Concentration of heavy metals and rare earth elements in patients with brain tumours: Analysis in tumour tissue, non-tumour tissue, and blood.

Inorganic elements have been associated with brain tumours for long. The blood concentration of 47 elements was assessed by ICP-MS in 26 brain tumour patients and 21 healthy subjects from Bucharest (Romania). All 47 elements were detected in the brain tumour tissue, and 22 were detected in > 80% of samples; this implies that these elements can cross the blood-brain barrier. Median blood levels of cadmium, lead, and nickel were higher than the reference values (1.14, 53.3, and 2.53 ng/mL). Gadolinium and tantalum showed significantly higher concentrations among cases. We observed considerable differences and different profiles of the presence of inorganic elements between the tumour and non-tumour brain tissue and between tissue from the primary tumour and tissue from brain metastasis. Our data suggest that similar to heavy metals, other elements - commonly used in high tech devices and rare earth elements - can also influence brain tumour.

Differential exposure to 33 toxic elements through cigarette smoking, based on the type of tobacco and rolling paper used.

Environmental pollution due to various elements is increasing all across the planet owing to their use in industrial processes. The tobacco plants and the vegetables used in the manufacturing of smoking paper may accumulate these elements from the environment. Thus, tobacco and smoking paper may be relevant contributors among the content of elements in cigarettes, including some emerging pollutants such as rare earth elements (REEs). Thirty-two elements related to hi-tech industrial processes were analyzed in tobacco, rolling paper, and filters (n = 257 samples) by ICP-MS. A variety of industrial brands and "roll-your-own" cigarette papers were considered. The potential maximum daily exposure to these elements by a hypothetical heavy smoker was calculated for each type of cigarette. We found significant differences in the levels of most elements, both in the tobacco and in the paper. Black tobacco cigarettes contained the maximum levels. We found that the paper used in roll-your-own cigarettes may significantly modify their concentration of elements. Fast-burning, bleached, and flavored papers also contribute to higher levels of these pollutants. Thus, the differences in theoretical exposure depending on the type of cigarette consumed-either branded or hand-rolled-may be very striking, of up to 35-40 times. In addition to the number of cigarettes consumed per day, it is necessary to consider the type of cigarette consumed to assess the risk of exposure to toxic elements. Tobacco paper is a prominent source of exposure to toxic elements. Cigarette smoke is another source of exposure to emerging contaminants such as REE.

Trophic behavior of inorganic elements in nesting sea turtles (Chelonia mydas, Eretmochelys imbricata, and Caretta caretta) in Quintana Roo: Biomagnification and biodilution effect in blood and scute tissues.

The biomagnification and biodilution of inorganic pollutants, have a close correlation on the structure and function of trophic change behavior; sea turtles represent an excellent bioindicator model to identify their impact in marine ecosystems. To understand pollution effects on marine ecosystems, we quantified the bioconcentration of 50 inorganic elements in the blood and scute tissues of three nesting species of sea turtles (Chelonia mydas, Eretmochelys imbricata and Caretta caretta), collected in Quintana Roo State from July 2017 to August 2018. As a general trend, essential mineral elements with toxic potential showed the highest concentrations in both tissues; significant increase concentration of arsenic, mercury, and cerium levels was observed with increasing trophic levels indicating its biomagnification while a significant decrease in manganese and bismuth showed a biodilution effect. We expect that our findings can be used as baseline data in future biomonitoring and contamination risk assessment programs in the region.

Evaluation of Essential, Toxic and Potentially Toxic Elements in Leafy Vegetables Grown in the Canary Islands.

