Dietary supplementation of mineral nanoparticles for channel catfish (Ictalurus punctatus).

This study evaluated the supplementation of iron and copper nanoparticles in channel catfish diets and their influences on growth and health. A comparative feeding trial was carried out for 9 weeks to evaluate combinations of iron and copper nanoparticles: only iron nanoparticles (IronNP), only copper nanoparticles (CopperNP), CopperNP + IronNP, and a control diet supplemented with inorganic iron and copper (FeSO4 and CuSO4). After a 9-week feeding trial, growth performance, hematological parameters, whole-body proximate composition, and intestinal microbiota were evaluated, and fish were subjected to a bacterial challenge against Edwardsiella ictaluri to evaluate the contribution of the experimental treatments to fish health status. No statistical differences were detected for catfish fed the various diets in terms of production performance or survival after bacterial challenge. The hematocrit and RBC counts from fish fed the diet containing copper nanoparticles were significantly lower than the control group. A higher relative abundance of gram-positive bacteria was found in the digesta of catfish fed diets containing copper nanoparticles. Furthermore, in the context of hematology, iron nanoparticles did not impact the blood parameters of channel catfish; however, reduced hematocrits were observed in fish fed the copper nanoparticle diet, which lacked supplemental dietary iron, thus reinforcing the importance of dietary iron to catfish hematopoiesis. Nonetheless, additional studies are needed to investigate the effects of dietary copper nanoparticle supplementation in catfish diets to better illuminate its effects on the intestinal microbiota.

Copper Deficiency Associated with Glycemic Control in Individuals with Type 2 Diabetes Mellitus.

Adequate copper (Cu) status has been associated with improved glycemic control, partly because of its role in reducing oxidative stress through superoxide dismutase (SOD) activity. Thus, the aim was to investigate the relationship between plasma Cu concentration and markers associated with glycemic control in individuals with type 2 diabetes mellitus (T2DM). This observational and cross-sectional study was conducted in individuals with T2DM of both sexes, aged between 19 and 59 years. Plasma Cu levels were analyzed using inductively coupled plasma optical emission spectrometry (ICP-OES). Fasting glucose and insulin concentrations, C-peptide levels, SOD activity, and glycated hemoglobin (%HbA1c) were measured. Homeostatic model assessments (HOMA%B, HOMA%S, and HOMA-IR) were also performed. Additionally, %body fat and waist circumference were measured, and body mass index was calculated. Participants were categorized based on their plasma Cu concentrations (< 70 µg/dL and ≥ 70 µg/dL). The associations between variables were analyzed using chi-squared or Fisher's test and binary logistic regression models. Statistical significance was set at P < 0.05. Of the 97 participants (74.2% women), 85.5% had Cu deficiency. Cu-deficient individuals showed elevated C-peptide concentrations and HOMA%B values compared to those with adequate Cu levels (2.8 ng/mL vs. 1.8 ng/mL, P = 0.011; and 71.4 vs. 31.0, P = 0.003), respectively. Cu deficiency was associated with insulin resistance (P = 0.044) and decreased likelihood of exceeding the target serum glucose level (OR = 0.147, P = 0.013). However, no significant association was found between SOD activity and plasma Cu concentration. Consequently, Cu deficiency was linked to improved glycemic control, although it was not associated with the other markers.

An overview of preconcentration techniques combined with inductively coupled plasma mass spectrometry for trace element determination in biological studies.

In the last decades, the determination of trace elements in biological materials has emerged as an important area of study because of its relevance to human health and the environment. Inductively coupled plasma mass spectrometry (ICP-MS) has proven to be a powerful tool for trace element analysis, owing to its high sensitivity and ability to determine several elements in a single measurement. However, given the complex nature of biological matrices and the presence of elements, most of them at ultratrace levels, it becomes crucial to complement ICP-MS with preconcentration techniques to increase the sensitivity and selectivity of analytical methods. This article presents an exhaustive overview of liquid- and solid-phase preconcentration techniques used in combination with ICP-MS for trace element determination in different biological samples from 2000 to the present. An in-depth discussion of the advances on the application of state-of-the-art solvents and materials in trace element extraction and preconcentration is presented. Special attention is given to different strategies for elemental speciation analysis, employing both chromatographic and non-chromatographic techniques. The role of automation in these methodologies is also described. Finally, future trends and challenges related to this topic are discussed.

