphenyls (PCBs), and heavy metals (mercury, cadmium, lead, copper and zinc) were measured in unhatched eggs of Lesser Kestrels (Falco naumanni) collected in southern Spain in 1988-1991. Although contaminants were detected in all eggs, the amounts were generally below levels known to have negative effects on reproduction. This is consistent with the relatively high hatching rate (about 80%) in the studied population. The nestling mortality was severe, however, apparently due to starvation. It cannot be discounted that pesticides had an indirect effect on the kestrel's breeding success by reducing the populations of prey.

A study on contamination levels by organochlorinated compounds (pesticides and PCBs) and heavy metals (Hg, Cd, Pb, Cu and Zn) in Doñana National Park (Spain) area and its surrounding region has been carried out. Residue levels of xenobiotics were determined in water and soils samples from seventeen sites selected through the park and nearest surrounding farm lands affecting to the inner Park. Also we analyzed some stations along the Guadiamar Basin in the north of Doñana region to determined the movement and influence of one mine situated over 40 km away, in Aznalcóllar, where the commercial expoitation of pyrites ores rich in Zn, Pb and Cu is being operated.

Eggs from Herring Gulls, Audouin Gulls and Gull Billed Terns were collected at three different locations in Spain during the breeding season of 1988. Organochlorine pesticides, total polychlorinated biphenyls (PCBs) and seven selected individual chlorobiphenyl congeners were determined in each of the thirty infertile eggs. The levels of DDE and total PCBs in eggs from the Delta Ebro River are greater than those gathered at Chafarinas Island and Cuenca. Among the species investigated, the Gull Billed Tern eggs showed the lowest level followed by the Herring Gull and the Audouin Gull eggs. The levels of the seven congeners of PCBs showed that 138 was the most prominent, followed by, in decreasing order, 153, 180, 170, 101, 151, and 194. Congener 138 constituted 10.5% ± 2.7 (S.D) of the total PCBs concentration, the 153 8.7% ± 4.2, the 180 7.5% ± 1.9, the 170 3.2% ±1.0, the 101 1.9% ± 3.06, the 151 1.1% ± 1.5 and the 194 0.9% ± 0.5. Polychlorinated biphenyl (PCB) residues (48 congeners) from gull eggs gathered at Ebro Delta and Chafarinas Islands were analyzed with SIMCA (Soft Independent Modeling of Class Analogy), a principal components analysis technique. A series of technical Aroclors® were also analyzed to provide a reference data set for pattern recognition. Environmental PCB residue profiles differed according to the sample's origin. This analysis discriminated between the two regions sampled.