Forty-seven elements in leafy green vegetables were studied to estimate the daily intakes from this food category in different scenarios (average and high consumers) and age groups of the Canary Islands population. The contribution of the consumption of each type of vegetable to the reference intakes of essential, toxic and potentially toxic elements was assessed and the risk-benefit ratio was evaluated. The leafy vegetables that provide the highest levels of elements are spinach, arugula, watercress and chard. While spinach, chard, arugula, lettuce sprouts and watercress were the leafy vegetables with the highest concentrations of essential elements (38,743 ng/g of Fe in spinach, 3733 ng/g of Zn in watercress), the high levels of Mn in chard, spinach and watercress are noteworthy. Among the toxic elements, Cd is the element with the highest concentration, followed by As and Pb. The vegetable with the highest concentration of potentially toxic elements (Al, Ag, Be, Cr, Ni, Sr and V) is spinach. In average adult consumers, while the greatest contribution of essential elements comes from arugula, spinach and watercress, insignificant dietary intakes of potentially toxic metals are observed. Toxic metal intakes from the consumption of leafy vegetables in the Canary Islands do not show significant values, so the consumption of these foods does not pose a health risk. In conclusion, the consumption of leafy vegetables provides significant levels of some essential elements (Fe, Mn, Mo, Co and Se), but also of some potentially toxic elements (Al, Cr and Tl). A high consumer of leafy vegetables would see their daily nutritional needs regarding Fe, Mn, Mo, and Co covered, although they are also exposed to moderately worrying levels of Tl. To monitor the safety of dietary exposure to these metals, total diet studies on those elements with dietary exposures above the reference values derived from the consumption of this food category, mainly Tl, are recommended.

Human biomonitoring of inorganic elements in a representative sample of the general population from Cape Verde: Results from the PERVEMAC-II study.

Inorganic elements such as heavy metals and other potentially toxic elements are frequently detected in humans. The aim of the present study was to analyze the blood concentrations of 49 inorganic elements in a cohort of 401 subjects from Cape Verde. The study was performed in the frame of the Pesticide Residues in Vegetables of the Macaronesia project (PERVEMAC-II). Concentration of inorganic elements, including elements in the ATSDR's priority pollutant list and rare earth elements (RREs) were measured by ICP-MS in the whole blood of participants. A total of 20 out of 49 elements (40.8%) were detected in ≥20% of participants. Arsenic, copper, mercury, lead, selenium, strontium and zinc were detected in ≥99% of samples. Among the REEs, 7 showed detection frequencies above 20%. The median number of different elements detected was 15. In the present series, 77.0, 99.2 and 33.4% of the participants showed values of arsenic, mercury and lead higher than Reference Values 95%. These percentages were much higher than those reported in similar studies. Niobium and tantalum showed the highest median concentrations: 1.35 and 1.34 ng/mL, suggesting an environmental source of these valuable REEs in Cape Verde. Age appeared as the most important factor influencing the blood levels of inorganic elements. Lifestyle had an effect on the concentration of some of these elements. Those subjects whose water source was pond water had significantly higher arsenic levels. The concentration of ∑REEs was significantly higher among individuals who purchase their food in supermarkets (P = 0.013). These variables are of relevance since they can be controlled individually to reduce exposure to these contaminants. Our results may be useful for the implementation of public health measures by the competent authorities.

Impact of chemical elements released by the volcanic eruption of La Palma (Canary Islands, Spain) on banana agriculture and European consumers.

The recent volcanic eruption on the island of La Palma has aroused the concern of banana producers and consumers, given that in its area of influence there are thousands of hectares of banana plantations with an annual production of about 100 million kilos for export. Since volcanoes are one of the main natural sources of heavy metal contamination, we sampled bananas from the affected area and determined the concentrations of 50 elements (Ag, Al, As, Au, Ba, Be, Bi, Cd, Ce, Co, Cr, Cu, Cu, Dy, Er, Eu, Fe, Ga, Gd, Hg, Ho, In, La, Lu, Mn, Mo, Nb, Nd, Ni, Os, Pb, Pd, Pm, Pr, Pt, Sb, Sc, Se, Sm, Sn, Sr, Ta, Tb, Th, Ti, Tl, Tm, U, Y, Yb and Zn). The levels of 36 elements were elevated but the washing implemented after the eruption can remove a good part. After the washout, bananas have elevated levels of Fe, Al, Ti, V, Ba, Pb, most of the rare earth elements, Mo, and Co. In all cases, except Mo, the elevation is much higher in the peel than in the flesh. In the case of Mo, the elevation in banana flesh would translate into a higher nutritional intake of this trace element, which could represent up to 35% of the daily nutritional requirements. Exposure to toxic or potentially toxic elements, does not represent a health risk, since would not exceed 5% of the tolerable daily intake, even in the worst-case scenario.