Deep eutectic solvents as a green alternative for trace element analysis in food and beverage samples: Recent advances and challenges.

Metals and metalloids have different effects on human health even at trace levels. Some of them are essential for living organisms while others can be toxic. Therefore, the determination of trace elements in food and beverage is highly important to understand their impact in human health. A new generation of solvents named deep eutectic solvents (DES) has emerged as a green alternative for trace element analysis, owing to their low toxicity, biodegradability, and high extraction capacity. In recent years, the application of DES in extraction techniques for trace element analysis in food and beverage samples has increased significantly. This review summarizes recent advances and challenges on the application of DES to develop microextraction techniques useful for the analysis of samples with complex matrices. The importance of the use of biodegradable substances instead of classic organic solvents, which are toxic, volatile, and flammable in methods for elemental analysis with a positive environmental impact is also highlighted. Finally, conclusions and future challenges arising from the use of DES in microextraction techniques are discussed.

Root development in Leucaena leucocephala (Lam.) de Wit enhances copper accumulation.

Potentially toxic elements (PTE) in soil like copper (Cu) have been common in agricultural and mining areas worldwide. The sustainable remediation of these areas has been shown to have high socio-environmental relevance and phytoremediation is one of the green technologies to be considered. The challenge is to identify species that are tolerant to PTE, and to assess their phytoremediation potential. The objective of this study was to evaluate the physiological response of Leucaena leucocephala (Lam.) de Wit and to determine the species tolerance and phytoremediation potential to concentrations of Cu in the soil (100, 200, 300, 400 and 500 mg/dm3). The photosynthetic rate was not affected, while the content of chlorophylls decreased as Cu concentrations increased. There was an increased in stomatal conductance and water use efficiency from the treatment of 300. The root biomass and the length were bigger than the shoots, in the treatments above 300. Cu accumulation was greater in the roots than in the shoot of the plants, thus, the Cu translocation index to the shoot was lower. The ability to absorb and accumulate, mainly, Cu in the roots, allowed the development and growth of plants, since the parameters of photosynthesis and biomass accumulation were not affected by the Cu excess. This accumulation in the roots is characterized as a strategy for the phytostabilization of Cu. Therefore, L. leucocephala is tolerant to the Cu concentrations evaluated and has a potential phytoremediation of Cu in the soil.

High aluminum content in bone of marine mammals and its relation with source levels and origin.

Although aluminum is widely distributed in the earth's crust, its environmental availability and wildlife assimilation rates are only partially known. Here we analyze aluminum concentrations in bone from 10 species of marine mammals inhabiting 3 geographic areas subject to different aluminum inputs: the Río de la Plata estuary (Uruguay), the coastal waters of Mauritania and the Galapagos archipelago (Ecuador). Overall, concentrations were unusually high as compared to those of terrestrial animals, with lowest concentrations in the Galapagos archipelago, then the Río de la Plata estuary and finally Mauritania. The aluminum source varied between regions, prevailing anthropogenic sources in the Río de la Plata Estuary and natural sources (wind-blown dust) in Mauritanian waters. The type of source determined contamination levels: anthropogenic sources were most significant for coastal species and showed a decline with distance of habitat from shoreline, while natural sources had a higher influence on open waters because of the dearth of biogenic silica that eliminates aluminum from the water column. Since aluminum remains in bone for several decades, marine mammal bone reflects historical levels of aluminum and therefore is a good bioindicator of the aluminum concentration of the marine environment.

Antiproliferative Effect of Inorganic and Organic Selenium Compounds in Breast Cell Lines.

