RESUMEN

Alkylphenol ethoxylates (APEOs) represent a non-ionic surfactant widely used as adjuvants in pesticide formulation, which is considered to cause an endocrine-disrupting effect. In the current study, we established a detection method for the APEOs residue in tea based on solid-phase extraction (SPE) for the simultaneous analysis of nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) by UPLC-MS/MS. In the spiked concentrations from 0.024 to 125.38 µg/kg for 36 monomers of APEOs (nEO = 3-20), the recoveries of APEOs range from 70.3-110.7% with RSD ≤ 16.9%, except for OPEO20 (61.8%) and NPEO20 (62.9%). The LOQs of OPEOs and NPEOs are 0.024-6.27 and 0.16-5.01 µg/kg, respectively. OPEOs and NPEOs are detected in 50 marketed tea samples with a total concentration of 0.057-12.94 and 0.30-215.89 µg/kg, respectively. The detection rate and the range of the monomers of NPEOs are generally higher than those of OPEOs. The current study provides a theoretical basis for the rational use of APEOs as adjuvants in commercial pesticide production.

Asunto(s)

RESUMEN

The continuous use of household and personal care products (HPCPs) produces an immense amount of chemicals, such as parabens, bisphenols, benzophenones and alkylphenol ethoxylates, which are of great concern due to their well-known endocrine-disrupting properties. These chemicals easily enter the environment through man-made activities, thus contaminating the biota, including soil, water, plants and animals. Thus, on top of the direct exposure on account of their presence in HPCPs, humans are also susceptible to secondary indirect exposure attributed to the ubiquitous environmental contamination. The aim of this review was therefore to examine the sources and occurrence of these noteworthy contaminants (i.e. parabens, bisphenols, benzophenones, alkylphenol ethoxylates), to summarise the available research on their environmental presence and to highlight their bioaccumulation potential. The most notable environmental contaminants appear to be MeP and PrP among parabens, BPA and BPS among bisphenols, BP-3 among benzophenones and NP among alkylphenols. Their maximum detected concentrations in the environment are mostly in the range of ng/L, while in human tissues, their maximum concentrations achieved µg/L due to bioaccumulation, with BP-3 and nonylphenol showing the highest potential to bioaccumulate. Finally, of another great concern is the fact that even the unapproved parabens and benzophenones have been detected in the environment.

Asunto(s)

RESUMEN

The everyday use of household and personal care products (HPCPs) generates an enormous amount of chemicals, of which several groups warrant additional attention, including: (i) parabens, which are widely used as preservatives; (ii) bisphenols, which are used in the manufacture of plastics; (iii) UV filters, which are essential components of many cosmetic products; and (iv) alkylphenol ethoxylates, which are used extensively as non-ionic surfactants. These chemicals are released continuously into the environment, thus contaminating soil, water, plants and animals. Wastewater treatment and water disinfection procedures can convert these chemicals into halogenated transformation products, which end up in the environment and pose a potential threat to humans and wildlife. Indeed, while certain parent HPCP ingredients have been confirmed as endocrine disruptors, less is known about the endocrine activities of their halogenated derivatives. The aim of this review is first to examine the sources and occurrence of halogenated transformation products in the environment, and second to compare their endocrine-disrupting properties to those of their parent compounds (i.e., parabens, bisphenols, UV filters, alkylphenol ethoxylates). Albeit previous reports have focused individually on selected classes of such substances, none have considered the problem of their halogenated transformation products. This review therefore summarizes the available research on these halogenated compounds, highlights the potential exposure pathways, and underlines the existing knowledge gaps within their toxicological profiles.

Asunto(s)

RESUMEN

Alkylphenol ethoxylates (APEs) have been used in several offshore oil and gas production applications including as emulsifiers in drilling mud formulations, which may have resulted in their disposal to sea. Despite concern over the endocrine disrupting potential of their alkylphenol (AP) degradation products, information on the presence of AP/APEs in marine sediments in the vicinity of oil and gas production facilities is scarce. This paper presents the occurrence of AP/APEs in marine sediment in North Sea oil and gas fields. The concentrations of octylphenol, nonylphenol and their ethoxylates near offshore installations were broadly comparable to, or higher than those of coastal and estuarine point source discharges. When compared to environmental assessment criteria, the NPCA Class V threshold values for octylphenol and nonylphenol were exceeded within 100 m and 500 m of infrastructure respectively, with higher concentrations of AP/APEs reported in fields that came online prior to 1986.

