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.

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.

Comparative study of organic contaminants in agricultural soils at the archipelagos of the Macaronesia.

The occurrence of organic pollutants in soil is a major environmental concern. These compounds can reach the soil in different ways. Point sources, related to pesticides that are used intentionally, can be applied directly to the soil, or reach the soil indirectly due to application to the aerial parts of crops. On the other hand, non-point sources, which reach soils collaterally during irrigation and/or fertilization, or due to the proximity of plots to industrialized urban centers. Long-range transport of global organic pollutants must also be taken into account. In this study, 218 pesticides, 49 persistent organic pollutants, 37 pharmaceutical active compounds and 6 anticoagulant rodenticides were analyzed in 139 agricultural soil samples collected between 2018 and 2020 in the Macaronesia. This region comprised four inhabited archipelagos (Azores, Canary Islands, Cape Verde, and Madeira) for which agriculture is an important and traditional economic activity. To our knowledge, this is the first study on the levels of organic compound contamination of agricultural soils of the Macaronesia. As expected, the most frequently detected compounds were pesticides, mainly fungicides and insecticides. The Canary Islands presented the highest number of residues, with particularly high concentrations of DDT metabolites (p,p' DDE: 149.5 ± 473.4 ng g-1; p,p' DDD: 16.6 ± 35.6 ng g-1) and of the recently used pesticide fenbutatin oxide (302.1 ± 589.7 ng g-1). Cape Verde was the archipelago with the least contaminated soils. Very few pharmaceutical active compounds have been detected in all archipelagos (eprinomectin, fenbendazole, oxfendazole and sulfadiazine). These results highlight the need to promote soil monitoring programs and to establish maximum residue limits in soils, which currently do not exist at either continental or local level.

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.

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.

Validation of a Method Scope Extension for the Analysis of POPs in Soil and Verification in Organic and Conventional Farms of the Canary Islands.

Persistent organic pollutants (POPs) are among the most relevant and dangerous contaminants in soil, from where they can be transferred to crops. Additionally, livestock animals may inadvertently consume relatively high amounts of soil attached to the roots of the vegetables while grazing, leading to indirect exposure to humans. Therefore, periodic monitoring of soils is crucial; thus, simple, robust, and powerful methods are needed. In this study, we have tested and validated an easy QuEChERS-based method for the extraction of 49 POPs (8 PBDEs, 12 OCPs, 11 PAHs, and 18 PCBs) in soils and their analysis by GC-MS/MS. The method was validated in terms of linearity, precision, and accuracy, and a matrix effect study was performed. The limits of detection (LOD) were established between 0.048 and 3.125 ng g-1 and the limits of quantification (LOQ) were between 0.5 and 20 ng g-1, except for naphthalene (50 ng g-1). Then, to verify the applicability of the validated method, we applied it to a series of 81 soil samples from farms dedicated to mixed vegetable cultivation and vineyards in the Canary Islands, both from two modes of production (organic vs. conventional) where residues of OCPs, PCBs, and PAHs were found.

An Easy Procedure to Quantify Anticoagulant Rodenticides and Pharmaceutical Active Compounds in Soils.

A modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction was validated for the extraction of seven coumarin anticoagulant rodenticides (ARs) and 36 pharmaceutical active compounds (PhACs) residues in soil samples using liquid chromatography tandem mass spectrometry (LC-MS/MS). The aim of this work was to develop a method for the monitoring of these compounds in agricultural lands as well as in forensic applications for the determination of ARs poisoning. As far as is known, this is the first time that a QuEChERS-based method is used for the extraction of ARs in soil, as well as on such a quantity of PhACs. A matrix effect study was carried out on samples of soil devoted to agriculture in the midland area of the Canary Islands (clay loam type). It was in house validated (accuracy, precision, and linearity) at seven spiked levels between 0.5 and 50 ng g-1. The limits of quantification (LOQ) ranged between 0.5 and 50.0 ng g-1 and the limits of detection (LOD) ranged from 0.024 to 6.25 ng g-1. The method was then successfully used for both the determination of the target analytes in the soils from the agricultural plots that had been irrigated with regenerated water, and in the soil collected from underneath wild bird carcasses (which had been the subject of forensic investigation).

Optimization and validation of a QuEChERS-based method for the simultaneous environmental monitoring of 218 pesticide residues in clay loam soil.

