Helping WWTP managers to address the volatile methylsiloxanes issue-Behaviour and complete mass balance in a conventional plant.

Volatile methylsiloxanes (VMSs) are a group of additives employed in different consumer products that can affect the quality of the biogas produced in wastewater treatment plants (WWTPs). The main objective of this study is to understand the fate of different VMSs along the treatment process of a WWTP located in Aveiro (Portugal). Thus, wastewater, sludge, biogas, and air were sampled in different units for two weeks. Subsequently, these samples were extracted and analyzed by different environment-friendly protocols to obtain their VMS (L3-L5, D3-D6) concentrations and profiles. Finally, considering the different matrix flows at every sampling moment, the mass distribution of VMSs within the plant was estimated. The levels of ∑VMSs were similar to those showed in the literature (0.1-50 µg/L in entry wastewater and 1-100 µg/g dw in primary sludge). However, the entry wastewater profile showed higher variability in D3 concentrations (from non detected to 49 µg/L) than found in previous studies (0.10-1.00 µg/L), likely caused by isolated releases of this compound that could be related to industrial sources. Outdoor air samples showed a prevalence of D5, while indoor air locations were characterized by a predominance of D3 and D4. Differences in sources and the presence of an indoor air filtration system may explain this divergence. Biogas was characterized by ∑VMSs concentrations (8.00 ± 0.22 mg/m3) above the limits recommended by some engine manufacturers and mainly composed of D5 (89%). Overall, 81% of the total incoming mass of VMSs is reduced along the WWTP, being the primary decanter and the secondary treatment responsible for the highest decrease (30.6% and 29.4% of the initial mass, respectively). This reduction, however, is congener dependant. The present study demonstrates the importance of extending sampling periods and matrices (i.e., sludge and air) to improve sample representativity, time-sensitivity, and the accuracy of mass balance exercises.

Nanofiltration combined with ozone-based processes for the removal of antineoplastic drugs from wastewater effluents.

Over the past years, there has been an increasing concern about the occurrence of antineoplastic drugs in water bodies. The incomplete removal of these pharmaceuticals from wastewaters has been confirmed by several scientists, making it urgent to find a reliable technique or a combination of techniques capable to produce clean and safe water. In this work, the combination of nanofiltration and ozone (O3)-based processes (NF + O3, NF + O3/H2O2 and NF + O3/H2O2/UVA) was studied aiming to produce clean water from wastewater treatment plant (WWTP) secondary effluents to be safely discharged into water bodies, reused in daily practices such as aquaculture activities or for recharging aquifers used as abstraction sources for drinking water production. Nanofiltration was performed in a pilot-scale unit and O3-based processes in a continuous-flow column. The peroxone process (O3/H2O2) was considered the most promising technology to be coupled to nanofiltration, all the target pharmaceuticals being removed at an extent higher than 98% from WWTP secondary effluents, with a DOC reduction up to 92%. The applicability of the clean water stream for recharging aquifers used as abstraction sources for drinking water production was supported by a risk assessment approach, regarding the final concentrations of the target pharmaceuticals. Moreover, the toxicity of the nanofiltration retentate, a polluted stream generated from the nanofiltration system, was greatly decreased after the application of the peroxone process, which evidences the positive impact on the environment of implementing a NF + O3/H2O2 process.

Incorporation of Moringa oleifera Leaf Extract in Yoghurts to Mitigate Children's Malnutrition in Developing Countries.

