Metals in commercial fish in the Galapagos Marine Reserve: Contribution to food security and toxic risk assessment.

Metal pollution in the marine environment can damage places with exceptional biodiversity such as the Galapagos Islands. For this reason, it is important to evaluate the toxic risk from metals derived from fish consumption and to perform a nutritional assessment. We sampled 20 individuals of demersal (Caulolatilus princeps and Mycteroperca olfax) and pelagic (Thunnus albacares and Seriolella violacea) species. The levels of the toxic elements (Al, B, Ba, Cd, Ni, Pb and Sr), and the macroelements, microelements and trace elements (Ca, Cr, Fe, K, Li, Mn, Mo, Mg, Na, V and Zn) of species muscle tissue were analyzed by Inductively Coupled Plasma Optical Spectrometry (ICP-OES). Demersal species have higher concentrations of Cr, K, Mg and Mo; while pelagic species have higher levels of Zn. M. olfax could potentially cause Cd toxicity so it is recommended not to ingest more than 86 and 73 g of this species (i.e. roughly, one serving) per week for men and women, respectively. None of the species could be marketed in Europe and the USA due to Cd level exceed the allowed limits by EFSA and FAO. Furthermore, the dietary intake of C. princeps is recommended due to its high concentration of Ca, Na, K, Mg and Cr, while T. albacares is recommended for people with Zn deficiency. However, due to the Cd level in C. princeps it is not recommended to ingest more than five servings per week. We attribute the source of metals in the studied fish from the volcanic origin of the islands rather than from human pollution. This is the first study that thoroughly estimate concentration of metals in commercial fish species and its contribution to food security in the Galapagos.

Trace element and toxic metal intake from the consumption of canned mushrooms marketed in Spain.

Mushrooms are a valuable foodstuff because they are an important source of fiber and essential amino acids, but they have a great capacity to capture metals from substrate. Due to this reason, the content of 14 metals (B, Ba, Cr, Cu, Fe, Li, Mo, Ni, Sr, V, Zn, Al, Cd, Pb) of 100 samples of canned mushrooms grown in Spain were analyzed by inductively coupled plasma atomic emission spectroscopy. Fe (9.55 mg/kg) was the most notable trace element, followed by Zn (2.39 mg/kg). The most abundant toxic metal was Al (17.80 mg/kg). Significant statistical differences between the absorption of metals have been observed when comparing species. Lentinula edodes and Lactarius deliciosus are the species which had the highest metal contents. Taking the average consumption 300 g per day for adults into account, the exposure to trace toxic metals from the consumption of the studied mushrooms does not pose a health risk. However, contribution percentages of Pb (87.6%) and Al (59.2%) found in Lentinula edodes and Pholiota nameko samples, respectively, are near the maximum intake.

Essential and toxic metals in taros (Colocasia esculenta) cultivated in the Canary Islands (Spain): evaluation of content and estimate of daily intake.

Taros are a staple in the diet of many people around the world, and they are an excellent source of minerals. Monitoring the levels of metals in food provides basic information that is useful from the perspectives of safety, regulation, and nutrition. Forty-two samples of taros were randomly obtained from supermarkets, vegetable markets, and farmer's plots on the island of Tenerife (Canary Islands, Spain). The edible portion (pulp) was the only part considered for analysis. Flame atomic absorption spectrometry (FAAS) was used to determine the contents of Na, K, Ca, Mg, Cu, Fe, Mn, and Zn. The levels of Cr, Ni, Cd, and Pb were determined using graphite furnace atomic absorption spectrometry (GFAAS). Mean concentrations (mg/kg) were 565.6 Na, 2947 K, 231.4 Ca, 364.5 Mg, 1.224 Cu, 3.818 Fe, 1.408 Mn, 2.242 Zn, 0.044 Cr, 0.021 Ni, 0.003 Cd, and 0.006 Pb. The mean concentrations of Cd and Pb were well below the accepted European Commission limits (0.1 mg/kg weight for both metals, respectively). Daily consumption of taro (10.41 g taro/person/day) contributes to the dietary intake of essential metals and trace elements, mainly Mg (1.265% in adult women and 1.084% in adult men) and Cu (1.182% for adult men and women). The average daily intakes of Cd (0.031 µg/day) and Pb (0.062 µg/day) from taro were below the legislated respective tolerable weekly intakes (TWIs). Thus, the samples analyzed were considered safe to eat based on their metal concentrations and legislated allowable intakes.