A modified QuEChERS method was optimized, validated and verified for the extraction of 218 pesticide residues in agricultural soil samples. The 218 analytes are extracted using a single step, without clean-up, with matrix-matched calibration, and two complementary techniques: liquid and gas chromatography tandem triple quad mass spectrometry (LC-MS/MS and GC-MS/MS). Some of the parameters such as salts, acidity of the extraction solvent, sample moisture and some mechanical changes in the procedure were optimized to improve the overall performance for the target compounds and the soil matrix. The method was fully validated on a representative agricultural soil sample of the Canary Islands (clay loam soil) in terms of linearity, accuracy and precision. To avoid matrix effects, matrix-matched calibration curves (R2 ≥ 0.99) were used for all target analytes. 100% of the compounds can be quantified with limits of quantification (LOQ) lower than the limit typically used in soils (50 ng g-1), with 92% of compounds presenting a LOQ that is at least 10 times lower than that normally required. The limits of detection (LOD) ranged between 0.024 and 6.25 ng g-1. The validated method was applied to a series of actual samples of agricultural soil (n = 18). In addition, as a further verification of its potential, the results of the application of the method in the investigation of clay loam soil samples that were obtained from underneath wildlife carcasses in the context of an environmental forensic investigation are also presented.

Supporting dataset on the optimization and validation of a QuEChERS-based method for the determination of 218 pesticide residues in clay loam soil.

The dataset presented in this article supports "Optimization and validation of a method for the simultaneous environmental monitoring of 218 pesticide residues in clay loam soil" [1]. A method based on QuEChERS (Quick, Easy, Cheap, Effective, Rugged & Safe) for the extraction of pesticide and some metabolites residues was developed. The quantification of the chemicals was performed by a combination of two complementary LC-MS/MS and GC-MS/MS analyses. Detailed optimization data of the QuEChERS extraction method is provided, including (1) salt combination, (2) acidification of the solvent (3) the amount of the selected acid (Formic Acid, FA) and (4) moisturization of the soil samples prior to extraction. In addition, all the validation data are presented, including the matrix effect, which was evaluated for each analyte using the recommended procedure.

Estimated exposure to EU regulated mycotoxins and risk characterization of aflatoxin-induced hepatic toxicity through the consumption of the toasted cereal flour called "gofio", a traditional food of the Canary Islands (Spain).

"Gofio" is a type of flour made from toasted grain, which is part of the staple food in the Canary Islands, Spain, in which the occurrence of Aflatoxins B1, B2, G1 and G2 (AFB1, AFB2, AFG1, AFG2), Fumonisins B1 and B2 (FB1 and FB2) Ochratoxin A (OTA), Deoxynivalenol (DNV) and Zearalenone (ZEA) was evaluated. 83% of the samples were contaminated with at least one mycotoxin and 69.2% of the analyzed samples showed co-occurrence of mycotoxins (range 2 to 8). All the concentrations were well below the established limits (maximum values of AFs=0.42 µg/kg; FBs=178.3 µg/kg; OTA=0.3 µg/kg; DON=92.5 µg/kg; and ZEA=9.9 µg/kg). The daily dietary exposure to total AFs was estimated to be 7.1% of the TDI. This value was almost double in children, and considering the upper-bound approach could reach 35% of the TDI. For the rest of mycotoxins, the consumers would be exposed to less than 2% of their TDIs. The risk characterization indicates that there is a potential risk in developing aflatoxin induced liver cancer due to gofio consumption in the subpopulation which is simultaneously exposed to other hepatocarcinogens, such as the hepatitis B virus.

Data related uncertainty in near-surface vulnerability assessments for agrochemicals in the San Joaquin Valley.

Precious groundwater resources across the United States have been contaminated due to decades-long nonpoint-source applications of agricultural chemicals. Assessing the impact of past, ongoing, and future chemical applications for large-scale agriculture operations is timely for designing best-management practices to prevent subsurface pollution. Presented here are the results from a series of regional-scale vulnerability assessments for the San Joaquin Valley (SJV). Two relatively simple indices, the retardation and attenuation factors, are used to estimate near-surface vulnerabilities based on the chemical properties of 32 pesticides and the variability of both soil characteristics and recharge rates across the SJV. The uncertainties inherit to these assessments, derived from the uncertainties within the chemical and soil data bases, are estimated using first-order analyses. The results are used to screen and rank the chemicals based on mobility and leaching potential, without and with consideration of data-related uncertainties. Chemicals of historic high visibility in the SJV (e.g., atrazine, DBCP [dibromochloropropane], ethylene dibromide, and simazine) are ranked in the top half of those considered. Vulnerability maps generated for atrazine and DBCP, featured for their legacy status in the study area, clearly illustrate variations within and across the assessments. For example, the leaching potential is greater for DBCP than for atrazine, the leaching potential for DBCP is greater for the spatially variable recharge values than for the average recharge rate, and the leaching potentials for both DBCP and atrazine are greater for the annual recharge estimates than for the monthly recharge estimates. The data-related uncertainties identified in this study can be significant, targeting opportunities for improving future vulnerability assessments.