Moringa oleifera, which is rich in bioactive compounds, has numerous biological activities and is a powerful source of antioxidants and nutrients. Therefore, M. oleifera can be incorporated into food to mitigate children's malnutrition. In this work, the bioactive compounds were extracted from M. oleifera leaf powder by ultrasound-assisted solid-liquid extraction. The antioxidant and antimicrobial activities and the phenolic composition of the extract were evaluated. The extract presented a total phenolic content of 54.5 ± 16.8 mg gallic acid equivalents/g and IC50 values of 133.4 ± 12.3 mg/L for DPPH and 60.0 ± 9.9 mg/L for ABTS. Catechin, chlorogenic acid, and epicatechin were the main phenolics identified by HPLC-DAD. The obtained extract and M. oleifera leaf powder were incorporated into yoghurts and their physicochemical and biological properties were studied. The incorporation of M. oleifera did not impair the yoghurts' stability over eight weeks when compared to both negative and positive controls. The extract presented higher stability regarding syneresis but lower stability regarding TPC compared to the powder. Also, the fortified yoghurts presented higher antioxidant properties than the negative control. These findings highlight the potential use of M. oleifera powder and extract as natural additives to produce fortified foods that can be used in the mitigation of malnutrition.

Using Design of Experiments to Optimize a Screening Analytical Methodology Based on Solid-Phase Microextraction/Gas Chromatography for the Determination of Volatile Methylsiloxanes in Water.

Volatile methylsiloxanes (VMSs) constitute a group of compounds used in a great variety of products, particularly personal care products. Due to their massive use, they are continually discharged into wastewater treatment plants and are increasingly being detected in wastewater and in the environment at low concentrations. The aim of this work was to develop and validate a fast and reliable methodology to screen seven VMSs in water samples, by headspace solid-phase microextraction (HS-SPME) followed by gas chromatography with flame ionization detection (GC-FID). The influence of several factors affecting the extraction efficiency was investigated using a design of experiments approach. The main factors were selected (fiber type, sample volume, ionic strength, extraction and desorption time, extraction and desorption temperature) and optimized, employing a central composite design. The optimal conditions were: 65 µm PDMS/Divinylbenzene fiber, 10 mL sample, 19.5% NaCl, 39 min extraction time, 10 min desorption time, and 33 °C and 240 °C as extraction and desorption temperature, respectively. The methodology was successfully validated, showing low detection limits (up to 24 ng/L), good precision (relative standard deviations below 15%), and accuracy ranging from 62% to 104% in wastewater, tap, and river water samples.

Multi-Matrix Approach for the Analysis of Bicalutamide Residues in Oncology Centers by HPLC-FLD.

Cytostatics are toxic pharmaceuticals, whose presence in surfaces puts healthcare workers at risk. These drugs might also end up in hospital effluents (HWW), potentially damaging aquatic ecosystems. Bicalutamide is a cytostatic extensively consumed worldwide, but few analytical methods exist for its quantification and most of them require advanced techniques, such as liquid chromatography mass spectrometry (LC-MS), which are very complex and expensive for large monitoring studies. Therefore, a simple but reliable multi-matrix high performance liquid chromatographic method, with fluorescence detection, was developed and validated to rapidly screen abnormal concentrations of bicalutamide in HWW and relevant contamination levels of bicalutamide in indoor surfaces (>100 pg/cm2), prior to confirmation by LC-MS. The method presents good linearity and relatively low method detection limits (HWW: 0.14 ng/mL; surfaces: 0.28 pg/cm2). Global uncertainty was below 20% for concentrations higher than 25 ng/mL (HWW) and 50 pg/cm2 (surfaces); global uncertainty was little affected by the matrix. Therefore, a multi-matrix assessment could be achieved with this method, thus contributing to a holistic quantification of bicalutamide along the cytostatic circuit. Bicalutamide was not detected in any of the grab samples from a Portuguese hospital, but an enlarged sampling is required to conclude about its occurrence and exposure risks.

Anti-Angiogenic Properties of Cafestol and Kahweol Palmitate Diterpene Esters.