Evaluation of metals in several varieties of sweet potatoes (Ipomoea batatas L.): comparative study.

Sweet potatoes are a staple in the diet of some people and an excellent source of minerals. Metal monitoring in food, like sweet potatoes, provides basic information on safety aspects in regulatory processes as well as nutritional values. One hundred five samples of three varieties of sweet potatoes were randomly obtained from supermarkets, farmers markets, and farmers' plots in Tenerife (Canary Islands, Spain). The edible portion (pulp) was the only part considered for analysis. Flame atomic absorption spectrometry was used to determine the contents of sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), copper (Cu), iron (Fe), manganese (Mn), and zinc (Zn), while the levels of chromium (Cr), nickel (Ni), cadmium (Cd), and lead (Pb) were determined using graphite furnace atomic absorption spectrometry. The mean concentrations were 500 Na, 4409 K, 564 Ca, 609 Mg, 1.291 Cu, 6.554 Fe, 2.324 Mn, 2.348 Zn, 0.028 Cr, 0.048 Ni, 0.001 Cd, and 0.003 Pb mg/kg, respectively. Potassium presented the highest contents in all varieties of sweet potatoes. Iron was the most abundant microelement. The orange fleshed sweet potato variety offered greater nutritional contributions to the recommended intakes than the rest of the varieties studied. The estimated mean daily intake of Ni (0.72 mg/day) detected in our samples was highly consistent with other studies. Average daily intakes of Cd (0.015 µg/day) and Pb (0.045 µg/day) were below toxicological reference values. In conclusion, the levels of Cd and Pb detected in the sweet potatoes analyzed do not represent any toxicological risk to consumers.

Comparative analysis of metal pollution in the Atlantic Ocean and Mediterranean Sea: insights from Anemonia sulcata study.

In this study, we investigated metal concentrations in Anemonia sulcata specimens from various locations in the Atlantic Ocean and the Mediterranean Sea. A total of 84 individuals were sampled from specific zones, and their tissue samples were processed for metal analysis using Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES). The results revealed notable differences in metal concentrations among the studied regions. The Atlantic Ocean and the Mediterranean Sea were found to have distinct patterns of marine pollution, influenced by a complex interplay of geographical, demographic, industrial, and environmental policy factors. Conversely, the semi-enclosed Mediterranean Sea has a lower natural dilution capacity, leading to the accumulation and prolonged presence of pollutants. Population density and industrial activities in coastal areas play a significant role in pollution disparities between the Mediterranean Sea and the Atlantic Ocean. The Mediterranean coasts, with higher population densities and intensive industrial operations, experience greater strain on marine ecosystems due to increased pollution sources. Additionally, environmental policies and management approaches differ between the two regions, contributing to variations in pollution response and regulation.

Metal content in Sardina pilchardus during the period 2014-2022 in the Canary Islands (Atlantic EC, Spain).

The contamination present in an organism varies depending on biological and oceanographic conditions, so monitoring the same species is of great importance to understand the state of the ecosystem. Fifteen specimens in Sardina pilchardus between 12 and 15 cm in total length were collected during the second half of January of each of the study years (2014, 2016, 2018, 2020 and 2022). Samples were analyzed with Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) to measure metals (Al, Cd, Cu, Fe, Li, Ni, Pb and Zn) in mg/Kg. There was a progressive decrease in Pb content over the period, with the highest concentration being obtained in 2014 (0.086 ± 0.065 mg/kg). Locally important oceanic-atmospheric events may occur in the study period that strongly impact the tissue composition of marine organisms. In this case, discontinuous trends were evident in some of the metal concentrations analyzed in the muscle of European sardine in the Canary Islands.

Environmental Factors Influencing Metal Concentrations in Scomber colias Along the Canary Islands.