Asunto(s)

RESUMEN

It has been widely demonstrated that endocrine disruptors play a central role in various physiopathological processes of human health. In the literature, various carcinogenic processes have been associated with endocrine disruptors. A review of the molecular mechanisms underlying the interaction between endocrine disruptors and the endometrial cancer has been poorly developed. A systematic review was performed using PubMed®/MEDLINE. A total of 25 in vivo and in vitro works were selected. Numerous endocrine disruptors were analyzed. The most relevant results showed how Bisphenol A (BPA) interacts with the carcinogenesis process on several levels. It has been demonstrated how BPA can interact with hormonal receptors and with different transcription proliferative and antiproliferative factors. Furthermore, the effect of Polycyclic aromatic hydrocarbons on Aryl hydrocarbon receptors was investigated, and the role of flame retardants in promoting proliferation and metastasis was confirmed. The results obtained demonstrate how the mechanisms of action of endocrine disruptors are manifold in the pathophysiology of endometrial cancer, acting on different levels of the cancerogenesis process.

Asunto(s)

RESUMEN

In this study, we conducted a comprehensive study of the distribution, transportation behavior and potential ecological risk of alkylphenol polyethoxylates (APnEOs) in the aquatic environments of Kaohsiung City, Taiwan because little information is available regarding the fate of APnEOs in the water bodies of a total environment. At Love River, APnEOs concentrations were much higher at upstream of interception stations L15 (27.33 ± 1.22 µg/L) and L16 (6.31 ± 0.14 µg/L) than at downstream of interception stations L1-L14 (0.69-2.54 µg/L). Additionally, the average ethoxy (EO) chain lengths of APnEOs at L15 and L16 were longer than at L1-L14. These observations were attributed to the sluice between L14 and L15 that intercepts and accumulates untreated sewage from upstream areas and to the infrastructure of the sewage system that prevents domestic sewage from flowing downstream in the river and to the Kaohsiung Port Area. At Kaohsiung Port Area, APnEO concentrations ranging from 0.63 to 6.50 µg/L were measured. The concentration range and average EO chain length of these APnEOs were similar to those of the downstream stretch of the river, which was attributed to the mixing efficiency of the Kaohsiung Port Area and Love River through tidal exchange. At Cijin Coastal Area, APnEO concentrations ranged from 0.14 to 18.77 µg/L. Notably, the APnEO concentration of surface waters was much higher than that of bottom waters. This observation was attributed to the sewage discharged from the ocean outfall buoying up to the surface instead of mixing with surrounding bottom waters. In potential ecological risk, 19 of 39 sampling points exceeded toxic equivalency of 1 µg/L, and approximately 48.7% of the sampling points would exceed the threshold. The result provides insight into the environmental implications of APnEOs contamination in aquatic environments and useful information for environmental policy and ecological risk assessments.

Asunto(s)

RESUMEN

Alkylphenol polyethoxylates (APEOs), such as nonylphenol ethoxylates (NPEOs), are high-production-volume surfactants used in laundry detergents, hard-surface cleaners, pesticide formulations, textile production, oils, paints, and other products. NPEOs comprise -80% of the total production of APEOs and are widely reported across diverse environmental matrices. Despite a growing push for replacement products, APEOs continue to be released into the environment through wastewater at significant levels. Research into related nonionic surfactants from varying sources has reported metabolic health impacts, and we have previously demonstrated that diverse APEOs and alcohol polyethoxylates promote adipogenesis in the murine 3T3-L1 pre-adipocyte model. These effects appeared to be independent of the base alkylphenol and related to the ethoxylate chain length, though limited research has evaluated NPEO exposures in animal models. The goals of this study were to assess the potential of NPEOs to promote adiposity (Nile red fluorescence quantification) and alter growth and/or development (toxicity, length, weight, and energy expenditure) of developmentally exposed zebrafish (Danio rerio). We also sought to expand our understanding of the ability to promote adiposity through evaluation in human mesenchymal stem cells. Herein, we demonstrated consistent adipogenic effects in two separate human bone-marrow-derived mesenchymal stem cell models, and that nonylphenol and its ethoxylates promoted weight gain and increased adipose deposition in developmentally exposed zebrafish. Notably, across both cell and zebrafish models we report increasing adipogenic/obesogenic activity with increasing ethoxylate chain lengths up to maximums around NPEO-6 and then decreasing activity with the longest ethoxylate chain lengths. This research suggests metabolic health concerns for these common obesogens, suggesting further need to assess molecular mechanisms and better characterize environmental concentrations for human health risk assessments.