A Method Scope Extension for the Simultaneous Analysis of POPs, Current-Use and Banned Pesticides, Rodenticides, and Pharmaceuticals in Liver. Application to Food Safety and Biomonitoring.

The screening of hundreds of substances belonging to multiple chemical classes in liver is required in areas such as food safety or biomonitoring. We adapted a previous QuEChERS-based method in blood to the liver matrix and applied to these fields of study. The validation of the method allowed the inclusion of 351 contaminants, 80% with a LOQ < 2 ng/g. In the analysis of 42 consumer liver samples, we detected trace levels of 29 different contaminants. The most frequent and concentrated was 4,4'-DDE. POPs accounted for 66% of the compounds detected. In no case was the MRL reached for any of the contaminants detected. We also applied the method to 151 livers of wild birds to perform a biomonitoring pilot study in the Canary Islands. We detected 52 contaminants in 15 bird species. These were also mostly POPs, although high frequencies and concentrations of anticoagulant rodenticides (AR) and some other agricultural pesticides also stand out. POPs and AR contamination levels were significantly higher in terrestrial birds, raptors and particularly in nocturnal birds. Pesticide contamination levels were also higher in terrestrial birds, as well as in non-raptors and diurnal birds. The validated method is simple, robust, and sensitive and performs well in a variety of practical scenarios, where it can be carried out relatively quickly and inexpensively.

Elemental composition, rare earths and minority elements in organic and conventional wines from volcanic areas: The Canary Islands (Spain).

The organic wine market is rapidly growing worldwide, both in terms of production and consumption. However, the scientific literature is not conclusive regarding differences in the elemental composition of wines according to their production method, including both major and trace elements. Minerals can be present in wine as a result of both anthropogenic and environmental factors. To date, this has not been evaluated in volcanic contexts, neither has the emergent issue of rare earths and other minority elements as potential sources of food contamination. This study using inductively coupled plasma mass spectrometry (ICP-MS) analyses organic and conventional wines produced in the Canary Islands (Spain), an archipelago of volcanic origin, to compare their content of 49 elements, including rare earths and minority elements. Our results showed that organic wines presented lower potential toxic element content on average than their conventional counterparts, but differences were not significant. Geographical origin of the wine samples (island) was the only significant variable differentiating wine samples by their composition profiles. By comparing our data with the literature, no agreement was found in terms of differences between organic and conventionally-produced wines. This confirms that other factors prevail over elemental composition when considering differences between wine production methods. Regarding the toxicological profile of the wines, five samples (three organic and two conventional) exceeded the maximum limits established by international legislation. This highlights the need for stricter analytical monitoring in the Canary Islands, with a particular focus on Cu and Ni concentration, and potentially in other volcanic areas.

Nutritional Evaluation and Risk Assessment of the Exposure to Essential and Toxic Elements in Dogs and Cats through the Consumption of Pelleted Dry Food: How Important Is the Quality of the Feed?

Dry feed for pets lacks specific legislation regarding maximum residue limits for inorganic elements. The aim of the present study was to determine the content of 43 inorganic elements in dog and cat feed, studying whether there were differences according to the supposed quality of the food and performing the risk assessment for health. Thirty-one and thirty packages of pelleted dry food for cats and dogs, respectively, were analyzed. After acidic microwave-assisted digestion, elements were detected and quantified by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). In general, we did not observe important differences in the content of elements according to the supposed quality of the brand. Among trace elements, selenium and manganese are above the dietary reference value. Arsenic and mercury showed the highest acute hazard indexes, which make them risk factors for the health of dogs and cats. Aluminum, uranium, antimony and vanadium contents were above the toxic reference value and showed the highest acute hazard indexes. It is necessary to improve the legislation regarding the food safety of pets, for their health and to protect the rights of consumers.

Epidemiology of Animal Poisonings in the Canary Islands (Spain) during the Period 2014-2021.