Epidemiological studies support the association of coffee-specific diterpenes, with various beneficial health effects. Although anti-antiangiogenic properties of free cafestol and kahweol have been recently described, available data regarding their esterified form, in particular palmitate esters as the main diterpene esters present in coffee, are still rare. Given that angiogenesis plays an important role in many pathological conditions, including cancer growth and metastasis, this study aimed to assess and compare the potential anti-angiogenic effects of cafestol palmitate (CP) and kahweol palmitate (KP) in an in vitro angiogenesis model. According to our findings, both compounds inhibited angiogenesis steps on human microvascular endothelial cells (HMVECs), although a more significant effect was observed for KP. Compared to control, HMVECs viability decreased in a dose-dependent manner upon incubation either with CP or KP. Concentrations of 75 and 100 µM of each compound were cytotoxic. Cell proliferation was also dramatically reduced by both diterpene esters at 50 µM, although KP had a stronger inhibitory effect. However, CP and KP did not induce apoptosis on HMVECs. Both compounds reduced cell migration, but this effect was only statistically significant after KP incubation. Inhibition of VEGFR2 expression and its downstream effector Akt, but not Erk, was also observed in CP- and KP-treated HMVECs. These findings were confirmed using ELISA assay for phosphorylated (active) VEGFR-2. Taken together, these data indicate that both CP and KP can be considered potent compounds against angiogenesis-dependent disorders. Our findings further indicate that KP exerts more potent anti-angiogenic effects than CP, in most of assays. J. Cell. Biochem. 117: 2748-2756, 2016. © 2016 Wiley Periodicals, Inc.

Variability of some diterpene esters in coffee beverages as influenced by brewing procedures.

Several coffee brews, including classical and commercial beverages, were analyzed for their diterpene esters content (cafestol and kahweol linoleate, oleate, palmitate and stearate) by high performance liquid chromatography with diode array detector (HPLC-DAD) combined with spectral deconvolution. Due to the coelution of cafestol and kahweol esters at 225 nm, HPLC-DAD did not give accurate quantification of cafestol esters. Accordingly, spectral deconvolution was used to deconvolve the co-migrating profiles. Total cafestol and kahweol esters content of classical coffee brews ranged from 5-232 to 2-1016 mg/L, respectively. Commercial blends contained 1-54 mg/L of total cafestol esters and 2-403 mg/L of total kahweol esters. Boiled coffee had the highest diterpene esters content, while filtered and instant brews showed the lowest concentrations. However, individual diterpene esters content was not affected by brewing procedure as in terms of kahweol esters, kahweol palmitate was the main compound in all samples, followed by kahweol linoleate, oleate and stearate. Higher amounts of cafestol palmitate and stearate were also observed compared to cafestol linoleate and cafestol oleate. The ratio of diterpene esters esterified with unsaturated fatty acids to total diterpene esters was considered as measure of their unsaturation in analyzed samples which varied from 47 to 52%. Providing new information regarding the diterpene esters content and their distribution in coffee brews will allow a better use of coffee as a functional beverage.

Liquid chromatography with diode array detection combined with spectral deconvolution for the analysis of some diterpene esters in Arabica coffee brew.

In this manuscript, the separation of kahweol and cafestol esters from Arabica coffee brews was investigated using liquid chromatography with a diode array detector. When detected in conjunction, cafestol, and kahweol esters were eluted together, but, after optimization, the kahweol esters could be selectively detected by setting the wavelength at 290 nm to allow their quantification. Such an approach was not possible for the cafestol esters, and spectral deconvolution was used to obtain deconvoluted chromatograms. In each of those chromatograms, the four esters were baseline separated allowing for the quantification of the eight targeted compounds. Because kahweol esters could be quantified either using the chromatogram obtained by setting the wavelength at 290 nm or using the deconvoluted chromatogram, those compounds were used to compare the analytical performances. Slightly better limits of detection were obtained using the deconvoluted chromatogram. Identical concentrations were found in a real sample with both approaches. The peak areas in the deconvoluted chromatograms were repeatable (intraday repeatability of 0.8%, interday repeatability of 1.0%). This work demonstrates the accuracy of spectral deconvolution when using liquid chromatography to mathematically separate coeluting compounds using the full spectra recorded by a diode array detector.

Relationship between levels of polycyclic aromatic hydrocarbons in pine needles and socio-geographic parameters.