RESUMEN

The wide range and complexity of cosmetic formulations currently available on the market poses a challenge from an analytical point of view. In addition, during cosmetics manufacture, impurities coming from raw materials or formed by reaction of different organic compounds present in the formulation may be present. Their identification is mandatory to assure product quality and consumer health. In this work, micro-matrix solid-phase dispersion (µMSPD) is proposed as a multi-target sample preparation strategy to analyze a wide number of unexpected families of compounds including polycyclic aromatic hydrocarbons (PAHs), pesticides, plasticizers, nitrosamines, alkylphenols (APs), and alkylphenol ethoxylates (APEOs). Analytical determination was performed by gas chromatography-mass spectrometry (GC-MS) for the determination of 51 target compounds in a single run, whereas liquid chromatography tandem mass spectrometry (LC-MS/MS) was employed for the analysis of six APs and APEOs. Both methodologies were successfully validated in terms of linearity, accuracy, and precision in leave-on and rinse-off cosmetics. Limits of detection (LODs) were calculated in the low ng g-1, showing their suitability to determine trace levels of impurities and banned compounds with different chemical natures, providing useful tools to cosmetic control laboratories and companies.

Asunto(s)

RESUMEN

Comprehensive separation and analysis of non-ionic surfactants have been conducted by coupling supercritical fluid chromatography (SFC) with ion mobility spectrometry-mass spectrometry (IMS-MS). Representative non-ionic surfactants were investigated, including alkylphenol ethoxylates (APEOs), e.g., octylphenol ethoxylates (OPEOs) and fatty alcohol ethoxylates (FAEs), e.g., lauryl alcohol ethoxylates (LAEs). A sub-2-µm high-density diol column was used for chromatographic separation by the first-dimensional SFC due to the differences in ethoxy chain prior to electrospray ionization (ESI). Maintaining the fidelity of pre-ionization separation in the first dimension, the introduction of IMS provided additional post-ionization resolution by broadly fractionating the oligometric ethoxymers based on their size and electric charge within 13.78 ms. Distinguishable series of singly and multiply charged non-ionic species could be clearly observed. The millisecond timescale ion mobility separation perfectly fits the elution time of a chromatographic peak, while effectively feeding components into the fast-scanning time-of-flight (TOF) mass analyzer for characterization and analysis. The orthogonality of the developed separation and analysis system was evaluated, revealing a correlation coefficient and peak spreading angle of 0.2729 and 74.16° for the studied OPEOs and 0.1962 and 78.69° for LAEs. Significant enhancement in peak capacity was achieved for the developed SFC-IMS-MS system with the actual peak capacity measured to be approximately 41 and 160 times higher than that of the dimensions of SFC and IMS, respectively, when used alone. Graphical abstract.

RESUMEN

Seeking alternatives for alkylphenol ethoxylates (APEOs) have been a heavily researched topic in the surfactant industry and agricultural systems. In this study, the combined effects of different ethoxylates and pesticides on the bioactivity against three pests and toxicological risks to Daphnia magna were investigated. Results showed that alcohol ethoxylates (AEOs) had higher synergistic effects on the bioactivity of pesticides against Spodoptera exigua, Agrotis ipsilon and Aphis citricola than did APEOs. In terms of the joint toxicity of the ethoxylates and pesticides to D. magna, additive index method, toxicity unit method, V value method and isobologram method were used in the tests. All of these methods indicated that the joint effects of APEOs + acetamiprid and APEOs + indoxacarb upon D. magna turned from synergism to antagonism with the increasing EO (ethylene oxide) numbers. Those of AEOs exhibited similar trends. Overall, AEOs may be potential alternatives for APEOs in agriculture as they synergize pesticides against three pests significantly more than do APEOs. However, further research should investigate the compounds' environmental risks to aquatic organisms because the AEOs were highly toxic to D. magna.