Triple-negative breast cancer (TNBC) is an aggressive, fast-growing tumor that is more likely to spread to distant organs. Among women diagnosed with breast cancer, the prevalence of TNBC is 20%, and treatment is currently limited to chemotherapy. Selenium (Se), an essential micronutrient, has been explored as an antiproliferative agent. Therefore, this study aimed to evaluate the effects of exposure to organic (selenomethionine, ebselen, and diphenyl diselenide) and inorganic (sodium selenate and sodium selenite) Se molecules in different breast cell lines. The compounds were tested at 1, 10, 50, and 100 µM for 48 h in the non-tumor breast cell line (MCF-10A) and TNBC derivatives cell lines (BT-549 and MDA-MB-231). The effects of Se on cell viability, apoptotic and necrotic processes, colony formation, and cell migration were analyzed. Exposure to selenomethionine and selenate did not alter the evaluated parameters. However, selenomethionine had the highest selectivity index (SI). The exposure to the highest doses of selenite, ebselen, and diphenyl diselenide resulted in antiproliferative and antimetastatic effects. Selenite had a high SI to the BT cell line; however, the SI of ebselen and diphenyl diselenide was low in both tumoral cell lines. In conclusion, the Se compounds had different effects on the breast cell lines, and additional tests are needed to reveal the antiproliferative effects of Se compounds.

Assessment on Solubility and Solid Phase Chemical Fractionation of Manganese in Hot Infusions of Green and Roasted Mate.

A solid phase chemical fractionation (SPCF) of the Mn in hot infusions prepared from commercial samples of roasted (RM) and green mate (GM) using a chelating resin Chelex 100 (NH4+ form) was performed to assess the relative lability of this essential trace element (ETE). In addition, total Mn contents in the RM and GM samples and their infusions were determined by flame atomic absorption spectrometry. Total polyphenol (TP) contents and the presence of soluble melanoidins (SM) were correlated with the Mn solubility in the RM and GM infusions. From the SPCF study, it was possible to observe that the soluble Mn forms in the mate infusions were essentially associated with relatively noninert chemical species (98.4-99.7%), suggesting that they may be potentially bioavailable. In addition, the soluble Mn contents in the GM infusions were 20.5% higher than those found in the RM. Mn solubility in the (RM) infusions was highly and directly correlated (r = 0.99) with the soluble TP, while in the GM infusions, it was high and inversely correlated with soluble TP (r = -0.87). On the other hand, Mn solubility in the RM and GM infusions was weakly correlated with the SM. It should be stressed that GM infusions can contribute with 57 and 44% more than the RM infusions to the recommended adequate intake of Mn established for females and males, respectively. Moreover, this work is the first to evaluate and compare the relative lability of Mn and its solubility in the RM and GM infusions.

Simultaneous external and internal marking of Triatoma sordida nymphs: trace element efficacy and microgeographic dispersal in a peridomestic Brazilian Cerrado rural household.

BACKGROUND: Chagas disease (American trypanosomiasis) is an important neglected tropical illness, which has the flagellate protozoan Trypanosoma cruzi as etiological agent and blood-feeding insects of the Triatominae subfamily as vectors. Despite its importance for disease epidemiology, field studies targeting microgeographic dispersal of triatomines in endemic areas are rare. The ability wingless nymphs have to move (crawl) within peridomestic settings is a key component regarding the design and development of rational control strategies. METHODS: We double-marked Triatoma sordida fourth-instar nymphs (N4) with a reliable fluorescent dye and a trace element. This new methodology allowed us to simultaneously evaluate (i) nymph dispersal and (ii) the effectiveness of copper (Cu), chromium (Cr), and cadmium (Cd) trace elements as potential new markers. In the mark-release-recapture (MRR) experiment, 390 T. sordida N4 were released in the peridomicile of a single rural household, 130 individuals at each of three release points, at distances of 2, 5, and 10 m from the chicken coop (CC) and 27, 32, and 35 m away from the horse corral (HC). All specimens were double marked (Cu/blue, Cr/orange, Cd/green). Recaptures occurred in two intervals: 1-3 days and 15-17 days after release. RESULTS: Specimens were successfully recaptured at all distances up to 10 m. A total of 19, 23, and 10 specimens were able to disperse 2, 5, and 10 m, respectively, to reach the CC. No insects were recaptured at the HC. Of the three analyte/paint combinations tested, Cr/orange gave the most promising results; Cu/blue marker and Cd/green marker performed very poorly with only 4/19 and 0/10 analyte/paint ratios, respectively. CONCLUSIONS: Triatoma sordida N4 could cover a distance of 10 m in 17 days. This indicates that nymphs seem to have a reduced dispersal capability compared to adults. Ninety-one percent of the 22 recaptured orange-marked nymphs were still Cr positive after the 17-day period evaluated. This makes this analyte a good candidate for future investigations that will apply this marking method in MRR studies.