Animal poisoning is one of the greatest conservation threats facing wildlife. In a preliminary study in the oceanic archipelago of the Canary Islands, we showed that the degree of threat from this circumstance was very high-even higher than that reported in other regions of continental Europe. Consequently, a legal framework for the effective prosecution of the crime of wildlife poisoning came into force in 2014 in this region. We present the results of the investigation of 961 animals and 84 baits sent to our laboratory for the diagnosis of animal poisonings during the period 2014-2021. We were able to identify poison as the cause of death in 251 animals and 61 baits. Carbofuran stands out as the main agent used in this archipelago. We have also detected an increasing tendency to use mixtures of several pesticides in the preparation of baits. The entry into operation of two canine patrols has led to the detection of more dead animals in the wild and a greater number of poisoned animals. The percentage of poison positives is significantly higher in areas with lower population density, corresponding to rural environments, as well as in areas with greater agricultural and livestock activity.

Intensive livestock farming as a major determinant of the exposure to anticoagulant rodenticides in raptors of the Canary Islands (Spain).

The Canary Islands (Spain) is a biodiversity hotspot, with more than 4500 registered endemic species. However, it is subject to high anthropogenic pressure that threatens its wildlife in various ways. In the context of forensic toxicological surveys, the presence of anticoagulant rodenticides (AR) has been investigated in the liver of 831 animal carcasses with georeferenced data from 2011 to May 2020. The high concentrations of toxic pesticides in carcasses and in baits found close to the corpses indicated that all the reptiles and most of the mammals tested positive for AR were intentionally poisoned, although mainly by other substances. The frequency of detection of AR in non-raptor birds (n = 343) was only 4.1%, being the Canary raven the most frequently affected species (7/97, 7.2%). On the contrary, in raptors (n = 308) the detection frequency was almost 60%, with an average of more than 2 ARs per animal. The highest concentrations were found in the common kestrel. We present for the first-time results of AR contamination in two species of raptors that are very rare in Europe, Eleonora's falcon (n = 4) and Barbary falcon (n = 13). The temporal trend of positive cases remains stable, but since the entry into force of the restriction to the concentration of the active ingredient in baits (<30 ppm), a decrease in the concentrations of these compounds in the raptors' liver has been detected. Conversely, we registered an increase in the number of ARs per animal. From the study of the geographic information system (GIS) it can be deduced that intensive livestock farms are an important determinant in the exposure of raptors to ARs. Those birds that have their territory near intensive production farms have higher levels of exposure than those of birds that live far from such facilities.

Dataset on the concentrations of anticoagulant rodenticides in raptors from the Canary Islands with geographic information.

The dataset presented in this article supports "Intensive livestock farming as a major determinant of the exposure to anticoagulant rodenticides in raptors of the Canary Islands (Spain)" (Rial-Berriel et al., 2020). A Geographic Information System (GIS) analysis on the influence of the influence of livestock activity on exposure to anticoagulant rodenticides in raptors in the Canary Islands was performed. This dataset provides geographic information on the localization of each raptor (either positive or negative for anticoagulant rodenticides, n = 308), as well as the concentrations of each compound found in their livers. In addition, we present complementary analyses to those included in the main article, such as the detailed analysis of the farming activity influence on anticoagulant rodenticide exposure of raptors, by island and by raptor species.

Association between Heavy Metals and Rare Earth Elements with Acute Ischemic Stroke: A Case-Control Study Conducted in the Canary Islands (Spain).

The role of inorganic elements as risk factors for stroke has been suggested. We designed a case-control study to explore the role of 45 inorganic elements as factors associated with stroke in 92 patients and 83 controls. Nineteen elements were detected in >80% of patients and 21 were detected in >80% of controls. Blood level of lead was significantly higher among patients (11.2 vs. 9.03 ng/mL) while gold and cerium were significantly higher among controls (0.013 vs. 0.007 ng/mL; and 18.0 vs. 15.0 ng/mL). Lead was associated with stroke in univariate and multivariate analysis (OR = 1.65 (95% CI, 1.09-2.50) and OR = 1.91 (95% CI, 1.20-3.04), respectively). Gold and cerium showed an inverse association with stroke in multivariate analysis (OR = 0.81 (95% CI, 0.69-0.95) and OR = 0.50 (95% CI, 0.31-0.78)). Future studies are needed to elucidate the potential sources of exposure and disclose the mechanisms of action.

Risk assessment of the exposure to mycotoxins in dogs and cats through the consumption of commercial dry food.