Asunto(s)

RESUMEN

In the present study, a quick and sensitive method was developed for simultaneous determination of nonylphenol ethoxylates (NPxEOs) and octylphenol ethoxylates (OPxEOs) (x=2-20) in three leafy vegetables, including cabbage, lettuce, and spinach using a modified "QuEChERS" method and ultra-high performance supercritical fluid chromatography-tandem mass spectrometry (UHPSFC-MS/MS) with scheduled multiple reaction monitoring (MRM). Under optimized conditions, the 38 target analytes were analyzed within a short period of time (5 min). The linearities of the matrix-matched standard calibrations were satisfactory with coefficients of determination (R2)>0.99 and the limits of detection (LOD) and quantification (LOQ) were in between 0.02-0.27 and 0.18-1.75µgkg-1, respectively. The recovery of all target analytes spiked at three (low, medium, and high) fortification levels in various leafy vegetables were ranged from 72.8-122.6% with relative standard deviation (RSD) ≤18.3%. The method was successfully applied to market samples and the target analytes were found in all monitored samples, with total concentrations of 0-8.67µgkg-1 and 15.75-95.75µgkg-1 for OPxEOs and NPxEOs (x=2-20), respectively. In conclusion, the newly developed UHPSFC-ESI-MS/MS method is rapid and versatile and could be extrapolated for qualitative and quantitative analysis of APxEOs in other leafy vegetables.

Asunto(s)

RESUMEN

High environmental concentrations for alkylphenol ethoxylates (APEs) and brominated flame retardants (BFRs) have been observed near cities than in rural environment. This is due, in part, to sewage systems receiving effluents from many industrial processes along with domestic wastewater. While these classes of compounds are being phased out in most developed countries, there is still widespread use in low to middle income countries. To better understand the extent of APEs and BFRs contamination in the environment, this study reports on the concentration and distribution of APEs and BFRs in sediments samples collected from Vaal River, South Africa. Measurable concentrations of these contaminants were obtained using GC-MS after heptafluorobutyric derivatization. The concentrations range (ng g(-1)) for these pollutants were as follows: nd-46, 20-127, 24-38, 3-5, 14-28, 16-54 for octylphenol penta ethoxylates, nonylphenol ethoxylates (mono- di), nonylphenol penta ethoxylates, PBB101, PBDEs, and HBCD; respectively. The distribution observed in this study indicated higher levels of sediment contamination by APEs relative to BFRs. These results underline the need to further investigate the burden and risks associated with chemical contamination in developing countries.

Asunto(s)

RESUMEN

The Mira River is a Portuguese water body widely known for its wilderness and is advertised as one of the less polluted European rivers. On this presumption, the levels of endocrine-disrupting compounds (EDCs) in Mira waters were never measured. However, because environmentalists have claimed that the Mira could be moderately polluted, a range of 17 EDCs were measured not only at the estuary but also along the river. The targeted EDCs included natural and pharmaceutical oestrogens (17ß-oestradiol, oestrone and 17α-ethynylestradiol), industrial/household pollutants (octylphenols, nonylphenols and their monoethoxylates and diethoxylates and bisphenol A), phytoestrogens (formononetin, biochanin A, daidzein, genistein) and the phytosterol sitosterol (SITO). For this propose, waters from six sampling sites were taken every 2 months, over a 1-year period (2011), and analysed by gas chromatography-mass spectrometry. Unexpectedly high levels of oestrogens and of industrial/household pollutants were measured at all sampling sites, including those located inside natural protected areas. Indeed, the annual average sum of EDCs was ≈57 ng/L for oestrogens and ≈1.3 µg/L for industrial/household chemicals. In contrast, the global average levels of phytoestrogens (≈140 ng/L) and of SITO (≈295 ng/L) were lower than those reported worldwide. The EDC concentrations were normalised for ethynylestradiol equivalents (EE2eq). In view of these, the oestrogenic load of the Mira River attained ≈47 ng/L EE2eq. In addition, phosphates were above legal limits at both spring and summer (>1 mg/L). Overall, data show EDCs at toxicant relevant levels in the Mira and stress the need to monitor rivers that are allegedly less polluted.