The ability of pine needles to capture polycyclic aromatic hydrocarbons (PAHs) from the surrounding air is well known. In this work the current knowledge of this affinity will be enhanced, investigating the plausible links between the concentrations of PAHs found in pine needles collected in different sites in Portugal, and several socio-geographic variables with environmental relevance. Canonical correlation analysis (CCA) has proven to be a suitable and innovative technique to look for relationships within environmental datasets. In the current work, CCA will simultaneously include chemical information (concentration of PAHs found in pine needles) and socio-geographic information associated to the sampling areas. In order to be more robust in these conclusions, Pinus pinea and Pinus pinaster species were considered separately, allowing an accurate direct comparison between them. The information concerning the different seasons and land occupation was also taken into account. Our results demonstrate how CCA can be a useful tool in environmental impact assessment, and highlight the importance of pine needles as trustful biomonitors of the influence of socio-geographic parameters on the levels of PAHs in a given area.

Long lasting perfume--a review of synthetic musks in WWTPs.

Synthetic musks have been used for a long time in personal care and household products. In recent years, this continuous input has increased considerably, to the point that they were recognized as emerging pollutants by the scientific community, due to their persistence in the environment, and hazardous potential to ecosystems even at low concentrations. The number of studies in literature describing their worldwide presence in several environmental matrices is growing, and many of them indicate that the techniques employed for their safe removal tend to be ineffective. This is the case of conventional activated sludge treatment plants (WWTPs), where considerable loads of synthetic musks enter mainly through domestic sewage. This review paper compiles and discusses the occurrence of these compounds in the sewage, effluents and sludge, main concentration levels and phase distributions, as well as the efficiency of the different methodologies of removal applied in these treatment facilities. To the present day, it has been demonstrated that WWTPs lack the ability to remove musks completely. This shows a clear need to develop new effective and cost-efficient remediation approaches and foresees potential for further improvements in this field.

Are volatile methylsiloxanes in downcycled tire microplastics? Levels and human exposure estimation in synthetic turf football fields.

Downcycled rubber, derived from end-of-life tires (ELTs), is frequently applied as crumb rubber (CR) as infill of synthetic turf in sports facilities. This practice has been questioned in recent years as numerous studies have reported the presence of potentially hazardous chemicals in this material. CR particles fall into the category of microplastics (MPs), making them possible vectors for emerging micropollutants. A preliminary study where volatile methylsiloxanes (VMSs) were found in CR originated the hypothesis that VMSs are present in this material worldwide. Consequently, the present work evaluates for the first time the levels and trends of seven VMSs in CR from synthetic turf football fields, while attempting to identify the main sources and impacts of these chemicals. A total of 135 CR samples and 12 other of alternative materials were analyzed, employing an ultrasound-assisted dispersive solid-phase extraction followed by gas chromatography-mass spectrometry (GC-MS), and the presence of VMSs was confirmed in all samples, in total concentrations ranging from 1.60 to 5089 ng.g-1. The levels were higher in commercial CR (before field application), a reflection of the use of VMS-containing additives in tire production and/or the degradation of silicone polymers employed in vehicles. The VMSs generally decreased over time on the turf, as expected given their volatile nature and the wearing of the material. Finally, the human exposure doses to VMSs in CR (by dermal absorption and ingestion) for people in contact with synthetic turf in football fields were negligible (maximum total exposure of 20.5 ng.kgBW-1.year-1) in comparison with the European Chemicals Agency (ECHA) reference doses: 1.35 × 109 ng.kgBW-1.year-1 for D4 and 1.83 × 109 ng.kgBW-1.year-1 for D5. Nevertheless, more knowledge on exposure through inhalation and the combined effects of all substances is necessary to provide further corroboration. This work proved the presence of VMSs in CR from ELTs, another family of chemical of concern to take into account when studying MPs as vectors of other contaminants.

New analytical method for the determination of musks in personal care products by Quick, Easy, Cheap, Effective, Rugged, and Safe extraction followed by GC-MS.