Dry feed for dogs and cats sold in Europe are mostly formulated with cereals and cereal by-products, so the contamination of this food with mycotoxins represents a potential risk for these pets. We analyzed a representation of the best-selling feed brands in Spain. The presence of Aflatoxins (B1, B2, G1, and G2), Ochratoxin A, T-2 and HT-2 toxins, Deoxynivalenol, Zearalenone, and Fumonisins (B1 and B2) was quantified, using immunoaffinity columns and LC-MS/MS. In general, mycotoxins were frequently and simultaneously (6-11) detected, with AFB1, FB1, FB2, Deoxynivalenol, and HT-2 detected in 100% of the samples. However, the concentrations of most of them are among the lowest reported so far. Fumonisins were the exception since we report the highest concentrations to date, particularly in cat feed. We practically found no significant differences in the level of mycotoxin contamination in relation to the presumed quality of the feed. We also calculated the daily exposure, and evaluated the acute and chronic health risk posed by these feeds. None of the brands analyzed presented acute risk for any of the mycotoxins. However, the high levels of fumonisins found in some samples could become problematic, if there are hidden forms of them. This is also evident in relation to long-term risk, since in the case of fumonisins the level of exposure exceeds the tolerable daily intake level in 3.5 and 12 times, for dogs and cats respectively. The exposure levels to zearalenone and deoxynivalenol could also be of long-term concern, especially considering the possibility that the continuous exposure to several mycotoxins simultaneously might produce potentiated toxic effects as a result of their synergistic action. Further research on the potential adverse health effects deriving from chronic exposure to low doses of multi-mycotoxin mixtures in pets is needed.

Dietary Intake of Essential, Toxic, and Potentially Toxic Elements from Mussels (Mytilus spp.) in the Spanish Population: A Nutritional Assessment.

The levels of forty-three elements were determined in fresh, preserved, and frozen mussels (n = 208) with the purpose of evaluating their contribution to the recommended dietary intake of essential elements and their potential risk to Spanish consumers' health. We found relevant differences in the element content in relation to the mode of conservation of mussels as well as in relation to their geographical origin, brand, or mode of production. According to our estimates, mussels are important contributors to the intake of most essential elements, contributing almost 70% of daily requirements of Se, 30-35% of Mo, Zn, and Co, and around 15% of Fe. At the same time, the pattern of average consumption of mussels in Spain does not seem to imply an excessive risk associated with any of the 36 toxic elements studied. However, it should be noted that, in the high percentile of consumption the exposure to Cd and As may be high, in particular that associated with the consumption of fresh and/or frozen mussels. According to the results of this study, a moderate consumption of mussels can be recommended as a valuable and safe source of trace elements.

Comparative study of the intake of toxic persistent and semi persistent pollutants through the consumption of fish and seafood from two modes of production (wild-caught and farmed).

Adverse effects of chemical contaminants associated with seafood counteract the undoubted benefits for the health of its valuable nutrients. So much so that many dietary guidelines recommend no more than one serving a week of fish and seafood. Although is estimated that aquaculture provides more than 50% of the fish and seafood consumed globally, few research studies have focused in the assessment of the intake of pollutants through aquaculture products. In this study we determined the levels of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and toxic elements (Pb, Cd, Ni, Al, As, and Hg) in a large sample of farmed and wild-caught seafood, and we estimated the intake of these contaminants in two hypothetical models of consumers: those consuming only farmed fish, and those consuming only wild fish. Measured levels of most organic and many inorganic pollutants were higher in aquaculture products, and consequently intake levels if only such products were consumed would be also significantly higher. Thus, the intake of ∑PAHs in adults consuming aquaculture seafood would be 3.30ng/kg-bw/day, and consuming seafood from extractive fishing 2.41ng/kg-bw/day (p<0.05); ∑OCPs, 3.36 vs. 1.85ng/kg-bw/day, respectively (p<0.05); ∑PCBs, 2.35 vs. 2.11ng/kgbw/day, respectively; and the intake of Pb, Ni, As, and Al would be also significantly higher consuming farmed seafood. For children the estimations were very similar, but the difference of intake of PCBs reached statistical significance. The implementation of several decontamination practices in aquaculture would allow not only match the levels of pollution from wild-caught seafood, but also could provide products with much lower levels of pollutants than those, which in turn would allow to increase consumption over the "one serving per week", and so benefit the consumer of the enormous positive health effects of the valuable nutrients of seafood.