Asunto(s)

RESUMEN

The antifouling performance of a siloxane-based elastomeric impression material (EIM) was compared to that of two silicone fouling-release coatings, Intersleek 757 and RTV-11. In field immersion trials, the EIM caused the greatest reduction in fouling by the solitary tunicate Ciona intestinalis and caused the longest delay in the progression of fouling by two species of colonial tunicate. However, in pseudobarnacle adhesion tests, the EIM had higher attachment strengths. Further laboratory analyses showed that the EIM leached alkylphenol ethoxylates (APEs) that were toxic to C. intestinalis larvae. The EIM thus showed the longest duration of chemical activity measured to date for a siloxane-based coating (4 months), supporting investigations of fouling-release coatings that release targeted biocides. However, due to potential widespread effects of APEs, the current EIM formulation should not be considered as an environmentally-safe antifoulant. Thus, the data also emphasize consideration of both immediate and long-term effects of potentially toxic constituents released from fouling-release coatings.

Asunto(s)

RESUMEN

Magnetic nanoparticles of cobalt ferrite with oleic acid as the surfactant (CoFe2O4/oleic acid) were used as sorbent material for the determination of alkylphenols in fruit juices. High sensitivity and specificity were achieved by liquid chromatography and detection using both diode-array (DAD) and electrospray-ion trap-tandem mass spectrometry (ESI-IT-MS/MS) in the selected reaction monitoring (SRM) mode of the negative fragment ions for alkylphenols (APs) and in positive mode for ethoxylate APs (APEOs). The optimized conditions for the different variables influencing the magnetic separation procedure were: mass of magnetic nanoparticles, 50mg, juice volume, 10mL diluted to 25mL with water, pH 6, stirring for 10min at room temperature, separation with an external neodymium magnet, desorption with 3mL of methanol and orbital shaking for 5min. The enriched organic phase was evaporated and reconstituted with 100µL acetonitrile before injecting 30µL into a liquid chromatograph with a mobile phase composed of acetonitrile/0.1% (v/v) formic acid under gradient elution. Quantification limits were in the range 3.6 to 125ngmL(-1). The recoveries obtained were in the 91-119% range, with RSDs lower than 14%. The ESI-MS/MS spectra permitted the correct identification of both APs and APEOs in the fruit juice samples.

Asunto(s)

RESUMEN

Ria de Aveiro is a Portuguese lagoon renowned for its ecological and economic importance. Nonetheless, in literature, few data exist about its organic pollution. Accordingly, this study chemically monitored for the first time a series of 17 endocrine disruptor compounds (EDCs). The target EDCs include natural (17ß-oestradiol, oestrone) and pharmaceutical (17α-ethynylestradiol) oestrogens, industrial/household xenoestrogenic pollutants (octylphenols, nonylphenols and their mono and diethoxylates and bisphenol A), phytoestrogens (formononetin, biochanin A, daidzein, genistein) and the phytosterol sitosterol (SITO). For the investigation of these EDCs, water samples were taken from eight sampling sites widely spread along the lagoon, at three different occasions in 2011, and analysed by gas chromatography-mass spectrometry. Results not only proved the ubiquitous distribution of all analysed EDCs but revealed that their amounts were extremely high at all sampling sites. The annual average concentrations were ≈ 46 ng/L for oestrogens, ≈ 3962 ng/L for industrial/household chemicals, ≈ 1740 ng/L for phytoestrogens and ≈ 908 ng/L for SITO. Normalising these values in ethynylestradiol equivalents (EE2eq), the oestrogenic load in this lagoon attained ≈ 50 ng/L EE2eq, which is a value well above that known to produce oestrogenic-induced disorders in aquatic fauna. Additionally, phosphate concentrations were also above the legal limits (>1 mg/L). Overall, data show EDCs at toxic relevant levels in the Ria de Aveiro and stress the need to enforce depollution measures in this habitat.