Synthetic musks are organic compounds used as fragrance additives and fixative compounds in a diversity of personal care products. A new method based on quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction followed by GC-MS for the analysis of 12 musks in personal care products was developed and validated. Some experimental parameters, such as total QuEChERS mass, sample mass/solvent volume ratio, type of extraction solvent, as well as salts and sorbents amount were investigated and optimized. The final method involves the musks extraction using acetonitrile, followed by the addition of anhydrous magnesium sulphate and sodium acetate. The clean-up step was performed using dispersive SPE with primary and secondary amine and octadecyl-silica sorbents. This extraction procedure is fast (about 10 min) when compared to other traditional approaches. The method was robust for the matrices studied and shows a high precision (%RSD < 15%) and accuracy (average recovery of 85%), allowing the detection of musks in minimum concentrations between 0.01 ng/g (galaxolide) and 15.80 ng/g (musk xylene). The developed method was applied to the analysis of 12 samples, which revealed musks concentrations ranging from 2 ng/g (toothpaste) to 882,340 ng/g (perfumed body lotion).

Theoretical rejection of fifty-four antineoplastic drugs by different nanofiltration membranes.

The rise of nanofiltration technologies holds great promise for creating more effective and affordable techniques aiming to remove undesirable pollutants from wastewaters. Despite nanofiltration's promising potential in removing antineoplastic drugs from liquid matrices, the limited information on this topic makes it important to estimate the rejection rates for a larger number of compounds, particularly the emerging ones, in order to preview the nanofiltration performance. Aiming to have preliminary estimations of the rejection rates of antineoplastic drugs by nanofiltration, 54 antineoplastic drugs were studied in 5 nanofiltration membranes (Desal 5DK, Desal HL, Trisep TS-80, NF270, and NF50), using a quantitative structure-activity relationship (QSAR) model. While this methodology provides useful and reliable predictions of the rejections of compounds by nanofiltration, particularly for hydrophilic and neutral compounds, it is important to note that QSAR results should always be corroborated by experimental assays, as predictions were confirmed to have their limitations (especially for hydrophobic and charged compounds). Out of the 54 studied antineoplastic drugs, 29 were predicted to have a rejection that could go up to 100%, independent of the membrane used. Nonetheless, there were 2 antineoplastic drugs, fluorouracil and thiotepa, for which negligible removals were obtained (<21%). This study's findings may contribute (i) to the selection of the most appropriate nanofiltration membranes for removing antineoplastic drugs from wastewaters and (ii) to assist in the design of effective treatment approaches for their removal.

Multi-target analysis of cytostatics in hospital effluents over a 9-month period.

The consumption of cytostatics, pharmaceuticals prescribed in chemotherapy, is increasing every year and worldwide, along with the incidence of cancer. The presence and the temporal evolution of cytostatics in wastewaters from a Portuguese hospital center was evaluated through a 9-month sampling campaign, comprising a total of one hundred and twenty-nine samples, collected from May 2019 to February 2020. Eleven cytostatics out of thirteen pharmaceuticals were studied, including flutamide, mycophenolate mofetil and mycophenolic acid, which have never been monitored before. Target analytes were extracted and quantified by solid-phase extraction coupled to liquid-chromatography-tandem mass spectrometry analysis; the method was fully validated. All pharmaceuticals were detected in at least one sample, bicalutamide being the one found with higher frequency (detected in all samples), followed by mycophenolic acid, which was also the compound detected at higher concentrations (up to 5340 ± 211 ng/L). Etoposide, classified as carcinogenic to humans, was detected in 60% of the samples at concentrations up to 142 ± 15 ng/L. The risk from exposure to cytostatics was estimated for aquatic organisms living in receiving bodies. Cyclophosphamide, doxorubicin, etoposide, flutamide, megestrol and mycophenolic acid are suspected to induce risk. Long-term and synergic effects should not be neglected, even for the cytostatics for which no risk was estimated.

Antineoplastic drugs in urban wastewater: Occurrence, nanofiltration treatment and toxicity screening.

