Validation of a Method Scope Extension for Simple Biomonitoring of 353 Pollutants in Serum Samples.

Animals and humans are exposed to various residues that can have a detrimental impact on health, including carcinogenic potential, endocrine disruption, or fatal toxicity. The toxic burden can be evaluated in several biological samples, with serum being one of the preferred and most convenient options. In this study, we have applied and validated a method for detecting several hundred toxins in serum samples. This technique involved a single-step QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction followed by analysis using gas and liquid chromatography coupled with mass spectrometry. With this methodology, we could detect and quantify up to 353 compounds, including persistent organic pollutants (POPs), pesticides, pharmaceuticals, and rodenticides, using just 250 µL of serum. Among them, 92% could be measured at concentrations below 1.25 ng/mL, making it ideal for biomonitoring. We applied this method to samples collected from camels (n = 40) and humans (n = 25). We detected naproxen, ketoprofen, paracetamol, levamisole, and some POPs in these samples. This study validated the ability to simultaneously detect a broad range of compounds in small volumes of serum.

Microplastics ingestion and chemical pollutants in seabirds of Gran Canaria (Canary Islands, Spain).

Plastic pollution constitutes an environmental problem in the Canary Islands nowadays. Nevertheless, studies evaluating the impact of plastics on its avifauna are still scarce. Gastrointestinal tracts of 88 birds belonging to 14 species were studied for the presence of plastics. Moreover, their livers were analyzed for the determination of bromodiphenyl ethers (BDEs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs). Among Cory's shearwaters (n = 45), the frequency of occurrence of plastic ingestion was considerably high (88.89 %). This species had the highest mean value of items (7.22 ± 5.66) and most of them were compatible with lines derived from fishing gear. PCBs and PAHs were detected in all of the samples and OCPs in the great majority of them (98.86 %). Our results highlight the problems that plastic debris (mainly for seabirds) and organic pollutants pose to these species.

Human biomonitoring of persistent and non-persistent pollutants in a representative sample of the general population from Cape Verde: Results from the PERVEMAC-II study.

International Public Health authorities recommend biomonitoring studies to assess the exposure to chemicals in the general population. The aim of the present study was to analyze the blood concentrations of a total 360 pollutants, including 230 pesticides in current or recent use, 59 persistent organochlorine pollutants (POPs), 11 anticoagulant rodenticides and 60 pharmaceutical active compounds (PhACs), in a cohort of 403 subjects from Cape Verde. The study was performed in the frame of the Pesticide Residues in Vegetables of the Macaronesia project (PERVEMAC-II). A total of 60 out of 360 toxic compounds (16.7%) were detected, at least, in one participant. The three most frequently detected substances were p,p'-DDE (100%), phenanthrene (94.0%) and hexachlobenzene (35.9%). 2-Phenylphenol and imidacloprid were detected in 29.0 and 14.4% of the population. The three substances with the highest serum concentrations were PhACs: naproxen (249.1 ng/mL), metronidazole (115.6 ng/mL) and acetaminophen (25.2 ng/mL). Median blood concentration of p,p'-DDE, HCB and phenanthrene were 1.87, 0.08 and 0.36 ng/mL. Blood concentrations of POPs were influenced by age, although both gender and body mass index may exert an influence in the presence of these substances. Lifestyle has an effect on the concentration of these substances, especially in terms of dietary habits. Both the frequency of detection and the concentration of the studied substances are similar to those of other biomonitored populations. This is the first biomonitoring study carried out in Cape Verde. 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.

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.

Extension of an extraction method for the determination of 305 organic compounds in clay-loam soil to soils of different characteristics.

Soil is one of the environmental compartments most affected by pollution. From this medium, the organic compounds can be emitted to the groundwater, the atmosphere, or the biota. Thus, having adequate methods of analysis of organic pollutants in this matrix is essential. However, the soil is a very complex matrix whose organic and inorganic components can determine the degree to which they are retained. Therefore, the methods must account for the various soil characteristics. In this study, the performance of an extraction method that had been already validated in clay loam soils for more than 300 organic compounds of very different nature including pesticides, PhACs, ARs, and POPs has been evaluated in four additional representative soil types of the agricultural land of the Canary archipelago: sandy loam, sandy clay, clay and loamy sand. For this purpose, recovery experiments have been performed at a single concentration (50 ng g-1) in each soil type. When there is a significant difference according to the criteria applied for a given compound, a factor has been calculated to correct the difference in performance in each soil type.•These results allowed to broaden the range of soils that can be analyzed with the proposed methodology.•In the worst case, which is the loamy sand soil, the original methodology allows the analysis of 180 organic contaminants with adequate recoveries. For analytes outside the acceptable range in this soil and the other soil type analyzed, correction factors are proposed.

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.

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.

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.

Persistence of Isothiazolinones in Clothes After Machine Washing.

BACKGROUND: Sensitization to methylchloroisothiazolinone (MCI) and methylisothiazolinone (MI) is a worldwide problem. Washing machine detergents are suspected to cause cutaneous symptoms in highly sensitized patients. Little is known about the persistence of isothiazolinones in clothes that have been washed. OBJECTIVE: The aim of the study was to analyze the possible persistence of MI, MCI, benzisothiazolinone, and octylisothiazolinone in common fabrics after machine washing. METHODS: Different clothes (cotton, polyester, linen, and wool) were collected, and 4 types of wash were done (control, standard, standard + conditioner, and standard + double rinse). The samples were analyzed using ultrahigh-performance liquid chromatography. RESULTS: The results showed that the concentrations of isothiazolinones were very low, independent of the type of material or wash. The highest levels were found in the control wash (hand wash), reaching a maximum of 0.4 ppm in the linen. CONCLUSIONS: Our findings suggest that it is not necessary to recommend that patients sensitized to MI avoid isothiazolinones in machine detergents or fabric conditioners or to double rinse. However, after using the detergent for hand washing (the control in our study), there may remain sufficient concentrations of isothiazolinones in clothes to produce symptoms in highly sensitized patients.

Isothiazolinones in cleaning products: Analysis with liquid chromatography tandem mass spectrometry of samples from sensitized patients and market.

BACKGROUND: Methylchloroisothiazolinone (MCI) and methylisothiazolinone (MI) contact dermatitis is a severe problem. The high concentrations of these substances and other isothiazolinones such as benzisothiazolinone (BIT) and octylisothiazolinone (OIT) contained in cleaning products may cause allergic contact dermatitis in sensitized patients. OBJECTIVES: To evaluate the exposure to isothiazolinones contained in cleaning products on the market and from sensitized patients, and to verify the accuracy of labeling. METHODS: A total of 34 cleaning products were collected (17 supplied by sensitized patients and 17 bought randomly). Analysis was made of the concentrations of MI, MCI, BIT, and OIT using liquid chromatography tandem mass spectrometry (LC-MS/MS). RESULTS: MI and BIT were the components most frequently detected. Of all the products analyzed, 76.5% contained at least one isothiazolinone. Twelve products had an MI concentration above the permitted level for rinse-off cosmetics. Most of them were coming into direct contact with the skin in daily use. Mislabeling occurred in eight products. CONCLUSIONS: Some cleaning products with high concentrations of isothiazolinones may cause cutaneous symptoms in sensitized patients, especially in spray form. The labeling should be correct, also regarding the use of each article.

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.