Asunto(s)

RESUMEN

Advanced oxidation processes based on the generation of reactive species including hydroxyl radicals are viable options in eliminating a wide array of refractory organic contaminants in industrial effluents. The assessment of transformation products and toxicity should be, however, the critical point that would allow the overall efficiency of advanced oxidation processes to be better understood and evaluated since some transformation products could have an inhibitory effect on certain organisms. This article reviews the most recent studies on transformation products and toxicity for evaluating advanced oxidation processes in eliminating classes of compounds described as "textile chemicals" from aqueous matrices and poses questions in need of further investigation. The scope of this paper is limited to the scientific studies with two classes of textile chemicals, namely chlorophenols and alkylphenol ethoxylates, whose use in textile industry is a matter of debate due to health risks to humans and harm to the environment. The article also raises the critical question: What is the state of the art knowledge on relationships between transformation products and toxicity?

Asunto(s)

RESUMEN

A sensitive and selective method for the determination of alcohol ethoxylates (AEOs) and alkylphenol ethoxylates (APEOs) using solid-phase extraction (SPE) and LC-MS/MS was developed and applied to the analysis of water samples. All AEO and APEO homologues, a total of 152 analytes, were analyzed within a run time of 11min, and the MS allowed for the detection of ethoxymers containing 2-20 ethoxy units (nEO=2-20). The limits of detection (LOD) were as low as 0.1pg injected, which generally increased as nEO increased (e.g., as high as 300pg for nEO=20). Additionally, the responses of the various ethoxymers varied by orders of magnitude, with ethoxymers with nEO=3-5 being the most sensitive and those with nEO>15 producing the least response in the MS. Absolute extraction recoveries of the analytes ranged from 37% to 69% in ultrapure water (RSD≤20%), with the recovery depending on the length of the alkyl chain. Abiotic stability studies were performed, and C14-18 ethoxylates showed significant degrees of degradation. Water samples from the Colorado River were then analyzed for AEOs and APEOs, with absolute extraction recoveries ranging from 33% to 45% (RSD≤12%). The predominant species observed in most samples were the octylphenol (OP) and nonylphenol (NP) ethoxylates, which contained total concentrations that were greater than 100ng/L APEOs in a couple samples. Other AEO homologues were identified in the river water samples, including C13, C15, C16, and C18 ethoxylates, but these compounds were generally present at much lower levels (i.e., <50ng/L total concentration).

Asunto(s)

RESUMEN

A gas chromatography-mass spectrometry (GC-MS) method was investigated for the simultaneous analysis of two types of endocrine disrupting compounds (EDCs), i.e., alkylphenol ethoxylates and brominated flame retardants (BFRs), by extraction and derivatization followed by GC-MS. Different solid phase extraction (SPE) cartridges (Cleanert PestiCarb, C18, Cleanert-SAX and Florosil), solvents (toluene, tetrahydrofuran, acetone, acetonitrile and ethyl acetate) and bases (NaHCO3, triethylamine and pyridine) were tested and the best chromatographic analysis was achieved by extraction with Strata-X (33 µm, Reverse Phase) cartridge and derivatization with heptafluorobutyric anhydride at 55 °C under Na2CO3 base in hexane. It was observed that APE together with lower substituted PBBs (PBB1, PBB10, PBB18 and PBB49), HBCD and TBBPA can be determined simultaneously under the same GC conditions. This simple and reliable analytical method was applied to determining trace amounts of these compounds from wastewater treatment plant samples. The recoveries of the target compounds from simulated water were above 60 %. The limit of detection ranged from 0.01 to 0.15 µg L-1 and the limit of quantification ranged from 0.05 to 0.66 µg L-1. There were no appreciable differences between filtered and unfiltered wastewater samples from Leeuwkil treatment plant although concentration of target analytes in filtered influent was slightly lower than the concentration of target analytes in unfiltered influent water. The concentrations of the target compounds from the wastewater treatment were determined from LOQ upwards.