Antineoplastic drugs are pharmaceuticals that have been raising concerns among the scientific community due to: (i) their increasing prescription in the fight against the disease of the twentieth century (cancer); (ii) their recalcitrance to conventional wastewater treatments; (iii) their poor environmental biodegradability; and (iv) their potential risk to any eukaryotic organism. This emerges the urgency in finding solutions to mitigate the entrance and accumulation of these hazardous chemicals in the environment. Advanced oxidation processes (AOPs) have been taken into consideration to improve the degradation of antineoplastic drugs in wastewater treatment plants (WWTPs), but the formation of by-products that are more toxic or exhibit a different toxicity profile than the parent drug is frequently reported. This work evaluates the performance of a nanofiltration pilot unit, equipped with a Desal 5DK membrane, in the treatment of real WWTP effluents contaminated (without spiking) with eleven pharmaceuticals, five of which were never studied before. Average removals of 68 ± 23% were achieved for the eleven compounds, with decreasing risks from feed to permeate for aquatic organisms from receiving waterbodies (with the exception of cyclophosphamide, for which a high risk was estimated in the permeate). Aditionally, no significative impact on the growth and germination of three different seeds (Lepidium sativum, Sinapis alba, and Sorghum saccharatum) were determined for permeate matrix in comparison to the control.

Microwave-assisted headspace solid-phase microextraction to quantify polycyclic aromatic hydrocarbons in pine trees.

A methodology for the extraction and quantification of 16 polycyclic aromatic hydrocarbons (PAHs) based on microwave-assisted extraction coupled with headspace solid-phase microextraction followed by gas chromatography/mass spectroscopy was validated for needles and bark of two pine species (Pinus pinaster Ait. and Pinus pinea L.). The limits of detection were below 0.92 ng g(-1) (dry weight) for needles and below 0.43 ng g(-1) (dw) for bark. Recovery assays were performed with two sample masses spiked at three levels and the overall mean values were between 70 and 110 % for P. pinaster and 75 and 129 % for P. pinea. In the first species, the increase in sample mass lowered the recoveries slightly for most PAHs, whereas for the second, the recoveries were higher for the needles. Naturally contaminated samples from 4 sites were analysed, with higher levels for urban sites (1,320 and 942 ng g(-1) (dw) vs. 272 and 111 ng g(-1) (dw) for needles and 696 and 488 ng g(-1) (dw) vs. 270 and 103 ng g(-1) (dw) for bark) than for rural ones and also for P. pinaster samples over P. pinea. It is also shown that gas-phase PAHs are predominant in the needles (over 65 % of the total PAHs) and that the incidence for particulate material in bark, reaching 40 % as opposed to a maximum below 20 % for the needles. The method has proved to be fit and improved some of the existing approaches, on the assessment of particulate PAHs and bark levels.

Distribution and sources of PAHs using three pine species along the Ebro River.

Needles of three pine species (Pinus halepensis, Pinus pinea and Pinus nigra) were analysed to assess the occurrence of polycyclic aromatic hydrocarbons (PAHs) in 34 sites located throughout the Ebro River, in Northeast Spain. Overall, the concentration varied between 55 and 808 ng g(-1) (dry weight). The three- and four-ring PAHs were the most representative, with phenanthrene having 43% of the total PAH load and naphthalene showing a high incidence in rural areas. Despite matrix apparent similarities, P. halepensis needles revealed higher entrapment levels than P. nigra and P. pinea, the latter showing the lowest levels. The assessment of possible sources using PAH ratios (phenanthrene/anthracene and fluoranthene/pyrene) did not reveal a clear tendency regarding the distinction of petrogenic and pyrogenic sources in general, reflecting heterogeneous sources of PAHs in the Ebro area.

Different extraction approaches for the biomonitoring of pesticides in pine needles.