A total of 140 specimens of Scomber colias were collected from the Canary archipelago waters during the first semester of 2021, with 20 samples from each of the seven main islands. After analyzing the concentrations of metals (Al, Zn, Cd, Pb, Fe, and Cu) with ICP-OES, significant variations were observed among islands, with specimens from Tenerife and Gran Canaria containing higher levels of Al, Cd, and Pb, while those from Lanzarote and Fuerteventura had elevated levels of Zn, Fe, and Cu. These differences are probably related to greater anthropogenic activity around Tenerife and Gran Canaria coasts, leading to higher pollution levels, and the influence of Saharan dust and African upwelling on Lanzarote and Fuerteventura, enriching the waters with nutrients. Specific management strategies to mitigate marine pollution and continuous monitoring are crucial to safeguard marine ecosystems and to ensure food security.

Impact of natural events on metal bioaccumulation in Anemonia sulcata.

Samples of Anemonia sulcata were collected in 2022 from different areas of the Canary Islands affected by different natural contamination sources, such sandstorms, submarine volcanic activity, continuous rainfall, upwelling and dinoflagellate blooms. Significant differences were observed between the zones for the metals and trace elements analyzed (Al, Zn, Cd, Pb, Ni, Co, Fe, B, Cu, Mg and Li). Anemones from volcanic areas showed higher levels of Cd, Pb and Ni. Individuals from sandstorm areas showed elevated levels of Al, Zn and Fe. Samples collected from areas affected by upwelling processes had higher concentrations of Cu, Mg and Li. Finally, the areas affected by dinoflagellates showed lower levels of Zn, Pb, Fe, Mg and Li. The study reveals how natural phenomena dramatically influence metal accumulation in A. sulcata, which is of great value for anticipating and managing potential problems associated with public health.

Impact of the lockdown period during the COVID-19 pandemic on the metal content of the anemone Anemonia sulcata in the Canary Islands (CE Atlantic, Spain).

Anemones, specifically the species Anemonia sulcata, are cnidarians that serve as bioindicators in marine ecosystems, indicating the health of the environment and changes in environmental conditions. Monitoring anemone populations and studying their well-being and distribution provide valuable insights into marine ecosystem conditions. This study aimed to investigate the impact of the SARS-CoV-2 pandemic on the metal content of Anemonia sulcata. Over a six-year period (2017-2022), twenty specimens of Anemonia sulcata were collected in Tenerife, Spain. The results showed that in 2020, during the two-month lockdown in Spain from March to May when tourism was halted, A. sulcata exhibited the lowest concentrations of various metals studied (Al, Cd, Cu, Fe, Pb, and Zn). This finding suggests that the reduced anthropogenic pressure on the coast due to the absence of tourism significantly decreased pollution levels. Therefore, the study emphasizes the importance of promoting sustainable tourism worldwide. The research highlights that minimizing human impact on coastal areas through responsible tourism practices can effectively reduce pollution in marine ecosystems.

Essential Metals and Trace Elements in Cereals and Their Derivatives Commercialized and Consumed in Cape Verde.

Cereals and their derivatives are basic foods in the human diet and a source of minerals, but the content of elements may vary depending on the type of cereal or its processing. The levels of Na, K, Ca, Mg, Fe, Cu, Zn, Mo, Co, and Mn have been determined in 126 samples of cereals and cereal derivatives (rice, corn gofio, corn flour, wheat flour, corn, and wheat) commercialized and consumed in Cape Verde using an inductively coupled plasma-optical emission spectrometer (ICP-OES) after a wet microwave digestion process. Some elements stand out in products such as corn gofio (K), wheat (Mg), and wheat flour (Fe). Negative correlations were found between Mo-Na and Na-Zn that could suggest interference between these elements. Bearing in mind the dietary intake evaluation and the guideline values provided by EFSA (European Food Safety Authority) or FAO (Food Authority Organization), the consumption of wheat (100 g/day) provides a notable contribution of Mo, Mn, Fe, and Mg. Considering the nutritional value of the analyzed essential and trace elements, the consumption of different cereals and their derivatives should be promoted.

Whey Protein Dietary Supplements: Metal Exposure Assessment and Risk Characterization.