Assessment of human health hazards associated with the dietary exposure to organic and inorganic contaminants through the consumption of fishery products in Spain.

In this work we have evaluated the potential carcinogenic and acutely toxic risks associated to the exposure to highly prevalent organic and inorganic contaminants through the consumption of fishery products by the Spanish population. The concentrations of 8 organochlorine pesticides (OCPs), 18 polychlorinated biphenils (PCBs), 7 polycyclic aromatic hydrocarbons (expressed as benzo[a]pyrene toxic equivalents (B[a]Peq)), and three inorganic toxic elements [arsenic (As), cadmium (Cd), and mercury (Hg)] were determined in 93 samples of the most consumed species of white fish, blue fish, cephalopods and seafood species, which were acquired directly in markets and supermarkets in the Canary Islands, Spain. The chemical concentration data were combined with the pattern of consumption of these foodstuffs in order to calculate the daily intake of these contaminants, and on this basis the risk quotients for carcinogenicity and acute toxicity were determined for Spanish adults and children. Our results showed that the daily intake of OCPs, PCBs and B[a]Peq, which is associated to blue fish consumption was the highest within the fish group. The estimated intake of pollutants can be considered low or very low for the individual contaminants, when compared to reference values, except in the case of HCB and As. All the estimated intakes were below the reported Tolerable Daily Intakes. Considering the additive effects of multiple contaminants, the risk of acute toxic effects can also be considered as low or very low. However, our results reflect that the current consumption of white fish in adults and children, and also the blue fish in the case of adults, poses a moderate carcinogenic risk to Spanish consumers, mainly related to their concentrations of As. The conclusions of this research may be useful for the design of appropriate risk communication campaigns.

Influence of the method of production of eggs on the daily intake of polycyclic aromatic hydrocarbons and organochlorine contaminants: an independent study in the Canary Islands (Spain).

Analysis of 16 polycyclic aromatic hydrocarbons (PAHs), 20 organochlorine pesticides (OCPs) and 18 polychlorinated biphenyls (PCBs) were performed on eggs from three different production types (conventional, free-run and organic) collected from the markets of the Canary Islands (Spain). Unlike other studies we did not found differences in the content of PCBs or OCPs of eggs in relation to its production type. Median ∑OCPs content was 3.87 ng g⁻¹ fat, being dieldrin, dicofol, hexachlorobenzene, p,p'-DDE and p,p'-DDT the most frequently detected. Median ∑PCBs value was 3.93 ng g⁻¹ fat, with 79.9% of this amount coming from the marker PCBs. Two samples, one free-run and one organic, greatly exceeded the current European Commission (EC) limit of 2.5 pg TEQ(PCDD/F) g⁻¹ lipid, but the rest were well below of this limit. The concentrations of PAHs in conventionally produced eggs were almost 4 times higher than in free-run or organic eggs. Mean dietary intake estimates of the organochlorine contaminants based on consumption of eggs, regardless of the type chosen, is negligible for the Canary Islands' population. However, the median dietary intake estimates of PAHs greatly depend on the type of eggs chosen, being much lower when free-run and organic eggs are consumed.

Levels of organochlorine contaminants in organic and conventional cheeses and their impact on the health of consumers: an independent study in the Canary Islands (Spain).

In the present work we have evaluated the levels of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in 61 commercially available brands of cheese (54 conventional and 7 organic) to estimate their relevance as a source of organochlorines. Our results showed that hexachlorobenzene, α-HCH, dieldrin, p,p'-DDE, and PCBs 153 and 180 were present in most of the samples independent of the cheese type. The concentration of OCPs was low for both types of cheese, although organic had lower concentrations than conventional. The estimated daily intake (EDI) of OCPs was lower than the tolerable daily intake (TDI). The levels of PCBs in cheese were also low; however, there were higher levels of PCBs in organic than in conventional brands. Levels of dioxin- like PCBs (DL-PCBs) in both types of cheese reached concentrations in the 75th percentile higher than 3 pg WHO-TEQ/g fat, and above 100% of the levels established by the EU. People consuming the most contaminated brands could have an EDI well above the recommended TDI (2 pg WHO-TEQ/kg bw/day). These results are of concern as the adverse health effects exerted by dioxin-like compounds are well known.