A Practical Procedure for Analysis of Lead Isotopes in Bivalve Shells Using Laser Ablation Multicollector Inductively Coupled Plasma Mass Spectrometry (LA-MC-ICP-MS).

Lead, like other trace elements, is incorporated in the growing bands of bivalve shells. The chemicals stored into the shells can provide valuable information about seawater conditions during the period of shell formation. In this study, we present a practical approach to determine Pb isotopic signatures in bivalve shells as a tool for evaluating lead pollution in coastal waters. To demonstrate the applicability of the method, Pb isotopic fingerprinting in bivalve shell layers were investigated using laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). Lead isotope ratios (208Pb/206Pb and 206Pb/207Pb) were measured along distinct sections of the maximum growth axis of the shells. Calibration and quantification of Pb isotopes were performed using NIST 612 as reference material. Our results demonstrated that Pb isotope ratios in the shells ranged from 1.143 to 1.201 for 206Pb/207Pb and from 2.061 to 2.161 for 208Pb/206Pb. The isotopic signatures recorded in the sample shells correspond to similar ranges of Pb signatures reported for marine sediments from the same study area. In general, this work shows that LA-MC-ICP-MS is a suitable technique for determining spatially resolved lead isotopic signatures in bivalve shells and that it can be used to estimate the origin of Pb pollution in aquatic environments.

Trophodynamics of trace elements in marine organisms from cold and remote regions of southern hemisphere.

Trace metals bioaccumulate in aquatic organisms and some of them biomagnify through food webs, posing a threat to the organisms or their human consumers. Although the trophodynamics of many trace metals is well known in the northern hemisphere, much less is known about metals in aquatic food webs from cold and remote coastal zones of the southern hemisphere. To fill this gap, we investigated the trophodynamics of Al, Co, Cr, Li, Mo, Ni, Sr, and V, which were measured in marine macroinvertebrates and fishes from inshore and offshore locations in each of the Chilean Patagonia and the Antarctic Peninsula area. In Patagonia, there was biodilution of these metals across the whole food web, while biomagnification of Li and Ni was significantly found across the lower food web at the offshore site. In Antarctica, significant biodilution of Al, Li, Ni, Mo, Sr and V occurred through the whole food web for the inshore site, but no tendency (biodilution or biomagnification) was found (p > 0.05) across the organisms at lower trophic levels for the offshore site. Our data suggest that the geographic location and species influences the trophodynamics of these trace elements and expand our understanding of metal fate in remote locations of the southern hemisphere.

Before the Dam: A Fish-Mercury Contamination Baseline Survey at the Xingu River, Amazon Basin Before the Belo Monte Dam.

In the last decades, mega-diverse rivers worldwide (e.g., the Amazon and their tributaries) have experienced several human-driven transformations, although impact assessments oftentimes lack baseline data or reference values to better estimate observed disturbances. Herein, we assessed THg and δ15N in fish muscle tissue to determine biomagnification processes, also including seasonal assessments, concerning Hg in fish from the Belo Monte reservoir, located on the Xingu River, prior to its impoundment. A total of 312 samples from 19 fish species belonging to distinct feeding guilds were sampled. None presented THg concentrations above the threshold levels of 0.5 µg g-1 established by the World Health Organization. However, biomagnification was observed (R = 0.8; p < 0.001), also confirmed by a trophic magnification factor of 1.76 for the entire food web. The THg content in the water was less than 0.001 mg L-1 and only Hemiodus unimaculatus presented seasonal variations for THg. Therefore, at the time of this study, the Xingu River presented low Hg contamination levels in both water and target fish.