Protein supplements (PS) are trendy foods, especially those made from whey. In addition to providing protein, these products are a source of metals, providing essential elements (Na, K, Mg, Ca, Mo, Mn, Fe, Co, Cu, and Zn) and other potentially toxic elements (Al, B, Sr, V Ba, and Ni). In this study, 47 whey PS samples were analyzed for mineral elements by ICP-OES, and their dietary exposures were assessed for three consumption scenarios. Elements found in higher concentrations were K (4689.10 mg/kg) and Ca (3811.27 mg/kg). The intake of 30 g PS (average recommended amount/day) provides about 20% of the established reference value (NRI) for Cr (18.30% for men and 25.63% for women) and Mo (26.99%). In a high daily consumption scenario (100 g PS/day) and when the maximum concentrations are considered, Cr, Zn, Fe, Mo, and Mg dietary intakes of these metals exceed the daily recommended intakes and could pose a risk. The daily intake of 30, 60, and 100 g of whey PS for 25 years does not pose a health risk since the hazard index (HI) is less than one in these consumption scenarios, and the essential elements contributing most to HI are Co, followed by Mo and Cr. It is recommended to improve the information to the consumers of these new products. Furthermore, to help in the management and prevention of these potential health risks, it would be advisable to improve the regulation of these dietary supplements and their labeling.

Proteins and Minerals in Whey Protein Supplements.

Sports nutrition supplementation is a widespread practice. Whey protein supplements contribute not only to protein intake but also to dietary exposure to minerals. The labelling present provides the percentage of protein and rarely refers to other components, such as potentially toxic elements such as B, Cu, Mo, Zn, and V that present tolerable upper intake levels set by the European Food Safety Authority. The percentage of protein declared on supplement labelling was checked using the Kjeldahl method, and the levels of Ca, Mg, K, Na, Ba, B, Co, Cu, Cr, Sr, Fe, Li, Mn, Mo, Ni, V, Zn, and Al were analyzed by ICP-OES with the aim of characterizing the protein and mineral contents of isolate and concentrate whey protein supplements representative of the European market. The protein content was 70.9% (18-92.3%) and statistically significant differences were observed between the declared and real protein percentages. Among the minerals, K (4689.10 mg/kg) and Ca (3811.27 mg/kg) presented the highest levels, whereas Co (0.07 mg/kg) and V (0.04 mg/kg) showed the lowest levels. It was concluded that the quality and safety of these products needs to be monitored and regulated. A high degree of non-compliance with labelling claims was detected. Furthermore, the contributions to the recommended and tolerable intakes among regular consumers need to be assessed.

Monitoring different sources of marine pollution in the Canarian intertidal zone using Anemonia sulcata as a bioindicator.

Sea anemones have often been used as bioindicators of contamination because they are semisessile organisms that rarelly leave their niche, which is why they are conducive to affecting the ecosystem at the local level. The objective of this work is to determine whether the concentrations of heavy metals and trace elements in the anemone Anemonia sulcata vary depending on the source of contamination present. In 2021 seventy specimens were collected at five sampling points and fourteen specimens were collected in each point (Control Zone, Thermal Power Plant, Sewage Pipe, Harbour and Tourism) in 2021, on the island of Tenerife. All the areas studied characterized by a pollution condition had higher concentrations of metals and trace elements than the control area. The anemones from Harbour presented a greater number of metals with a higher concentration than the other study areas.

Structuring algae as buffers for heavy metals and trace elements in the Canary Islands intertidal habitat.

Coastal marine pollution from sewage pipes, waste discharges, can seriously affect intertidal organisms. Therefore, the aim of this study is to know if the structuring algae in the Canary intertidal can act as buffers against pollution. Samples were taken in the island of Tenerife (Canary Islands, Spain) from the intertidal water of Anemonia sulcata (anemone), Palaemon elegans (shrimp), Gongolaria abies-marina and Jania virgata (both structuring algae). Each sample was analyzed by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) obtaining values for metals and trace elements (Al, Cd, Pb, Ca, K, Mg, Na, B, Ba, Ba, Co, Cr, Cu, Fe, Li, Mn, Mo, Ni, Sr, V and Zn). Higher concentrations were obtained in the two structuring algal species, with J. vigata having higher concentrations than G. abies-marina. Specimens of A. sulcata showed higher concentrations of trace elements and heavy metals than P. elegans. P. elegans y A. sulcata showed higher heavy metal concentrations and trace elements when algae were not present in the pool. Algae have a great buffering role in the intertidal of the Canary Islands.