An ultrasonic extraction (USE) procedure followed by two alternative clean-up approaches using solid-phase extraction (SPE) cartridges (ENVI 18 and Florisil) and QuEChERS extraction and clean-up methodology were tested and compared for the determination of20 pesticides in Pinus pinea needles. The analysis and quantification were performed by gas chromatography-mass spectrometry (GC-MS) in selected ion storage (SIS) mode, using triphenyl phosphate (TPP) as the internal standard. One sample mass (5 g) and two pesticide spiking levels (20 and 100 ng g(-1)) were used in the validation assays. The limits of detection (LODs) were lower than 15.96 ng g(-1) for ENVI 18, 11.36 ng g(-1) for Florisil and 16.67 ng g(-1) for QuEChERS. Florisil yielded higher coefficients of variation for replicated analysis as did QuEChERS for the intermediate precision. To test pine needles' capacity as biomonitors for these pesticides, naturally contaminated needle samples were analyzed. With a 34% overall detection rate, concentrations ranged from 0.10 to 17.73 ng g(-1) (dry weight). USE + ENVI 18 and USE + Florisil were overall the best options for pesticide assessment in pine needles.

A review of bioaccumulation of volatile methylsiloxanes in aquatic ecosystems.

Volatile methylsiloxanes (VMSs) are found in a broad range of industrial and consumer products. They are categorized as "high production volume chemicals" by the U.S. Environmental Protection Agency and listed as candidates of substances of very high concern in 2018, by the Registration, Evaluation, Authorization and Restriction of Chemicals (REACH). Industrial wastewater and treated effluents may contain VMSs in different amounts, which can be discharged in the receptor media and may lead to environmental contamination. This can result in direct exposure to aquatic receptors in the water column or to benthic invertebrates from contact and/or ingestion of sediments, and indirect exposures through the aquatic food chain. The possible toxicological effects of VMSs for the aquatic biota and human ecology are not very well known since published information regarding this topic is scarce. VMSs have been subjected to regulatory scrutiny for environmental concerns and have already been screened to determine their environmental risk and ecological harm. This paper aims to assess VMSs bioaccumulation and potential biomagnification on food webs, using several bioaccumulation metrics. The result is a high-level overview of all the collected data, comparing the findings and the experimental conditions applied during the assessments. Several studies present conflicting results regarding the bioaccumulation categorization. Some aquatic organisms demonstrated a high bioconcentration and bioaccumulation of these contaminants. Trophic magnification factors (TMFs) have been suggested as the most reliable tool to assess a chemical behaviour in food webs. However, bioaccumulation studies in food webs provided mixed information, with some studies indicating trophic dilution and others presenting a potential of trophic biomagnification of VMSs. Efforts should be directed to obtain field-based levels of VMSs at different trophic levels and a wider range of linear VMSs should be analysed, since most studies focused on D4, D5 and D6.

Presence of metals and metalloids in crumb rubber used as infill of worldwide synthetic turf pitches: Exposure and risk assessment.

Crumb rubber derived from end-of-life tires (ELTs) is frequently used as infill of synthetic turf pitches, promoting circular economy. Although important to reduce the accumulation of waste, the use of recycled ELTs can be a problem to human health and the environment, both by direct contact during pitch use and by the release of these elements to the surroundings, mostly via volatilization and leaching. The present study aimed to evaluate the distribution of metals in ELT-derived crumb rubber collected in artificial turf worldwide and assess possible trends by country, pitch age and type (indoor vs. outdoor). The concentration ranges observed are very wide, especially in outdoor fields and for the most abundant metals, namely Zn (2989-5246 mg/kg), Fe (196-5194 mg/kg), Mg (188-1795 mg/kg) and Al (159-1882 mg/kg). For Zn, the levels were mostly above the safe limits set in European directives for relatable matrices (soils and toy materials), and the same happened for Pb, a much more toxic metal at lower concentrations. A multi-pathway human exposure study was also performed, and the risk assessment shows non-carcinogenic and carcinogenic risks from accidental crumb rubber ingestion (with Cr and Pb as major contributors) above the acceptable values for all the receptors except adult bystanders, with a higher significance to younger individuals. These results bring a different perspective regarding most of the studies reporting low risks related with exposure to metals in crumb rubber.