A Selective Fluorescent Probe for the Determination and Imaging of Fluoride in Living Cells

Abstract Fluoride anions are indispensable trace elements required for sustaining life. To investigate the homeostasis and action of fluoride in the body, a new highly sensitive and selective fluorescence detection method was designed for fluoride in aqueous solutions. A fluorescent probe for fluoride (FP-F) was synthesized for imaging F- in living cells. The design strategy for the probe was based on the specific reaction between fluoride and silica to mediate deprotection of this probe to fluorescein. Upon treatment with F-, FP-F, a closed and weakly fluorescent lactone, was transformed into an open and strongly fluorescent product. Under the optimum conditions, the detection limit for fluoride was 0.526 nM. FP-F could detect micromolar changes in F- concentrations in living cells by confocal microscopy.

Trace element fluxes during the "Anthropocene" in a large South American industrial and port area (Santos and São Vicente estuarine system, SE, Brazil).

The worldwide evidence of human activities on the environment led the scientific community to recognize a new geologic time unit known as the "Anthropocene." Since the twentieth century, urbanization and industrialization needs driven by population and economic growth have impacted several ecosystems including the estuaries. To assess the contamination, provenance, and fluxes of trace elements (As, Cr, Cu, Ni, Pb, Sc, V, and Zn) over the last century, a geochemical and chemometric technique was employed in sediment cores of an industrial and port region of international importance, the Santos and São Vicente Estuarine System (SSVES). The results indicated low contamination, with the highest enrichment factors (EFs) for Cu (EF = 3.1), Pb (EF = 2.7), Zn (EF = 2.4), and As (EF = 2.3) found next to the harbor area. The Pre-industrial records confirm the relatively high concentrations of As and its naturally enriched occurrence on the Brazilian shelf. Sediment accumulation rates and trace element fluxes showed a general increase over the years, since the early 1960s, associated with the "Great Acceleration" of the mid-twentieth century. These alterations are human-induced and include urbanization and industrialization. Nonetheless, as the contents and enrichment of trace elements indicate that the region is not severely polluted, we hypothesize that the contamination in the SSVES is likely related to the drainage and erosion of the urbanized adjacent area, rather than direct disposal of inorganic contaminants from the industrial activity.

Trace element proxies and stable isotopes used to identify water quality threats to elkhorn coral (Acropora palmata) at two national parks in St. Croix, USVI.

Biological impairments have been documented on reefs at two national parks in St. Croix, USVI. Although several water quality parameters have been out of compliance with USVI criteria, whether these parameters or other pollutants are responsible for coral health impacts is unknown. Trace elements quantified in sediment showed four sites at SARI, which is closer than BUIS to settlements and land-derived anthropogenic outflows, had Cu mass fractions above sediment quality guidelines for invertebrate toxicity. Trace elements were also analyzed in the skeleton of threatened elkhorn coral, Acropora palmata, to evaluate potential exposure. Heavy metals (Pb, Zn) were significantly greater in coral skeleton at SARI than BUIS. Cu, Pb, and Zn may be impacting coral health in these parks. Potential anthropogenic sources of these metals were revealed by the coral tissue stable isotope levels (δ13C and δ15N). These findings provide a framework for determining heavy metal impacts on these invaluable reefs.

On-Line Preconcentration and Simultaneous Determination of Cu and Mn in Water Samples Using a Minicolumn Packed with Sisal Fiber by MIP OES.

An on-line preconcentration system for the simultaneous determination of Copper (Cu) and manganese (Mn) in water samples was developed and coupled to a microwave-induced plasma optical emission spectrometer (MIP OES). The flow injection system was designed with a minicolumn packed with sisal fiber (Agave sisalana). A multivariate experimental design was performed to evaluate the influence of pH, preconcentration time, and eluent concentration. Optimal conditions for sample preparation were pH 5.5, preconcentration time was 90 s, and HCl 0.5 mol L-1 was the eluent. The main figures of merit were detection limits 3.7 and 9.0 µg L-1 for Cu and Mn, respectively. Precision was expressed as a relative standard deviation better than 10%. Accuracy was evaluated via spiked recovery assays with recoveries between 75-125%. The enrichment factor was 30 for both analytes. These results were adequate for water samples analysis for monitoring purposes. The preconcentration system was coupled and synchronized with the MIP OES nebulizer to allow simultaneous determination of Cu and Mn as a novel sample introduction strategy. The sampling rate was 20 samples/h. Sisal fiber resulted an economical biosorbent for trace element preconcentration without extra derivatization steps and with an awfully time of use without replacement complying with the principles of green analytical methods.