A Comparative Analysis of Sparisoma cretense in Island Environments: Unraveling Metal Accumulation Differences in the Canary Islands (Spain, NW African Waters).

This study investigates the impact of varying environmental conditions on the metal composition within the tissues of Sparisoma cretense, contributing to the understanding necessary to offer scientifically sound advice regarding the health status of this species. This knowledge extends beyond fishery production, encompassing implications for food security. The data span the years 2022 and 2023, encompassing both cold and warm climatic seasons. The concentrations of various metals, such as Al, Zn, Cd, Pb, Fe, and Cu, exhibited noteworthy variations across the islands, with significant increases recorded in 2023, particularly during the warm season. The intricate interplay between multiple factors shaped the availability of the analyzed elements in S. cretense. Factors such as rising temperatures during the warm season increased biological activity in marine ecosystems, seasonal fluctuations in weather conditions, water quality, and anthropogenic influences, all contributing to the observed variations in metal concentrations. Additionally, the geological composition of each island and the patterns of marine currents and sediment transport play pivotal roles in these differences. Comprehensive scientific research, monitoring, and environmental surveillance are essential for a holistic understanding of this variability and providing valuable insights for the conservation and management of marine ecosystems in the Canary archipelago.

Influence of Seminal Metals on Assisted Reproduction Outcome.

Increased levels of metal ions in human seminal fluid have a significant correlation with male fertility. Few publications explain the effect of metals in semen and their influence on assisted reproductive treatments. Semen parameters and the levels of twenty-two metals were measured in the seminal fluid of 102 men attended in a Reproductive Unit. Metals were determined by optical emission spectrophotometry. A statistical relationship was found between spermiogram and iron, which was lower than expected in pathological spermiograms (p = 0.032); zinc (p = 0.066), calcium (p = 0.047), and magnesium (p = 0.048) mean levels were higher in normozoospermics. More days of sexual abstinence correlates with higher seminal zinc (p = 0.001) and magnesium levels (p = 0.002). Lower vanadium values were found to be associated with higher fertilization rates (p = 0.039). Higher values of lead (p = 0.052) and vanadium (p = 0.032) were obtained in patients who did not reach 100% embryo cleavage rate. Aluminium (p = 0.042) and sodium (p = 0.002) were found in lower amounts associated with better blastocyst rates. The implantation rate shows an inverse association with women's age and iron and calcium content, compared to magnesium and sodium which presented a significant direct association with this percentage. A significant direct relationship was found between the positive evolution of pregnancy and the values of zinc (p = 0.004), calcium (p = 0.013), potassium (p = 0.002), and magnesium (p = 0.009). The study confirms that zinc, iron, calcium, sodium, aluminium, magnesium, vanadium, and lead have positive-negative effects on reproduction and support the analysis of metals in semen as a new line of study on male fertility with implications for reproductive outcomes.

Analysis of metals and metalloid in commercial fish species from the Galapagos Marine Reserve: Toxicological and nutritional assessment.

Aquatic pollution derived from metal presence in the Galapagos Islands could affect biodiversity and human health. This research provide a baseline on food safety in commercial fish species of the Galapagos Islands. We sampled muscle tissue of pelagic (Acanthocybium solandri) and demersal (Caulolatilus affinis, Pontinus clemensi, Hyporthodus mystacinus, and Paralabrax albomaculatus) species. Metal and metalloid concentrations per species were analyzed by Inductively Coupled Plasma Optical Spectrometry (ICP-OES). According to the Food and Agriculture Organization (FAO) regulation none of the studied species should be ingested; and according to the European Food Safety Authority (EFSA) regulation, all the studied species were above the Maximum Allowable Concentration (MAC) for Cd. According to EFSA, C. affinis should not be commercialized. Finally, A. solandri, P. clemensi and H. mystacinus do not represent a human health risk since its Margen of Safety (MoS) < 1 for people of up to 100 kg of body weight.