Pesticide and trace element bioaccumulation in wild owls in Brazil.

Owls are outstanding environmental quality bioindicators due to their position at the top of the food chain and susceptibility to pollutant accumulation. Exposure to chemical contaminants is often a risk for these animals. Moreover, studies addressing the bioaccumulation of trace elements and pesticide residues in tropical nocturnal raptor species are scarce. We analyzed the 26 organs (heart, liver, and kidney) of Tyto furcata (n=3), Megascops spp. (n=5), Pulsatrix koeniswaldiana (n=1), and Asio stygius (n=1) carcasses, collected from June 2018 to May 2019 in the Southern region of Brazil. The original vegetation consisted of areas of Araucaria forests and grassy-woody steppes with gallery forests, which were greatly modified by the introduction of agriculture. In four animals and eight organs, the pesticides abamectin, atrazine, chlorpyrifos-ethyl, and diurom were analyzed through high-performance liquid chromatography coupled with a mass detector. In six animals and eighteen organs, the trace elements cadmium, lead, chromium, and nickel were identified via atomic absorption spectrophotometry. Chlorpyrifos-ethyl was detected in the livers of the genus Megascops. Chromium was found at high concentrations in all matrices analyzed for this trace element. Moreover, P. koeniswaldiana presented lead levels indicative of high exposure. The bioaccumulation of these toxics in owls described here can impact the population levels of these species, impact on its ecological function, and consequently unbalance the ecosystem. Moreover, owls are considered bioindicators; therefore, the occurrence of bioaccumulation indirectly gives us information about the quality of the environment.

Influence of agricultural system transition on trace element contamination in salt marsh and seagrass sediments from a coastal Ramsar site.

Vegetated coastal ecosystems have an important role as contaminant filters. Temporal variations in concentrations, enrichment factors (EF), and fluxes of trace elements (As, Cd, Co, Cr, Cu, Ni, Pb, V, and Zn) were evaluated in 210Pb-dated sediment cores from salt marsh and seagrass ecosystems at San Quintín Bay (Mexican northern Pacific). Trace element contamination was negligible in seagrass sediments, but minor to severe, depending on the element, in salt marsh cores, owing to higher organic carbon and fine sediment contents. EF temporal variation in salt marsh cores was attributed to agriculture technology changes (e.g. installation of greenhouses, and improved irrigation and fertilization systems). Trace element flux ratios increased during the past 100 years, likely caused by steadily increasing sediment accumulation rates promoted by land-use changes in the catchment. The conservation of salt marsh areas is important to preserve their function as contaminants biofilters and the health of adjacent ecosystems.

Anthropogenic and climate induced trace element contamination in a water reservoir in northwestern Mexico.

Water reservoirs are essential for regional economic development, as populations depend on them for agriculture irrigation, flood control, hydroelectric power generation, water supply for human consumption, and subsistence fishing activities. However, the reservoir environmental quality can be disturbed by enhanced sediment input and trace metal contamination, affecting human health as a consequence of contaminated water and fish consumption. With the purpose to understand the trends and extent of sediment accumulation and trace element contamination in the Oviachic reservoir (OV, northwestern Mexico) since its construction, the temporal variations of sediment accumulation, and As, Cr, Cu, Hg, Ni, Pb, and Zn concentrations, enrichment, and fluxes, were evaluated through the study of two 210Pb-dated sediment cores. We assumed that siltation and trace element contamination were driven by the development of anthropogenic activities in the region within the past ~ 70 years. Elemental concentrations accounted from null to minor enrichment for most elements, but moderate to significant enrichment by Hg. Mercury, As, and Cu fluxes have notably increased since the past decade, most likely because of a combination of anthropogenic and natural processes, including catchment erosion, artisanal gold mining, and recent drought conditions in the region. Arsenic and Hg concentrations may pose deleterious risks to biota in the reservoir, and consequently to humans through fish consumption, for which further biological and toxicological tests are advisable. This study highlights the importance of using sediment dating to assess historical trends of metal contamination and identify possible sources, to support decision-making in programs addressed to reduce environmental and health risks in aquatic ecosystems.