The Influence of Follicular Fluid Metals on Assisted Reproduction Outcome.

Infertility has become more common, with an increased exposure to toxic compounds including heavy metals (HM). Follicular fluid (FF) surrounds the developing oocyte in the ovary and can be analysed to assess metal content. The levels of twenty-two metals were measured in the FF of ninety-three females in a reproduction unit, and their influence on assisted reproduction technique (ART), were examined. The metals were determined by optical emission spectrophotometry. Low values of copper, zinc, aluminium, and calcium favour polycystic ovary syndrome. The relationships between the number of oocytes and metals: iron (rs=0.303; p=0.003) and calcium (rs=-0.276; p=0.007) are significant, as well as between the number of mature oocytes with iron (rs=0.319; p=0.002), calcium (rs=-0.307; p=0.003) and sodium (rs=-0.215; p=0.039) and are near to significance in the case of aluminium (rs=-0.198; p=0.057). In the group with a fertilisation rate ≤ 75%, 36% of the women presented calcium >176.62 mg/kg compared to the group with a fertilisation rate ≥ 75% where this percentage was only 10% (p=0.011). An excess of iron and calcium reduces the good quality embryo rate, and an excess of potassium impairs the blastocyst rate. If potassium is above 237.18 mg/kg and calcium is below 147.32 mg/kg, these conditions favour embryo implantation. Pregnancy is influenced by high potassium and low copper levels. Controlling exposure to toxic elements is recommended for all couples with reduced fertility or receiving an ART.

A total diet study of nickel intake in a Spanish population (Canary Islands).

The aim of this study was to analyse nickel content in foods and beverages most commonly consumed by the Canary Island people to determine the dietary intake of this metal throughout the Canary Islands as a whole and in each of the seven islands. A total of 440 samples were analysed by graphite furnace atomic absorption spectrometry. Nickel concentrations ranged between 2.348 ± 1.716 mg/kg in nuts and 0.002 ± 0.002 mg/l in water. Estimated total intake of nickel was 0.093 mg/day for the Canary population, which is far below the tolerable upper intake level (UL) established for adults. Gran Canaria turned out to be the island with the highest nickel intake. Differential analysis of nickel intake by age and sex of the Canary Island community showed that values were below the UL in children as well as in adults. These outcomes were compared with data from other populations at the national and international levels.

Assessment of Toxic Metals (Al, Cd, Pb) and Trace Elements (B, Ba, Co, Cr, Cu, Fe, Mn, Mo, Li, Zn, Ni, Sr, V) in the Common Kestrel (Falco tinnunculus) from the Canary Islands (Spain).

The monitoring of trace elements and toxic metals in apical predators of the trophic chain provides data on the degree of contamination in ecosystems. The common kestrel is one of the most interesting raptors in this respect in the Canary Islands; therefore, the study of the levels of trace elements and toxic metals in this species is of much scientific value. The content of trace elements and toxic metals (B, Ba, Co, Cr, Cu, Fe, Mn, Mo, Li, Zn, Ni, Sr, V, Al, Cd, Pb) was determined in the liver, muscle, and feathers of 200 specimens of common kestrel carcasses (Falco tinnunculus canariensis) from Tenerife. Cr (0.82 ± 2.62 mg/kg), Cu (11.82 ± 7.77 mg/kg), and Zn (198.47 ± 520.80 mg/kg) are the trace elements that stand out in the feather samples; this may be due to their affinity for the pigments that give them their coloring. Li was noteworthy in the liver samples (8.470 ± 5.702 mg/kg). Pb stood out in the feathers (4.353 ± 20.645 mg/kg) > muscle (0.148 ± 0.095 mg/kg) > liver (0.187 ± 0.133 mg/kg). The presence of metals in feathers correlates with recent exposure and reflects environmental contamination. When using raptor feathers as indicators of metal contamination, it is important to know what the levels of each metal signify. The analysis of the different tissues and organs of raptors, such as the common kestrel, provides valuable information on the degree of environmental contamination of the ecosystem in which it lives. Gender was not an influencing factor in this study.